Petroleum Science and Technology

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STUDY OF COMPOSITION OF NIGERIAN TAR SAND

BITUMEN

OKECHUKWU UKWUOMA

To cite this article: OKECHUKWU UKWUOMA (1999) STUDY OF COMPOSITION OF

NIGERIAN TAR SAND BITUMEN, Petroleum Science and Technology, 17:1-2, 57-65, DOI:
10.1080/10916469908949706

To link to this article: http://dx.doi.org/10.1080/10916469908949706

Published online: 16 May 2007.

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 PETROLEUM SCIENCE AND TECHNOLOGY, 17(1&2),57-65 (1999)

STUDY OF COMPOSITION OF NIGERJAN TAR SAND BITUMEN

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BY
OKECHUKWU UKWUOMA
DEPARTMENT OF CHEMICAL ENGINEERING
ENUGU STATE UNIVERSITY OF SCIENCE AND TECHNOLOGY
INDEPENDENCE LAYOUT, P, M, B, 01660, ENUGU NIGERIA.

AJJSTRACT
Compositional characterization techniques developed for high-boiling heavy ends of
petroleum have been applied to Nigerian tar sand bitumen. The bitumen was subjected to ion-
exchange and ferric chloride coordination chromatography to separate acids. bases and neutral
nitrogen compounds. The remaining lIydrocarbon plus fraction was separated into saturates,
manoarnuuics, diaromatics and potyaromatic plus polar compounds 011 dual packed column of
silica - alumina gels. Simulated distillation data were a/so obtained for the bitumen and were
used to plot a boiling point distribution curve.
Results of the characterization are compared with results in literature for tar sand
bitumens and petroleum. Comparison of the results with the Utah and the Athabasca bitumens
provides a basis for the evaluation of the Nigerian bitumen because considerable information
about the processing characteristics of the Athabasca bitumen have been reponed by many
researchers.
Simulated distillation and chromatographic separation data indicate that the bitumen used
in this present study closely resembles the Athabasca and the Utah tar sand bitumens with respect
to hydrocarbon/non-hydrocarbon distribution, and the high-boiling petroleum fraction with
respect to non-distilling portion. Information about the composition of bitumens and heavy oils
is needed because of the prospect of using heavy oils including bitumens as energy sources.

57

Copyright 01999 by Marcel Dekker, Inc www.dekkes .com

 58 UKWUOMA

INTRODUCTION
Detailed compositional Analyses of bitumens and high-boiling Heavy ends of Petroleum
arevery important because increased energyrequirements. together with increased environmental
constraints require moreefficient use of heavy oils. Bitumen is a viscous, high-boiling mixture
containing aliphatic and aromatic hydrocarbons. and considerable amounts of organic acids.
bases and hereucyclic compounds (Bunger, 1976).
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Tar-sand bitumens can be converted into more useful products and sources of energy.
The efficient recovery and processing of these resources requires detailed scientific analyses of
their compositions. The physical and chemical properties of the bitumens depend on their
compositions, and they ultimately determine their value because these properties influence
recovery. processing, conversion and utilization of fossil energy resources.

(Allinson, 1973; Bailey, 1974; and Brooks et ai, 1950) recognized and discussed the
importance of feedstock chemical composition to refiningprocesses. Feedstock compositionhas
a direct effect on yields and the value of the product produced. The composition, propenies and
chemical reactivity of Athabasca bitumen have been reported (Speight, 1973; Moschopedis et
al, 1976; Hayes et al , 1972; end Milan et al , 1977) and Utah bitumens (Strausz, 1977; Bunger,
1976 and Bunger CI al 1979).

This paper discusses the investigations carried OUI on the composilion of Nigerian Tar
Sand Bitumen. The separation scheme was essentially similar to the one previously described
(Jewel et al, 1972). It consisted of the removal of acids and bases with ion-exchange resins,
neutral nitrogen compounds by complexation with ferric chloride adsorbed on Anapulgus clay,
and the fractionation of the remaining hydrocarbon and polar non-hydrocarbon compounds into
saturates. monaromatics, diaromatics, and polyaromatic plus polar compounds on a dual packed
column of silica-alumina gels. This last stage was similar to that previously reported (Hirsch
et al, 1972). However, simulated distillation on Gas-Liquid chromato-graphy was also carried
out on the bitumen.

EXPERIMENTAL SECTION
Sources and Preparation of Bitumen Samples
The bitumen investigated in this present study was extracted from Nigerian tar sand
deposit in the South Western Nigerian Area lying between the latitudes 545' and 550 ' Nonh,
and between the longitudes 4 00' and 4 30' East.
 NIGERIAN TAR SAND BITUMEN 59

The procedure for extraction of the bitumen from the tar sand sample. filtration and the
removal of solvent from the extracted bitumen has been described (Ukwuoma, 1985).

Analysis of Bitumen
The physical properties of the bitumen were determined by the conventional ASTM
techniques. Sulphur content was determined by quartz tube method similar to the one
recommended by ASTM1551 but with some modifications. The viscomsities were estimated
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using Co-axial Rotating Visconeter (Haake Instrument, ROTOVISCO-RV3). Simulated

Distillation of the whole bitumen was made on a varian Instrument, AEROGRAPH SERIES
3700 GAS CHROMATOGRAPH by method which has been previously applied (worman and
Green, t965). The method for separation of the bitumen into acids, bases neutral nitrogen
compounds, saturated hydrocarbons, and aromatic have been previously described (Bunger.
1976) but the solvent used for elution in the study was cyclohexane while the anion-exchange
resin was Ambcrlite lRA-140 and the cation-exchange resin was Amberlite IR-120.

Asphaltenes were precipitated by digesting the bitumen in n-heprane at room temperature

for 24 hours. The mixture was filtered. and the precipitated asphaltenes were washed with n
heptane until the washings were colourless. The asphaltenes were dried and weighed.

RESULTS AND DISCUSSION

Bitumen Properties
Table I lists the physical properties and sulphur content as well as distillate yield
(< 538C) of the extracted bitumen used in this present study. The sulphur content of 3.57 %
is in the range observed for other bitumens from their respective deposits in USA and Canada
(Bunger et ai, 1979) and this is higher than those observed in many virgin petroleum.

Ash content and specific gravities all compared well with the literature values for tar-sand
bitumens. The viscosity values at 100F and 210F are high and may not accurately represent
the viscosity of the bitumen in place owing to the unknown effects of incomplete removal of
extraction solvent and the loss of light ends.
Condradson carbon residue of 14.8% compared weIl with what is observed for heavy
ends of petroleum. The conradson carbon residue roughly correlates with the amount the of
n-heptane insoluble asphaltenes present in the bitumen (10.6%).
 60 UKWUOMA

TABLE J

Characteristics of Nigerian tar sand bitumen

Specific gravity 60F \.008

API gravity 8.7

Viscosity (est) at 100F 323,834

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Viscosity (est) at 210F 364

Sulphur, wt % 3.57

Ash, wt % 0.24

Conrodson carbon residue, wt % 14.8

Asphaltenes (heptane insoluble) wt % 10.6

Saturates wt % 33.1

Aromatics, w! % 2\.9

Polar Compounds, wt % 24.0

Total hydrocarbons, W( % 55.0

Distilla,e yield 538C), wt % 65.2

Table 11 lists the simulated distillation data for the bitumen used in the present
experiment. The data are comparable to the data obtained by the method described for obtaining
a boiling point distribution curve equivalent to that obtained from a lOO-theoretical plate
analytical distillation (Green et ai, 1964), but the advantage is that simulated distillation allows
extension of temperatures above IOOOF (538C) without decomposition.

Separation of bitumen into fractions

The bitumen was separated into simplified, defined fractions by ion-exchange, ferric
chloride compexation and adsorption chromatography (Jewell et at, 1972 and Bunger, 1976).
The results of the separation of the bitumen, the proportions (wt%) of the fractions are shown
in Table Ill.
 NIGERIAN TAR SAND BITUMEN 61

TABLE 11
Simulated distillation of tar sand bitumen, weight % and cumulative wt % of the bitumen

Cut point wt distilled Cumulative \\1

('C) (%j distilled (%j

215 Initial
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225 1.2 J .2

250 1.6 2.8

275 3.7 6.5

305 7.4 12.9

335 4.2 17.1

365 5.1 22.2

395 6.5 28.7

425 6.9 35.6

450 8.5 44.1

490 11.7 55.8

520 3.9 59.7

538 5.5 65.2

Residue 34.8 100.0

The 7 fractions that were generated by this procedure are labelled acids. bases, neutral
nitrogen compounds, saturates, monoarmatics, diaromatics, and polyaromatic-polar compounds.
This separation facilitates a more precise and accurate analysis by analytical techniques primarily
because it highlights the concentrations of certain functionalities in certain fractions. A
compound is defined as an acid or a base if it has ability to associate with ethnoJamrnonium
hydroxide of anion resin or the sulphuric acid of he cation resin, respectively.
 62 UKWUOMA

TABLE III
RESULTS OF COMPOUND TYPE SEPARATION OF TAR SAND BITUMEN (WT %J

Compound type Weight % of bitumen

Acids 5.4

Bases 11.4
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NCUIral Nitrogen Compounds 3.7

Saturates 33.1

Monoaromatics 12.4

Diaromatics 95

Total hydrocarbons 55.0

Polyaromatic-polar" compounds 21.2

(Unclassified polar compounds)

Total recovery 96.7

The results shown that the bitumen has low saturates and total hydrocarbons compared
to conventional high-boiling petroleum fractions (Chandra and Bhatia, 1984, Mckay, 1981).
Aromatics and unclassified polarcompounds accountfor the largestportionof the bitumen. The
proportion of polyaromatics and polar compounds (acids, bases, neutral nitrogen compounds)
is high and this may account for the high specific gravity of the bitumen (1.008). The total
hydrocarbons content is in the rangeobserved for those of Athabasca and Utah tar sand bitumens
while its total acids and neutral nitrogen contents are rather lower compared to their contents,
and the result of the bases is similar to values reponed for the two bitumen deposits mentioned
above.

Simulated distillation of the bill/men

The bitumen was also analysed by simulated distillation on Gas Liquid Chromatography
(GLC). Simulated distillation chromatogram is shown in figure II while the boiling point
distribution curve plotted from the data generated is shown in Figure I. The simulated
 NIGERIAN TAR SAND BITUMEN 63

TEMPERATURE ('C)
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o 10 20 30 40 50 60 70

Cumulative amount distilled (t)

Figure I Cumulative simulated distillation curve Jar tar sand bitumen analysed

Figure II. Chromatogram of Simulaled distil/ation of the bitumen.

 64 UKWUOMA

distillation data showed that the total bitumen distillable is 65.2% 538C). This result is
higher in value than those reported for athabasca and Utah tar sand bitumens (Bunger et aI,
1979). The results of the simulated distillation arc comparable with results for high-boiling
petroleum reactions (Worman and Green, 1965). In the distillable portion the tar sand bitumen
is similar to petroleum samples. However, because of the nature of bitumen as indicated in
Table I, more heteroatomic cnmpounds are likely to be present in the distillable portion of the
bitumen compared to petroleum.
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REFERENCES
Allinson. J. P. (Ed.) 1973. Criteria For Quality of Petroleum Products. John Wilcy,NewYork.

Bailey, W. A. Jr., ami G. P. Hinds, Jr. 1974. ACS, Div. Fuel Chern. Preprints 19 (I) 14.

Brooks, B. T., and A. E. Dunstan (Eds). 1950. The Science of Petroleum, Vol V, Part I,
Oxford University Press London.

Bunger, J. W. 1976. Characterization of a Utah Tar Sand Bitumen. Advances in Chemistry

Series, No. 151 ACS, 121,

Bunger, J. W., K. P. Thomas and S. M Dorence. 1979 Compound Types and Propcrucs of Utah
and Athabasca tar sand bitumens. Fuel 58, 183.

Chandra, D. and V. K. Bhatia. 1984. Study of the composition of Heavy Ends of Petroleum.
J. Chern. Tech. Biorecbnol 34 A, 203.

Green L. E., L. J. Schmauch, and J. C. Worman. 1964. Simulated Distillation by Gas

Chromatography. Analytical chemistry 36 (8), 1512.

Hayes, M. H. B., M. Stacey, and J. Standley. 1972. Studies on Bitumen; Part I,

Characterization of Bitumen by USe of Physical Methods. Fuel 51,27.

Hirsch, D. E; R. L. Hopkins, H. J. Coleman, F. O. Cotton and C. J. Thompson. 1972.

separation of High-Boiling Petroleum Distillates Using Gradient Elution Through Dual-
Packed (Silica Gel Alumina Gel) Adsorption Columns. Analytical Chemistry 44 (8) 915.

Jewell, D. M., J. H. Weber, J. W. Bunger, Henry Planche, and D. R. Latham. 1972. 10n-
Exchange, Coordination, and Adsorption Chromatographic Separation of Heavy-End
Petroleum distillates. Analytical Chemistry 44 (8), 1391.

Mckay, J. F., P. M. Harnsberger, P. J. Amend, T. E. Cogswell and D. R. Lathan. 1981.

Composition of Petroleum Heavy ends. Fuel 60, 14.

Milan, L. S., Yingli Chu, Tomoki Ruo, and O. T. strausz. 1977. Chemical composition of
Athabasca Bitumen Fuel 56, 369.

Moschopedis, S. E., and J. G. Speight. 1976. Fuel 55, 187. Speight, J. G. 1973. Fuel 52,
300.
 NIGERIANTAR SAND BITUMEN 6S

Strausz, O.P. 1976. ACS., Div. Petro. Chern. Preprints 21 (3), 456.

Worman, J. C. and L. E. Green. 1965. Simulated Distillation of High-Boiling Petroleum

Fractions. Analytical Chemistry 37, 1621.
Ukwuoma, F. O. 1985. Unpublished M. Sc. Thesis, University of Ife, Nigeria.

Received: October 6, 1997

Accepted: May 18, 1998
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