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© IPA, 2006 - 14th Annual Convention Proceedings, 1985
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PROCEEDINGS INDONESIAN PETROLEUM ASSOCIATION
Fourteenth Annual Convention, October 1985
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PETROLEUM GENERATION POTENTIAL OF COALS AND ORGANIC
RICH DEPOSITS: SIGNIFICANCE IN TERTIARY COAL RICH BASINS
P.A. Kelley , K.K. Bissada, B.H. Burda, L.W.Elrod, and R.N. Pheifer*
ABSTRACT
Coals, as massive concentrations of organic matter, are
present in many petroleum prospective basins worldwide.
The roles of these organic concentrates and their organic
constituents (macerals) in the generation of crude oil in
commercial quantities have been subjects of controversy
for many years. To assess the contribution of coal and the
various types of dispersed organic matter to accumulated
hydrocarbons, pyrolysis-gas chromatographic analyses of
individual macerals, bulk coals and organic rich rocks have
been performed and the results compared. Qualitatively,
only alginite produces a molecular range fingerprint that
closely resembles crude oil. The fingerprints of exinite
pyrolysates contain oil-range hydrocarbons; however, the
fingerprints are not similar to a normal oil. The hydro-
carbons generated by vitrinite in these experiments do not
show distributions resembling those of crude oils. Semi-
quantitative evaluation of the fingerprints suggests that
alginite generates significant quantities of oil-range hydro-
carbons and undoubtedly could source crude oil. Exinites
appear to generate smaller amounts of hydrocarbons,
though not similar in character to normal crudes. If pre-
sent in high concentrations, exinites may impart a signifi-
cant overprint on the character of the crude. Quantitatively,
vitrinite generates minor quantities of hydrocarbons and
must therefore be discounted as a viable oil source. These
observations support current geochemical concepts that
algae and bacteria probably represent the common basis
for all crude oils. The fact that C7-C22 n-paraffins, which
are primarily the products of thermal decomposition of
algae and bacteria, constitute a significant portion of
unaltered crudes may explain the great similarity in the
overall composition of crude oils worldwide. The hydro-
carbon contribution of other macerals would superimpose
specific chemical components on the overall crude oil
character.
INTRODUCTION
Recently there has been considerable discussion on the
generation potential of coals, particularly as a source for
oil. Coal has been postulated as an oil source because of
close association of coal measures and oil pools in areas
such as the Niger Delta, the Mahakam Delta, the Gippsland
Basin, and other basins in Australia and Indonesia. Such
inferences have had worldwide ramifications for oil explo-
* Texaco Inc. Houston, Texas, USA
ration not only in Australia and Indonesia but also in the
Bering Sea, the Beaufort Sea, and off the east coast of
Canada and United States. To evaluate the potential of
coals and coaly sediments to generate oil we have carried
out laboratory studies on the generation potential of
isolated macerals and of natural assemblages of macerals,
both dispersed in rocks and concentrated in bulk coals.
Our studies are similar to those performed by Evans et. al.,
1964; Romovacek & Kubat, 1968; Giraud, 1970; Leven-
thal, 1976; Giam et.al., 1977; Matters et.al., 1977; van de
Meent et.al., 1480; Dembicki et.al., 1983; Chaffee et.al.,
1983; Durand & Paratte, 1983; Gormly & Mukhopadhyay,
1983; and Larter, 1984. Figure 1 lists the geochemical
parameters examined in this investigation. Emphasis is
placed on pyrolysis-gas chromatographic analysis with
particular attention to the significance of the resulting
pyrolysate yields. Figure 2 shows a schematic diagram of the
pyrolysis-gas chromatographic method used in this study.
Briefly, a sample is heated in the absence of oxygen and a
portion of the hydrocarbons evolved during thermal decom-
position of the organic matter (S2) is trapped. The hydro-
carbons are subsequently separated by gas chromatography
to form a chromatogram with a distinct fingerprint. The
fingerprints provide clues to the natural hydrocarbon pro-
ducts that should be expected under geologic settings.
This paper will review the results of our investigations and
discuss the petroleum exploration significance of these
results.
RESULTS AND DISCUSSION
Hydrocarbon Generation Potential of Macerals
Figure 3 lists the general categories of maceral groups
and their natural precursors. The chemical composition of
the various macerals, expressed as H/C and O/C atomic
ratios, and the changes in elemental composition they
undergo during thermal maturation are shown in Figure 4.
On thermal decomposition, inertinite was observed to
yield virtually no hydrocarbon decomposition products
and therefore will not be considered further. Vitrinite
displays a significant loss of oxygen followed by a minimal
loss of hydrogen. This is a result of the release of
oxygenated products, mainly water and carbon dioxide
(Tissot & Welte, 1978). Alginite displays a very rapid loss
of hydrogen resulting from the release of hydrocarbons
(Tissot & Welte, 1978). Exinites show a simultaneous loss
of both hydrogen and oxygen accompanying the release of
hydrocarbons and oxygenated products (Tissot & Wwelte
1978).
Changes in elemental composition alone do not reveal
the nature of the hydrocarbon products (oil versus gas).
The hydrocarbon fingerprints resulting from pyrolysis-gae
chromatography, however, provide this detailed informa-
tion. The hydrocarbon fingerprints for the examined
isolated macerals are shown in Figure 5. Consistent with
the elemental data, vitrinite fingerprints display no signi-
ficant hydrocarbons, except for some aromatic peaks.
Exinites (sporinite, cutinite, and resinite) yield greater but
variable amounts of straight-chain, branched, cyclic, and
aromatic hydrocarbdns. Only the alginite fingerprint
displays a full spectrum of straight-chain hydrocarbons
with minor branched, cyclic, and aromatic hydrocarbons.
The alghite fingerprint very closely resembles the
fingerprint of the unaltered crude oils (Figure 6). The
exinite fingerprints are substantially different from those
of unaltered crude oils. Clearly the vitrinite fingerprint
bears no similarity to either the typical crude or the high-
wax crude oils.
A comparison of the quantities of hydrocarbons released
by the individual macerals is shown in Figures 7 and 8.
Figure 7 shows that vitrinite produces very small amounts
of hydrocarbons and therefore cannot be considered a
viable oil source. Exinites produce larger and more variable
quantities of hydrocarbons, however the amounts are
insufficient for them to be considered important oil sources
unless present in high concentration. Alginite yields the
largest amounts of hydrocarbons and could clearly act as
an important source of oil if present in sufficient quantities.
The xylene to octene ratio displayed in Figure 8 is a
good indicator of aromaticity. Low ratios appear to be
characteristic of alginite and cutinite. The degradation
products of these macerals are dominantly straight-chain.
High ratios appear to be characteristic of vitrinite whose
degradation products are dominantly aromatic. Interme-
diate ratios are observed for sporinite and resinite. These
macerals have degradation products that are mixed-aromat-
ic, straight-chain, branched, and cyclic.
Hydrocarbon Generation Potential of Coals-and Rocks
The three types of kerogens and the two types of coals
are distinctly different as shown by their chemical composi-
tion on the plot of pyrolysis yield (Figure 9),and on the
plot of elemental composition (Figure lo), and by their
maceral assemblage (dicussed below). Typical coaly rocks
(type I11 kerogen) are represented by the Upper Cretaceous
shales in the Douala Basin and the Devonian Gas Shales
in the Appalachian Basin. Rocks containing type I1 kerogen
are represented by the Kirnmeridgian of the North Sea,
the Monterey of California, and the New Albany Shale in
the Illinois Basin. Rocks containing type I kerogen are
represented by the Green River Shale in the Uinta Basin,
the Rundle Shale of Australia, and the Brown Shale of
Indonesia. Humic coals are represented by the humic coals
in the Applachian Basin. Cannel-boghead coals are repre-
sented by the torbanites of France and South Africa,
and the cannel-boghead of Kentucky.
The humic coal examined consisted predominately of
vitrinite and inertinite with small amounts of exinites and
no alginite. The type I11 kerogen examined consisted solely
of vitrinite and intertinite. Both samples are immature
(Ro 0.6%). Figure 11 displays the hydrocarbon finger-
prints of the humic coal and the coaly rock. Referring to
the maceral hydrocarbon fingerprint for comparison
(Figure 9, the exinite fingerprints dominate the finger-
perint of the humic coal sample whereas the vitrinite finger-
print dominates the fingerprint of the coaly rock.
The investigated type I1 kerogen of a marine rock is a
grouping of generally all maceral types with a large alginite
contribution and is immature (Ro 0.6%). Figure 11 dis-
plays the hydrocarbon fingerprint of this marine rock. Its
hydrocarbon fingerprint displays predominately straight-
chain hydrocarbons with subordinate levels of aromatic,
branched, and cyclic hydrocarbons. The overall straight-
chain appearance of the fingerprint is similar to the finger-
print of alginite. The fine structure of the fingerprint is
similar to the exinite fingerprints.
The cannel-boghead coal is composed predominately of
alginite and subordinate amounts of sporinite and other
maceral types. This coal is mature (Ro 0.75%). The hydro-
carbon fingerprint of the cannel-boghead coal (Figure 11)
displays predominately straight-chain hydrocarbons similar
to the fingerprint of alginite.
The examined type I kerogen of a lacustrine rock is
composed almost solely of alginite and is immature (Ro
0.6%). Its hydrocarbon fingerprint displays dominantly
straight-chain hydrocarbons and is nearly identical to the
fingerprint of alginite.
The above observations suggest that when alginite is
present in significant quantities such as in type I and type
I1 kerogens and cannel-boghead coal, the alginite finger-
print dominates the fingerprint of the sample. Exinites in
the presence of alginite modify the fine structure of the
sample fingerprint as in type I1 kerogen. In the absence of
alginite, the fingerprint of the exinites dominate the finger-
print of the sample as in the humic coal. In the absence of
alginite and exinites, the vitrinite fingerprint dominates
the sample fingerprint as in type I11 kerogen.
The elemental compositions of the three kerogens and
the two coals examined is shown in Figure 10. Based on
this figure, we expect the humic coal and coaly rock to
generate primarily oxygenated products and minimal hy-
drocarbons. Both oxygenated products and hydrocarbons
are expected from the degradation of type I1 kerogen.
Large amounts of hydrocarbons are expected from type I
kerogen. A comparison of the quantities of hydrocarbons
released by the rocks and coals is shown in Figures 12 and
13. Figure 12 shows that the rock containing solely alginite
(type I kerogen) generates far greater quantities of hydro-
carbons than the rock containing mixed maceral type
kerogen (type I1 kerogen) and the coaly rock (type I11
kerogen). In addition, the coaly rock generates insufficient
quantities of hydrocarbons to be considered a viable oil
source. The cannel-boghead coal having approximately
fifty percent alginite content and fifty percent organic
carbon content has generation capabilities similar to the
rock consisting solely of alginite (type I kerogen) with
only approximately twenty percent organic carbon con-
tent. The humic coal (approximately ten percent exinites
and absence of illginite and seventy percent organic carbon
content) generates quantities of hydrocarbons equivalent
to the rock containing mixed maceral type kerogen (type
I1 kerogen having approximately thirty-five percent alginite
and three percent organic carbon content).
Figure 13 shows the xylene to octene ratio of coals and
rocks. Low ratios are observed for type I kerogen and
cannel-boghead coal. Both of these samples produce degra-
dation products which are predominantly straight-chain.
High ratios are measured for the humic coal and the type
I11 kerogen, which yield degradation products which are
dominantly aromatic. Intermediate ratio appears charac-
teristic of type I1 kerogen that gives degradation products
which are mixed-aromatic, straight-chain, branched, and
cyclic.
Although humic coals apparently generate significant
quantities of hydrocarbons, the liquid hydrocarbon pro-
duct is not similar to crude oil as shown by the hydro-
carbon fingerprint (Figure 1I), by group type characteri-
zation of pyrolysate from sealed vessel pyrolysis (Figure
14), and by elemental composition of hydrogenated coal
tar (Figure 15). Even the hydrogenated coal tar (which
represents a high graded hydrocarbon product from coal)
contains significantly less hydrogen (greatest H/C of 1.3)
than the heaviest degraded crude oil (represented by asphalt
having lowest H/C of 1.4).
In addition, we believe that generated hydrocarbons are
not expelled from true coals, in particular humic coals,
because a difference exists in the expulsion performance
between humic coals and rocks. Rocks fracture during
heating (burial), thus providing avenues for the generated
hydrocarbons to escape. Humic coals, on the other hand,
swell during heating (burial) thereby providing room to
retain the generated hydrocarbons until they are thermally
cracked to gaseous hydrocarbons (sufficiently mobile to
escape) or the coal deposit is tectonically fractured and
the trapped hydrocarbons are released.
Conclusions
In conclusion, we have presented observations that
support the view that coals and kerogens (rocks) may be
considered as groupings of macerals and that their hydro-
carbon potential in part reflects the hydrocarbon potential
of the composing macerals (hydrogenenrichment). Vitrinite
does not generate hydrocarbons in sufficient quantities or
of proper type to be considered a viable oil surce. Although
exinites can generate significant quantities of hydrocarbons
if present in high concentrations, the fingerprints of these
hydrocarbons are not similar to the fingerprints of unaltered
oils. However, exinites may impart a signscant overprint
on the character of a crude oil. The quantity and character
of the pyrolysate of alginite and algal-rich rocks suggest that
alginite is probably the primary source of crude oils world-
wide. These observations are consistent with published
concepts that algae and bacteria probably represent the
common basis for all crudes (Lijmbach, 1975), In fact, the
great similarity in the overall composition of all crude oils
may be explained by the fact that the C7-C22 n-paraffins,
which are primarily the products of thermal decomposition
of algae and bacteria, constitute a significant portion of
unaltered crudes. The hydrocarbon contribution of other
macerals would superimpose specific components on the
overall crude oil character.
Given this view, humic coal (vitrinite-rich, relatively
hydrogen poor) is not a viable source for crude oil. Cannel-
boghead coal (containing alginite, relatively hydrogen
enriched) generates appropriate quantities and types of
hydrocarbons to be considered a viable source for crude oil.
However, true cannel-boghead coals are usually limited
volumetrically in natural systems and often are not true
coals but oil shales. Therefore, it is doubtful that cornrner-
cially significant quantities of hydrocarbons can be sourced
solely from true cannel-boghead coals.
We are presently investigating the concept of dilatancy
of coals and rocks, the relative interaction energies of
hydrocarbons on coals and rocks, and the generation and
release of hydrocarbons from coals during sealed vessel .
pyrolysis (hydrous pyrolysis). Based on the observations
presented in this study and because of the usually limited
volumes of true algal-rich coals, we believe that coals in
general are not viable sources for commercial quantities of
crude oils, and we doubt that the crude oils of the Niger
Delta, the Mahakam Delta, and the Gippsland Basin are
sourced from true coals.
ACKNOWLEDGEMENT
The authors would like to thank Texaco Inc. for per-
mission to present this paper.
SELECTED REFERENCES
Chaffee, A.L., G.J. Perry, and R.B. Johns, 1983, Pyrolyisis-
Gas Chromatography of Australian Coals: Fuel,v.62,
pp303-316.
Dembicki Jr.,H,B. Horsfield, and T.T.Y. Ho, 1983, Source
Rock Evaluation by Pyrolygk-Gas Chromatography:
A.A.P.G.,6707,pplO941103.
Durand,B. and M. Paratte, 1983, Oil Potential of Coals:
A Geochemical Approach: in Petroleum Geochemistry
and Exploration of Europe, J. Brooks editor, pp255-
265.
Evan, W.D., B.S. Cooper, and R.K. Gum, 1964, Pyro-
Chromatography: in Advances in Organic Geochemistry
1962, U. Colombo and G.D. Hobson editors, pp417-
421.
Giam, G.S.et.al., 1977, Characterization of Lignites by
Pyrolysis-Gas Chromatography: Analytical Chemistry,~.
49,pp1540-1543.
Giraud,A., 1970, Application of Pyrolysis and Gas Chro-
matography to Geochemical Characterization of kerogen
in Sedimentary Rock: A.A.P.G., 5403, pp439-455.
 Gorrnly, J.R. and P.K. .Mukhopadhyay, 1983, Hydrocarbon LIST OF FIGURES
Potential of Kerogen Types by Pyrolysis-Gas Chromato-
graphy: in ~dvances or$& Geochemistry 1981, Figure Source Rock Characterization
Bjoroy et.al. editors, pp597-606. Figure Schematic Diagram of Pyrolysis Gas Chro-
Larter, S.R., 1984, Application of Analytical Pyrolysis matography
Techniques to Kerogen Characterization and Fossil Figure Kerogen and Coal Macerals
Fuel Exploration/Exploitation: in Analytical Pyrolysis, Figure Elemental Composition of Macerals
K.J. Voorhees editor, pp212-275. Figure Pyrolysis Yield Fingerprints of Isolated
Leventhal, J.S., 1976, Stepwise Pyrolysis-Gas Chromato- Macerals
graphy of Kerogen in Sedimentary Rocks: Chemical Figure Whole Oil Chromatograms of Unaltered
Geology, v.18, pp5-20. Crudes
Lijmbach, G.W.M., 1975, On the Origin of Petroleum: Pro- Figure Relative Pyrolysis Yields From Isolated
ceedings of the Ninth World Petroleum Congress, v.2, Macerals
pp357-369. Figure Xylene to Octene Ratios of Isolated Macerals
Matters, W.L. et.al., 1977, Curie-Pcint Pyrolysis in Organic Figure Rock-Eva1Pyrolysis of Coals and Rocks
Geochemistry in Analytical Pyrolysis, C.E.R. Jones and Figure Elemental Composition of Coals and Kero-
C.A. Cramers editors, pp 203-216. gens
Romovacek, J. and J. Kubat, 1968, Characterization of Figure Pyrolysis Yield Fingerprints of Coals and
Coal Substances by Pyrolysis-Gas Chromatography: Rocks
Analytical Chemistry, v.40, pp1119-1126. Figure Relative Pyrolysis Yields From Coals and
Tissot, B.P. and D.H. Welte, 1978, Petroleum Formation Rocks
and Occurrence, Springer-Verlag, Berlin, 538p. Figure Xylene to Octene Ratios of Coals and Rocks
' Van de Meent, D. et.al., 1980, Pyrolysis-High Resolution Figure Group Type Characterization of Sealed
Gas Chromatography and Pyrolysis Gas Chromatography- Vessel Pyrolysates of Coals and Rocks
Mass Spectrometry of Kerogen and Kerogen Precursors: Figure Elemental composition of Coal Tar and
Geochim.et. Cosmochim. Acta, v.44, pp999-1013. Crude Oil
ORGANIC CARBON ENRICHMENT

PYROLYSIS YIELD (ROCK-EVAL)

KEROGEN TYPE
ELEMENTAL COMPOSITION
MACERAL CONTENT

PYROLY SlS YIELD FINGERPRINT

PYROLYSIS G A S CHROMATOGRAPHY
SEALED VESSEL PYROLYSIS

FIGURE 1
A L G l N l T E ( A N D BACTERIA)
ALGAE AND BACTERlA

LEAF CUTICLE

SPORlNlTE
SPORES AND POLLEN

Vl TRlNl T E
WOODY MATERIAL

INERTlNl TE
CHARCOAL

FIGURE 3
FIGURE 4
FIGURE 5
 L..ey e n d
C19 C 1 - C 4
ca c r , - c 1 4 TOTAL
E?3 C 6 - C 1 4 S T R A I G H T C H A I N t 1 Y I ) R O C A R B O N S
Q C 16 -t T O T A L
EiSJ C 1 6 - t S T R A l G H T C H A I R H Y D R O C A R B O N S

FIGURE 7
FIGURE 8
FIGURE 9
F I G U R E 10
 TYPE I KEROGEN

I I

TYPE TT KEROGEN

I
cs i
, cts
<
%6

TYPE I11 K;ISx(C>GEN

I I I

FIGURE 11
 L.ogond
m C1-C4
C 6 - C l 4 TOTAL
C6-C1.1 S T R A I G H T C l l A l t J H ' Y D A O C A R B O N S
IZ1 C 1 6 - t T O T A L
E Y C16+ S T R A l O H T C H A I N I i Y D R O C A R B O N S

TYPE I TYPE II TYPE Ill CANNEL I-IUMIC

KEROGEN KEROGEN KEROGEN BOGHEAD COAL
COAL

FIGURE 12
 TYPE I T Y P E 11 CANNEL- IlUMIC
KEROGEN REROGEN BOGIIEAD COAL
COAL
 AROMATIC HC

/ANNEL BOGHEAD COAL

0

TYPE I KEROGEN-ROCK
\
a
TYPE II KEROGEN-ROCK

SATURATE HC NON

FIGURE 14