170 Energy & Fuels 1988,2, 170-175

pyridine. Unless such extracts are well protected from air

oxidation and clarified by membrane filtration or ultra-
centrifugation, the extracts contain colloidal material.
With attention to anaerobic conditions and solvent purity,
extraction can reliably produce extracts characteristic of
the original coal. Extract yield and molecular size of the
extracts increase with the swelling ability of the solvent
for the coal in question. For Illinois coals, air oxidation
at room temperature decreases total extract yield and the
average molecular size of most of the extracts. The reactive
material in extracts of fresh coal is not present in extracts
of oxidized coals. Pyridine and DMF are tightly bound
to coals, extracts, and residues but can be removed by
washing with 80% (v/v) methanol/water, a solvent mix-
ture with both a large heat of immersion and a high wetting
rate for coal surfaces.
Acknowledgment. We thank the Illinois Coal Devel-
opment Board for financial support provided through the
Center for Research on Sulfur in Coal, Dr. Carl W. Kruse,
Illinois State Geological Survey, and Dr. Karl Vorres,
Argonne National Laboratory, for coal samples; Dr. R.
Malhotra, SRI International, for FIMS spectra; and a re-
viewer for helpful comments.
Registry No. THF, 109-99-9; DMF, 68-12-2; C6H,CH3, 108-
88-3; pyridine, 110-86-1.
Hydrocarbon Characterization of Resinitef
R. J. Hwang* and S. C. Teerman
Chevron Oil Field Research Company, P.O. Box 446, La Habra, California 90633-0446
Received August 24, 1987. Revised Manuscript Received October 16, 1987
Resinites were pyrolyzed by using both closed- and open-flow-system pyrolysis techniques to evaluate
their generative potential. The composition of generated products and the temperature of thermal
breakdown of the resinite are dependent on the pyrolysis process. Differences between closed- and
open-system pyrolysis are explained by detailed pyrolyzate anlaysis and chemical processes involved
in the different pyrolysis techniques. Hydrous pyrolysis most closely simulates the natural process
of hydrocarbon generation, including the temperature of generation and the composition of generated
products. Open-system pyrolysis data can lead to the erroneous conclusion that resinite generates
significant quantities of hydrocarbons at low temperatures. Hydrous pyrolysis experiments on pure
resinites indicate that generation of liquid hydrocarbons occurs at similar or slightly higher levels
of thermal maturity than for most other kinds of oil-prone kerogen. Characterization of hydrous
pyrolysis residues with fluorescence microscopy, infrared spectroscopy, and elemental analyses also
indicates that resinite does not generate liquid hydrocarbons at thermally immature levels. Oil
pyrolyzates, generated at various temperatures, are light and nonpardfinic, consisting predominantly
of cyclic isoprenoids and their aromatic derivatives. Minor amounts of naphthenic components also
are present. The composition of generated products differs with resinite precursor. The resinite
pyrolyzates are chemically distinct from most naturally occurring oils. The dissimilarity of these
pyrolyzates to natural oils suggests that resinite is not an important source of petroleum.
Introduction
As a maceral, resinite usually originates from terrestrial
plant and tree resins and occurs in coals and other sedi-
mentary rocks, usually as a minor component (<20% of
the total organic matter). Resinite is hydrogen rich and
therefore has been considered as an oil-prone organic
matter. Evaluation of the liquid hydrocarbon potential
of resinite has important exploration implications in areas
where resinite-rich, terrestrial organic matter occurs. Its
potential to generate commercial quantities of oil has at-
tracted considerable attention since Snowdonl suggested
that certain light oils and condensates from the Beau-
fort-Mackenzie Basin, Canada, were derived from resinite.
He also emphasized that resinite can generate light oil/
condensate at low levels of maturity (R, <0.50%). Philp
et a1.2 concluded that there was a negligible resinite con-
tribution to terrestrial-sourced oils in the Gippsland Basin,
'Presented at the Symposium on Pyrolysis in Petroleum Ex-
ploration Geochemistry, 193rd National Meeting of the American
Chemical Society, Denver, CO, April 5-6, 1987.
Australia, despite the proximity of resinite-bearing coals
to reservoirs. Lewan and Williams3 also state that the
limited occurrence and localized concentration of resinite
limits its potential as a commercial source of oil. In view
of this apparent contradiction regarding the role of resinite
as a source for liquid hydrocarbons, further investigation
is necessary to better understand the generative potential
and properties of resinite.
To evaluate the liquid hydrocarbon potential of resinite,
a study was undertaken to (1) quantitatively asseas the
generative potential of resinite, (2) determine the maturity
level of hydrocarbon generation, and (3) characterize the
composition of resinite-derived oil pyrolyzate. This study
illustrates how various pyrolysis methods, in conjuction
(1) (a) Snowdon, L. R. Mem.-Can. SOC. Pet. Geol. 1980,6, 509. (b)
Snowdon, L. R.; Powell, T. G. Am. Assoc. Pet. Geol. Bull. 1982,66, 775.
(2) Philp, R. P.; Simoneit, B. R. T.; Gilbert, T. D. Aduances in Organic
Geochemistry 1981; Bjory, M. , et al., Eds.; Wiley: New York, 1983; pp
698-704.
(3) Lewan, M. D.; Williams, J. A. Am. Assoc. Pet. Geol. Bull. 1987, 71,
207.
0887-0624/88/2502-Ol70$01.50/0 0 1988 American Chemical Society
Hydrocarbon Characterization of Resinite Energy & Fuels, Vol. 2, No. 2, 1988 171
Table I. Bulk Geochemical Properties of Original Resinite
extractable
organic matter,
resinite w t % H/C O/C
Kauri (New Zealand) - 40 1.56 0.08
Far East - 42 1.50 0.05
with chromatographic and spectrometric techniques, were
used to evaluate the generative potential of resinite.
Experimental Section
Hydrous pyrolysis procedures were similar to those described
by Lewan et al.4 Rock-Eval pyrolysis was performed using
standard For programmed-pyrolysis-GC (PPGC)
analysis, the Rock-Eval pyrolysis temperature program was used
to pyrolyze the resinites in a Model 820 geochemical analyzer
(Chemical Data System). The pyrolyzates (hydrous and PPGC)
were analyzed by GC-FID and GC-MS under the same chroma-
tographic conditions (15 X 0.25 m DB-1 column programmed from
50 to 300 C at a rate of 8 OC/min). The GC-MS anaysis was
performed on a HP 5970 operated at 70 eV for ionization.
The resinites were extracted by methylene chloride to yield
extractable organic matter. Elemental compositions (CHNO) of
the resinites were determined by a Perkin-Elmer 240 elemental
analyzer. API gravity of oil pyrolyzates derived from hydrous
pyrolysis was measured by a pycnometer.
Results and Discussion
Kauri resinite from New Zealand and a Tertiary resinite
from the Far East were selected for artifical maturation
techniques (pyrolysis) because of their availability, large
sample size, and purity. The Kauri resinite, from the genus
Agathis, is less than loo00 years old and corresponds to
the peat stage of coalification.6 The Far East sample
consists of resinite isolated from a lignite (R, <0.35).
Results of geochemical characterization of the unheated
resinites are listed in Tables I and 11. High H/C and low
O/C ratios indicate both resinites are equivalent to type
I oil-prone kerogen. Their high yields of solvent-extract-
able organic matter are unique and consistent with those
reported by Snowdon and Thomase. High yields of ex-
tractable organic matter normally indicate either that
hydrocarbons have been generated from in situ kerogen
or that the sample contains migrated oil. However, the
high solubility of these resinites is related to the absence
of insoluble, high cross-linked polymers, which will be
discussed later.
Rock-Eva1 Pyrolysis. This is a widely used technique
(open-system pyrolysis) to rapidly assess petroleum gen-
erative potential of a prospective source rock.5 Results of
Rock-Eval analysis of the two resinites are listed in Table
II. Both resinites give unusually large SI and S2, low T-
(<400 C), and relatively large production index [S,/(S,
+Sa] values. Interpreted in the conventional geochemical
manner, Rock-Eva1 results, combined with large weight
percentages of extractable organic matter, could lead to
the erroneous conclusion that resinite generates significant
amounts of liquid hydrocarbons at thermally immature
levels.
Thermogravimetric analysis (TGA), like Rock-Eval, is
an open-system pyrolysis technique, which also can lead
to the erroneous conclusion of immature generation. On
the basis of observations from TGA that resinite lost sig-
(4) Lewan, M. D.; Winters, J. C.; McDonald, J. H. Science (Wash-
ington, D.C.) 1979, 203, 896.
( 5) Espitalie, J.; Madec, M.; Tissot, B.; Mennig, J. J.; Leplat, P. In
Proceedings of the 9th Annual Offshore Technology Conference; Off-
shore Technology Conference: Dallas, TX, 1977, Vol. 3, p 439.
(6) Thomas, B. R. In Organic Geochemistry; Eglinton, G., Murphy,
M. J. T., Eds.; Springer-Verlag: New York, 1969; pp 599-618.
Fi gure 1. Programmed pyrolysis gas chromatograms (PPGC)
of Kauri resinite, New Zealand.
0
0- 150
f
250
- + - Kaur i
I I I l l I I I l l l
0 200 400 600 800 1000
Pyr ol ysat e mqlgm TOC
(Fl oat )
Fi gure 2. Pyrolyzate from hydrous pyrolysis experiments for
resinites.
nificant weight at lower temperatures compared to al-
gal-rich and vitrinite-rich coals and sapropelic kerogen,
Snowdonl concluded that resinite is capable of generat,ing
hydrocarbons at low levels of thermal maturity (Ro as low
as 0.45%). Using additional observations, Snowdon sug-
gested that resinite present in thermally immature Ter-
tiary/Cretaceous sediments is the source of certain light
oils recovered in the Beaufort-MacKenzie Delta
Programmed Pyrolysis Gas Chromatography
(PPGC). PPGC combined with a mass spectrometer was
used to obtain molecular characterization of the volatiles
and the generated pyrolyzates from the Rock-Eval Sl and
S2 peaks. The PPGC analysis used the Rock-Eval pyro-
lysis temperature program to reproduce the pyrolyzates
(Sa and volatiles (S,) for chromatographic separation and
mass spectrometric identification of their components.
Similar PPGC procedures were used by Mukhopadhyay
and Gormly, providing information about generated
products of various resinites.
Figure 1 shows the P1 and P2 chromatograms from
PPGC (correspsonding to the S1 and S2 peaks, respec-
tively), of Kauri resinitie. Bicyclic diterpenoids are the
major components of the pyrolyzates (P2) and mono-
terpenoids of the volatiles (Pl), as indicated by the mass
spectral analysis. Their molecular structures are tenta-
tively assigned, based on comparison and extrapolation of
the mass spectral data of diterpene resin acids compiled
by Zinkel et al.8 These bicyclic diterpenoids (unsaturated
oxygen-containing compounds) were not observed in the
pyrolyzates generated by hydrous pyrolysis of the resinites.
Hydrous Pyrolysis. This closed-system pyrolysis
technique is widely used to simulate the generation of
(7) Mukhopadhyay, P. K., Gormly, J . R. Org. Geochem. 1984,6,439.
(8) Zinkel, D. F.; Zank, L. C.; Wesolowski, M. F. Diterpene Resin
Acids; Gen. Tech. Rep. FPL-US., For Prod. Lab., Mndison, Wis., 1971;
pp CM28.
172 Energy & Fuels, Vol. 2, No. 2, 1988 Hwang and Teerman
Table 11. Rock-Eva1 Results of Resinites"
oxygen
resinite wt 5% TOC rock rock rock T,,, "C oc of oc
SI, mg of S2, mg of S3, mg of hydrogen index, index, mg
HC/g of HC/g of C02/g of mg of HC/g of of C02/g
Kauri (New Zealand) 80.5 292 651
Far East 83.7 96 749
Key: TOC, total organic carbon; OC, organic carbon.
15.4 388 809 19
2.5 398 895 3
9
300OC
12 15
' I
1 32OoC
LILY, 1 , '[ 3600c
5 10 15 20 25 30
Retent on T me I m n I
,&&a ~~~-------
Figure 3. Total ion chromatograms (GC-MS) to show the tem-
perature effect on Kauri resinite. Pyrolyzatepeak identifications
are listed in Table 111.
petroleum from potential source rocks! Hydrous pyrolysis
experiments on unextracted resinites were undertaken at
various temperatures for 72 h to determine product yields,
compositions, and the temperature necessary for liquid
hydrocarbon generation. Figure 2 shows the pyrolyzate
(floating oil) yields versus pyrolysis temperature for the
two resinites. The temperatures at the onset of liquid
hydrocarbon generation are 300 "C for the Kauri resinite
and 280 "C for the Far East resinite, which correspond
approximately to 0.8 and 0.7% Ro, respectively (vitrinite
reflectance values based on hydrous pyrolysis experiments
of lignite). Hydrous pyrolysis data indicate that these
resinites do not generate liquid hydrocarbons at low levels
of thermal maturity (i.e. <0.6% Ro). These results are
consistent with the findings of Philp et al.2 and Lewan and
william^.^
Figure 2 also shows that 91 % of the organic carbon from
the Kauri resinite is converted to oil pyrolyzate compared
to only 43% for the Far East resinite. The yields are
comparable to or greater than those obtained for Green
River shale (i.e., 50%h9 The yields from these two resinites
are similar to the yields from pyrolysis experiments for
other resinitiea performed by Lewan and william^.^These
high yields support the idea that resinite is highly oil prone,
as indicated by high hydrogen index values and H/C ratios.
The difference in oil-pyrolyzate yields of the two resinites
may be attributed to differences in the chemical compo-
sition of the two resin precursors.
Pyrolyzate Composition. Oil pyrolyzates generated
at various temperatures from hydrous pyrolysis were an-
alyzed by GC and GC-MS to determine their composition.
Figure 3 shows total ion chromatograms of the Kauri re-
sinite pyrolyzates. The oil pyrolyzates contain predomi-
nately cyclic isoprenoids and their hydroaromatic and
aromatic derivatives with low carbon numbers (SC20), but
no paraffins. These pyrolyzates are chemically distinct
from virtually all naturally occurring crude oils. Their
unique chemical composition is reflected in unusual
physical properties, i.e., high volatility but low API gravity
Table 111. Major Components of Kauri Resinite
Pvrolszates Derived from Hsdrous Pvrolssis
~ ~~ ~~
chemical
peak no. formula assignmenta
1 CloHla C4-subst cyclohexene
2 CloH14 p-cymene
3 C1&4 C3-subst decahydronaphthalene
4 C13H22 C3-subst octahydronaphthalene
5 C14H24 C4-subst octahydronaphthalene
6 C12H12 dimethylnaphthalene
7 C13H18 C3-subst tetrahydronaphthalene
8 trimethylnaphthalene
9 C14H240 sesquiterpene alcohol
10 Cl9Hz8 dehydroabietin isomer
11 CleHga dehydroabietin isomer
12 CI9Hzs dehydroabietin*
13 CleH14 pimanthrene*
14 Cl8Hzz demethylated simonellite
15 C19H24 simonellite
16 ClaHla retene*
17 CzoHzaO2 dehydroabietic acid
18 C24H%O4 bis(2-ethylhexy1)phthalate (contaminant)
a For those compounds marked with an asterisk, assignment was
confirmed by comparison with authentic compounds. Otherwise,
assignment was tentatively based on comparison with literature
data or the fragmentation pattern.
(12-20 "API). Their major components, listed in Table
111, are identified by comparing their mass spectra with
those in the literaturelo or are tentatively assigned on the
basis of the fragmentation pattern.
The yields of diaromatics (mainly C2- and C3-substituted
naphthalenes) and triaromatics (pimanthrene and retene
particularly) increase with temperature. Minor amounts
of naphthenic components are identified in the 360 "C
Kauri pyrolyzate.
In contrast to most hydrous pyrolysis studies, there is
no significant shift to lower molecular hydrocarbons (<CIS)
with increased pyrolysis temperature, as shown in the
GC-MS total ion chromatograms of the oil pyrolyzates
(Figure 3). Crude oils generally show a shift to lower
molecular hydrocarbons with increasing thermal maturity.
The absence of almost all Clo and lower molecular weight
hydrocarbons on the total ion chromatograms of the 300
"C oil pyrolyzate is attributed to low yields and experi-
mental losses during the product recovery processes. GC
analyses of pyrolysis aliquots taken at the completion of
hydrous pyrolysis experiments, but prior to the product
workup, clearly demonstrate that this is the case.
The oil pyrolyzates generated from the Far East resinite
are also characterized by light, nonparafiinic components.
The dominance of cyclic isoprenoids and their hydro-
aromatic and aromatic derivatives in the pyrolyzates re-
sembles the Kauri pyrolyzates. However, the two differ
in the distribution and types of cyclic isoprenoids and their
derivatives. Figure 4 shows a comparison of the oil py-
rolyzates generated at 360 "C from the two resinites. While
Kauri pyrolyzate contains abundant aromatic derivatives
(9) Peters, K. E., unpublished results.
(10) Wakham, S. G.; Schaffner, C.; Giger, W. Geochim. Cosmochim.
Acta 1980, 44, 415.
Hydrocarbon Characterization of Resinite
e c 6 -c10 e c l l -c15 -cl6 -c20*
30r I I
Energy & Fuels, Vol. 2, No. 2, 1988 173
15 11
Kauri Rerinite
New Zeal and
36OOC
3~ I
k c 3 0 4
15 I 1 I 1 1 1
Far Earl Reiinite
360OC
Retention T ~me (min I
Figure 4. Gas chromatograms to show composition of resinite
pyrolyzates.
o r----
50 1
I
300 01
3 2 0 1 i
340 0
I
350 ~ i
360 8 1 1 1 1
0 20 40 60 80 100
Wt % Extractable
0
0
.
I
-
15 14 1 3 12 1 1
H C
.
0
0 0 2 04 06 08 1
Redj Gr een R ati n ..
I EI emental Anal ysi s1 [Quantitative Fluorescence)
Figure 5. Geochemical and microscopic data for Kauri resinite
confirming the absence of early generation.
of mono- and diterpenoids, the Far East resinite pyrolyzate
mainly consists of aromatic derivatives of sesquiterpenoids
with a small amount of non-hopane-type triterpenoids.
The compositional differences may reflect different pre-
cursors for the the two resinites.
Residual Resinite Characterization. The residual
(pyrolyzed) Kauri samples were characterized by quanti-
tative fluorescence and infrared spectrometry (IR) to de-
termine the effect of thermal stress on its chemical
structure and to help evaluate the onset of liquid hydo-
carbon generation.
Microscopically, both unheated and heated (pyrolyzed)
resinite samples are homogenous and fluoresce with a
maximum intensity at about 470-480 nm (green). With
increasing maturity, most macerals that fluoresce display
a shift in the spectral maxima (emitted fluorescence) to-
ward longer wavelengths as described by Van Gijzel." A
useful way of quantifying this shift in flurescence is by
measuring the redlgreen quotient (650/500 nm). Below
200 "C, the redlgreen quotient remains essentially un-
changed because the resinite is resistant to increased
temperature and produces no thermal degradation prod-
ucts (Figure 5) . At 250 "C, a small increase in the red/
green quotient is observed, suggesting a change in the
chemical structure related to thermal stress. Spectral
measurements were not completed on samples heated
above 250 "C because they consist of a molten resin.
,3060 0' 1800 0 '1000 0,6000 - i i
Wavenumberr ICm1 1
3000 0 1800 0'1000 0 k% 0
Wavenumberr (Cm 11
Figure 6. IR spectra of heated and unheated Kauri resinite.
The IR results (Figure 6) also show that the resinite
undergoes little change up to 200 "C, consistent with
fluorescence data. At 250 "C, the absorption band at 890
cm-', attributable to the exocyclic >C=CH2 of bicyclic
diterpenoids, disappears while the carbonyl band of a
conjugated acid at 1690 cm-' is reduced in intensity.
Despite these minor changes, the IR spectrum closely re-
sembles those of the residues at lower temperature, with
an intense carbonyl peak of the ester linkage at 1720 cm-'
and a C=C absorption at 1640 cm-l. The IR character-
istics of the residual resinite are similar to those of im-
mature resinite, isolated from lignite and described by
Murchison.12 Aromatic absorption bands develop (1610,
1515, and 818 cm-') at the expense of 1720- and 1640-cm-'
bands for the solid residue formed at 300 "C. The oil
pyrolyzates generated at 300 "C and higher temperatures
display similar IR characteristics, featuring the typical
hydrocarbon absorption bands at 2900,2800,1460,1380,
and -810 cm-'. These IR spectra are indicative of
transformation of resinite from the aggregatves of unsat-
urated nonhydrocarbons (carboxylic acid mainly) to hy-
drocarbons (saturates and aromatics) as a result of hydrous
pyrolysis.
Quantitative fluorescence and IR results reflect a small
structural change at 250 "C, which corresponds to a sharp
increase in soluble organic matter (100% soluble), as shown
in Figure 5. Although formation of oil pyrolyzate at this
temperature could account for the small structural change,
the amount of generated product is probably too small to
be expelled from the resinite matrix (polymeric structure).
The absence of oil pyrolyzates at this temperature supports
this. The lack of development of aromatic characteristics,
which normally occurs with hydrocarbon generation,13 and
the preservation of the ester linkage14 in the resinite res-
idue does not support hydrocarbon generation at 250 "C.
A sharp increase in the solubility is probably due to the
cleavage of the cross-linkages between the resinite polymer
chains and should not be interpreted as hydrocarbon
generation. Thus, both IR and fluorescence characteri-
zation of residues suggest that no significant conversion
to liquid products occurs below 300 "C.
Comparison of Pyrolysis Techniques. Composition
of generated product and the thermal breakdown of re-
sinite are different for hydrous pyrolysis and Rock-Eva1
(PPGC) techniques. Detailed product analysis is the key
to understanding why resinite behaves differently for the
two pyrolysis techniques. Molecular information derived
from detailed pyrolyzate analysis provides insight into the
(11) Van Gijzel, P. Presented at the 12th Annual Meeting of the Am-
erican Association of Stratigraphic Palynologists, Dallas, TX, October
29-November 2, 1979.
(12) Murchison, D. G. Fuel 1978, 55, 79.
(13) Tissot, B.; Deroo, G. Geochim. Cosmochim. Acta 1978,42,1469.
(14) Behar, F.; Vandenbroucke, M. Org. Geochem. 1987, 11, 15.
174 Energy & Fuels, Vol. 2, No. 2, 1988 Hwang and Teerman
n/
COOH I
Agathic Acid
Abi et i c Acid 17
COOH
Pcmarir Actd Pimanthrene
Figure 7. Suggestad processes for product formation in hydrous
pyrolysis of Kauri resinite-polymer of diterpenoids.
chemical structure of the resinites and the chemical pro-
cesses involved in the two pyrolysis techniques. Differ-
ences in pyrolysis results can beexplained on the basis of
chemical structure and chemical processes by using Kauri
resinite as an example.
Chemical Structure. Kauri resin is known for its
richness in diterpene resin acids.e Its complete chemical
structure, however, has not been clearly established be-
cause of its complexity and source variation.ls As de-
scribed earlier, hydrous pyrolysis of the resinite yields
hydroaromatic and aromatic derivatives of diterpenoids
as the major end products. Rock-Eval and PPGC anal ps
give rise to diterpenoids, i.e., unsaturated bicyclic acids and
alcohols as end products. These results indicate that Kauri
resinite is mainly composed of diterpenoid polymers and
some unpolymerized diterpenoids and monoterpenoids.
Figure 7 shows the proposed processes that lead to the
observed products formed from hydrous pyrolysis.
The resinite is probably not a highly cross-linked poly-
mer, and hence it is readily soluble in organic solvents. In
contrast, most sedimentary organic matter largely consists
of highly cross-linked macromolecules that are insoluble
in organic s~l vents. ~~J ~~~ Although resinite has a high yield
of extractable organic matter when immature, this soluble
organic matter mainly consists of unsaturated and oxy-
genated components and not hydrocarbons, which would
be expected if the resinite had undergone significant
thermal stress.
Chemical Processes. In any chemical reaction, the
products are process dependent. Compositional differences
between the hydrous and PPGC pyrolyzates reflect dif-
ferences in chemical processes of the two pyrolysis tech-
niques. Figure 8 shows the proposed reaction schemes for
both pyrolysis techniques. In the pyrolysis experiments
the resinite undergoes depolymerization to yield monomers
at low temperatures. The monomers mainly include un-
saturated bicyclic acids and alcohols. Because these
unstable monomers cannot escape from the hot zonen
(heated reactor) when formed in the hydrous pyrolysis
(closed) system, they tend to repolymerize to yield the
resinite polymer again. Thus no significant amount of
hydrocarbon-like products (oil pyrolyzate) is formed at
lower temperatures. As the hydrous pyrolysis temperature
increases, those monomers undergo further reactions, such
as thermal degradation, dehydrogenation, and rearrange-
(15) Wilson, M. A.; Collin, P. J.; Vassllo, A. M.; Russel, N. J. Org.
(16) Young, D. K.; Yen, T. F. Geochim. Cosmochim. Acta 1977, 41,
Ceochem. 1984, 7,161.
1411.
Hydrous Pyrolysis
lClosed System!
____
!Polymer!
Depolymerization &P:lymerization
Monomers iOlefins!
/
Lower
Temperature
Rearrangement,
Dehydrogenation
Higher
Temoerature
Stable Products
Rock Eva1Pyrolysis
!Open System!
Resi ni t e
Depolymerization
Polymerization
Monomers /
[Olefins!
Lower
Temperature
Figure 8. Models for hydrocarbon generation fromresinite using
open- and closed-systempyrolysis.
ments, which lead to the stable products; i.e. hydro-
aromatic and aromatic derivatives of diterpenoids.
Therefore, pyrolyzates are formed at higher temperature
(thermal maturity). In contrast, the monomers formed at
lower temperatures in the Rock-Eva1 or PPGC (open)
system are carried away from the hot zonen by the con-
stant carrier gas flow and detected by a FID detector be-
fore they polymerize. Because TGA is similar to Rock-Eval
(open system), it too suggests thermal breakdown of the
resinite at low temperatures. These data can be misin-
terpreted to suggest that resinite generates hydrocarbons
at lower temperatures (maturity) than other kinds of
oil-prone kerogen. These unsaturated, oxygenated di-
terpenoids, which are formed at low temperatures, are
unstable and have little chance to survive in geological
environments.
Maturity of Oil Generation. Hydrous pyrolysis gen-
erates stable, petroleum-like products, providing infor-
mation about the level of thermal maturity needed for
hydrocarbon generation from resinite. Product analyses
suggest that resinite is unlikely to generate liquid hydro-
carbons at low levels of thermal maturity. Quantitative
fluorescence and infrared spectrometric data of Kauri
pyrolysis residues support these results. Work by Lewan
and Williams3 correlating vitrinite reflectance and pyrolysis
yield also demonstrates that early generation from resinite
is unlikely.
Conclusions
1. On the basis of hydrous pyrolysis (closed system) and
other geochemical techniques, data obtained from this
study suggest that the Kauri and Far East resinites are (a)
highly oil-prone organic matter (however, their chemical
structures are distinctly different from those of other
oil-prone kerogens), (b) unlikely to generate oil at a low
level of thermal maturity (Le., Ro <0.6% vitrinite reflec-
tance), and (c) likely to generate a nonparaffinic, light oil
with low API gravity when thermally mature. The gen-
erated products are quite different from virtually all
naturally occurring oils. The dissimilarity of these py-
rolyzates to natural crude oils suggests that resinite is not
a significant source of petroleum.
2. Knowledge of the chemistry of the original material
and pyrolysis reaction products is essential to understand
Energy & Fuels 1988,2,175-180 175
Acknowledgment. We wish to thank Chevron Oil
Field bearch Co. for support of this work and permission
to publish. Appreciation is extended to P. C. Henshaw,
S. R. J acobson, D. A. J effrey, and P. Sundararaman for
critical review of this manuscript.
the generative potential of resinite.
3. Pyrolysis results for resinite vary depending on the
technique used. Hydrous pyrolysis more closely defines
the temperature at which liquid hydrocarbon generation
occurs and the type of products generated.
Characterization of Arsenic in Oil Shale and Oil Shale
Derivatives by X-ray Absorption Spectroscopy$
S. P. Cramer,* M. Siskin,? L. D. Brown,$ and G. N. Georget
Schlumberger-Doll Research, Old Quarry Road, Ridgefield, Connecticut 06877, and Exxon
Research and Engineering Company, Route 22 East, Annandale, New Jersey 07830,
and P.O. Box 4255, Baytown, Texas 77520
Received June 12, 1987. Revised Manuscript Received September 29, 1987
X-ray absorption spectroscopy using synchrotron radiation is ideally suited for in situ charac-
terization of trace elements down to the 1 ppm level. With this technique, the chemical nature of
the arsenic species in oil shales and derivatives was investigated. Model compound studies revealed
that the arsenic absorption edge is sensitive to the oxidation state and covalency of the arsenic
environment, shifting from 11870 eV in metal arsenides and arsenic(II1) sulfides to 11876 eV in
arsenic(V) oxides. The arsenic edge of a Green River oil shale (GROS) showed two peaks, consistent
with the presence of a metal arsenide or arsenic(II1) sulfide as well as an As(V) species. The relative
intensities of these two peaks varied in other shales, indicating primarily oxidized arsenic in Rundle
Munduran Creek shale to primarily reduced arsenic in Brazilian Irati shale. Concentration of the
GROS kerogen resulted in selective removal of the oxidized arsenic species. The merits and potential
pitfalls of applying X-ray absorption to complex materials are discussed.
Introduction
Arsenic is present in most oil shales at concentrations
of about 10-200 ppm.' Because it is a potent catalyst
poison, the successful conversion of oil shale into useful
liquid fuels is hindered by the presence of this element.
The environmental and toxicological problems associated
with disposal of guard bed materials and disposal and
leaching of spent and combusted shale piles, and in waste
water cleanup are signifi~ant.~J In order to improve ar-
senic removal methodology, a good understanding of the
nature of the arsenic species present is clearly desirable.
Chemical analysis by HPLC and other methods has been
applied to oil shale methanol extract^,^revealing the
presence of arsenate and organoarsonic acids. However,
only a small fraction of the arsenic was extracted. On the
basis of electron beam5 and magnetice techniques an as-
sociation between the bulk of the arsenic and iron sulfide
minerals was proposed. Recently, a combined SEM-EDS
and X-ray powder diffraction study has revealed the
presence of skutterudite (Co,Fe,Ni)As3 and safflorite
(Co,Fe)As2 particles.' However, quantitation and char-
acterization of diffuse or noncrystalline arsenic is impos-
sible by this method. A complementary technique that
* To whomcorrespondence should be addressed at Schlumber-
ger-Doll Research.
)Presented at the Symposium on Advances in Oil Shale Chemis-
try, 193rd National Meeting of the American Chemical Society,
Denver, CO, April 5-10, 1987.
t Exxon Research and Engineering Co., Annandale, NJ .
* Exxon Research and Engineering Co., Baytown, TX.
0887-0624/88/2502-0175$01.50/0
is ideally suited for in situ analyses of arsenic-containing
materials is X-ray absorption spectroscopy.8
X-ray absorption spectroscopy is ideally suited for
characterization of the arsenic in oil shale and related
materials. With synchrotron radiation sources and X-ray
fluorescence detection: the sensitivity is such that con-
centration levels below 10 ppm can be studied. The edge
region, sometimes referred to as XANES or X-ray ab-
sorption near edge structure, is sensitive to the absorbing
atom oxidation state, site symmetry and ligand covalency.1
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Prins, R., Eds.; Plenum: New York, 1987. (b) EXAFS and Near Edge
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1988 American Chemical Society