Ganz 1987

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Short Communications

good. The utilization of an ultrasonic Trowbridge, T. D. Fuel 1984,63, 616 Proceedings of the ‘Characterization of
bath and glass filter of desired porosity 3 Poirier, M. A. and George, A. E. J. Heavy Crude Oils and Petroleum
met the required flocculation lapse Chrom. Sci. 1983,21, 331 Residues’, International Symposium,
4 Lambelin, A., Julliat, P., Ciais, A. and Lyon, June 25-27, 1984,273. Editions
resulting in a shorter analysis time.
Mille, G. Proceedings of the Technip, Paris 1984
Therefore, the method could be used: to
‘Characterization of Heavy Crude Oils 7 Hubbard, R. L. and Stanfield, K. E.
characterize bituminous products or
and Petroleum Residues’, International Anal. Chem. 1948,20,460
process feeds; to follow
up a refining Symposium, Lyon, June 25-27, 1984, 8 Ramljak, Z., Duer-Siftar, D. and Sole,
process (deasphaltening, upgrading); to 190. Editions Technip, Paris 1984 A. 1. Chromatogr. 1976, 119,445
prepare maltenes samples for compound- 5 Bouquet, M. and Hamon, J. Y. 9 Burke, F. P., Winschel, R. A. and
type analysis by h.p.1.c. Proceedings of the ‘Characterization of Wooton, D. Fuel 1979,58, 539
Heavy Crude Oils and Petroleum 10 Cohn, J. M. and Vion, G. ‘Mtthode de
REFERENCES Residues’, International Symposium, microdtasphaltage pour la
I Snape. C. E. and Bartle, K. D. Fuel Lyon, June 25-27, 1984, 196-199. dktermination de la teneur en
1984.63. 883 Editions Technip, Paris 1984 asphalt&es’, Compagnie Francaise de
2 Speight. J. G., Long, R. B. and 6 Bononi, A., Brion, Y. and Brul&, B. Raffinage, Internal Report

Application of infrared spectroscopy to the classification of kerogen-


types and the evaluation of source rock and oil shale potentials

H. Ganz and W. Kalkreuth”


Technische Universitit Berlin, SFB 69, Ackerstr. 71-76, 1 Berlin 65, Germany
*Institute of Sedimentary and Petroleum Geology, 3303-33rd St. N. W., Calgary, Alberta, Canada
(Received 23 October 7986)

In the present study maturation levels and kerogen types (which can be used to estimate the hydrocarbon
generating potential of source rocks and oil shales) were defined by infrared spectroscopy. The spectra display
distinct peaks for aiiphatic, carboxyl/carbonyi and aromatic compounds which can be used to classify
kerogen types similar to the traditional H/GO/C van Krevelen diagram and to estimate the maturation
levels. Parameters obtained from infrared spectroscopy also allow the prediction of oil and gas potentials. A
combination of Rock-Eva1 pyrolysis and infrared spectroscopy appears to be an effective tool to group
source rocks into oil and/or gas prone categories. Organic petrology provides additional insight into the
nature of the organic materials.

(Keywords: oil shale; source rock; kerogen; infrared spectroscopy; organic petrology)

Source rocks and oil shales contain ~ these rocks vitrinite reflectance measure- (aromatic C=C bonds). With increasing
depending on their depositional environ- ments do not appear to be a reliable maturation the aiiphatic peaks initially
ment - a variety of organic materials maturation parameter, since reflectances increase while the carboxyijcarbonyi
which can be classified by methods of are apparently depressed by the peak decreases. As maturation continues
organic geochemistry and organic associated liptinite macerais, i.e.
petrology into a number of kerogen- alginite6v7*‘0.
types. In particular, Rock-Eva1 pyrolysis The present study introduces the
has been used extensively over the past application of an additional method”*”
years as a screening tool to assess to classify kerogen types, maturation
kerogen-types and to evaluate source levels, and source rocks and oil shale
rock potentials1m3. In oil shales the potentials on the basis of parameters
Fischer Assay test is commonly used to obtained from infrared spectroscopy.
Evolution path
define the shale oil potential4 and appears Preliminary results are given for 39 twe I kerogen
to correlate well with data obtained from samples representing well defined
Rock-Eva1 pyrolysis’. Optical analysis kerogen-types from various locations
provides additional information on the (Table 1). The infrared spectroscopical
nature of the organic materials. Methods parameters are then compared to data
of incident light microscopy (i.e. vitrinite obtained from Rock-Eva1 pyrolysis,
reflectance measurements and the Fischer Assay yields and petrographic
determination of fluorescence properties composition of the samples.
of liptinite macerals) are used to assess
the maturation level of the organic
materials and macerai-analysis is used to
EXPERIMENTAL
determine the petrographic composi-
tion6.‘. The accuracy of the Rock-Eva1 Infrared spectra of demineralized
pyrolysis technique appears to be limited kerogens were measured between 0 ’ 1 1 ’ 1 1 1 1 1 /
0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.9 0.9 1.0
by effects of the associated mineral matrix 20&4OOOcm-’ using the KBr-pellet
c Factor 11710cm-‘11(1710t 163ocn-‘I
and level of organic enrichment’ and technique”. The infrared spectra typically
may also be influenced by varying degrees display distinct peaks at 2860cm-’ and Figure 1 Classification of kerogen-types
of oil and bitumen saturation in the 293Ocm-’ (CH, and CH, aiiphatic according to A and C Factors obtained from
samples’. Limitations occur also in the groups), at 1710cm-’ (carboxyi and infrared spectroscopy: 0, Type I; n , Type II;
petrographic analysis of oil shales. In carbonyi groups), and at 1630cm-’ A, Type III; 0, Type I-II; 0, Type II-III
0016-2361/87/050708-04$3.00
0 I987 Butterworth & Co. (Publishers) Ltd.
708 FUEL, 1987, Vol 66, May
Short Communications

Table 1 Summary of the sample locations, lithologies, kerogen types, total organic carbon contents (TOC), and parameters derived from Fischer
Assay test, Rock-Eva1 pyrolysis and infrared spectroscopy

Oil and
Fischer gas poten-
assay tial”.*
yields” S, + S, Infrared spectroscopy
(US (kg hydro-
gallon/ carbon/ A Factor
Kerogen TOC ton tonne x TOC
Sample Location Lithology type (%) of rock) of rock) A Factor C Factor x IO

1 New Brunswick, Canada Oil shale I 15.76 31.3 132.5 0.86 0.36 135.5
2 New Brunswick, Canada Oil shale I 11.29 21.1 94.7 0.86 0.30 97.1
3 New Brunswick, Canada Oil shale I 9.28 26.1 88.6 0.86 0.28 79.8
4 New Brunswick, Canada Oil shale I 8.59 21.6 76.6 0.84 0.28 72.1
5 New Brunswick, Canada Oil shale I 8.66 20.5 86.3 0.86 0.29 74.5
6 New Brunswick, Canada Oil shale I 8.04 16.6 61.5 0.82 0.22 65.9
7 New Brunswick, Canada Oil shale I 1.69 5.2 21.1 0.74 0.19 56.9
8 New Brunswick, Canada Oil shale I 4.18 12.1 42.6 0.81 0.24 33.8
9 Nova Scotia, Canada Coal III 53.14 _ 113.0 0.40 0.18 212.6
10 Nova Scotia, Canada Oil shale I 15.06 89.3 0.84 0.19 126.5
11 Nova Scotia, Canada Oil shale I 3.3 10.4 0.11 0.22 24.0
12 Nova Scotia, Canada Carbonaceous shale III 7.3 _ 8.3 0.39 0.21 28.5
13 Nova Scotia, Canada Coal III 54.6 96.5 0.42 0.18 229.3
14 Nova Scotia, Canada Oil shale I 11.4 _ 69.3 0.82 0.11 93.6
15 Nova Scotia, Canada Coal III 45.1 _ 101.2 0.50 0.15 225.5
16 Nova Scotia, Canada Oil shale I 12.5 79.8 0.71 0.16 96.3
17 Nova Scotia, Canada Torbanite I 27.0 95.0 0.12 0.15 194.4
18 Quseir, Egypt Marlstone, mudstone II 3.3 _ 16.2 0.59 0.49 19.5
19 Quseir, Egypt Black shale II 8.4 _ 58.1 0.10 0.56 58.8
20 Quseir, Egypt Black shale II 9.0 60.5 0.72 0.51 64.8
21 Quseir, Egypt Black shaIe II 8.8 56.3 0.10 0.56 61.6
22 Quseir, Egypt Dolomitic marlstone II 1.7 _ 10.6 0.11 0.50 12.1
23 Quseir, Egypt Silty mudstone II-III 1.0 _ 1.0 0.52 0.43 5.2
24 Younis, Egypt Dolomitic marlstone II 5.6 32.9 0.52 0.46 29.1
25 Younis, Egypt Dolomitic marlstone II 4.8 34.0 0.58 0.49 21.8
26 Younis, Egypt Black shale II 10.9 _ 95.0 0.71 0.54 71.4
27 Younis, Egypt Black shale II 12.1 121.3 0.73 0.50 88.3
28 Younis, Egypt Marlstone/mudstone II 6.2 42.9 0.66 0.56 40.9
29 Safaga, Egypt Black shale II 17.9 _ 130.6 0.62 0.55 1Il.0
30 Safaga, Egypt Black shale I-II 19.7 183.1 0.72 0.41 141.8
31 Safaga, Egypt Black shale II 9.7 _ 99.9 0.73 0.50 70.8
32 Younis, Egypt Silty shale III 2.2 _ 4.0 0.42 0.37 9.2
33 Well F, Canada Shale II 2.6 _ 42.0 0.11 0.20 18.2
34 Green River Fm, USA Oil shale I 9.0 61.0 0.79 0.46 71.0
35 Ptolemais, Greece Coal III 41.6 _ 13.0 0.41 0.58 170.4
36 Stockheim, Germany Coal III 12.1 _ 9.7 0.44 0.11 52.8
37 Macedonia, Greece Coal III 48.5 62.8 0.33 0.50 160.0
38 Macedonia, Greece Coal III 46.4 _ 18.2 0.39 0.43 181.0
39 Macedonia, Greece Coal III 56.1 _ 112.5 0.43 0.43 244.0

“From Macauley and Ball’ and MacauIey and Ba11’4


b Rock-Eva1 data for samples 18 to 31 and 36 to 39 determined at ISPG, Calgary

to increase the aliphatic peaks decrease 1710cm-’ amounts of alginite (19 vol%), which is
while there is no apparent change in the C Factor =
1710cm-’ + 1630cm-’ the predominant organic material in
peak representing the aromatic C=C kerogen type I. The kerogen type II
bonds’,’ 3. The changes in the intensities samples show a wider scatter indicating
of the aiiphatic peaks and the for some of the samples transitions into
carboxyl/carbonyl peaks relative to the RESULTS
kerogen type III.
aromatics are used in the new method to The infrared spectroscopical data for the The sample pairs 9-10, 12-11, 13-14
describe kerogen-type and maturation various kerogen types are summarized in and 15-16 in Figure I represent coals and
levels. Changes taking place in the peak Table I. The A and C Factors can be used oil shales from the Pictou Coalfield, Nova
intensities of the aliphatic groups are in a similar manner to the traditional Scotia, which occur as alternating layers
expressed as: H/C-O/C van Krevelen diagram to in the so called ‘oil-coal seam’6.
classify kerogen types and maturation Petrographic analysis showed that the
A Factor levels (Figure 1). There is a clear coals are of high volatile A bituminous
2930cm-’ +2860cm-’ separation for the oil shales (evolution rank (0.85%0.96% R,,,) whereas the oil
~2930cm-1+2860cm~‘+1630cm-1 path type I kerogen) and for the coals shales were characterized by significantly
(evolution path type III). One coal lower vitrinite reflectances (0.38-0.41%
appears to be out of position (sample 15); Rrand,,m)indicating immaturity for these
while changes in the peak representing A and C Factors indicate type I kerogen. sample@. Infrared spectroscopy appears
carboxyl/carbonyl groups are expressed Petrographic analysis (Figure 2) revealed to give a more accurate assessment of the
as: that this coal indeed contains larger true maturation levels in these oil shales

FUEL, 1987, Vol 66, May 709


Short Communications

Alginite Rock-Eva1 pyrolysis Infrared spectroscopy


(vol %I I ,
Correlation Correlation
coefficient = 0.9838 coefficient = 0.9702

140 120 100 80 60 40 20 20 40 60 80 100 120 140

Oil and gas potential (S, + S2) A Factor x TOC x 10


(kg hydrocarbons/tonne of rock)

Vitrinite and lnertinite Figure 3 Oil and gas potentials of oil shales from New Brunswick, Canada (samples l-8).
liptinite macerals (vol %I Comparison of data obtained from Fischer Assay, Rock-Eva1 pyrolysis and infrared spectroscopy
except alginite
(vol %)

Figure 2 Ternary diagram illustrating


maceral composition of samples 1-17: 0, oil S, +.S> = 183.1 1 S, + S2 = 172.5f
shale; A, torbanite; W, coal and carbonaceous
shale

since C Factors determined for the coals


and oil shales are identical or very
similar, Figure 1.
The A Factor can be used to define the
hydrocarbon potentials of the organic-
rich rocks. This is illustrated in Figure 3
for a set of oil shale samples (samples 1-8,
Table I), where the A Factor multiplied
by the total organic carbon content x 10
is shown to correlate well with results
obtained from Fischer Assay test and
Rock-Eva1 pyrolysis. The anomalous
low Fischer Assay yield for sample 7 can
be explained by results from petrographic
analysis (Figure 2), which indicated for
this sample, in contrast to the other oil
shales, only a moderate content of
alginite but greater amounts of the
maceral liptodetrinite (other liptinite)
along with a low organic carbon content.
The effects of petrographic
composition on the hydrocarbon poten- 100 200 3f
tials of the source rocks analysed in this A Factor x TOC x 10
study are also demonstrated clearly in
Figure 4. In this figure the samples are Figure 4 Diagram illustrating oil and gas potentials from Rock-Eva1 pyrolysis versus source rock
grouped according to oil and gas and oil shale potentials obtained from infrared spectroscopy: 0, Type I; W, Type II; A, Type III;
potentials derived from Rock-Eva1 0, Type I-II; 0, Type II-III
pyrolysis and to the A Factor obtained
from infrared spectroscopy. Two trends
are apparent, namely a group of samples
comprising kerogen types I and II which
CONCLUSIONS group source rocks and oil shales into
form the ‘oil prone’ organic materials and
‘oil and/or gas prone’.
a group of samples comprising the The organic materials contained in
source rocks and oil shales can be 4. Petrographic analysis using incident
kerogen type III samples which are
light microscopy provides additional
clearly separated from the former. classified into kerogen types by using
insight into the nature of the organic
Exceptions from the general trend are oil parameters derived from infrared
materials.
shale No. 7, which was found to contain spectroscopy.
only moderate amounts of alginite Oil and gas potential of source rocks
ACKNOWLEDGEMENTS
(Figure 2) and a torbanite (sample No. and oil shales can be predicted by the
17), which according to Figure 2 A Factor derived from infrared The authors thank the Organic
contained larger amounts of humic spectroscopy. Geochemistry Laboratory at ISPG for
materials. The positioning of these two Combined analysis of Rock-Eva1 analysing samples 18 to 31 and 36 to 39
samples in Figure 4 indicates the ‘gas pyrolysis and infrared spectroscopy using Rock-Eva1 pyrolysis and F.
prone’ nature of the organic material. appears to be an effective tool to Biittcher and M. Bussman (SFB 69) for

710 FUEL, 1987, Vol 66, May


Short Communications

analytical assistance. The authors also 4 Sladek, T. Mineral Industries Bulletin Characterizing Kerogen Type and
thank C. Thompson, ISPG, for typing 1974, 17(6), 20 Thermal Maturation. 12th Int.
the manuscript. This study was 5 Macauley, G. and Ball, F., New Meeting on Organic Geochemistry,
Brunswick Dept. of Natural Resources, Sent. 16-20.1985. Jiilich. W. Germanv.<
financially supported by DFG (Deutsche Open File Report 82-12, 1982 A&tracts, i985, b. 94 ’
Forschungsgemeinschaft). 6 Kalkreuth, W. and Macauley, G. Bull. 12 Ganz, H. Organisch- und anorganisch-
Can. Petrol. Geol. 1984, 32(l), 38 geochemische Untersuchungen an
7 Kalkreuth, W. and Macauley, G. agyptischen Schwarzschiefer/Phos-
Organic Petrology and Geochemical phoritsequenzen - Methodenentwick-
REFERENCES (Rock-Eval) Studies on Oil Shales and lung und genetisches Model]. Berliner
1 Tissot, B., Durand, B., Espitalie, J. and Coals from the Pictou and Antigonish Geowissenschaftliche Abhandlungen,
Combaz, A. A.A.P.G. Bulletin 1974, Areas, Nova Scotia, Canada, in press Verlag von Dietrich Reimer in Berlin,
58(3), 499 8 Katz, B. Limitations of ‘Rock-Eval’ 1986, 113 pp.
2 Harwood, R. A.A.P.G. Bulletin 1977, pyrolysis for typing organic matter. 13 Tissot, B., Deroo, G. and Hood, A.
61(12), 2082 Oraanic Geochemistrv 1983.4(3/4), 195 Geochim. et Cosmochimica Acta 1978,
3 Espatalie, J., Madec, M. and Tissot, B. 9 Clementz, D. A.A.P.G. B&e& 1979, 42, 1469
Source-Rock Characterization Method 63(12), 2227 14 Macauley, G. and Ball, F. Oil shales of
for Petroleum and Exploration. 9th 10 Hutton, A. and Cook, A. Fuel 1980,59, the Big Marsh and Pictou Areas, Nova
Annual Offshore Technology 711 Scotia. Geol. Survey of Canada, Open
Conference, Houston, Texas, May 2-5, 11 Ganz, H. and Robinson, V. Newly File Report 0F1037, 1984
1977, VIII, p. 439 Developed Infrared Method for

Effect of impregnation with ZnCI, and other catalysts on coal pyrolysis

R. John O’Brien,* Graham W. Brierst and Rafael Kandiyoti


Department of Chemical Engineering and Chemical Technology, Imperial College, University of
London SW7 2BY, UK
tDepartrnent of Metallurgy and Materials Science, Imperial College, University of London, London
SW7 2BY, UK
(Received 28 August 1986; revised 20 November 1986)

Similarity of product distributions from the pyrolysis of ZnCl,-impregnated coals and ZnCl,+oal
admixtures suggests that the catalyst does not distribute itself uniformly within the coal mass upon
impregnation from solution. Elemental distribution maps for zinc and chlorine, obtained by electron probe
microanalysis, confirm that the catalyst is deposited around the periphery of coal particles upon
impregnation. Uniform distribution of the ZnCl, within the particles, however, appears to take place on
heating to temperatures as low as 160°C.

(Keywords: pyrolysis of coal; catalyst; electron probe microanalysis)

Impregnation of Linby Coal (NCB class hydropyrolysis of coal in a coiled tube impregnation of the catalyst from
902) with ZnCl,, while causing a small reacto?. ethanolic solution did not result in the
decline in the tar/oil yield during slow A study6 of the mobility of SnCl, in catalyst diffusing into the particle before
pyrolysis, has recently been shown to coal hydrogenation, using optical and the coal was heated. The similarity of
increase substantially tar/oil yields from electron microscopy, showed that product distributions obtained from
flash pyrolysis in a quartz fluidized bed in
an inert atmosphere’*‘. The effects of
impregnation with other catalysts are Table 1 Effect of impregnation with ZnCl, and SnCl, on coal pyrolysis. Yields on wt % dacf”
shown in Table 1. Although ZnBr,, ZnI, basis
and AICl, behave in a similar fashion to
Flash pyrolysisb Slow pyrolysis’
ZnCl,, the reversal in the tar/oil
production trend upon flash heating was Catalyst Tar Char Tar Char
not observed with SnCl,. To study the
influence of the impregnation procedure None 31.0 58.0 14.6 68.4
itself (from aqueous and methanolic 5 % ZnCl, 35.8 51.3 12.7 69.3
solutions), a set of slow pyrolysis runs 10% ZnBr, 38.5 51.2 nd” nd“
was performed in a Gray-King4 retort 10% ZnI, 35.8 53.1 nd“ nd*
where the ZnCl, was directly mixed with 10% AlCl, 38.8 52.1 nd” nd’
the coal rather than by impregnation. 10% SnCl, 26.8 66.8 nd*,’ ndd,’
Results appeared insensitive to the
“dacf=dry ash- and catalyst-free. All the catalyst is assumed to remain with the char
method of mixing, within experimental bResults from flash pyrolysis experiments in a quartz fluidized bed*
error’. A similar observation had earlier cResults from pyrolysis at 5°C min-’ in a Gray-King assay’
been reported for the ZnCl,-catalysed %d = not determined
‘Bodily et aL3 found that in the slow pyrolysis (5°C min-‘) of Hiawatha coal impregnation with
* Present address: British Gas plc, London 20 wt % SnCl, caused the char yield to increase from 72.5 to 89.6 %, while impregnation with
Research Station, London, UK 12 wt % ZnCl, increased the yield to 85 %

0016-2361/87/050711-05!$3.00
0 1987 Butterworth & Co. (Publishers) Ltd. FUEL, 1987, Vol 66, May 711

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