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Structural features of resins, asphaltenes

and kerogen studied by diffuse reflectance


infrared spectroscopy

Alfred A. Christy, Birger Dahl” and Olav M. Kvalheim


Department of Chemistry, University of Bergen, N-5007 Bergen, Norway
* Norsk Hydro Research Centre, PO Box 4313, N-5001 Bergen, Norway
(Received 30 August 7988)

Traditional transmittance i.r. techniques to analyse heavy fractions of source rocks such as resins,
asphaltenes and kerogen can be replaced by the relatively simple and easy diffuse reflectance technique. From
spectroscopic analysis, parallel information on the content between these three fractions is obtained. It
appears that either heavy fractions or kerogen can be used. Furthermore, hydropyrolysis experiments have
been carried out to follow the thermal evolution of the heavy fractions. In all these cases, attention was given
mainly to the change in infrared absorptions arising from the elimination of carbonyl groups and increased
aromatization. This is the main process taking place during late diagenesis and early catagenesis. An attempt
has also been made to determine thermal maturity quantitatively, in terms of a spectroscopically calculated
ratio’,‘.

(Keywords: asphaltene; structural properties; infrared spectroscopy)

Kerogen is the tiny fraction of organic matter in 1.r. spectroscopy has been used for a long time to
sedimentary rocks that is insoluble in organic solvents. determine structural properties of kerogen and
Determination of its composition is important in the asphaltenes. The technique has revealed some main
assessment of the genetic potential of a sediment. Analysis structural features of kerogen that are not easy to identify
of kerogen involves demineralization and bitumen by other chemical analytical methods due to the
extraction. Demineralization without alteration of the insolubility of kerogen in common organic solvents. King
kerogen structure is difficult when a high proportion of et al.‘O,” used i.r. spectroscopy to study structural
minerals is present3. features of organic matter. Robin” characterized
Parallel behaviour between kerogen, asphaltenes and kerogen, and studied its evolution by determining
resins has been suggested by Pfeiffer et ~1.~ as early as carbonyl and carboxyl groups. The advent of FT-i.r. led
1936. Unambigious determination of the molecular to broad applications in research and industrial
structure of kerogen or asphaltenes is not possible laboratories. Painter et u/.13*14 and others have used FT-
because of their polymeric nature. However methods i.r. to characterize coal samples. Furthermore, FT-i.r.
such as X-ray diffraction and i.r. spectroscopy have enables researchers to use low energy throughput
provided much information about the overall structure of sampling techniques, such as diffuse reflectance for the
kerogen and asphaltenes. Structural models have been determination of organic species”-“.
proposed on the basis of the above mentioned methods of Diffuse reflectance has been used by many authors to
analysis3s5+. study coal samples18*‘9. Kuehl et a1.‘O used an
Petroleum is generated through the degradation of h.p.l.c./diffuse reflectance infrared Fourier Transform
kerogen. Degradation results in the release of aliphatic (DRIFT) interface to record diffuse reflectance spectra of
and aromatic hydrocarbons, together with molecules of organic components eluted from an h.p.1.c. system. In this
higher molecular weight containing N, S, 0 atoms. technique, the eluted sample was deposited in a cup
Preservation of an overall molecular structure in kerogen containing KC1 and the solvent was eliminated by
is possible for asphaltenes and resins, although to a lesser evaporation.
extent in the case of resins because of small amounts of The aim of this paper is to report the first set of diffuse
free heteroatomic compound?. Resins and asphaltenes reflectance i.r. spectra of resins, asphaltenes and kerogens
undergo thermal evolution parallel to the parent kerogen, and to compare their structural features. Furthermore,
and therefore one can postulate a similarity between these hydrous pyrolysis is carried out to study the thermal
compounds throughout the evolution of the sediment. evolution of resins and asphaltenes in controlled
This is evident from the work of Behar et ~1.~. They experiments.
concluded that the structure of asphaltene is very close to
the structure of the source kerogen, differing only in size
EXPERIMENTAL
compared with kerogen. Furthermore, during thermal
evolution asphaltenes and kerogen generate hy- Kerogen, asphaltenes and resins from different sources
drocarbons of the same type and distribution. Thus, have been analysed. Kerogen, asphaltene and resin
asphaltenes can probably be used in place of kerogen in fractions of three samples of kerogen type III (coal
such studies. samples); seven pairs of resin and asphaltene fractions of
00162361/89/040430-06$3.00
0 1989 Butterworth & Co. (Publishers) Ltd.
430 FUEL, 1989, Vol 68, April
Structural features of resins, asphaltenes and kerogen: A. A. Christy et al.

the sediment extracts from different locations in the dropped gently on the KBr using a 10~1 gas
North Sea; and seven pairs of resin and asphaltene chromatographic syringe. The sample cup was then
fractions of oils from USA, Africa, China and Norway placed in an oven set at 50°C to facilitate the evaporation
were analysed. of the solvent. DRIFT spectra of the asphaltenes
A sample of Kimmeridge oil shale (type II) from upper deposited on KBr were recorded, and the difference
Jurassic was used in the hydrous pyrolysis experiment. spectra were calculated by subtracting the background
Analytical procedures for the separation of resins and spectrum of KBr from each sample spectrum. The
asphaltenes are given below. difference spectrum was subsequently transformed into
Kubelka-Munk format’ 5*23*24.
Separation of asphaltenes from oils
Asphaltenes from oils were precipitated by the addition
RESULTS AND DISCUSSION
of 40 w/v of n-pentane to each of the oil samples
(z 350 mg) in a small test tube. The contents were placed The DRIFT spectra recorded in this study are excellent
on an ultrasonic bath for 5 min and kept overnight. The for qualitative and semi quantititave purposes. The bands
contents were then centrifuged for 10min at are much more intense in a DRIFT spectrum than in a
2500 rev min - i. The supernatant was decanted to a new transmittance spectrum when the same sample was
container, and the residue was washed with pressed into a disc with KBr of the same diameter (Figure
approximately 1 ml of n-pentane, centrifuged and I). Kuehl and Grifhths” made the same observation in
decanted for supernatants. This was repeated four times. their study of organic compounds eluted by liquid
Supernatants were finally combined with the original chromatography using a diffuse reflectance technique.
supernatant and evaporated for solvent down to dryness Furthermore, the spectrum recorded by the transmit-
on a rotary evaporation (at 200 mbar and 30°C). The dry tance technique had a relatively lower S/N ratio than the
oil was then dissolved in 1 ml n-hexane and 150 ~1 of the spectrum obtained by the diffuse reflectance technique.
solution was used for h.p.1.c. analytical separation into Diffuse reflectance is almost a surface technique.
aliphatic, aromatic and resin fractions. The resin fraction Although the depth of penetration of i.r. radiation into
was evaporated for solvent and redissolved in a suitable the sample bulk is not yet exactly known, it is believed to
volume of dichloromethane. be within the first few pm of the surface’5*25. This fact
allows one to disperse the sample just to a few pm of the
Separation of resins and asphaltenes from sediments
Source rocks were extracted using dichloromethane
containing 7 % methanol and Soxhlet apparatus for 4 h.
The extract was evaporated for solvent to dryness and the
deasphaltening was carried out as in the case of oil. Resins
were separated by chromatography as described above.

Hydrous pyrolysis and separation of resins and asphaltenes


A Kimmeridge clay oil shale (kerogen type II) from
Upper Jurassic North Sea was hydrous pyrolysed. Pre-
extracted oil shale (5g) was placed in a steel autoclave. g -
::
Distilled water was added to the sample so that the total :
amount of liquid water in the autoclave at eacy pyrolysis ::
:
temperature was estimated to 5 ml. The system was
purged with nitrogen and quickly heated to the pyrolysis
temperature. After 72 h of pyrolysis, the autoclave was air
cooled to the ambient temperature and the pyrolysed
sample was filtered from the water phase. The residue was
Soxhlet-ectracted with dichloromethane for 24 h using a
water separator. The solvent was evaporated under
nitrogen, and the resins and asphaltenes were separated
as described above.

SPECTROSCOPIC ANALYSIS
The spectroscopic analysis was performed using a PE
1700 FT-i.r. spectrometer (Perkin-Elmer, Norwalk, CT,
USA) equipped with a DTGS detector and a diffuse
reflectance accessory (Harrick Scientific, Ossining, NY,
USA). Finely ground KBr (40-80pm) was packed in a
sample cup (4mm diameter and 6 mm depth) using a
sample packing unit designed and manufactured by
Christy et al.“. The diffuse reflectance spectra of KBr was
recorded from 4000 cm - 1 to 600 cm - ’ using 20 scans at a
resolution of 4 cm - ‘. The spectra were intended for
qualitative study, and therefore the cup was not Figure 1 Diffuse. reflectance spectra of asphaltene and absorption
rotatedz2. Asphaltenes (10 ~1) in dichloromethane were spectra of the same amount of sample using transmittance technique

FUEL, 1989, Vol 68, April 431


Structural features of resins, asphaltenes and kerogen: A. A. Christy et al.

asphaltenes and resins (Figure 2) show some interesting


structural features especially in OH, aromatic CH,
aliphatic CH, carbonyl and C=C stretching regions.
While kerogen gives a broad absorption band in the
region 3750-3 100 cm- ‘, the corresponding asphaltene
spectrum shows a moderately broad band and the resins a

w
4000 3000 2000 1600 1200 1000 edb l/c:

+..l.....,.“‘,‘..‘.‘,..c Figure 3 DRIFT spectra of asphaltenes and resin fractions ofsediment


4000 2000 2000 1000 ,000 200 lhn samples from different locations in the North Sea

Figure 2 DRIFT spectra of kerogen, asphahenes and resin fractions


extracted from coal samples
Table 1 General infrared band assignments of
kerogen/asphaltenes/resins
sample bulk to be able to record a diffuse reflectance Wavenumber (cm-‘)
spectrum of the sample. Thus, very small quantities of kerogen/asphaltene/resins Type of functionality
resins and asphaltenes are enough to record DRIFT
spectra. In the present study, we were able to record 35otK3300 NH, OH stretching
H-bonded
diffuse reflectance spectra with 10~1 of a solution aromatic stretch
30X%3000
containing 1.5 ppm of the asphaltene/resin sample. 2950 shoulder asymmetric CH,-stretch.
The DRIFT spectra of kerogen, asphaltene and resin 2920 CH stretching
fractions of kerogen type III are shown in Figure 2. 2850 CH stretching
1735 open chain C=O
Spectra of asphaltene/resin fractions of bitumen extracts
1720-1690 aldehyde, ketonic and acidic
and oils are shown in Figures 3 and 4, respectively. Figure amide carbonyl
1700-1650
5 shows DRIFT spectra of asphaltene/resin fractions of 1600 aromatic C=C
hydrous pyrolysed samples. C-CH,
1465 asymmetric
Apart from the absolute quantities of the various -X.X- 1
functional groups, all the spectra show similar structural 1377 symmet& CCH a bend
features for kerogen, asphaltenes and resins. 1.r. 1050 -0- ether linkage
880 one hydrogen on aromatic ring
absorption band assignments for kerogen/asphalte- two adjacent hydrogen
840
nejresins are given in Table 1’7’ 3. 820 three adjacent hydrogen
The diffuse reflectance infrared spectra of kerogen,

432 FUEL, 1989, Vol 68, April


Structural features of resins, asphaltenes and kerogen: A. A. Christy et al.

1(1600cm-‘)/(1(1700cm-‘)+1(16OOcm-’)) provided an
excellent correlation with temperature in hydropyrolysed
samples*. This seems to be a very good parameter for
samples with similar input of organic material. There are
three justifications for using this ratio as a maturity
indicator.
In the van Krevelen diagram aromatization of all three
types of kerogen is represented by a decrease in the
H/C and O/C ratios. Change in these two ratios take
place simultaneously during thermal evolution of an
organicsediment.Thusitispossibletouseoneofthemto
determine maturity level of certain types of kerogen.
Aromatization in kerogen is related to oxygen lossesz6.
Elimination of oxygen takes place in the form of
carbonyl function elimination during diagenesis and
early catagenesis. Elimination of carbonyl function is
represented by a decrease in the C=O stretching

4000 3000 2000 1600 1200 1000 600 l/Cm

Figure 4 DRIFT spectra of asphaltenes and resin fractions of oils


samples from different countries

relatively weak band in this region. This band is


attributed to phenolic/alcoholic OH band stretching. In
the kerogen samples, the broad band may be due to a
combination of free OH groups and hydrogen bonded
OH groups. It appears that the OH stretching in
asphaltenes is more intense than in kerogen and resins.
However, total OH content in kerogen and asphaltenes
may be comparable. The OH functionality shows a
minimum in resins.
There are clear differences in the aromatic and aliphatic
CH stretchings that appear around 3050 cm - ’ and 3000-
2800 cm-‘, respectively. Comparison clearly shows the
difference in aromatic character between these fractions.
In each set, the kerogen fraction is more aromatic than
asphaltenes and resins, and asphaltenes are more
aromatic than resins. For type III kerogen with a low H/C
and high O/C ratio, these differences appear to be easily
identified by their i.r. spectra. A comparison between the RESINS
diffuse reflectance spectra of the kerogen fractions of the
coal samples clearly shows that the ratio aromatic J
CH/aliphatic CH increases with increasing vitrinite
reflectance. This is evident both in the asphaltene and
ASPH.
resin fraction. Comparison

tion at 1700cm-’
of the aromatic char-
acter can also be made by the use of carbonyl absorp-
and aromatic C=C stretching
1
4000
r
3000 2000 1600 1200 600 l/ml

absorption at 1600 cm- ‘. In a previous paper, we Figure 5 DRIFT spectra of asphaltenes and resins from
showed that the fraction defined by hydrous pyrolysed samples

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Structural features of resins, asphaltenes and kerogen: A. A. Christy et al.

Table 2 Maturity index values of resin/asphaltene/kerogen fractions carbonyl functions in oil resins and asphaltenes seems to be
less compared with bitumen resin and asphaltenes.
1(1600)/(1(1700)+1(1600))
Hydroxyl functions in the form of phenolic/alcoholic OH
Resins Asphaltene Kerogen are reduced-in-oil asphaltenes compared with bitumen
asphaltenes.
Coal 1 R,=0.67 0.237 0.425 0.535
Tissot and Welte3 in their statistical analysis of the
Coal 2 R,=0.7 0.333 0.422 0.549
Coal 3 R,=0.9 0.364 0.472 0.668
chemical composition of resin and asphaltene fractions
from several bitumen and oil samples give an average
Sediments
Well No. 1. 2608 m 0.379 0.621
value of approximately 7 y0 for bitumen resins and
Well No. 2 2908 m 0.350 0.862 asphaltenes and 2% for oil resins and asphaltenes. This
Well No. 3 0.338 0.608 reduction in oxygen content was explained by the
Oils elimination of heteroatomic bonds in oil produced during
China 0.548 0.736 catagenesis. Aromatic CH stretching and bending are
Africa 0.475 0.700 weak in oil resins and asphaltenes as in the type II
USA 0.490 0.500
bitumen resins and asphaltenes.
Pyrolysed samples The resins and asphaltenes of the hydrous pyrolysed
280°C 0.310 0.380 samples show the same pattern as the bitumen (type
300°C 0.335 0.473
320°C 0.443 0.582
II)/oil resins and asphaltenes. Although it is difficult to
340°C 0.456 0.672 compare the phenolicjhydroxyl functions in the
resins/asphaltenes obtained from hydropyrolysed
samples, we observed a slight increase in the
phenolic/hydroxyl content in the asphaltenes (Figure 4).
around 1700 cm-‘. Increase in aromatization is During hydrous pyrolysis, resins and asphaltenes loose
represented by a relative increase in the C=C carbonyl functional groups progressively. This elim-
stretching around 1600 cm-‘. ination and relative increase in the -C=C- stretching
3. Resins are considered as intermediates in going from around 1600 cm - ’ take place simultaneously. It has been
oils to asphaltenesz7. If this is true, condensation of shown that the factor defined by
aromatic rings should be coupled with a decrease in I(1600cm-‘)/(I(1700cm-1)+I(1600cm-’)) gives an
oxygen content when going from resins to asphaltenes. excellent correlation with temperature. In artificial
This trend is observed in every pair of resins and maturation, the same kind of relationship exists also for
asphaltene samples. Therefore, the defined index can resins. The relative increase in the C=C stretching band is
be used to compare the aromatic character between explained3’ as being due to the dehydrogenation of
fractions of a sample or asphaltenes/resins from a naphthenic clusters with cleavage of short aliphatic side
particular type of kerogen. Estimated values of this chains and increased condensation.
parameter are tabulated in Table 2. It is very difficult to comment on the fate of the amide
carbonyl group which appears around 1650cm-’ with
The DRIFT spectra of asphaltenes and resins obtained maturation. A comparison of the i.r. spectra of the resin
from bitumen extracts of coal samples (type III) and and asphaltene fractions of oil and bitumen samples
sediment extracts (type II) (Figures 2 and 3) show main indicates that the amide carbonyl groups are also
differences in the regions 3500-3300 and 1700cm-‘. A eliminated during catagenesis.
relatively intense broad band in the 3500-3300cm-’
region for the asphaltene fraction compared with the resin
fraction, and a relatively intense band at 1700 cm-’ and CONCLUSION
1050cm-’ for the resin fraction compared with the
asphaltene fraction clearly indicate that the oxygen In this paper, we have shown a relatively simple way to
functionalities in the resins and asphaltenes are obtain i.r. spectra of resin and asphaltenes samples. The
quantitatively different. Thus, these observations imply technique is fast, and eliminates the need for making KBr
that oxygen exists mainly in the form of pellets to study such samples. The acquired spectra are
phenolic/alcoholic OH in asphaltenes and in the form of suitable for both qualitative and semi-quantitative
carbonyl and bridged -O-functions in resins. A similar purposes. The technique is currently being evaluated for
observation was made by Moschopedis et al.” for the quantitative purposes. The difference in oxygen
resin and asphaltene fractions from Athabasca bitumen functionalities in resins and asphaltenes has been shown.
samples. A smaller contribution to the 3500-3300 cm-’ 1.r. spectra of resin and asphaltene fractions from
band is from pyrrolic type NH absorption. hydropyrolysis experiments indicate a parallel thermal
In asphaltenes and resins of type II kerogen (Figure 3), evolution of the fractions. Structural similarity of
the aromatic CH stretch at 3050 cm-’ and aromatic CH kerogen/asphaltenes/resins suggests that asphaltenes or
bending vibrations around 900-700 cm-’ are weak. This resins can replace kerogen for the determination of the
may be due to a scarcity of aromatic CH due to thermal evolution of a sediment. However, further work
substitution in the aromatic ringsz9. To compare the is necessary to establish quantitative parameters, and to
aromatic character instead of the aromatic CH/aliphatic explore their range of validity.
CH, we can use the factor mentioned above (Table 2).
As in the case of bitumen asphaltenes, the relative
ACKNOWLEDGEMENTS
amountofoxygenintheformofcarbonylgroupsseemstobe
enriched-in-oilresinscomparedwithoilasphaltenes.Thisis Norsk Hydro Research Centre (Bergen) is acknowledged
thecaseinallthepairsofresin/asphaltenefractionsstudied. for use of their i.r. facilities. Lotte Aakvaag, Norsk Hydro
Furthermore, the relative amount of oxygen in the form of Research Centre (Bergen) is thanked for the extraction

434 FUEL, 1989, Vol 68, April


Structural features of resins, asphaltenes and kerogen: A. A. Christy et al.

and separation into fractions of the coal samples. Anne 13 Painter, P. C., Snyder, R. W., Starsinic, M., Coleman, M. M.,
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