INGEPET 2002 (EXPR-1-RP-30) SEPARATION OF WAXES AND ASPHALTENES IN CRUDE OILS

R. Paul Philp, M. Hsieh School of Geology and Geophysics, University of Oklahoma USA

ABSTRACT Heavy organics are the primary culprits of deposition problems encountered during the production and transportation of crude oils, and are important constituents in the formation of tar mats. In general, high molecular weight hydrocarbons (HMWHCs >C40) and asphaltenes are the principal classes of heavy organics associated with crystallization, agglomeration, and other deposition-related problems. The traditional method for isolating asphaltenes is by precipitation with excessive amounts of low boiling point solvents such as pentane, hexane, or heptane, which can result in the co-precipitation of a significant amount of microcrystalline waxes (>C40). The presence of microcrystalline waxes (>C40) in the asphaltene fraction potentially can provide misleading and ambiguous results affecting any modeling or treatment program. The sub-surface phase behavior of an asphaltene fraction will be quite different from the subsurface behavior of a wax-contaminated asphaltene fraction. Similarly accurate modeling of wax drop-out requires information on pure wax fractions and not asphaltene dominated waxes. Hence the goal of this paper is to describe a novel method for the preparation of wax-free asphaltenes and asphaltene-free waxes. In addition, this method provides a quantitative subdivision of waxes into pentane soluble and insoluble waxes which, when correlated with physical properties of crude oil such as viscosity, pour point, cloud point, etc., may help to explain causes of wax deposition problems during production, transportation and storage of crude oils. Oils from a variety of basins worldwide, including examples from Peru, will be used to illustrate the application of this method to the determination of their wax and oil content and how this information may be used for production purposes. In addition the significance of the distribution of individual compounds within the wax fraction will be discussed in detail with the use of appropriate examples.

1. INTRODUCTION The development of high temperature gas chromatography (HTGC) has permitted the geochemist to enter the realm of high molecular weight hydrocarbons (HMWHCs) in the range C40-C120 in crude oils, and to lesser extent, source rock extracts (LIPSKY and DUFFY, 1986a and b; PHILP, 1994; HEATH et al., 1997; MUELLER and PHILP, 1998; HSIEH and PHILP, 2001). A number of papers have already been published on this topic including those by CARLSON et al. (1993), DEL RIO et al. (1992a and b) and WAVREK and DAHDAH (1995). These papers generally have been concerned with the characterization of waxes isolated from crude oils and pipelines and discuss the potential use of this type of information. In most crude oils these compounds typically extend to about C 70 with only a few oils that have been analyzed containing compounds in the C70-C120 range. The distribution of HMWHCs in a crude oil will be primarily determined by source materials with factors such as migration distances, pressure, and temperature gradients between reservoir and well-head also playing an important role in determining the distribution of HMWHCs observed in produced oils. Hydrocarbons with more than 20 carbon atoms are solid at room temperature and thus crude oils containing large amounts of hydrocarbons above C20, and more importantly above C 40, have the potential to give rise to serious wax deposition problems during production, and in some cases in the reservoir itself (TRINIDADE et al., 1997). Waxes may be precipitated in the production tubing or anywhere along the pipelines and production facilities until the oils reach the storage tanks. Even in storage tanks, wax deposition may be a problem and co-mingling of two or more oils, neither of which have paraffin problems when produced separately, may lead to precipitation of waxes. Movement and shearing may prevent deposition in the pipeline but the wax crystals formed will readily be deposited in the storage tank. Although the terms micro- and macro-crystalline waxes have been in use for many years to differentiate wax-types on the basis of their carbon number distributions and other properties, detailed molecular characterization of waxes were rarely undertaken in the past due to the lack of suitable analytical techniques. In many cases the concentration of these HMWHCs may be relatively low, hence techniques may be required to enhance the concentration of these compounds. PHILP and BISHOP (1995) and PHILP et al. (1995) described one such concentration technique and another standardized method involving acetone precipitation was published several years ago (BURGER et al., 1981). One of the major problems

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associated with this work is the separation of wax es from non-hydrocarbons dominated by resin and asphaltene fractions. Precipitation of asphaltenes with n-pentane will, in many cases, produce fractions containing high concentrations of microcrystalline waxes (>C40), whose presence can lead to the misinterpretation of geochemical characteristics of asphaltenes. Asphaltenes exist as suspensions in crude oils and are stabilized by peptizing agents such as resins and other aromatic compounds. Destabilization of asphaltenes will result in its deposition and agglomeration. Asphaltene particulates have the potential to act as nucleation points from which wax growth/crystallization can occur (HSIEH, 1999). Asphaltene flocculants acting as sites for wax crystallization have been demonstrated to increase crude oil cloud point and also interfere with wax inhibitors (GARCIA, 2000). Likewise when waxes are concentrated, they often contain significant amounts of asphaltenes. In this paper, a method for the quantitative and qualitative separation of waxes from asphaltenes will be described and used to illustrate the approach with results obtained from its application to oils from a variety of sources. It should be noted that waxy oils are not necessarily limited to those sourced from terrigenous, or higher plant, source materials as previously suggested by HEDBERG (1968) but many oils from lacustrine and marine sources also contain significant quantities of high molecular weight hydrocarbons. The HEDBERG (1968) paper also noted that waxy oils typically originated from stratigraphic sequences of non-marine origin, shale-sandstone lithology, water salinities less than that of marine waters, and ages ranging from the Devonian to Pliocene. KINGHORN (1983) also suggested that petroleum waxes were restricted to terrigenous sources; however, since those studies evidence has appeared suggesting that waxy crude oils may also be derived from marine or lacustrine source materials (MOLDOWAN et al., 1985; TEGELAAR et al., 1989; CARLSON et al., 1993; HSIEH, 1999). The wax fractions isolated from oils are not simply composed of n-alkanes, but also include complex mixtures of long chain alkylcycloalkanes, methylbranched alkanes, and alkylaromatic hydrocarbons. The presence of alkylcyclopentanes, extending beyond C 40, can be used to predict the depositional environments of the original source material. Possible sources for these compounds include indigenous components of living organisms (e.g. cuticular waxes preserved in kerogen), fatty acids, or wax esters (TISSOT and WELTE, 1984; KISSIN, 1990). NAlkanes and fatty acids sourced from blue-green algae and various types of bacteria are associated with hypersaline, carbonate environments (DEMBECKI et al., 1976). Significant fractions of organic sedimentary matter are comprised of algaenans in various classes of marine microalgae. Catagenesis of aliphatic algaenans in the sediments can provide an important source of n-alkanes in marine oils (GELIN et al., 1999). HMW mono-, di-, and trimethylalkanes have been observed in Holocene cyanobacterial mats from Abu Dhabi and are believed to originate from insects that grazed on the cyanobacterial mats (KENIG et al., 1995). Complex mixtures of waxy compounds are widespread in many varieties of insects and are commonly encountered as cuticle/surface lipids and internal lipids. These lipids are present as complex mixtures of long-chain n-alkanes, methylbranched alkanes, wax esters, aldehydes, fatty acids, long-chain alcohols, ketones, and sterol esters (NELSON and BLOMQUIST, 1995). It is important that we improve our understanding of these HMW compounds ( i.e. their structures, physical/chemical properties, and origin) in order to alleviate and better address production problems that result in reduced production, clean-up and remedial expenses, elevated operations costs, and investigative/research expenses (TUTTLE, 1983; ESCOBEDO and MANSOORI, 1992; LEONTARITIS, 1996).

2. EXPERIMENTAL The method, summarized in Fig.1, was developed to concentrate waxes in crude oils, separate microcrystalline waxes from macrocrystalline waxes, and to provide a method for separating waxes from asphaltenes. The initial step in this method involves adsorption of the oil on alumina (1-these numbers refer to the steps numbered in Fig.1), using approximately 1g of oil dissolved in 10 ml of hot iso-octane (at o least 80 C) to ensure complete dissolution of any wax crystals. Following adsorption, the alumina is extracted with iso-octane for a period of 48hrs (2) although this time period can be significantly reduced if the microcrystalline wax content (>C40) of the oil is low. Following the extraction, the iso-octane extract is o concentrated and the wax precipitated with acetone at -21 C (3, BURGER et al., 1981). Cold pentane (o 21 C) is added to the precipitate to a concentration of about 2mg/ml and the solution allowed to stand overnight (4). Following stirring and centrifugation with cold n-pentane, two fractions are obtained with the

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macrocrystalline waxes being in solution (5) and microcrystalline waxes with predominance of HMW HCs beyond C40 being present as precipitate (6). The material that remains adsorbed to the alumina after the initial extraction step is extracted with a mixture of chloroform/methanol (95:5) for at least 6hrs (7). This procedure will effectively extract the adsorbed asphaltenes and resins from the alumina which can subsequently be separated by pentane precipitation (8). The end products of this procedure are: (i) A wax-free asphaltene fraction; (ii) an asphaltene-free wax concentrate which, if desired, can be subdivided into micro(5)- and macrocrystalline(6) wax fractions. GC Analysis All GC analyses described in this paper were performed using a Carlo Erba GC8000 gas chromatograph equipped with an on-column injector and a SGE HT-5 column (25m x 0.32mm I. D. x 0.1?m film). Helium o o was used as the carrier gas and the column was programmed from 60 C to 380 C with a program rate of o 4 C/min.

3. RESULTS AND DISCUSSION The work described in the first part of this paper is specifically concerned with a method for the qualitative and quantitative separation of waxes from asphaltenes, and macrocrystalline waxes from microcrystalline waxes. The procedure has been designed to work on samples of approximately 1g in size but can be scaled down depending upon the amount of oil available and how much material is required from the separation step. The wax extraction time with iso-octane is mainly dependent upon the amount of microcrystalline waxes in the crude oil, and can be significantly reduced if a preliminary idea of the nature of the waxes (micro vs macro) is available. The importance of such a wax isolation is illustrated in Fig.2a which shows the high temperature gas chromatogram of a crude oil with HMWHCs extending to at least C65. Precipitation of asphaltenes by the classical pentane precipitation method produced a precipitate, whose chromatogram is shown in Fig.2b. A significant part of the asphaltene fraction in this case was present as a microcrystalline wax, which it should be noted is a more common occurrence than has been noted in the past. In most cases asphaltenes are not routinely analyzed by HTGC so the presence of these waxy components is not observed. Further purification of the asphaltenes would not necessarily remove the wax component simply because of their HMW and extremely poor solubility in solvents such as pentane commonly used to purify the asphaltenes. In Fig.2c the HTGC trace is shown for the asphaltene fraction isolated from the same oil using the procedure shown in Fig.1 and clearly the asphaltene fraction no longer contains any wax component, indicating complete separation of the wax from the asphaltene fraction. The corresponding wax fraction isolated from this oil using the procedure in Fig.1 is shown in Fig.3a, which is further separated into n-pentane soluble and insoluble waxes (Fig.3b and c, respectively). The pentanesoluble waxes contain predominantly n-alkanes (<C40-C45) and the insoluble waxes containing mainly microcrystalline waxes (>C40) whose extremely poor solubility may potentially cause wax deposition problems, especially in storage tanks. The quantitation of these higher carbon number components can be correlated with other physical properties such as pour point, cloud point or viscosity, to help explain causes of wax deposition problems. Case studies have demonstrated that a wax content as low as 2% can potentially result in wax deposition problems (HOLDER and WINKLER, 1965; TUTTLE, 1983; AJIENKA and IKOKU, 1990). The development of the above method has permitted detailed analyses of the isolated wax fractions to be undertaken. This is an extremely important aspect of the work since in many engineering and modeling studies the molecular composition of the waxes has been overlooked. For the most part it has been assumed that waxes all have similar compositions. This is clearly not the case and it is important to investigate the molecular composition of the isolated waxes to get a more comprehensive picture of their properties. The melting points of branched hydrocarbons are dramatically lower than n -alkanes and hence the relative concentrations of these compounds in a wax can have a significant effect on the pour point of a crude oil. GARCIA et al., (2000) have demonstrated that iso- and cycloalkane concentrations >40 wt.% can hinder wax crystal arrangements and increase the cloud point of an oil. It is also important to note the ubiquity of HMWHCs in oils from all types of source materials.

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Wax components are not simply restricted to oils sourced from any one type of environment or source material. As part of our on-going research a wide range of oils from marine, freshwater lacustrine, saline lacustrine, and terrigenous environments; with shale or carbonate source rock lithologies; and ages ranging from Ordovician to Pliocene have been examined (Fig. 4a-c). The majority of these oils have several homologous series of compounds in the HMW region (Fig. 5). In an effort to identify these compounds, selected fractions have been analyzed by GCMS which revealed at least seven homologous series of compounds with major fragment ions at m/z 56, 57, 68, 70, 82, 84, and 92 (Fig. 6). The precise structures for each of these compounds is still the subject of an on-going investigation. Homologous series that have been identified to date however, include methylbranched alkanes (m/z 57), alkylcyclopentanes (m/z 68), alkylcyclohexanes (m/z 82), and alkylbenzenes (m/z 92), and are discussed in more detail by HSIEH (1999) and HSIEH et al. (2000). More recently two additional series of methylbranched alkanes have been identified by comparison of retention times and mass spectra for similar compounds present in microbial mats from Abu Dhabi. The homologous series of alkylcyclopentanes extending beyond n-C40 in crude oils have predominance patterns that can be associated with source environments as observed by CARLSON et al. (1993), and WAVREK and DAHDAH (1995). Predominance patterns of alkylcyclopentanes between C 40 and C 46 were observed to be most consistent in relation to depositional environments, whereas patterns above C46 were sometimes unclear or changed to an opposite pattern (HSIEH, 1999; HSIEH and PHILP, 2001). Oils demonstrating a high even/odd predominance pattern were found to be associated with saline lacustrine environments (Fig. 7a); freshwater lacustrine oils were characterized by a low even/odd to no clear predominance pattern (Fig. 7b); and marine oils had distinct odd/even predominance patterns (Fig. 7c). These compounds along with the other complex mixtures of methylbranched- and alkylcycloalkanes (>C40) have the potential to be used as supplemental tools in biomarker studies. Quantitative and qualitative differences are not necessarily restricted to samples coming from different geographical areas or source materials. Wax composition can be highly variable in oils as observed in Fig. 8a and b, illustrating wax fractions from two oils collected from the same formation, equivalent depths of production, but different well locations. The oil in Fig. 8b contains a bimodal distribution of hydrocarbons in the range C20-C35 and C40-C60; whereas the oil in Fig. 8a is dominated by hydrocarbons in the C20-C45 range. Such a variation in wax distribution may be related to temperature gradients along the migration pathway, with the oil located closer to the source (Fig. 8b) having a higher microcrystalline wax content. As indicated these chromatograms are obtained from the wax concentrates since in many oils, the hydrocarbons above n -C35 are present in relatively low concentrations (~2%) and need to be concentrated prior to analysis. In another study published some years ago, HEATH et al. (1998) noted the stability of these HMWHCs towards biodegradation. As an extension to that observation it should be noted, heavily biodegraded oils may indeed contain trace amounts of these HMWHCs which cannot be seen in the whole oil GC but become evident upon isolation of the wax fraction as illustrated for a heavily biodegraded oil in Fig. 9a and b. The alkylcyclopentanes predominate in the HMW region of some oils and are suspected to be the predominant series in cases where precipitation has already begun (HSIEH and PHILP, 2001), as shown in Fig. 10 which illustrates an oil where the n -alkanes predominate over the alkylcyclopentanes in the HMW region. When wax precipitation is induced, it is observed that the n-alkanes are preferentially precipitated while the alkylcyclopentanes in solution are enhanced. N-Alkanes have higher melting points than iso-alkanes and lower melting points than cycloalkanes. But, when we add a long alkyl- side chain to the cycloalkane, the melting point will become lower than the n-alkanes due to steric interference. In this case, it is reasonable that we observe the n-alkanes (>C40) to precipitate at higher temperatures than the alkylcyclopentanes.

4. SUMMARY Waxes are common to most oils regardless of the depositional environment of original source materials and have been observed in oils sourced from marine, freshwater lacustrine, and saline lacustrine environments. A method is described which permits the qualitative and quantitative separation of waxes and asphaltenes from crude oils. The quantity and nature of waxes vary from one oil to another, including

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oils produced from different wells of the same reservoir. HTGC and GCMS analyses have revealed the presence of complex series of compounds comprised of long-chain alkylbenzenes, methylbranched alkanes, and alkylcycloalkanes. These compounds are very resistant to biodegradation and are present in significant amounts, but have yet to be utilized to their full potential. While we do not know the exact structures or origins of wax compounds (>C40), it is apparent that they are present in most crude oils regardless of source environments, they have the potential to be useful tools for biomarker studies, and they will continue to hinder oil production until we gain a better understanding of these compounds. Further improvements in extraction techniques for HMWHCs in source rocks will result in better oil-source rock correlations of high-wax oils, and also give greater insights into the origin of HMWHCs in crude oils.

5. REFERENCES AJIENKA, J. A., IKOKU, C. U., 1990. Waxy crude oil handling in Nigeria: practices, problems, and prospects. Energy Sources , 12, 463-478. BURGER, E. D., PERKINS, T. K., STRIEGLER, J. H., 1981. Studies of wax deposition in Trans Alaska Pipeline. J. Petrol. Tech. , 33, 1076-1086. CARLSON, R. M. K., TEERMAN, S. C., MOLDOWAN, J. M. JACOBSON, S. R. CHAN, E. I., DORROUGH, K. S., SEETOO, W. C., MERTANI, B., 1993. High temperature gas chromatography of nd high-wax oils. Indonesian Petroleum Association, 22 Annual Convention Proceedings , Jakarta, Indonesia, 483-507. DEMBICKI, H. J., MEINSCHEIN, W. G., HATTIN, D. E., 1976. Possible ecological and environmental significance of the predominance of even-carbon number C 20-C30 n-alkanes. Geochim. et Cosmochim. Acta, 40, 203-208. ESCOBEDO, J., MANSOORI, G. A., 1992. Heavy organic deposition and plugging of wells (analysis of Mexicos experience). Paper SPE 23696 -Proceedings of the II LAPEC, Richardson, TX., 349-362. GARCIA, M. C., 2000. Crude oil wax crystallization. The effect of heavy n-paraffins and flocculated asphaltenes. Energy and Fuels, 14, 1043-1048. GARCIA, M. C., CARBOGNANI, L., OREG, M., URBINA, A., 2000. The influence of alkane class-types on crude oil wax crystallization and inhibitors efficiency. J. Petrol. Sci. and Engineering, 25, 99-105. GELIN, F., VOLKMAN, J. K., LARGEAU, C., DERENNE, S., SINNINGHE DAMSTE, J. S., DE LEEUW, J. W., 1999. Distribution of aliphatic, nonhydrolyzable biopolymers in marine microalgae. Org. Geochem., 30, 147-159. HEATH, D. J., LEWIS, C. A., ROWLAND, S. J., 1997. The use of high temperature gas chromatography to study the boidegradation of high molecular weight hydrocarbons. Org. Geochem., 26, 769-786. HEDBERG, H. D., 1968. Significance of high-wax oils with respect to genesis of petroleum. AAPG Bulletin, 52, 736-750. HOLDER, G. A., WINKLER, J., 1965. Wax crystallization from distillate fuels, parts 1, 2, and 3. J. Inst. Petrol., 51, 228-252. HSIEH, M., PHILP, R. P., 2001. Ubiquitous occurrence of high molecular weight hydrocarbons in crude oils. Org. Geochem., 32, 955-966. HSIEH, M., PHILP, R. P., DEL RIO, J. C., 2000. Characterization of high molecular weight biomarkers in crude oils. Org. Geochem., 31, 1581-1588. HSIEH, M., 1999. Characterization of waxes in high pour-point crude oils. M.S. Thesis, University of Oklahoma, 113p. KENIG, F., SINNINGHE DAMSTE, J. S., KOCK-VAN DALEN, A. C., RIJPSTRA, W. I. C., HUC, A. Y., DE LEEUW, J. W., 1995. Occurrence and origin of mono-, di-, and trimethylalkanes in modern and Holocene cyanobacterial mats from Abu Dhabi, United Arab Emirates. Geochim. Cosmochim. Acta. , 59, 2999-3015. KINGHORN, R. R. F., 1983. An introduction to the p hysics and chemistry of petroleum. John Wiley & Sons Ltd., Chichester, 420p. KISSIN, Y. V., 1990. Catagenesis of light cycloalkanes in petroleum. Org. Geochem., 15, 575-594. LEONTARITIS, K. J., 1996. Offshore asphaltene and wax deposition: problems/solutions. World Oil, 217, 57-63. LIAEEN-JENSENN, S., 1990. Marine carotenoids -selected topics. New J. Chem., 14, 747-759. LIPSKY, S. R., DUFFY, M. L., 1986a. High temperature gas chromatography: the development of new aluminium clad flexible fused silica glass capillary columns: Part I. J. High Res. Chromatog. , 9, 376-381.

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LIPSKY, S.R., DUFFY, M. L., 1986a. High temperature gas chromatography: the development of new aluminium clad flexible fused silica glass capillary columns: Part I. J. High Res. Chromatog. , 9, 725-730. MUELLER, E., PHILP, R. P., 1998. Extraction of high molecular weight hydrocarbons from source rocksAn exaple from the Green River Formation, Uinta Basin, Utah. Org. Geochem., 28, 625-631. MOLDOWAN, J. M., SEIFERT, W. K., GALLEGOS, E. J., 1985. Relationship between petroleum composition and depositional environment. AAPG Bulletin, 69, 1255-1268. NELSON, D. R., BLOMQUIST, G. J., 1995. Insect waxes. In: R. J. Hamilton (ed.) Waxes: chemistry, molecular biology and functions. The Oily Press, Scotland, 1-90. PHILP, R. P., 1994. High temperature gas chromatography for the analysis of fossil fuels: A review. J. High Res. Chrom., 17, 398-406. PHILP, R. P., BISHOP, A. N., 1995. Exploration and reservoir geochemistry: Concepts, applications and results. In: Proceedings of PETROTECH-95, New Delhi, India, January 1995., 57-77. PHILP, R. P., BISHOP, A. N., DEL RIO, J. C., ALLEN, J., 1995. Characterization of high molecular weight hydrocarbons (>C40) in oils and reservoir rocks. In: The Geochemistry of Reservoir Rocks, (Eds. J.M. Cubitt and W.A. England) Geological Society Special Publication No. 86, London. 71-85. DEL RIO, J. C., PHILP, R. P., 1992a. Nature and Geochemistry of High Molecular Weight Hydrocarbons (Above C40) in Oils and Solid Bitumens. Org. Geochem. 18, 541-553. DEL RIO, J. C., PHILP, R. P., 1992b. High Molecular Weight Hydrocarbons: A New Frontier in Organic Geochemistry. Trends in Anal. Chem., 11, 187-193. TEGELAAR, E. W., MATTHEZING, R. M., JANSEN, J. B. H., and HORSFIELD, B., DE LEEUW, J. W., 1989. Possible origin of n-alkanes in high-wax crude oils. Nature, 342, 529-531. THANH, N. X., HSIEH, M., PHILP, R. P., 1999. Waxes and asphaltenes in crude oils. Org. Geochem., 30, 119-132. TISSOT, B. P., WELTE, D. H., 1984. Petroleum Formation and Occurrence. New York, Springer-Verlag, 699p. TUTTLE, R. N., 1983. High pour-point and asphaltic crude oils and condensates. J. Petrol. Tech. , 35, 1192-1197. TRINDADE, L. A. F., PHILP, R. P., MIZUSAKI, A. M. P., DOS SANTOS, R. L. A., TCHOUPAROVA, E., SIAMAK DJAFARIAN, M., 1996. Geochemical characterization of waxy oils from the Dom Joao oil field, Reconcavo Basin, Brazil. In: Proceedings of the 5th Latin American Organic Geochemistry Congress, Cancun, Mexico, October 1996, 281-283. WAVREK, D. A., DAHDAH, N. F., 1995. Characterization of high molecular weight compounds Implications for advanced-recovery technologies. SPE 28965, 207-210.

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7
CRUDE OIL (1g) Dissolved in 10ml hot iso-octane

1. ALUMINA ADSORPTION

2. FIRST SOXHLET EXTRACTION with iso-octane, 48hrs

ISO-OCTANE EXTRACT

ADSORBED MATERIAL

CONCENTRATE

7. SOXHLET EXTRACTION with CHCl3:CH 3OH (95:5, v/v), at least 6hrs

3. WAX PRECIPITATION O ACETONE, -21 C, at least 2hrs ELUATE PRECIPITATE (TOTAL WAX) SOLUBLES CONCENTRATE ADSORBED MATERIAL

4. n-PENTANE, -21 C with concentration of 2mg/ml solution stands overnight STIR & CENTRIFUGE with cold pentane

8. PENTANE PRECIPITATION

ASPHALTENES

RESINS

5. PRECIPITATE (MICROWAXES, >C 40)

6. SOLUBLES (MACROWAXES)

Fig.1. Proposed scheme for the qualitative and quantitative separation of asphaltenes, micro-, and macrocrystallinewaxes. The numbers of each important step are given and these are referred to in the text.

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FIG.2a 30 20 40

50

60

15

40

50

60

FIG.2b

FIG.2c

12

24

36

48

60 Minutes

72

84

96

108

120

Fig. 2a. HTGC chromatogram of a crude oil from the Uinta Basin. GC conditions are described in the text and this oil had lost the light ends through evaporation. However for the purposes of this study that was not a major problem. Fig. 2b. HTGC chromatogram of the asphaltene precipitate isolated from the crude oil used for Fig. 2a and isolated by the classical pentane precipitation method. Fig. 2c. HTGC chromatogram of the asphaltene fraction isolated from the same oil using the procedure described in this paper. Note the complete absence of any wax components in this sample illustrating the quantitative separation of the wax from the asphaltene.

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FIG.3a
A C E T O N EW A X E S

30
40 5 0 60

20

40

50

4 0 C 5 -S O L U B L EW A X E S 4 5

50
C 5 -I N S O L U B L EM I C R O C R Y S T A L L I N EW A X E S

40 60 0 12 24 36 48 60 M inutes 72 84 96 108 120

Fig.3a. HTGC chromatogram of the total wax fraction isolated using the procedure described in this paper. This corresponds to the total wax isolated at step 3 of the procedure shown in Fig. 1. Fig. 3b and 3c respectively show the chromatograms for the macro- and micro-crystalline waxes recovered from steps 5 and 6 shown in Fig. 1.

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Fig. 4. Wax components are not simply restricted to oils sourced from any one type of environment or source material, and have been observed in oils sourced from marine, freshwater lacustrine, and saline lacustrine environments as illustrated here in chromatograms 4a-c respectively.

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C 38H 76 C 37H 74 C 35H 70 20 C 38H 78

n-C 38

n-C 39 2.433 E+05 C 39H 78 C 38H 76 C 36H 72 C 39H 80 C 37H 68 C 37H 74 C 37H 74 C 40H 82 C 40H 80 C 39H 78

C 36H 72

C 38H 76

10 C 39H 78

C 38H 70

C 40H 80

alkylcyclopentane alkylcyclohexane 25:00

methylbranched alkane alkylbenzene 26:40 28:20 30:00 31:40

Retention time (min)

Fig. 5. An expanded region of the higher molecular weight compounds clearly show the presence of several homologous series of compounds, some of which have been identified, some of which remain unknown.

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12

m/z:56 10

C 34H 68

C 35H 70

C 36H 72 C 37H 74 C 38H 76

E+06 1.076

m/z:57 20

C 36H 74

C 37H 76

C 38H 78 C 39H 80 C 40H 82

E+06 3.997

m/z:68 20

C 37H 74

C 38H 76

C 39H 7
8

C 40H 80

C 41H 82

E+05 7.416

m/z:70 10

C 33H 66

C 34H 68

C 35H 70

C 36H 7
2

C 37H 74

E+06 1.085 C 38H 76 E+05 8.427

50

m/z:82 C 36H 72 m/z:84

C 37H 74

C 38H 76

C 39H 78

C 40H 80

C 41H 8
2

10

C 35H 70

C 36H 72

C 37H 74

C 38H 76

C 39H 78

C 40H 80 C 38H 70

E+05 4.179

100 50

m/z:92

C 34H 62

C 35H 64

C 36H 66

C 37H 68

E+04 9.132

n-C 36 20

n-C 37

n-C 38

n-C 39

n-C 40

E+07 4.750

23:20

26:40

30:00

33:20

Fig. 6. In an effort to identify these compounds, selected fractions have been analyzed by GCMS which revealed at least seven homologous series of compounds with major fragment ions at m/z 56, 57, 68, 70, 82, 84, and 92 as shown in these single ion chromatograms.

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Fig. 7. Oils demonstrating a high even/odd predominance pattern were found to be associated with saline lacustrine environments (Fig. 7a); freshwater lacustrine oils were characterized by a low even/odd to no clear predominance pattern (Fig. 7b); and marine oils had distinct odd/even predominance patterns (Fig. 7c).

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25

14
(a) Anadarko Basin (a) Anadarko Basin Oil #1 - Wax Fraction Oil #1 Wax Fraction Depths: 10160ft - 10210ft Depth: 10160-10210ft

30 45

40 20

50 55 60

65 90 100

10

20

30

40

50 Minutes

60

70

80

Retention time (min)

25

(b)(b) Anadarko Basin Anadarko Basin Oil #2 Wax Fraction Oil #2 - Wax Fraction Depth: Depths: 10530-10546ft 10530ft - 10546ft
30 45

50

35 40 20 0 10 20 30 40 50 MinutesRetention 60 45 70 80 90 100

time (min)

Fig. 8a and b. Wax composition can be highly variable in oils, as illustrated by the wax fractions isolated from two oils collected from the same formation, equivalent depths of production, at different well locations.
Pr

(a) Biodegraded Oil

Ph

40

10

2 0

30

40

50

60

70

80

90

100

Retention time (min) (b) Wax Fraction

30 40 44a 48a

25

n-C40

20 0 10 20 30 40 50 60 70 80 90 100

Retention time (min)

Fig. 9. The HMWHCs are relatively resistant to biodegradation as illustrated in this example of a heavily biodegraded oil (Fig. 9a). Isolation and concentration procedures led to the isolation of the wax fraction shown in Fig. 9b.

INGEPET2002 (EXPR1-RP-30)

15

15 25 (a) (a) Original Original Whole Whole Oil

Oil

alkylcyclopentanes
20 30 40 50 60

40

50

60 96 108 120

12

24

36

48 60 Minutes Retention

72

84

time (min)

15 25

(b)Residual Residual (b) Oil

Oil

20 30 40

alkylcyclopentanes

40

12

24

36

48 60 Minutes Retention

72

84

96

108

120

time (min)
50

(c) (c) Precipitated Precipitated Fraction Fraction

45 55

**

60 40 65 30

0
*

12

24

36

C36 D74

48 60 Minutes Retention

72

84

96

108

120

time (min)

Fig. 10. The alkylcyclopentanes predominate in the HMW region of some oils and are suspected to be the predominant series where precipitation has already begun as illustrated by this oil where the n -alkanes predominate over the alkylcyclopentanes in the HMW region indicating precipitation has been initiated.