Chapter 2 Method development and methodology

This chapter comprises two sections. The first section address background issues relating to the techniques used to fractionate sedimentary organic matter, and a study undertaken to select a method for asphaltene precipitation. The second section details the experimental methods used in this study.

2.1 Selection of asphaltene separation method

2.1.1 Kerogens As described in the introduction, the different fractions of sedimentary organic matter are operationally defined, and this makes the properties they exhibit and their chemical composition extremely sensitive to the separation methods employed. Thus, although the classical definition of kerogen (Durand, 1980) is often accompanied by the assumption that the insoluble residue is polymeric and macromolecular in nature, this is not necessarily the case. Biomarkers, as well as other organic molecules, can still be liberated from extracted sediments and kerogens by further treatments (mild thermolytic and solvent treatments) that do not break covalent bonds. Pelet et al. (1986) proposed a continuum of material held by decreasing bond strength associations; Hbonding, electron intermolecular attractions, Van der Waals forces, physical adsorption and steric entrapment in micropores. When non-covalently bound material (particularly biomarkers) in kerogens is quantified, it is generally found to be of very low abundance in the total sedimentary organic matter and relative to the kerogen fraction. The proportion of hopanes in the bitumen II fraction from a number of kerogens has been found to represent less than 1% of the total hopanes (Bishop et al., 1998), and pyridine extracts (which can also contain large proportions of non-covalent bound biomarkers) have been found to liberate a similarly low proportion (less than 5%) of the total hopanes and steranes (Love et al., 1995). Mild thermolytic treatment of various Precambrian kerogens released non-covalently bound compounds of similar composition to the extracted bitumen fraction (Brochs et al., 2003). The proportion of occluded/trapped phenanthrenes in the kerogen seemed to increase with the degree of methylation, perhaps consistent with steric trapping of bulkier compounds in micropores. The proportions of aromatic compounds present in this trapped phase were 47

of one to two orders of magnitude less than that covalently bound into the kerogen. Thus, most studies show that in the kerogen fraction the greater proportion of biomarkers appear to be present as compounds that are covalently bound into host macromolecular networks. 2.1.2 Asphaltenes The procedures used for recovering asphaltenes vary far more than those for preparing kerogens. Three main methods exist: chromatographic methods (Monin and Pelet, 1983), sequential extraction (Rubinstein et al., 1979) and precipitation from solution by addition of excess solvent (Long, 1981). Precipitation from solution is by far the method most commonly employed, although many variations of this method exist (e.g. choice of solvent or combination of solvents). The effects of solvent choice are shown in Figure 1.2.

effect of solvent on asphaltene recovery

70 60 50 Wt% insoluble 40 30 20 10 0 1 2 3 4 5 6 7 8 9 10 11 Carbon number of n-paraffin solvent

Figure 2.1. Taken from Long, (1981). The % of insoluble material recovered from Arabian light crude oil for different solvents.

From Figure 2.1 it can be seen that n-heptane is considerably more selective than npentane. It is preferable to be as selective as possible because of the many compounds that co-precipitate with the asphaltene fraction, including waxes (Del Rio et al., 1992; Than et al., 1999), a wide range of sulphur and oxygen-containing compounds (Strausz et al., 1999) and pregnanes and tricyclic terpanes (Gurgey et al., 1998). The reasons for the co-precipitation of this wide group of compounds varies, in the case of the sulphoxide compounds this is due to the similar polarities (Strausz et al., 1999), whereas for waxes it is a combination of molecular weight (Del Rio et al., 1992) and the ability of asphaltene micelles to provide sites for wax deposition (Chouparowa and

48

Philp, 1998). This led Long (1981) to propose that asphaltenes be characterised by both their molecular weight and polarity, essentially excluding compounds such as waxes and suphoxide compounds. However, it is still common practice in organic geochemistry to treat the precipitate resulting from the addition of excess n-heptane to a solution as the asphaltene fraction. 2.1.3 Biomarker chelation in asphaltene aggregates The degree to which the co-precipitation of biomarkers in the asphaltene fraction occurs can be reduced by repeated precipitation. Gurgey (1998) found that the ratio of hopane/tricyclic terpanes, and pregnanes/steranes in the free hydrocarbon fractions of a number of oils was significantly altered by the re-precipitation of asphaltenes. This was attributed to the asphaltene aggregates retaining the smaller components (tricyclic terpanes and pregnanes) in their pore structure. The interaction of co-precipitating compounds with the asphaltene molecules is complicated by the nature of asphaltene molecules themselves. The molecular weight exhibited by asphaltenes depends on the methods used, and asphaltenes may exhibit a unit, particle or micelle weight. Individual units are 1000 daltons or less, whereas micelles are considerably larger (40000 daltons) and formed from many smaller units (Yen, 1981; Wilhelms and Larter, 1995; Groenzin and Mullins, 2000). Disruption of asphaltene clusters (aggregates) and micelles by repeated solution and precipitation presumably releases chelated hydrocarbons. 2.1.4 Geological variability In addition to the application of different preparative methods causing variation in the type of asphaltenes precipitated, the nature and chemical characteristics of asphaltenes will also vary depending on their source. For example coal and petroleum asphaltenes (Yen, 1981), and asphaltenes from different types of source rocks (Behar et al., 1984; Pelet et al., 1986) show variations in their elemental composition depending on their source. Asphaltenes from type III source rocks and coals tend to be more aromatic, have lower H/C ratios and have a smaller unit size. 2.1.5 Other fractions containing bound biomarkers Geochemical studies have also considered the bound biomarkers present in other polar non-hydrocarbon fractions present in the solvent extracts of source rocks and other sedimentary rocks. These include the aromatic, alkylsulphide, ketone and resin fractions 49

(Richnow et al., 1991; Koopmans et al., 1996; Murray, 2001). Many of the compounds that are solublised, and partitioned to the maltene fraction by increasingly selective asphaltene precipitation procedures will end up in the resin and other polar fractions. Given this, and the close structural similarity between resins and asphaltenes (Koots and Speight, 1975; Pelet et al., 1996), it is logical to ask whether separating the asphaltene and resin fractions is necessary to quantify bound biomarkers present in these fractions? First, to answer this question fully it is necessary to quantify and compare the compositions of biomarkers present in these different fractions. Second, as discussed in Chapter 1, there is every indication that resins have particular a very similar composition to type I organic matter and source rocks, and that their biomarker content may be significantly different to that of other fractions (Pelet et al., 1986; Richnow et al., 1991). If the decision is made to separate resin and asphaltene fractions then it is important that the separation of the two fractions be made as precisely as possible, and that the products produced are comparable to those of other studies. 2.1.6 Method selection The key features of an asphaltene fractionation method are that it be as precise and reproducible as possible, and that hydrocarbons and biomarkers chelated in, or occluded by, asphaltene aggregates are removed. Two asphaltene fractionation methods were considered: sequential extraction and precipitation. Sequential extraction uses extraction by solvents of gradually increasing polarity to fractionate samples in this instance n-heptane followed by a DCM/MeOH mixture. Two forms of asphaltene precipitation were considered. One method involved the settling of precipitates by standing a solution overnight, a relatively lengthy and involved procedure. The other precipitation procedure used a centrifuge to speed up settling. These methods were tested on samples of the Athabasca Tar Sand, a bitumen extracted from the Jet Rock Formation and a 3 North Sea oils from the Norwegian sector.

50

65mg 5.4% 157mg 13.1%

precipitate in arm

asphaltene

973mg 81.4%

maltene

Figure 2.2 Soxhlet extraction of tar sand by n-heptane showing the quantities present in the different areas of the apparatus. 2.1.7 Sequential extraction A sample of the Athabasca Tar Sand was soxhlet extracted in n-heptane for 48hrs. During the extraction quantities of bitumen were observed to precipitate in the reflux arm of the soxhlet unit. This can be attributed to the drop in temperature of the solvent in the soxhlet arm. This precipitate was recovered later by repeated flushing with DCM/MeOH. After a subsequent DCM/MeOH 93/7 (v/v) soxhlet extraction of the nheptane extracted tar sand to recover the asphaltene fraction left behind, the soxhlet thimble appeared to still be darkly stained suggesting that a small quantity of bitumen may have irreversibly interacted with the cellulose thimble. (Weighing the empty thimble before and after extraction indicated a weight gain of 32.5 mg, although a large proportion of the mass will include remaining traces of inorganic material from the rock). Given the precipitation of bitumen in the soxhlet arm and the possible loss of bitumen to the soxhlet thimble, further investigation of this process as a potential method for separating an asphaltene fraction was halted. This decision was made on the basis that the method would produce fractions that were too different from those produced by the methods commonly used in organic geochemistry to separate asphaltenes (e.g. addition of excess n-paraffins to a bitumen or oil). 2.1.8 Precipitation Two methods of asphaltene precipitation were tested: a quick centrifuge precipitation method in which the maltene fraction is decanted off between steps, and a slower gravity settling method in which the solution is filtered in a sinter funnel between steps. The gravity settling precipitation method requires that the excess mixture of dissolved

51

oil and n-heptane be stood over night, and so a (routinely applied) four times reprecipitation takes five days in total and requires that the precipitate and maltene/nheptane solution be sintered between each step. In contrast, the centrifuge settling method takes only a few hours, does not involve sintering, and so is far less time consuming. The overnight precipitation method has been used extensively to provide pure asphaltene fractions (upon successive reprecipitations) for hydrous pyrolysis (e.g. Jones et al., 1988), and so is a proven method for purifying asphaltenes, whereas the centrifuge method has mostly been used to provide asphaltene-clean maltene fractions. However, it can only be assumed that the two methods are interchangeable because there has been no investigation previously conducted to prove this. 2.1.9 Experimental details Gravity settling and sintering method 1) Sample is dissolved in a known volume of DCM (minimum 0.5 ml) and transferred to a conical flask. 2) A 40-fold excess of n-heptane (n-heptane/DCM, v/v) is added, and the sample stirred for 30 minutes in the conical flask. 3) Solution is stood in fridge overnight and precipitate allowed to settle. 4) Solution (maltene) and precipitate (asphaltene) are transferred to a sinter funnel and the maltene fraction collected. 5) Precipitate is washed repeatedly with chilled n-heptane. 6) Precipitate is recovered from sinter funnel by dissolution in DCM, collected and reduced to dryness. 7) The asphaltene fraction is redissolved in a known volume of DCM and the process repeated a further three times. Centrifuge settling method 1) Sample is dissolved in a known volume of DCM (minimum 0.5 ml) and transferred to a conical flask. 2) A 40-fold excess of n-heptane (n-heptane/DCM, v/v) is added, and the sample stirred for 30 minutes in the conical flask. 3) Solution is transferred to, and equally distributed between, two centrifuge tubes.

52

4) Solution is centrifuged for 5 minutes at 2500 rpm. This is repeated until the solution is clear. 5) Solution (maltene fraction) is decanted from the centrifuge tubes. 6) Precipitate (asphaltene fraction) is dissolved in a known volume of DCM and the process repeated a further three times. For the purposes of method investigation, very small quantities of the precipitate (asphaltene) were collected after each precipitation. To investigate any potential loss of asphaltene to the maltene fraction, after the final fourth precipitation had been performed and the maltene fraction decanted off it was reduced in volume, dissolved in a known volume of DCM and a single precipitation performed and the precipitate collected and weighed. 2.1.10 TLC-FID (Iatroscan) analysis To assess the purity of asphaltene fractions produced by each precipitation method, samples were collected after each reprecipitation and analysed by TLC-FID. Initially the method used closely followed the technique described by Karlsen and Larter (1991). A small amount of sample (~0.015 mg) is placed in duplicate on silica rods (Chromarod-S III 60 A pore diameter, 5 m particle size). A rack of five duplicates (e.g. ten in total) containing quantitative standards (for aliphatic, aromatic and resin fractions) is then sequentially developed in three tanks containing hexane, toluene and a 95:5 DCM:methanol mix. Between each chromatography stage and prior to TLC-FID analysis the rods are dried of solvent. Data were digitally recorded and collected on an Iatron Labs Inc. Tokyo, Iatroscan TH-10, Mk IV within the range of FID hydrogen flow rates, scan times and rod to burner distance used in Karlsen and Larter (1991). However, it was found to be necessary to use lower quantities of asphaltene to achieve better chromatographic separation of resin and asphaltene peaks, and to avoid overloading the FID detector when analysing asphaltenes. This became more apparent with the more pure asphaltene factions. When quantifying asphaltenes in the three oils and Jet Rock and Athabasca extracts, Iatroscan was found to overestimate the quantities of asphaltene present by approximately a factor of ten. This wasnt observed by Karlsen and Larter (1991), and so perhaps this is a feature unique to the samples or equipment used in this study. Because of this, quantification was not used to assess the

53

cleaning effects of repeated precipitation on asphaltenes, instead changes in the ratios of the peak areas of different fractions were monitored at each successive precipitation. 2.1.11 Samples A bitumen extracted from the Jet Rock (sample 11, see Chapter 3) and an oil collected by a wireline formation tester from a North Sea reservoir were analyzed by Iatroscan and their compositions are reported in Table 2.1. To compare the two asphaltene precipitation techniques the source rock extract was fractionated by both gravity and centrifuge precipitation methods. The North Sea oil was fractionated by the centrifuge method to assess the influence of the initial composition of the staring oil on asphaltene recovery, and to investigate if the centrifuge method was reproducible with small initial quantities of asphaltene. Table 2.1. % bitumen composition determined by TLC-FID Iatroscan
Jet Rock Extract Jet Rock Extract WFT sample of a North Sea Oil WFT sample of a North Sea Oil For sample description see text Aliphatic 10 7 23 23 Aromatic 33 30 38 40 Resin 45 49 32 33 Asphaltene 12 14 7 5

2.1.12 Comparison of the two asphaltene precipitation methods The TLC-FID chromatograms (Figure 2.3) show that in general the Iatroscan separations were good, and allow for the identification of aliphatic, aromatic, resin and asphaltene constituents. The traces show that effectively the gravity settled and sintered precipitate was clean of aliphatic and aromatic hydrocarbons after one precipitation, and the centrifuged precipitate was clean after two precipitations. However, although the centrifuge method takes more precipitations to clean hydrocarbon material from the asphaltene fraction it is still quicker as no overnight settling is involved. Thus, both the methods are suitable for cleaning hydrocarbon components from asphaltene fractions, which suggests that the key process common to all methods, mixing in solvent for 30 mins, is the most vital for the releasing of occluded or chelated hydrocarbons from asphaltenes.

54

gravity settling, sintering asphaltene aromatic

solvent direction

centrifuge, no sintering aromatic asphaltene

solvent direction

resin

Original DCM extract

aliphatic

Prep 1

small proportion of aliphatic

Prep 2

aliphatic

Prep 3

na

Prep 4

Maltene

Figure 2.3. Iatroscan TLC-FID traces showing the compositions of the untreated Jet Rock extract, precipitates at various stages and final maltene fractions. Small residual quantities of compounds are still present in the centrifuge precipitate after one precipitation, but essentially the products of the two methods are similar. na = graphic not available for the third centrifuge precipitate.

Given that both precipitates are effectively hydrocarbon free after two precipitations, is there any need for repeated precipitations at stage 3 and 4? The answer to this is yes, for two reasons. Firstly, Iatroscan is not very sensitive to trace quantities of biomarker compounds; studies of trace level concentrations of compounds including biomarkers (Gurgey, 1998) have shown that free hydrocarbons can still be recovered from the asphaltene fraction. Secondly, the resin/asphaltene ratio doesnt stabilize until the third or fourth precipitation (Figure 2.4). This suggests that in order to be as precise and selective as possible it is desirable to reprecipitate several times. Although the resin/asphaltene ratios of the final stage precipitates appear similar (Figure 2.3), and both seemed to have stabilized by the same precipitation stage, the ratios are lower in the precipitates from the centrifuge method (Figure 2.4). The initial resin/asphaltene value of the whole extract analyzed at the same time as the precipitates prepared by the centrifuge method (right hand side of Figure 2.4), is higher than that of the whole extract analyzed with the precipitates prepared by the gravity settling method. This suggests that instrumental drift is not the cause of the lower resin/asphaltene ratio 55

resin

seen in the final stage precipitates from the centrifuge method. (If it was, the resin/asphaltene ratio of the precipitate produced by the gravity method would be expected to be lower as its starting value was lower).

peak area ratio resin/asphaltene

4 3 2 1 0 0 1 2 3 4 5
number of precipitation gravity

4 3 2 1 0 0 1 2 3 4 5
number of precipitation centrifuge

Figure 2.4. Effects of reprecipitation on the resin/asphaltene ratios of the Jet Rock extracts produced by the two precipitation methods.

One cause for this difference in resin/asphaltene ratio may be enhanced selectivity of asphaltene polymers and macromolecules by centrifuge settling. This is attributable to denser particles and aggregates (comprised of higher molecular weight, more aromatic compounds which are more densely packed), settling faster than their lighter counterparts (comprising more aliphatic, less condensed material). In gravity settling, where the solution is stood overnight for a longer period of time, lighter particles have more time to settle and the difference between the more aliphatic and resin-like material, and the denser more asphaltene-like material is less noticable. However, the overall difference between the products of the two methods, while outside of the variation shown by the duplicates, or that which can be attributed to instrumental drift, is still very small. Essentially the two methods produce equivalent asphaltene fractions. 2.1.13 Reproducibility of the centrifuge method for samples with small initial proportions of asphaltenes The reproducibility of the centrifuge method was checked using a North Sea oil. This had the additional advantages of testing whether the centrifuge method could be used to separate asphaltenes as effectively in oils (where they are present at lower concentrations) as in source rock extracts and tar sands. The same procedure was used as in the previous method, with the exception that an additional final stage was added in 56

which the combined maltene fraction recovered after each stage was redissolved in DCM and the precipitation procedure repeated.

aromatic

aliphatic

asphaltene

Whole Oil

Prep 1

Figure 2.5. Some of the TLC-FID chromatograms of the precipitates at different stages in the centrifuge asphaltene precipitation of a North Sea oil.

The final precipitate in Figure 2.5 is clean of aliphatic and aromatic hydrocarbons, and shows that the centrifuge method can be used to purify asphaltenes as effectively for oils as it can for source rocks. However, one feature of applying the method to oils appears to be that small proportions of hydrocarbons are still present in the asphaltene fraction after the second precipitation, when they were not visible in the TLC-FID traces of the source rock extract at the same stage of the process. This is probably linked to the greater initial quantities of aromatic and aliphatic hydrocarbons in the sample. The resin/asphaltene ratio of the oil (Figure 2.6) changes in a similar manner to that seen for the source rock extract (Figure 2.4), suggesting that the precipitate has a stable Iatroscan TLC-FID resin/asphaltene ratio after four precipitations. The graph is also of a similar shape to that seen in Figure 2.4, including a sudden drop then gradual equilibration of values. This further supports the reproducibility of the method.

Prep 4

Prep 2

aliphatic

aromatic

asphaltene

resin

resin

57

5
peak area ratio resin/asphaltene

4 3 2 1 0 0 1 2 3 4 number of precipitation 5

Figure 2.6. Plot of the stabilization of the resin/asphaltene TLC-FID ratio for a North Sea oil with repeated centrifuge precipitation stages during asphaltene purification.

2.1.14 The effects of the initial extract/oil composition on asphaltene recovery The effects of the initial bitumen or oil composition on asphaltene recovery were assessed by re-precipitating the maltene fraction and weighing the products. This was done both a for the three North Sea oils from the Norwegian sector, a reservoir core extract, a WFT (wireline formation tester) and DST (drill stem test) (oils with correspondingly less asphaltene in each sample), and for a number of samples of the Athabasca Tar Sand. The three North Sea oils had different proportions of asphaltene because they were collected by different methods, and the tar sands samples had different proportions of asphaltene because they weathered to different extents.

Tar sand North Sea Oil % asphaltene (tar sand) 80 60 40 20 0 0 2 4 6 8 mg of n-heptane insolubles in final maltene fraction 1.25 % asphaltene (oil) 1 0.75 0.5 0.25 0

Figure 2.7. Graph of the loss of n-heptane insoluble material to the maltene fraction plotted against the % asphaltene fraction. In general the greater the proportion of asphaltene material present the greater the loss of asphaltene.

Although there does appear to be a general trend of increasing loss of asphaltene material with increasing proportions of asphaltene in the sample, the data from the two

58

types of sample (oils and tar sands) lie along different lines. This suggests that the loss of asphaltene like material to the maltene fraction depends on the nature of the extract or oil concerned, rather than on the method alone. This would be consistent with this material being selectively removed from the asphaltene fraction due to its chemical properties, rather than being the result of a small but consistent quantity of asphaltene being accidentally decanted of with the maltene fraction. 2.1.15 Conclusions The repeated centrifuging of extracts and oils in an excess solution of n-heptane is a relatively quick, reproducible and precise method for separating asphaltenes from aliphatic and aromatic hydrocarbons that maybe occluded by, or chelated in asphaltene aggregates. This method is quicker, and better lends itself to the preparation of many samples for hydropyrolysis than the gravity settling and sintering method. This method will therefore be used to separate asphaltene fractions for this study.

59

2.2 Experimental Methods

2.2.1 Sample preparation and fractionation After the removal of any extraneous material with a sharp knife, samples of the Jet Rock and Barney Creek Formation were rinsed sequentially in distilled water, methanol and DCM. Large fragments were quartered twice. Pieces were taken from each quarter set and crushed in brief bursts in a Tema mill to a fine powder. The powdered rock and samples of the Athabasca Tar Sand (~50 g of each) were exhaustively soxhlet extracted for >60 hours with 93:7 dichloromethane/methanol (DCM/MeOH) in the presence of activated copper. EOM data was obtained by measuring the weight of one tenth (1/10 by volume) of the extract and multiplying the result. Silica, copper, cotton wool and steel wool were extracted with 93:7 dichloromethane/methanol (DCM/MeOH) for 24 hrs and petroleum ether for 24 hrs prior to use. The extracted bitumen component was then deasphalted by a 4 stage 40-fold excess nheptane asphaltene precipitation (see section 2.1.9). The maltene fractions of the Jet Rock and Barney Creek Formation were then separated on a packed silica column into aliphatic, aromatic and resin fractions by elution with petroleum ether, DCM/petroleum ether (3:1 v/v) and DCM/MeOH (2:1 v/v) respectively. The Athabasca Tar Sand maltene fractions were separated by silica gel thin layer chromatography using petroleum ether as a developer in order to better separate hydrocarbon fractions and non-macromolecular compounds from the resin fraction. 2.2.2 Hydropyrolysis To provide a stable substrate for hydropyrolysis, resin and asphaltene fractions were adsorbed from solution onto coarse-grained (30-70 mesh) silica gel. These silica adsorbed fractions, and the solvent extracted sediment (containing the kerogen fraction) were then impregnated with an aqueous/methanol solution of the ammonium dioxy dithiomolybdate catalyst [(NH4)2MoO2S2] (Murray, 2001) which was extracted with DCM prior to use. Samples were freeze-dried under vacuum prior to hydropyrolysis treatment to remove any water present after catalyst loading.

60

Analytical hydropyrolysis was undertaken after Love et al. (1995), and the apparatus used is shown in Figure 2.9. In order to prevent cross-contamination between successive runs, and contamination by extraneous organic matter, the apparatus was subject to a rigorous cleaning regime. The apparatus was broken at the locations shown in Figure 2.9 and all the removable components cleaned with a DCM/MeOH mixture between every run; removable parts (excepting the reactor carps) were further subjected to calcination at 420oC for 30mins every two runs. Samples were run in batches of approximately 15 samples. Procedural blanks were obtained at the beginning of every batch of samples after the solvent cleaning and calcination of removable parts of the apparatus (reactor caps were not calcined), and subsequent to cleaning hydropyrolysis runs at reduced hydrogen pressures, slower flow rates and faster heating rates. Procedural blanks and the products of cleaning runs were recovered by a DCM/MeOH mixture and the solutions reduced in volume before analysis by GC-MS (see section 2.2.3). If any compounds above a 1g threshold were detected, as determined by comparison to a 5(H)-cholane internal standard, than the cleaning procedure was repeated and new blanks obtained. This stage was deemed important and necessary as samples were processed in batches during visits of limited duration. Any residual contamination could have effected entire batches of samples, thus it is necessary to ensure that the apparatus is clean before processing a large batch of samples. The same cleaning hydropyrolysis procedure that was used to prepare the apparatus for use at the beginning of a batch of samples, using reduced hydrogen pressures and faster heating rates, was also carried out every five to six samples to supply additional blanks. The trap contents of these shorter duration blanks runs were also recovered and monitored for the build up of any contamination during the processing of samples. To further ensure that the risk of cross contamination was kept to a minimum, after every two samples trap procedural blanks, copying exactly the procedure used to recover hydropyrolysis products for fractionation and GC-MS analysis, were employed to monitor the efficiency of the solvent rinsing and calcination of the trap and other fixtures.

61

Thermocouple High Pressure H2 Reactor cap Upstream pressure gauge

sample Electrical connectors used to resistively heat sample bed. Temperature is controled by thermocouple monitoring sample temperature in situ

silica steelwool

Reactor cap Flow valve High Pressure H2

Downstream pressure gauge Dry ice cooled trap

Figure 2.9. Hydropyrolysis apparatus. Important features are the pressure, temperature and flow rate controls, as well as the locations at which the apparatus can be broken which are denoted by the black arrows.

Temperature programmed fixed bed analytical hydropyrolysis was carried out at high hydrogen pressures (15 MPa), in the presence of a dispersed ammonium dioxydithiomolybdate [(NH4)2MoO2S2] catalyst, with a stepped temperature program (50 to 260 oC at 300 oC/min holding for 1 min before heating to 260 to 500 oC at 8
o

C/min) and in a fast sweeping (~6 dm3 min-1) hydrogen stream. This is a method

repeatedly proven to obtain a high conversion of geological macromolecules (greater than 90 %) to hydrocarbon biomarkers (Love et al., 1995; Love & Snape, 1996; Love 62

et al., 1998; Murray et al., 1998; Brocks et al., 2003). Products were collected in a dry ice-cooled trap, recovered in DCM/MeOH (4:1 v/v) and treated with activated copper to remove elemental sulphur prior to separation of hydrocarbon fractions using silica column chromatography as described in section 2.2.1 for the maltene fractions. 2.2.3 Product analyses The preparative scheme utilizing solvent separation and hydropyrolysis described above is shown in Figure 2.10. It leads to the recovery of four (three in the case of the tar sand) aliphatic and aromatic hydrocarbon fractions amenable to analysis by GC-FID or GC-MS. The product yields achieved by solvent extraction, precipitation, preparative chromatography and hydropyrolysis are presented as per gram of TOC for samples of the Jet Rock and Barney Creek Formations, and per gram of extractable organic matter for the Athabasca Tar Sand. Errors for the yields achieved by solvent extraction and fractionation are typified by those shown for the Athabasca Tar Sand in Chapter 5 (Figure 5.2). These represent the difficulties in balancing the analytical need for small manageable quantities from which solvent can be easily removed, with the need for large quantities for hydropyrolysis (a minimum of 3 mg of organic matter). This effect is most is noticeable for the asphaltene fractions where errors can be the greatest, because the complete removal of solvent is difficult when small quantities of asphaltene are involved (less than 5 mg). However, errors are very small for the other fractions, and where larger quantities of asphaltene are involved. Errors are estimated to be less the +/- 5 % for non-asphaltene fractions, and highly variable for the asphaltene fraction (but within +/- 20 %). The reproducibility of hydropyrolysis yields can be gauged from two repeat runs conducted on a Jet Rock kerogen and Athabasca asphaltene shown in Table 2.2. Total product yields after separation are within +/-20 % of each other, yields of individual biomarker compounds are generally within a similar range of each other (20 30 % depending on biomarker type and abundance).

Table 2.2, Comparison of the yields mg/g TOC or EOM obtained in duplicate hydropyrolysis of samples from the Jet Rock and Athabasca Tar Sand
tot Ali Aro Polar

63

Can7u1 Can7u2 JR 11a JR 11b

75 94 530 460

23 35 170 190

40 46 170 130

12 12 190 140

tot= sum of separated products, Ali = aliphatic, Aro = aromatic, Pol = polars and NSO; Can7u = asphaltene fraction of an unweathered sample of the Athabasca Tar Sand in mg/g EOM; JR 11 = kerogen fraction from the Jet Rock Formation in mg/g TOC.

Kerogen extraction

Bitumen/EOM precipitation

Asphaltene

Maltene CC

Resin

Extracted Hydrocarbons CC

CC

HyPy

CC

HyPy

CC

HyPy

Aliphatic

Aromatic

Aliphatic

Aromatic

Aliphatic

Aromatic

Aliphatic

Aromatic

Figure 2.10. Shows the fractionation scheme employed in this study. In source rocks this leads to the recovery of four aliphatic and aromatic biomarker fractions; in the case of the Athabasca Tar Sand three aliphatic and aromatic biomarker fractions are recovered. HyPy = hydropyrolysis; CC = column chromatography. * note that thin layer chromatography was used to fractionate the maltene fraction in the Athabasca Tar Sand.

Molecular characterization of the hydrocarbon fractions was undertaken by gas chromatography (GC) and gas chromatography-mass spectrometry (GC-MS). GC-FID analysis was performed using a Carlo Erba Mega series 5160 fitted with a DB-5 coated fused silica column (0.25 m film thickness; 30 m x 0.25 mm ID). The oven heating program used was: 50 oC for two minutes, 50 310 oC at 4 0C/minute and holding at 310 oC for 20 minutes. Cold on column injection was used and the detector was maintained at 310 0C. GC-MS analysis was undertaken using a HP 5890 Series 2 GC fitted with a HP-1 or DB-5 (see Table 2.3) coated fused silica column (0.25 m film thickness; 30m x 0.25 mm ID) and connected to a HP 5972 mass selective detector (ionization energy 70 eV).

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The oven heating program used when the mass spectrometer was operated in SIM mode was: 50 to 175 oC at 6 oC/min and then from 175 to 300 oC at 4 oC/min finally holding at 300 oC for 4 min. The oven heating program used when the mass spectrometer was operated in full scan mode was: 40 to 300 oC at 4 oC/min finally holding at 300 oC for 4 min. Table 2.3. Column types used in the different studies Jet Rock Athabasca Tar Sand Barney Creek Formation Aliphatic Aromatic HP-1 DB-5 DB-5 DB-5 HP-5 HP-5

Compound identification was achieved by comparison to known reference oils and rock extracts (Brent crude for aliphatic biomarkers, and Blue Liass for aryl isoprenoids) or by use of mass spectra and comparison of elution orders and relative retention times in published work. Quantification of aliphatic sterane, hopane and tricyclic terpane biomarkers was performed relative to an internal 20R 5(H), 14(H), 17(H) [2, 2, 4, 4 d4] cholestane standard. Integrated GC-MS peak areas were used to quantify biomarker concentrations and to calculate biomarker parameters. Aromatic and n-alkane parameters were calculated using peak height data obtained from GC-FID data. The unresolved compound mixture (UCM) area was obtained by subtracting a blank run from a sample to first correct for base line drift, and then subtracting the total area of resolvable compounds from the total area (resolvable compounds + UCM). Because of the extensive fractionation scheme and slight variations in the work up for each fraction (e.g. sample splitting), four quantification equations are required. These are derived from the basic relationship between a standard compound of known mass (Ms) and with an integrated peak area (As), and a compound of unknown mass (Mx) with peak area (Ax); Ax = As Mx Ms

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Back calculation along the scheme shown in Figure 2.10 leads to four separate terms for the concentration of biomarkers per gram of total organic carbon in the kerogen, asphaltene, resin and free fractions. These relate the peak area of a given biomarker present in a vial analyzed by GC-MS, back to the extracted sample with a known quantity of organic carbon. Ax (Ms As-1) . = Mx (gTOC 1) [Hx Ho-1] (TOC [Sx So-1]) Ax (Ms As-1) . = Mx (gTOC 1) [Hx Ho-1] [Cx Co-1] gTOC Ax (Ms As-1) . = Mx (gTOC 1) [Hx Ho-1] [Px Po-1] gTOC Ax (Ms As-1) . = Mx (gTOC 1) [Cx Co-1] gTOC kerogen

resin

asphaltene

free

Ax = peak area of biomarker; Mx = mass of biomarker; As = peak area of standard; Ms = mass of standard; Sx = mass of sediment to hypy; So = mass of sediment extracted; Hx = mass of hypy product to column separation; Ho = mass of total hypy product; Cx = maltene fraction; Co = mass of maltene fraction to column separation; gTOC = grams TOC The Jet Rock formation and Blue Liass Rock-Eval pyrolysis data (S1 and S2 peaks only) were collected on a Rock-Eval II instrument and reported according to Peters (1986). They were measured in duplicate and due to their acceptable precision were averaged. Total organic carbon and whole rock sulphur data were determined on a Leco CS-244 instrument, with total organic carbon values measured on HCl(aq) decarbonated samples.

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