Fuel 92 (2012) 281287

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Fuel
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Evaluation of several methods of extraction of oil from a Jordanian oil shale

Yi Fei a,b, Marc Marshall a,b, W. Roy Jackson a,b, Martin L. Gorbaty d, Mohammad W. Amer a,b, Peter J. Cassidy c, Alan L. Chaffee a,b,
a

School of Chemistry, Monash University, Victoria 3800, Australia Centre for Green Chemistry, Monash University, Victoria 3800, Australia c The Sentient Group, Suite 2401, Level 24, Australia Square Tower, 264 George Street, Sydney, NSW 2000, Australia d Fuels Science Consulting, 6635 Via Dante, Lake Worth, FL 33467, USA
b

a r t i c l e

i n f o

a b s t r a c t
A Jordanian oil shale from the El Lajjun deposit has been reacted with N2, H2 and CO in the presence and absence of water in the temperature range 300425 C. The effect of adding Fe, Cu, Ni, Sn and NaAlO2 as potential catalysts to some of these reactions has been studied but none led to improved oil yields. Most of the organic material in the oil shale was converted to asphaltene at 355 C, but the oil yield was low at this temperature. At 425 C nearly all the organic product was in the form of oil. 2011 Elsevier Ltd. All rights reserved.

Article history: Received 18 April 2011 Received in revised form 7 July 2011 Accepted 3 August 2011 Available online 22 August 2011 Keywords: Oil extraction High temperature High pressure Solvent separation Gas chromatography

1. Introduction The projected decline in the reserves of crude petroleum ([1], p. 1) has led to renewed interest in the recovery of oil from oil shale with the major intention of increasing the supply of transport fuels. Commercial-scale extraction has so far been limited and almost exclusively based on retorting mined shale at temperatures in the range 425525 C ([1], p. 183). Signicant interest in applying retorting to in situ extraction of oil has been developed, particularly by Shell ([1], p. 185186), who propose heating the deposit at lower temperatures around 350 C for 3 or 4 years. Many oil shales e.g. those in Colorado and Utah contain limestone and dolomite and thus it is imperative to keep the retorting temperature as low as possible to minimize CO2 evolution ([1], p. 186). Much research has been carried out on a small scale to develop extraction methods which operate at lower temperatures and which remove as much organic material from the shale as possible to maximize the oil yield. These include the use of supercritical, non-hydrogen donor solvents such as water, CO2 [2] methylcyclohexane [3], toluene [4] and methanol [5]. A wide range of hydrogen donor solvents have also been used including tetralin [6] and hydrogenated recycle distillate [7]. Reducing gases, H2 and COH2O, have been used either alone [8,9] or with solvents [10]. The effect of Fe [9]
Corresponding author at: School of Chemistry, Monash University, Victoria 3800, Australia. Tel.: +61 3 9905 4626; fax: +61 3 9905 4597. E-mail address: Alan.Chaffee@monash.edu (A.L. Chaffee).
0016-2361/$ - see front matter 2011 Elsevier Ltd. All rights reserved. doi:10.1016/j.fuel.2011.08.019

and alkaline catalysts [11] on COH2O extraction has also been examined. In this paper we compare a range of extraction methods using a Jordanian oil shale from the El Lajjun deposit. Although most of the individual methods have been used with other oil shales, no systematic comparison of the various methods for a single shale appears to have been carried out. Some of these methods will not be commercially applicable to this Jordanian oil shale, particularly those involving large amounts of water, but the experiments should provide a useful basis for future comparisons with other oil shales. We have deliberately omitted methods which involve heating with organic solvents as we believe this leads to added complications in any process, making comparisons difcult. 2. Experimental 2.1. Materials H2, CO and N2 were purchased from BOC. Hexane and CH2Cl2 (liquid chromatography grade) and tetrahydrofuran (THF; empura grade) were purchased from Merck. 2.2. Oil shale preparation Oil shale from the El Lajjun deposit in Jordan was received as 2 mm particles and was ground to 180 lm. Ash yields were determined by heating at 490 C in air to nearly constant weight.

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A low ashing temperature was used to minimize carbonatesilica reactions and ensure the ash yields were similar to the inorganic content of the shale. The water content of the oil shale was taken as the loss of weight observed when the shale was heated under a ow of N2 for 3 h at 105 C. The shale was washed with 0.5 M HCl following the procedure of Redlich et al. [12]. Elemental analyses were carried out by HRL Technology Ltd. for C, H, N, S, Cl and Fe for raw and acid-washed oil shale. The values of organic C, H and N content and the concentrations of the different forms of S were calculated from the elemental analyses, the ash yields and the loss of weight on acid washing. The solid state 13C NMR spectrum for acidwashed oil shale was determined using a Bruker 400(1H)/100(13C) MHz spectrometer with cross polarization-magic angle spinning. X-ray diffraction (XRD) was carried out using a Philips PW 1140 diffractometer which was scanned over the 2h range from 2 to 70 at 1/min. Fe(II), Cu(II) and Ni(II) were added as solutions of their acetates to give 0.5 mol/kg db of the metal. SnO2 was added as a nely divided suspension in distilled water and sodium aluminate was added as a ltered solution of NaAlO21.5H2O to give 0.5 mol/kg db. After addition of the metal source the mixture was stirred for a few minutes under vacuum to wet the oil shale and then stirred overnight under N2 at ambient temperature. The water was removed in a ow of N2 and the products stored wet under N2 until use. Before loading into an autoclave, the sample of oil shale to be used was dried at 105 C in owing N2 for 3 h and cooled in a desiccator. For calculating product yields it was assumed that in the solid product from CO runs Ni and Fe were present as NiCO3 and FeCO3. Following the work of Cook et al. [13] on brown coal liquefaction, the form of Sn in the product was taken to be SnO. The results indicated that Cu formed a high molecular weight complex in the product, which was assumed to be [Cu(OH)2(HCO3)2]2 because this species has been observed [14]. Any smaller Cu compound, such as CuCO3, would result in negative oil yields as determined by difference. 2.3. Reactions and workup Reactions were carried out in 27 ml stainless steel autoclaves tted with a stainless steel liner containing 2.1 g of oil shale (not including catalyst content) with 2.1 g or no distilled water or 1.4 g oil shale and 4.2 g distilled water and 3 MPa (cold) of the appropriate gas. The autoclave was evacuated and weighed before and after gas was charged, so that the free space in the autoclave could be calculated. In the case of H2 runs, the autoclave was evacuated and weighed before and after charging a known pressure of N2, then the autoclave was vented and evacuated before again weighing, charging with H2 and weighing. The preliminary charging with N2 permitted a more accurate determination of free space than would have been possible from the small weight of H2 charged. The autoclave was lowered into a preheated sand bath and came to the required temperature in 24 min. The autoclave was continuously shaken while in the sand bath. The autoclave was held at temperature for the required time, removed, allowed to cool and weighed. The gas was vented through an Agilent 3000 Micro Gas Chromatograph, equipped with four columns: MS 5A PLOT, 10 m 0.32 mm (110 C column temperature) for N2, CH4 and CO, PLOT U, 8 m 0.32 mm (100 C column temperature) for CO2, C2 hydrocarbons H2S and COS, Alumina PLOT, 10 m 0.32 mm (140 C column temperature) for C3C5 hydrocarbons and OV-1, 10 m 0.15 mm 2.0 lm (90 C column temperature) for isobutane and n-hexane. The inlet and injector temperatures were 100 C. After the analysis the autoclave was vented and the total weight of the gas in the autoclave was calcu-

lated. On the assumption that the gases detected (and hydrogen or nitrogen by difference) were the only gases present, the yields of all the gases detected and the hydrogen consumption could be calculated. The solid and liquid products were washed and scraped out of the autoclave with CH2Cl2 into a ask, and subjected to Lundin distillation to remove water. The water-free material was ultrasonicated for 10 min, ltered, more CH2Cl2 added to the lter cake and the process repeated. The CH2Cl2 insolubles were dried at 105 C in owing N2 for at least 2 h, cooled, weighed and extracted with THF using 10 min ultrasonication and ltered. Most of the THF was removed from the ltrate by rotary evaporation and the remainder in a vacuum oven (0.1 KPa) at 55 C. The remaining ltrate (asphaltol) was weighed. Most of the CH2Cl2 was removed from the CH2Cl2-soluble material by rotary evaporation and n-hexane (20:1 by weight) added. The mixture was ultrasonicated for 3 min and ltered to give insoluble material, asphaltene, which was dried in a vacuum oven (0.1 KPa) at 55 C and weighed. Most of the n-hexane was removed from the ltrate by rotary evaporation and the residual hexane solubles (oil) were stored at 4 C for later analysis. The oil yield was determined by difference and can therefore be negative, though any negative value should be within measurement error. A problem arises in determining oil yield for CO runs, because much of the CO2 comes from the CO charged, not the oil shale. Inspection of the COCO2 balance as determined by the gas analysis indicated that, within the limits of error, the oil shale derived CO2 in CO runs was the same as the CO2 yield in N2 runs under the same conditions (temperature, time, water to oil shale ratio). Therefore, oil yield was calculated for CO runs using the CO2 yield for N2 runs under the same conditions. The gas analyses indicate, however, that the oil shale derived CO2 in CO runs was probably generally less than in the N2 runs under the same conditions (though not signicantly so) so that it is likely that oil yields in CO runs were underestimated slightly. Based on weighing uncertainties and the spread of results for replicated runs, the uncertainty in CH2Cl2 solubles and gas was about 1.5 wt.% dry oil shale charge, and in oil + H2O and asphaltene yields about 2 wt.% dry oil shale charge. The uncertainty in the yields of individual gases taking into account weighing and calibration uncertainties was about 15% of the result, but the spread of results for replicated runs indicated higher variability than this (larger error bars). This higher variability is probably due to the small amount of gas produced in reactions on the scale used. The generally good agreement between errors calculated from weighing uncertainties and the standard deviations for duplicated runs for CH2Cl2 solubles and gas, oil + H2O, asphaltol and asphaltene indicates reproducible experimental technique. Error bars are only given in the gures below where runs were duplicated and indicate the standard deviation. Only differences greater than twice the estimated errors (e.g. 3 wt.% dry oil shale charge for CH2Cl2 solubles and gas and 4 wt.% dry oil shale charge for oil + H2O) were taken to be signicant.

2.4. Product analysis Some oil samples were analyzed by gas-chromatographymass spectrometry (GCMS) on a HP6890 instrument in splitless automode. For GC, a HP 19091S-433 capillary column (HP-5MS 5% phenylmethyl siloxane), 30 m long, 0.25 mm diameter, 0.25 lm nominal lm thickness, was used. The inlet temperature was 230 C. The oven temperature was initially held at 50 C for 2 min then raised to 200 C at a rate of 4 C/min, held at 200 C for 2 min, then raised to 300 C at 8 C/min and held at 300 C for 3 min. For MS, the ionizing potential was 70 eV, the accelerating

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voltage 1.9 kV, the mass range scanned 45600 m/z and the ion source temperature 200250 C. For 1H NMR, the oil or CH2Cl2 solubles were dissolved in CDCl3 and spectra were obtained using a 400 MHz instrument, with a 90 pulse ip angle (9.5 ls). THF solubles were dissolved in d8-THF. The designation of the hydrogen types was similar to that used by Charlesworth [15] except that the shift boundaries differed slightly as follows: Har, 96 ppm; Ha, 4.51.96 ppm; Hb, 1.95 1 ppm; Hc, 10.5 ppm. Elemental analysis of selected CH2Cl2 soluble samples was carried out by the Campbell Microanalytical Laboratory, University of Otago, for C, H, N, S and Cl. The Cl value allowed for estimation of any residual CH2Cl2. XRD of selected THF insoluble samples was carried out as described in Section 2.2. 3. Results and discussion 3.1. Characterization of the oil shale The Jordanian oil shale was obtained from the El Lajjun deposit in the Karak region. The organic content as determined from the ash yield at 490 C was 24.2 0.5 wt.% db. The acid-soluble fraction of the oil shale was 51.9 0.5 wt.% db, indicating a high carbonate concentration. XRD indicated that the minerals present were calcite (CaCO3), quartz, and, in small amounts, kaolinite and apatite, as observed previously for this oil shale [16]. The total S and Fe were 3.6 and 1.9 wt.% db respectively and the organic material in the shale had C, 17.4; H, 2.1; N, 0.4 and S, 2.4 wt.% db of the total oil shale. These values are typical of those reported previously [17]. A solid state 13C NMR spectrum of the acid-washed shale showed a Car to Caliph of 0.21:0.79 indicating a high aliphatic content with an H/C atomic ratio for the total organic material of 1.44. 3.2. Effect of gas and temperature on extraction yields The shale was heated at three temperatures (300, 355 and 425 C) for one hour with either no water or water/oil shale, 1:1 w/w. Oil + H2O, asphaltene and asphaltol yields, together with the yields of CO2, H2S and hydrocarbon gases C1C6 are tabulated in Appendix 1. The key yields of oil + H2O and asphaltene are summarized in Fig. 1. For comparison it may be noted that the oil + H2O yield for room temperature solvent extraction with ultrasonic irradiation was 1.6 0.1 wt.% db, asphaltene yield was 0.71 0.06 wt.% db and asphaltol yield was 0.86 0.02 wt.% db (measurement errors). It can be seen that similar results are obtained for reactions of the three gases at 300 C where ca. 3 3 wt.% db oil + H2O and a similar amount of asphaltenes are obtained. Again at 355 C the

three gases gave similar results, with 69 wt.% db oil + H2O and 611 wt.% db asphaltene. These results indicate that there was little reaction of either CO or H2 with the kerogen and the products were the result of thermal breakdown. At 425 C thermal breakdown led to a much higher oil + H2O to asphaltene ratio. H2 reactions gave similar values both in the presence and absence of water but a signicant increase in oil + H2O yield was observed when N2 and CO reactions were carried out in the presence of water, to the level obtained for H2 both with and without water. H2 was efcient in producing oil, indicating a denite participation of the gas in the reaction, so that adding water had no effect. N2 and CO were less efcient and water could exert a benecial effect.

3.3. Effect of increasing the water to oil shale ratio on extraction yields In general, increasing the water to oil shale ratio to 3:1 for 1 h reactions (data for water to oil shale ratio 0:1 and 1:1 is in Fig. 1, data for water to oil shale 3:1 is not shown) had virtually no effect on the asphaltene yields relative to those at 0:1 and 1:1. Similarly increasing the amount of water present had no signicant (i.e. outside measurement error) effect on the oil + H2O yields for reactions at 300 or 355 C. However, all reactions at 425 C showed large drops in oil + H2O yields from 1618 wt.% db to 69 wt.% db when the water to oil shale ratio was increased from 1:1 to 3:1. The change was associated with a big increase in the yields of CO2 seen for reactions involving N2 or H2 where values rose from ca. 1 wt.% db to 810 wt.% db. This large increase in CO2 yield could be associated with decomposition of CaCO3 because comparison of the XRD pattern of the original oil shale with that of a typical THF insoluble sample suggested loss of CaCO3 during the reaction; the ratio of peak heights for the principal calcite and quartz peaks decreased from 2.8 for the oil shale to 2.2 for the THF insolubles. It is difcult to see why a decrease in the oil yield should be correlated with an increase in CO2 yield. Perhaps decomposition of CaCO3, giving an increase in CO2 yield, resulted in easier access of gas and water to the organic material in the shale, which in turn leads to increased disproportionation of the organic material into higher molecular weight materials and gas.

3.4. Effect of reaction time on reactions of oil shale A series of reactions were carried out with N2, CO and H2 and water to oil shale ratio of 1:1 and 3:1 at 300 and 355 C for 1 h and 5 h (Fig. 2). Reactions with N2 and CO at 300 C with a water to oil shale ratio 3:1 showed an increase in oil + H2O yield when reaction time was increased from 1 h to 5 h. In contrast reactions with H2 showed no signicant change. At 355 C a general trend was observed, in that an increase in reaction time to 5 h led to a
N2 CO H2

Effect of gas at 300oC

18 15 12
0:1 1:1

Effect of gas at 355oC

0:1 1:1

Effect of gas at 425oC

0:1 1:1

wt% db

9 6 3 0
Oil+H2O Asphaltene Oil+H2O Asphaltene Oil+H2O Asphaltene Oil+H2O Asphaltene Oil+H2O Asphaltene Oil+H2O Asphaltene

Fig. 1. Oil + H2O and asphaltene yields of Jordanian oil shale as a function of water to oil shale ratio (0:1 or 1:1), reaction temperature and reactant gas (for 1 h reaction time). The error bars give standard deviations determined from duplicated experiments.

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1:1
300 C
12
o

355 C
H2 N2 CO H2

Oil+H2O Asphaltene

N2

CO

wt% db

0 1h 5h 1h 5h 1h 5h 1h 5h 1h 5h 1h 5h

300 C
12

3:1
H2 N2

355 C
CO H2

Oil+H2O Asphaltene

N2

CO

wt% db

1h

5h

1h

5h

1h

5h

1h

5h

1h

5h

1h

5h

Fig. 2. The effect of reaction time on the oil + H2O and asphaltene yields of Jordanian oil shale at different temperatures and water to oil shale ratios and with different reactant gases. The error bars give standard deviations determined from duplicated experiments.

decrease in asphaltene yield accompanied in most cases by an increase in oil + H2O yield. The changes were not large in any case. A series of reactions with CO were carried out with a water to oil shale ratio of 1:1 for 5 h using a range of potential catalysts (Fig. 3) to compare with the 1 h reactions discussed in Section 3.6. At 300 C no benet was seen for any of the additives except Ni, which may have given improved conversion and oil + H2O yields. At 355 C longer reaction time gave improved oil:asphaltene ratios in all cases but none gave an oil + H2O yield higher than the reaction without additive. This improved oil:asphaltene ratio was especially notable in the case of Cu as shown in Fig. 3. Again the results from the longer time reactions conrm the ease of conversion of the shale-derived asphaltenes to oil. 3.5. Effect of reaction conditions on gas yields Detailed analyses of the gas yields and compositions are given in Appendix 2. Highlights and major trends, restricted to changes in the yields of total hydrocarbon gases (C1C6), H2S and CO2, are summarized below. All reactions at 300 C gave total hydrocarbon gas yields of less than 0.1 wt.% db.

3.5.1. Reactions with 1:1 water to oil shale ratio The effects of reaction time and temperature and reactant gas on the yield of total hydrocarbon gas are summarized in Fig. 4. Yields at 355 C were low, not much greater than those at 300 C. Increase in reaction time to 5 h had little effect, in contrast to the effect of raising the reaction temperature to 425 C, where gas yields became signicant, especially for reactions in H2. This effect of increasing temperature was also shown in the increase in oil yields at the expense of asphaltenes (see Fig. 1). In contrast, increase in reaction temperature from 355 to 425 C had little effect on yields of H2S and CO2, which were ca. 0.3 wt.% db for H2S and 1 2 wt.% db for CO2 in reactions with N2 and H2. 3.5.2. Reactions with 3:1 water to oil shale ratio The effects of reaction time, temperature and reactant gas on the yields of total hydrocarbon gas, H2S and CO2 are summarized in Fig. 5. The HC gas yields showed similar trends to those obtained with 1:1 water to oil shale ratios but the yields were roughly twice as high, rising to between 3.0 and 4.6 wt.% db at 425 C. This increase in HC gas yields was associated with a decrease in oil yields (see Fig. 1) and a large increase in CO2 yields to 8.510 wt.% db at

300 C
20 16 Non-cat Na Cu Ni Sn Fe Non-cat Na

355 C
Cu Ni Sn

Oil+H2O Asphaltene

Fe

wt% db

12 8 4 0 1h 5h 1h 5h 1h 5h 1h 5h 1h 5h 1h 5h 1h 5h 1h 5h 1h 5h 1h 5h 1h 5h 1h 5h

Fig. 3. The effect of reaction time on the oil + H2O and asphaltene yields of Jordanian oil shale reacted in CO with 1:1 water to oil shale ratio at 300 and 355 C with different additives. The error bars give standard deviations determined from duplicated experiments.

Y. Fei et al. / Fuel 92 (2012) 281287

N2 CO H2

285

Hydrocarbon gas C1-C6

1.8 1.5 1.2

Yields of oil + H2O and asphaltenes were not signicantly inuenced by the addition of Fe(OAc)2 or SnO2 at 425 C. The conversion to CH2Cl2 solubles and gas were ca. 90 wt.% on a daf basis even for the non-catalyzed run and thus there was very limited opportunity to detect catalytic effects. Reactions at 300 C showed a small increase in the oil + H2O yield and a decrease in asphaltene yield when SnO2 was added. 3.6.2. Reaction of oil shale with a range of catalysts in water A series of reactions was carried out with CO at a water to oil shale ratio of 1:1. NaAlO2, Cu(OAc)2, Fe(OAc)2, SnO2 and Ni(OAc)2 were added and reactions at 300, 355 and 425 C for 1 h were carried out The results for reactions at 300 and 355 C are given in Fig. 3, those for the reaction at 425 C without additives are given in Fig. 1 and those for reactions with additives at 425 C are not shown. Very low conversions were obtained at 300 C and, perhaps surprisingly, all the additives had, if anything, a negative effect on oil + H2O yield and little effect on asphaltene yield. Again at 355 C no improvements in oil + H2O or asphaltene yields were obtained with any of the additives, except that the asphaltene yield increased to 18 wt.% db for Cu compared to values of 611 wt.% db for the other reactions. Even at 425 C the yield of asphaltene for the Cu reaction (6 wt.% db) was signicantly greater than those from the other reactions (ca. 2 wt.% db). These results contrast with those for reaction of a Victorian brown coal with CO/H2O, where addition of Cu had no effect on oil or asphaltene yields [18]. Oil + H2O yields at 425 C again showed no signicant increase for any of the additives (818 wt.% db compared to 17 wt.% db for the reaction without additives). There is a report that Fe increased the oil yield from reactions of some oil shales with CO/H2O [9], but for this oil shale adding Fe decreased the oil + H2O yield from 17 to 10 wt.% db, so that a benecial effect of adding Fe clearly does not apply to all oil shales. The lack of activity of these additives in oil shale reactions contrasts with their good catalytic effectiveness in coal reactions [18]. It has been suggested that their action is to inhibit repolymerisation reactions of pyrolysis fragments rather than to promote depolymerisation of larger molecules [19]. If the pyrolysis fragments of oil shale kerogen are more stable than those of coal then such additives will have no role in oil shale reactions and will therefore have no benecial effect. 3.6.3. Reactions of oil shale with different gases and water in the presence of NaAlO2 Reactions of oil shale in the presence of NaAlO2 with water to oil shale ratios of 1:1 and 3:1 were carried out with N2, CO and H2 at 300 and 355 C, and at 425 C with water to oil shale ratio of 1:1, all for 1 h. The results for reactions without NaAlO2 and with water to oil shale ratio 1:1 are given in Fig. 1, those for reactions without
N2 CO H2

wt% db

0.9 0.6 0.3 0.0

355 C (1h)

355 C (5h)

425 C (1h)

Fig. 4. The effect of reaction temperature, reactant gas and reaction time on the yield of C1C6 hydrocarbon gas from reactions of Jordanian oil shale with 1:1 water to oil shale ratio. The error bars give standard deviations determined from duplicated experiments.

425 C for reactions in H2 and N2. These large increases in CO2 yields may be associated with the decomposition of CaCO3, which could lead to an increase in gas yields and a decrease in oil yield as discussed in Section 3.3. H2S yields were approximately double those from reactions with 1:1 water to oil shale ratio. 3.5.3. Reactions with 0:1 water to oil shale ratios The HC gas yields were similar to those from the 1:1 water to oil shale ratio at 355 C, signicantly higher at 425 C, but not as high as from reactions with 3:1 water to oil shale ratio. H2S and CO2 yields were similar to those obtained at 1:1 water to oil shale ratio and again did not signicantly increase with an increase of temperature to 425 C. The results show that the addition of an equivalent amount of water to the oil shale has little effect on the yields of all gases. In contrast addition of 3 equivalents of water had a deleterious effect leading to large increases in all gases at the expense of oil yields. 3.6. Effect of catalysts on extraction yields The effects of a range of potential catalysts have been examined under a variety of conditions with different reactant gases. 3.6.1. Reaction of dry oil shale with H2 Reactions of dry shale with H2 were carried out at 300 C and 425 C in the presence of Fe and Sn additives. The results for reactions without additives are given in Fig. 1, those for reactions with additives are not shown.

Hydrocarbon gas C1-C6

5 1.0

H2S
10

CO2

0.8

wt% db

0.6

0.4

0.2

355C (1h) 355oC (5h) 425oC (1h)

0.0

355C (1h) 355oC (5h) 425oC (1h)

355C (1h) 355oC (5h) 425oC (1h)

Fig. 5. The effect of reaction temperature, reactant gas and reaction time on the yield of C1C6 hydrocarbon gas, H2S and CO2 from reactions of Jordanian oil shale with 3:1 water to oil shale ratio. The error bars give standard deviations determined from duplicated experiments.

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Y. Fei et al. / Fuel 92 (2012) 281287 Table 1 Elemental analysis of CH2Cl2 solubles at 425 C, 3:1 water to oil shale ratio, 1 h reaction time. The uncertainties given are standard deviations based on duplicate analyses. Gas charge C wt.% db N2 CO H2 78.79 0.21 80.32 0.09 79.14 0.09 10.29 0.08 9.43 0.04 9.55 0.36 0.71 0.03 1.39 0.01 1.34 0.05 8.07 0.14 6.88 0.01 6.66 0.20 1.56 0.02 1.40 0.01 1.44 0.06 H N S Atomic H/C ratio

NaAlO2 and with water to oil shale ratio 3:1 at 300 and 355 C are given in Fig. 2, those for reactions with NaAlO2 under CO and with water to oil shale ratio 1:1 at 300 and 355 C are given in Fig. 3 and those for the other reactions are not shown. At 300 C the presence of NaAlO2 reduced the oil + H2O yield for N2 and CO runs at water to oil shale ratio 1:1 from 5 to 6 wt.% db to negligible values (2 to 1 wt.% db) with no signicant effect on asphaltene yield (34 wt.% db) and had no signicant effect on oil + H2O or asphaltene yields for N2 and CO runs at water to oil shale ratio 3:1. At 355 C adding NaAlO2 did not alter signicantly the oil + H2O yield for N2 and CO runs at either water to oil shale ratio. At 425 C, water to oil shale ratio 1:1, adding NaAlO2 had no signicant effect on oil + H2O or asphaltene yields for any of the three gases. However, there was a signicant benet for reactions with H2 at both water to shale ratios at 300 and 355 C, where the oil + H2O yield rose from 4 to 8 wt.% db (1:1, 355 C), from 4 to 10 wt.% db (3:1, 300 C) and from 7 to 12 wt.% db (3:1, 355 C). The behavior of NaAlO2 is in contrast to what is observed for brown coal, where it has strong benecial effects for reactions in CO/H2O [20]. It has been suggested that CO/H2O/NaAlO2 reactions in brown coals are strongly inuenced by the presence of phenolic groups [21] and, in the absence of phenolic groups NaAlO2 may be less effective.

to some disruption of the mineral matter, allowing for more facile extraction of organics. The oils from reaction at 425 C with H2 and CO with a water to oil shale ratio of 1:1, which now constitute a high proportion of the organic matter derived from the oil shale, show some increase in Har and Ha with decreases in Hb and Hc. Values of Har 0.12 0.13, Ha 0.27, Hb 0.490.47 and Hc 0.120.13 were obtained, which clearly show some differences to the values quoted above for oils generated at 355 C. Surprisingly the oil from a reaction under N2 at 425 C showed similar 1H NMR parameters, Har 0.08, Ha 0.19, Hb 0.57 and Hc 0.16 to the oils generated at 355 C even though they were obtained in higher yield (16 wt.% db versus 6 9 wt.% db for reaction at 355 C). 4. Conclusion The organic material in this deposit at El Lajjun, Jordan is readily extracted at temperatures as low as 355 C with no water or a water to oil shale ratio of 1:1. Values of HC gas + THF soluble material (oil, asphaltene and asphaltol) as high as 86% of the organic material in the shale can be extracted at 355 C (5 h, CO) and close to 100% at 425 C. Reactions at 425 C give much higher oil to asphaltene ratios than reaction at 355 C. N2, CO and H2 reactions give similar conversions under the same conditions of temperature and water to oil shale ratio. The one exception is the reaction of a 1:1 water to oil shale mixture in CO at 425 C which gave the highest oil yield (18 wt.% db). This high value compares with oil yields reported for pyrolysis of El Lajjun shale of 12 wt.% db [22] and 8 17 wt.% db [23]. The literature values are for reaction at temperatures greater than 400 C but are for distilled material. Increasing the water to oil shale ratio to 3:1 generally decreased the oil yield and increased the yields of HC gas and CO2. Addition of NaAlO2 and a range of metal catalysts useful in coal conversion gave no signicant increases in yields of useful products. Acknowledgment We acknowledge The Sentient Group for nancial support of this research. Appendix A. Supplementary material Supplementary data associated with this article can be found, in the online version, at doi:10.1016/j.fuel.2011.08.019. References
[1] Speight JG. Synthetic fuels handbook: properties process and performance. New York: McGraw-Hill; 2008. [2] Tucker JD, Masri B, Lee S. A comparison of retorting and supercritical extraction techniques on El-Lajjun oil shale. Energy Sources 2000;22:45363. [3] Williams DF, Martin TG. Extraction of oil shales and tar sands. AU Pat. 7721394; 1979. [4] Sinag A, Canel M. Comparison of retorting and supercritical extraction techniques of Goynuk oil shale (Turkey). Energy Sources 2004;26:73949. [5] McKay JF, Blanche MS. Effect of time and pressure on recovery of oil from Green River oil shale in extraction experiments conducted at 400 C. Fuel Sci Technol Int 1986;4:41331.

3.7. Chemical structure of the organic products 3.7.1. Elemental analysis Elemental analyses are given in Table 1 for the CH2Cl2 soluble material obtained from reactions of the oil shale at 425 C with 3:1 water to oil shale ratio. The results show high sulfur values for the products from reactions with N2, CO and H2 in agreement with values obtained for a similar Jordanian oil shale by retorting it [22]. The high H/C ratios are in agreement with the values reported for the organic matter in the shale and with the low aromaticity values of these materials as shown by solid state 13C NMR data (see Section 3.1). 3.7.2. 1H NMR spectra The 1H NMR spectra of the oil fractions from reactions at 355 C with N2, CO and H2 for 1 h or 5 h with water to oil shale ratio of 0:1, 1:1 and 3:1 with and without the addition of NaAlO2 were all similar, with Har 0.040.07, Ha 0.180.24, Hb 0.530.60 and Hc 0.15 0.21. These results were similar to those for oil extracted under ambient conditions, which gave Har 0.03, Ha 0.18, Hb 0.60 and Hc 0.18. Very similar results to these (Har 0.07.09, Ha 0.25 0.30, Hb 0.510.56 and Hc 0.110.14) were obtained (a) for samples of asphaltenes extracted at ambient temperature or at 300 C (b) for asphaltenes extracted under N2 with 3:1 water to oil shale ratio, (c) for asphaltol from a reaction with H2 at 355 C with 1:1 water to oil shale ratio in the presence of NaAlO2 and (d) for the total THF solubles (oil + asphaltene + asphaltol) from a reaction with N2 at 355 C with 1:1 water to oil shale ratio. These results suggest that all of the material extracted from ambient temperature to 355 C is remarkably similar in chemical structure. The increase in temperature from 300 C to 355 C appears to lead

Y. Fei et al. / Fuel 92 (2012) 281287 [6] Haddadin RA. Kinetics of tetralin extraction of Jordanian oil shale. Fuel 1980;59:5358. [7] Green MI, Gelbein AP. Hydrogenation/extraction of organics contained in rock. US Pat. 80-176008; 1982. [8] Nappa L, Klesment I, Vink N. Hydrogenation and conversion of the Suzak oil shale of the Uzbek SSR. Eesti NSV Teaduste Akadeemia Toimetised, Keemia 1988;37:15764 [CA 109:193428]. [9] Berkowitz N, Dunn SR. Method for recovering and concurrently partly upgrading heavy oils, bitumens and oil shale organic matter, and for extracting certain wastes. Can Pat. 97-2208046; 1999. [10] Abel O, Behrendt U. Studies on the hydrogenation extraction of oil shale. Erdoel Kohle Erdgas Petrochem 1982;35:258. [11] Funazukuri T, Mizuta K, Wakao N. Oil extraction from Australian Condor oil shale with water and carbon monoxide in the presence of sodium carbonate. Fuel 1988;67:15105. [12] Redlich P, Jackson WR, Larkins FP. Hydrogenation of brown coal. 9. Physical characterization and liquefaction potential of Australian coals. Fuel 1985;64:138390. [13] Cook PS, Cashion JD, Cassidy PJ. Moessbauer study of the tin chemistry occurring during the hydroliquefaction of tin-treated Victorian brown coal. Fuel 1985;64:11216. [14] Shirai H. The reduction waves of copper and lead ions in potassium hydrogen carbonate solution. Nippon Kagaku Zasshi 1961;82:117982. CA 57:74010. [15] Charlesworth JM. Inuence of temperature on the hydrogenation of Australian Loy-Yang brown coal. 2. Structural analysis of the asphaltene fractions. Fuel 1980;59:86570.

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[16] Al-Harahsheh A, Al-Harahsheh M, Al-Otoom A, Allawzi M. Effect of demineralization of El-lajjun Jordanian oil shale on oil yield. Fuel Process Technol 2009;90:81824. [17] Haddadin RA, Mizyed FA. Thermogravimetric analysis kinetics of Jordan oil shale. Ind Eng Chem Process Des Dev 1974;13:3326. [18] Cassidy PJ, Jackson WR, Larkins FP, Sakurovs RJ, Sutton JF. Hydrogenation of brown coal. 8. The effect of added promoters and water on the liquefaction of Victorian brown coal using hydrogen, carbon monoxide and synthesis gas. Fuel 1986;65:3749. [19] Larkins FP, Jackson WR, Rash D, Hertan PA, Cassidy PJ, Marshall M, et al. Mechanistic studies on the hydroliquefaction of Victorian brown coal. In: Schobert HH, editor. The chemistry of low rank coals. Washington, DC: American Chemical Society; 1984. p. 27586. [20] Hughes CP, Sridhar T, Chuan LS, Redlich PJ, Jackson WR, Larkins FP. Reactions of brown coals with carbon monoxide/water in the presence of sodium aluminate. Fuel 1993;72:20510. [21] Clemow LM, Favas G, Jackson WR, Marshall M, Patti AF, Redlich PJ. Humic acids and methylated humic acids as models for reactions of brown coal with CO/ H2O and with H2. Fuel 1999;78:56772. [22] Al-Harahsheh A, Al-Otoom AY, Shawabkeh RA. Sulfur distribution in the oil fractions obtained by thermal cracking of Jordanian El-Lujjan oil shale. Energy (Amsterdam, Netherlands) 2005;30:278495. [23] Hamarneh YM. Oil shale deposits in Jordan. Prepr Pap Am Chem Soc Div Fuel Chem 1984;29:4150.