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Journal of Analytical and Applied Pyrolysis 55 (2000) 217 234 www.elsevier.

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Two stage pyrolysis of oil shale using a zeolite catalyst


Paul T. Williams *, Hafeez M. Chishti 1
Department of Fuel and Energy, The Uni6ersity of Leeds, Leeds, LS2 9JT, UK Received 30 September 1999; accepted 8 December 1999

Abstract Oil shales were pyrolysed in a xed bed reactor and the chemical composition of the oils and gases from the pyrolysis of the oil shales were characterised. The reactor system was then modied to incorporate a second reactor where the derived vapours from oil shale pyrolysis were upgraded on-line using zeolite ZSM-5 catalyst at low pressure. The inuence of catalyst temperature from 400 to 550C, on the yield and composition of the derived oils and gases was determined. In particular, the aromatic and polycyclic aromatic composition of the oils was determined. Gases were analysed before and after catalysis by off-line packed column gas chromatography. The oils were analysed by liquid chromatography fractionation followed by gas chromatography/mass spectrometry. The results showed that the main gases from the pyrolysis of oil shales were, CO2, CO, H2, CH4, C2H4, C2H6, C3H6, C3H8 and minor concentrations of other hydrocarbon gases. After catalysis the concentration of all the hydrocarbon gases were increased. The yield of oil after catalysis was reduced with a consequent higher yield of gases and formation of coke on the catalyst. The inuence of catalyst temperature was to further increase the gas yield and decrease the yield of oil. Total nitrogen and sulphur contents in the oils were markedly reduced such that at the catalyst temperature of 550C a 67% reduction in nitrogen and a 56% reduction in sulphur was achieved. The pyrolysis oil contained mainly alkanes and alkenes however, after catalysis almost all of the long chain alkanes and alkenes were converted to lower molecular weight material, of the short chain, alkyl substituted and iso forms. In addition, the pyrolysis oil contained signicant concentrations of single ring aromatic compounds and polycyclic aromatic hydrocarbons, consisting of mainly, benzene, naphthalene, biphenyl and phenanthrene and their alkylated derivatives. After catalysis the concentrations of these species were

* Corresponding author. Tel.: + 44-113-2332504; fax: + 44-113-2440572. E -mail address: p.t.willianms@leeds.ac.uk (P.T. Williams) 1 On leave from the Institute of Geology, Punjab University, Lahore, Pakistan. 0165-2370/00/$ - see front matter 2000 Elsevier Science B.V. All rights reserved. PII: S 0 1 6 5 - 2 3 7 0 ( 0 0 ) 0 0 0 7 1 - 1

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increased in the derived catalysed oils. The aromatic and polycyclic aromatic compounds in the oils showed a marked increase in concentration as the catalyst temperature was increased to 550C. Nitrogen and sulphur containing aromatic and polycyclic aromatic compounds were reduced in concentration after catalysis, reecting the overall decreases in nitrogen and sulphur contents in the oils. 2000 Elsevier Science B.V. All rights reserved.
Keywords: Oil shale; Zeolite; Catalysis; Polycyclic aromatic compounds; Pyrolysis

1. Introduction Pyrolysis of oil shales produces an oil which has a similar caloric value, density and viscosity to petroleum derived oils. However, the oils also have properties which make them less attractive than petroleum, including their high heteroatomic content. In addition, the relatively low price of crude petroleum oil has meant that there is reduced interest in nancing the processing costs of oil shales to produce an oil of potentially lower quality. To overcome the quality issue, research into post-pyrolysis upgrading of shale oil has been undertaken. This usually involves catalytic hydrotreatment of the shale oil at high pressure and moderate temperatures to both reduce the heteroatomic content and also improve the quality and yield of the rened oil end product [1 4]. The use of high pressure and temperature catalytic hydrotreatment for processing heavy crude petroleum oils and renery residues is routinely used in petroleum rening industry to remove heteroatomic compounds prior to further upgrading the oil through uid catalytic cracking [5]. The removal of nitrogen and sulphur species is a main aim of shale oil processing prior to rening since shale oils contain high concentrations of sulphur and nitrogen species compared to crude petroleum oils. It has been shown that the majority of the nitrogen and sulphur are contained in the aromatic fraction of shale oil and are present as single ring and polycyclic aromatic species [2,3]. The necessity to reduce nitrogen levels in shale oils is due to the associated problems of the presence of these species in down stream processing or utilisation. The presence of nitrogen in the rening process may lead to catalyst poisoning during the uid cracking process [2]. Nitrogen in shale oil also reduces the stability of the fuel and causes problems of storage and also leads to increased emissions of NOx on combustion [1]. Similarly, the presence of high sulphur contents in shale oil results in the formation of SOx when the oil is combusted. The uid catalytic cracking of heavier petroleum fractions involving low pressure zeolite catalysis is well known [6]. Catalysis in this context is used mainly to crack higher molecular weight compounds to a lighter more commercially valuable product. However, zeolite catalysts have also been shown to reduce sulphur levels and nitrogen in the derived oils during catalytic cracking [6,7]. If the, pyrolysis-heteroatomic reduction-catalytic upgrading, could be combined in a single process, this would markedly improve the economic potential of oil shale

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processing. Because pyrolysis of oil shale is an essentially low pressure process whilst catalytic hydrotreatment involves high pressure there is limited scope for coupling the processes. However, the potential of low pressure catalytic upgrading combined with pyrolysis is a possibility, but has hitherto not been investigated in detail to the authors knowledge. In this work, oil shale has been pyrolysed in a xed bed reactor in relation to pyrolysis temperature to determine the optimum temperature of pyrolysis for maximum oil yield for the experimental process conditions. The oil shale was then pyrolysed at the optimum temperature and the pyrolysis gases passed directly over a xed catalyst bed of zeolite ZSM-5 in relation to catalyst temperature. The derived pyrolysis and pyrolysis/catalysis oils were characterised to determine their content of single ring aromatic compounds, polycyclic aromatic hydrocarbons (PAH), nitrogen containing PAH (PANH) and sulphur containing PAH (PASH). The total nitrogen and sulphur contents of the oils were also determined to demonstrate the effectiveness of low pressure zeolite catalysis in removing nitrogen and sulphur compounds from shale oil.

2. Experimental section

2.1. Oil shale


The oil shale used was the Kark oil shale from the Kohat basin area of northern Pakistan. The Kohat geological basin contains a folded and faulted rock sequence from Eocene to recent in age. The Kark oil shales are of Eocene age, green to dark grey in appearance, medium hard and compact and vary in thickness from 0.56.0 m. The organic carbon and hydrogen contents of the Pakistani oil shales are higher

Table 1 Characteristics of the oil shale sample (wt%) Kark oil shale Moisture Volatile matter Fixed carbon Ash Total carbon Organic carbon H N S CV (MJKg1) Density (kg m3) 5.5 34.4 4.12 61.3 24.4 22.0 3.0 0.08 0.4 9.6 1.63

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than many oil shales found throughout the world. Table 1 shows an analysis of the Kark oil shale.

2.2. Catalyst
The catalyst was of the high acidity, shape selective, zeolite ZSM-5 type and was obtained commercially from the BDH Company (Dorset, UK). The zeolite consisted of 2 mm diameter spheres, the silica/alumina ratio of the catalyst was 50 and , , the surface area the binder was clay. The catalyst pore size was a mean of 5.5 A was 300 m2 g 1, the pore volume was 0.48 g cm 3 and the average bulk density was 0.72 g cm 3.

2.3. Pyrolysis reactor


A xed bed gas purged pyrolytic reactor was used to pyrolyse the oil shales and was operated at atmospheric pressure. The reactor consisted of a 200 cm3 stainless steel reactor externally heated by an electric ring furnace. The furnace was controlled by a programmable temperature controller which enabled the shales to be heated at a xed heating rate of 10C min 1 to the nal pyrolysis temperature of either, 460, 520, 580 and 640C. The oil shale was held at the nal temperature for 1 h or until there was no signicant yield of gas. A sweep gas of nitrogen was used as the carrier gas at a xed metered ow rate to sweep the evolved products quickly from the reaction zone, to minimise secondary reactions such as thermal cracking, repolymerisation and recondensation. The liquid oil phase was trapped in glass liners inside a series of cold traps, maintained at different temperatures with the aid of ice/water and solid CO2/methanol mixtures and a glass wool condenser trap. The non-condensed gases after the condensation system were sampled using a series of gas syringes throughout the experiment and were analysed off-line using packed column gas chromatography. Fig. 1 shows a schematic diagram of the xed bed reactor.

2.4. Pyrolysis /catalysis reactor


The reactor used for pyrolysis was modied for the pyrolysis/catalysis experiments. A second stainless steel reactor was attached directly to the pyrolysis reactor so that the pyrolysis gases generated were passed directly over the xed catalyst bed. The catalysis reactor was separately heated. For the pyrolysis/catalysis experiments, the oil shale was heated at xed pyrolysis conditions of 520C at 10C min 1 and the catalyst temperatures investigated were 400, 450, 500 and 550 C. The pyrolysis temperature of 520C was chosen because, as will be shown later, this gave the maximum yield of oil. The efuent from the reactor was passed to the condensation system described for the pyrolysis reactor to trap the derived oils. The gases were again sampled using gas syringes and analysed off-line using packed column gas chromatography. After the experiment, the catalyst was removed and the formation of coke was determined by the difference in mass before and after

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Fig. 1. Schematic diagram of the pyrolysis reactor.

catalytic regeneration. The regeneration took the form of heating the used catalyst in a furnace at a temperature of 550C in the presence of air for a period of 8 h. Fig. 2 shows a schematic diagram of the pyrolysis/catalysis reactor.

2.5. Gas analysis


The non-condensable gases from the pyrolysis and pyrolysis/catalysis experiments were analysed off-line by packed column gas chromatography. Three separate gas chromatographs with different columns were used for analysis to fully analyse for a range of gaseous species. Gaseous hydrocarbons up to C4 were determined on a Porasil C80100 column with nitrogen as the carrier gas, using a ame ionisation detector. A molecular sieve SA 60 80 column with argon as the carrier gas and a thermal conductivity detector were used for the analysis of CO, H2, CH4, and O2. Nitrogen which was the purge gas used in the reactor was also determined on this column and the volumetric ow rates of the other gases were calculated by comparison with the nitrogen ow rate. Carbon dioxide was determined separately using a silica gel column and argon as the carrier gas with a thermal conductivity detector. In this work, the gas yield was calculated from the total individual gas concentrations rather than by difference.

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2.6. Analysis of pyrolysis oil


The derived oils from pyrolysis and pyrolysis/catalysis were analysed for their molecular weight distribution using size exclusion chromatography. The system incorporated two 150 4.6 mm i.d. columns with Polymer Laboratories 5 mm RPSEC 100 A type packing. A third column of the same material was placed in line between the pump and the injection valve, to ensure pre-saturation of the solvent with the column packing material and also to avoid analytical column dissolution and hence loss of performance. The solvent used for the mobile phase was tetrahydrofuran (THF). The calibration system used was based on polystyrene samples of low polydispersity in the MW range of 800 to 860 000, also included was benzene for low MW calibration. Samples were introduced through a 2 ml loop injection valve. The detector was a refractive index detector from Varian. The output from the detector was recorded on a micro-computer which analysed the data. Chemical class fractionation was performed on the pyrolysis oil produced at 520C and the pyrolysis/catalysis oils. The derived oil fractions were analysed for their PAH, PANH and PASH concentrations. Details of the analytical methodologies for the analysis of the oils have been reported earlier [8,9]. The oils consisted

Fig. 2. Schematic diagram of the pyrolysis-catalysis reactor.

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of an aqueous phase and an oil phase which were separated by centrifuging, decanting and removal of the aqueous phase by pipette. The oils were separated into chemical class fractions using open column liquid chromatography. Glass columns, 10 cm high 1 cm diameter, packed with silica, Bondesil (sepralyte) sorbent were used which had been pre-treated at 105C for 2 h prior to use. Sequential elutions of pentane, benzene, ethyl acetate and methanol were used to produce, aliphatic, aromatic, ester and polar fractions, respectively. Each of the fractions was evaporated to dryness using nitrogen blow down, weighed, and the percentage mass in each fraction calculated. The nitrogen blow down step was carried out carefully to avoid loss of volatile material. It has been shown that nitrogen blow down as a solvent reduction method produces acceptable recoveries for polycyclic aromatic species [10,11]. The eluted pentane fraction for the pyrolysis oils, prior to nitrogen blow down, was analysed for aliphatic compounds and the benzene fraction was analysed for their content of PAH, PANH and PASH. Light hydrocarbons were analysed prior to fractionation. PAH were analysed by capillary column gas chromatography/mass spectrometry (g.c./m.s.), together with retention indices, to identify the PAH [1214]. The system used was a Carlo Erba, Vega HRGC with cold on-column injection, coupled to a Finnigan Mat ion trap detector (ITD) via a heated transfer line. The column used in the gas chromatograph was a 25 m long 0.3 mm i.d., fused silica capillary, coated with DB5 stationary phase and the temperature programme was 60C for 2 min followed by a 5C min 1 heating rate to 270C. The carrier and make-up gas was helium with a carrier ow rate of 2 cm3 min 1 at 270C. The ITD had a mass range from 20 to 650 amu with scan times of between 0.125 and 2s. The ITD was linked to an IBM PC/XT computer with an NBS/EPA mass spectral library. Single ion monitoring (SIM) was also carried out to conrm the presence of species. Quantication for PAH was determined separately by capillary column g.c. with cold on-column injection, but with a ame ionisation detector (g.c./FID) instead of an ion trap detector. The g.c./FID system was found to give much better resolution of peaks than the g.c./ITD system and hence its use for quantication. Internal standards together with the identications found from the g.c./ITD allowed quantication of the PAH in the oil shale pyrolysis oils. The PAH standards used were naphthalene, anthracene, uoranthene and chrysene. The g.c./FID system used was a CarloErba Mega Series HRGC 5300 gas chromatograph and the capillary column, temperature programme, carrier gas and ow rate was identical to that used in the g.c./ITD system. The pentane fraction containing the aliphatic species were also analysed on this gas chromatograph. PANH were identied with the aid of the g.c./m.s. system described earlier and retention indices and also using gas chromatography with alkali salt, nitrogen selective detection. PANH standards used were pyridine, indole, phenazene and acridine. The gas chromatograph used was the CarloErba Mega Series 5300 described earlier for the PAH analysis but with a nitrogen selective detector. The gas chromatographic conditions, capillary column and temperature programme were as for the determination of PAH.

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PASH were identied with the aid of the g.c./m.s. and the characteristic mass numbers of sulphur containing species and retention indices and also using g.c. with ame photometric sulphur selective detection. PASH standards used were benzothiophene and dibenzothiophene. The gas chromatograph used in this case was a HewlettPackard 5890 capillary column system with on-column injection. The column used was a DB5 column and the temperature programme, carrier gas and ow rate conditions were identical to those used for the determination of PAH. For PAH, PANH and PASH, the response factors of the standards of known concentration were used to quantify those species closest in retention time to the appropriate standard.

3. Results and discussion

3.1. Pyrolysis product yield and gas composition


Table 2 shows the pyrolysis product yield for the pyrolysis of the Kark oil shale at 460, 520, 580 and 640C. The mass closure for the experiments was very good being between 97.79 to 99.21%. The losses may be represented by sulphurous gases such as hydrogen sulphide which were not analysed for using the present gas analysis system. The oil yield was maximised at 520C pyrolysis temperature with a progressive increase in gas yield from 460 to 580 C, whilst the product water also appeared to be maximised at 520C. Other workers have shown that the optimum pyrolysis temperature for maximising oil yield is in the region of 500 to 530C [1518]. At lower temperatures, below the maximum oil yields are reduced due to coking reactions of the oil via conversion of the liquid oil to solid carbonaceous products [19]. At higher temperatures, above the optimum, a decrease in oil yield coupled with an increase in gas yield is found which is attributed to secondary gas phase cracking reactions of the oil [20,21]. The total gas yield increased from 4.71 wt% at 460C to 7.15 wt% at 640C. Table 2 shows that the main gases consisted of hydrogen, carbon monoxide, carbon dioxide, methane, ethane, ethene, propane, propene, with lower concentrations of iso-butane, butane and butene as has been reported by many authors [2123]. The origin of the gases being assigned to the thermal degradation of kerogen at lower temperatures and to thermal degradation of bitumen, carbonate minerals and secondary vapour phase cracking reactions at higher temperatures [2125]. Table 3 shows the product yield and detailed gas composition from the combined pyrolysis/catalysis of oil shale. Pyrolysis was undertaken at a temperature of 520C for all runs and the catalysis temperature was 400, 450, 500 and 550C. Pyrolysis shale oil vapours were evolved from about 400C to the nal temperature of 520C and at decreasing levels as the oil shale was held at 520C for a further 60 min. The maximum yield of gases was at about 500C and at this time there was a corresponding decrease in the catalyst bed temperature of between 10 and 15C which occurred for about 8 10 min until the temperature controller restored the programmed temperature. This suggests that the shale oil vapour cracking reaction

P.T. Williams, H.M. Chishti / J. Anal. Appl. Pyrolysis 55 (2000) 217234 Table 2 Product yield from the pyrolysis of Kark oil shale in relation to temperature (wt%) Product Pyrolysis temperature (C) 460 Oil Gases Water Spent shale Mass closure Non -hydrocarbon gases Hydrogen Carbon monoxide Carbon dioxide Total Hydrocarbon gases Methane Ethane Ethene Propane Propene Isobutane Butane Butene Total Sum of alkanes (C1C4) Sum of alkenes (C1C4) Ethene/ethane Propene/propane Butene/butane Alkenes/alkanes 12.10 4.71 8.70 73.42 98.93 0.06 0.21 1.69 1.96 0.33 0.28 0.20 0.14 0.04 0.11 0.11 B0.01 1.21 0.97 0.24 0.71 0.28 0.25 520 14.62 5.25 9.22 70.12 99.21 0.08 0.26 2.09 2.43 0.42 0.34 0.23 0.17 0.06 0.13 0.13 0.03 1.48 1.19 0.32 0.67 0.35 0.23 0.27 580 13.98 6.72 8.98 69.10 98.78 0.10 0.29 2.30 2.69 0.66 0.41 0.30 0.18 0.11 0.14 0.14 0.06 1.94 1.53 0.47 0.73 0.61 0.43 0.31 640 13.10 7.15 8.82 68.72 97.79 0.10 0.31 2.51 2.92 0.72 0.41 0.34 0.20 0.14 0.16 0.16 0.11 2.24 1.65 0.59 0.83 0.70 0.69 0.36

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was endothermic. Venuto and Habib [6] have reported that cracking and de-alkylation reactions typical of those found in a petroleum uid catalytic cracker unit are endothermic. Isomerisation and dehydrogenation reactions of hydrocarbons over zeolite catalysts have also been reported to be endothermic [26]. Also, Parasada Rao [27] has found that aromatisation of alkanes over ZSM-5 catalyst are endothermic and shale oils have been shown to contain high concentrations of alkanes. Comparison of Tables 2 and 3 shows that the inuence of the presence of the catalyst was to reduce the yield of oil, increase the yield of gases and form coke on the catalyst. As the catalyst temperature was increased, the yield of oil decreased and gas yield increased. Coke formation on the catalyst showed a small, but signicant decrease as catalyst temperature was increased. Coke formation has largely been attributed to the reactions of asphaltenes, aromatic compounds and alkenes [6], all of which occur in high concentrations in shale oils. In addition, Ono

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et al. [28] found that the amount of coke was higher for lower temperatures of catalysis, as was found in this work. Venuto and Habib [6] also showed that coke formation was reduced as the catalyst temperature was increased from 480 to 590C for the catalytic cracking of petroleum. They also showed that the gas yield, particularly alkene gases also increased with catalyst temperature with a corresponding decrease in the yield of light oil. The product water, which showed a negligible inuence of temperature for pyrolysis alone, showed a decrease in the pyrolysis/catalysis experiments with increasing temperature of the catalyst. As expected, the residual spent shale yield remained fairly constant, as the pyrolysis was undertaken at identical conditions for the catalyst experiments. Table 4 shows the elemental composition of the derived oil after pyrolysis at 520C and for the oils produced from pyrolysis/catalysis in relation to increasing catalyst temperature from 400 to 550C. Initial nitrogen and sulphur contents in the
Table 3 Inuence of catalyst temperature on the pyrolysis/catalysis of Kark oil shale (wt%) Product Catalyst temperature (C) 400 Oil Gases Coke Water Spent shale Mass closure Non -hydrocarbon gases Hydrogen Carbon monoxide Carbon dioxide Total Hydrocarbon gases Methane Ethane Ethene Propane Propene Isobutane Butane Butene Total Sum of alkanes (C1-C4) Sum of alkenes (C1-C4) Ethene/ethane Propene/propane Butene/butane Alkenes/alkanes 6.87 9.14 4.03 8.12 70.23 98.39 0.14 0.44 3.73 4.31 0.68 0.49 0.94 1.15 1.01 0.25 0.10 0.06 4.67 2.66 2.01 1.90 0.97 0.59 0.75 450 6.58 10.07 3.82 7.62 70.32 98.41 0.16 0.49 4.11 4.75 0.75 0.55 1.04 1.27 1.22 0.27 0.11 0.07 5.27 2.94 2.32 1.90 0.96 0.58 0.79 500 5.26 12.65 3.76 6.63 70.26 98.56 0.20 0.61 5.13 5.94 0.94 0.70 1.33 1.61 1.52 0.34 0.14 0.18 6.76 3.73 3.03 1.90 0.94 0.58 0.81 550 4.10 14.47 3.64 4.58 70.18 97.05 0.26 0.65 5.47 6.38 1.06 0.81 1.69 1.56 1.91 0.39 0.24 0.25 7.91 4.01 3.72 1.93 1.26 1.04 0.93

P.T. Williams, H.M. Chishti / J. Anal. Appl. Pyrolysis 55 (2000) 217234 Table 4 Elemental composition of pyrolysis and pyrolysis/catalysis oils (wt%) Process conditions (C) Element Carbon Pyrolysis 520 Pyrolysis /catalysis 520/400 520/450 520/500 520/550 Hydrogen Nitrogen

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Sulphur

80.78 84.73 87.85 88.71 89.50

10.08 9.74 9.33 9.08 8.97

0.36 0.17 0.15 0.13 0.12

1.47 0.74 0.72 0.67 0.65

raw pyrolysis shale oil were 0.36 and 1.47 wt%, respectively. However, with catalysis these were markedly reduced to levels of 0.17 wt% nitrogen and 0.74 wt% sulphur at a catalyst temperature of 400C. There was a further and signicant reduction in the oil nitrogen and sulphur contents with increasing temperature of the catalyst, such that at the catalyst temperature of 550C a 67% reduction in nitrogen was achieved and a 56% reduction in sulphur. The removal of nitrogen and sulphur from shale oils at such levels is signicant. Whilst there are no detailed data on the inuence of zeolite catalysis on the removal of sulphur and nitrogen from shale oils, there is data for petroleum oil. For example, Peters et al. [7] have shown that for the catalytic cracking of petroleum, the nitrogen is transferred approximately equally between the derived oil and coke, with some formation of nitric oxide. However, because different feeds contain varying amounts of nitrogen and of different species, the correlation with coke nitrogen is loose. It has also been shown [29] that the distribution of sulphur in the products from the uid catalytic cracking of petroleum is approximately 45% in the derived oil, only about 6% in the coke with the remaining sulphur being evolved as hydrogen sulphide. Wormsbecher et al. [30] found a higher transfer of sulphur into the derived oil at 5060% for the catalytic cracking of petroleum, but conrmed that the majority of the remaining sulphur was evolved as hydrogen sulphide. They also showed that the distribution of sulphur between the catalysis products was dependent on several factors including the composition of the petroleum feed, catalyst type and operating conditions. Fig. 3 shows the molecular weight distribution of the pyrolysis oil and the pyrolysis/catalysis oils as determined by size exclusion chromatography. The results show a marked decrease in molecular weight distribution when the catalyst was used. The results also suggest that as the temperature of the catalyst was increased there was a corresponding decrease in molecular weight distribution of the oils. The molecular weight of the uncatalysed shale oil ranged from a nominal 60 Daltons (Da) to over 2300 Da, whereas in the presence of the catalyst the range was reduced to between 60 and : 1000 Da. The peak molecular weight for the uncatalysed oil was 600 Da. whereas after catalysis the oils had a peak molecular weight of : 200 ,, Da. The zeolite ZSM-5 catalyst used in this work had a mean pore size of 5.5 A

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with a uniform channel system which allows certain size compounds to enter and gain access to the catalyst active sites. The uniform pore size also limits the size of catalysis products which can leave the catalyst. It has been suggested [31] that the maximum reactive species which can leave the catalyst pore of zeolite ZSM-5 are C10 hydrocarbons such as naphthalene which has a molecular weight of 128 Da. The molecular weight distribution data however, show that a signicant proportion of higher molecular weight material was produced with the catalysis reaction. The higher MW material detected in the upgraded zeolite catalyst oils could either be unconverted pyrolysis vapours, catalysis products formed on the outer surface of the catalyst or low molecular weight products which polymerise on condensation.

Fig. 3. Molecular weight range of the oils derived from the pyrolysis and pyrolysis/catalysis of oil shale. Table 5 Chemical class fractionation of pyrolysis and pyrolysis/catalysis oils (wt%) Process conditions (C) Fraction Pentane Pyrolysis 520 Pyrolysis /catalysis 520/400 520/450 520/500 520/550 Benzene Ethyl acetate Methanol

19.10 23.33 24.78 25.38 27.10

28.67 36.55 41.36 42.48 45.30

34.65 19.62 15.92 14.10 11.54

8.82 2.61 2.10 1.32 0.50

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Fig. 4. Gas chromatogram of the pentane fractions of the pyrolysis oil (a) and the pyrolysis/catalysis oil (b).

Table 5 shows the chemical class fractionation of the oil derived from pyrolysis of oil shale at 520C and for the oils produced from pyrolysis/catalysis in relation to pyrolysis at 520C with increasing catalyst temperature from 400 to 550C. The inuence of the catalyst was to markedly reduce the ethyl acetate and methanol fractions in the oil. The ethyl acetate and methanol fractions will contain the more polar material and complex heteroatomic material including sulphur and nitrogen species. The inuence of the catalyst was to decrease the fraction of these species, increasing the concentration of aromatic compounds in particular and aliphatic material. Increasing the temperature of the catalyst from 400 to 550C resulted in a further decrease of the ethyl acetate and methanol fractions with a corresponding increase in the pentane and benzene fractions. Fig. 4 shows the pentane fraction of the pyrolysis oil produced at 520C and for a typical oil produced from pyrolysis/catalysis. The uncatalysed oil shows the characteristic alkanes and alkenes typical of shale oils, with a carbon number range was from about C10 to C35. After catalysis almost all of the long chain alkanes and alkenes have been converted to lower molecular weight material, of the short chain, alkyl substituted and iso forms. Reactions of long chain aliphatic compounds with zeolite catalysts have been described before and involve, chain scission, isomerisation, hydrogen transfer and saturation [6,3133].

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Table 6, Table 7 and Table 8 shows the PAH, PANH and PASH present in the benzene fractions of the shale oil produced at 520C pyrolysis temperature and the pyrolysis/catalysis oils in relation to catalysis temperature. The tables only include those compounds which could be positively identied since the benzene fraction contained other polycyclic aromatic compounds which could not be identied using the available retention indices and mass spectra. The data on chemical class fractionation shown in Table 5 indicates that the oils become much more aromatic with post catalytic reaction, and becoming progressively more aromatic with increasing temperature of pyrolysis. These results are reected in the analyses of the oils shown in Table 6 Table 7 and Table 8 for the PAH, PANH and PASH. Table 6 shows a marked increase in the single ring and polycyclic aromatic hydrocarbon content of the oils when the catalyst was present compared to the uncatalysed oil and further increases in content as the catalyst temperature was increased. The benzene fraction clearly contains a range of PAH, PANH and PASH, however, the ethyl acetate fraction may also contain some PAH, PANH and PASH species but

Table 6 Aromatic and polycyclic aromatic hydrocarbons (PAH) in pyrolysis and pyrolysis/catalysis oils (ppm)a Compound Pyrolysis oil 520C Benzene Toluene Ethylbenzene Dimethylbenzenes Trimethylbenzenes Indene Decahydronaphthalene Naphthalene 2-Methylnaphthalene 1-Methylnaphthalene 2-Ethylnaphthalene Dimethylnaphthalenes Methylbiphenyls Acenaphthene Dibenzyl 2,3,6-Trimethylnaphthalene 2,3,5-Trimethylnaphthalene Dihydroanthracene Octahydroanthracene Phenanthrene Anthracene Fluoranthene Pyrene Chrysene
a

Pyrolysis/catalysis oil 400C 4365 5165 1500 4520 630 215 nd 6390 9910 7200 2705 20875 1480 1140 980 1785 1435 620 nd 720 1035 835 710 370 450C 7740 9070 2530 7865 1045 800 nd 9650 13550 9140 3135 30410 1225 1425 775 2045 1575 450 nd 855 1475 920 775 385 500C 12500 15730 4285 13570 1760 1395 nd 15210 19770 12455 3875 46700 795 1910 420 2480 1805 165 nd 1090 2225 1060 880 405 550C 16625 19345 4240 16670 2145 1560 nd 18225 23145 14260 4275 55530 560 2175 230 2715 1935 10 nd 1215 2635 1135 935 415

170 315 215 360 110 155 390 2340 5380 4780 2165 9010 3720 790 1240 1470 1265 825 945 550 485 735 635 355

nd, Not detected.

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of a more complex nature, of higher polarity and higher molecular weight. The analytical system used, and gas chromatographic column in particular, however, precluded further analysis of the ethyl acetate and also methanol fractions, these fractions producing unresolved peaks on the chromatogram. Table 6 shows that the single ring aromatic compounds present in the shale oil were mostly benzene, toluene and alkylated benzenes and the PAH present were mainly naphthalene and alkylated derivatives whilst other PAH included, phenanthrene, anthracene, uoranthene, pyrene and chrysene. A wide range of PAH, including those identied in this work have been identied previously in raw shale oils [3438]. There are no detailed compositional data regarding PAH from the zeolite ZSM-5 catalytic upgrading of shale oils available in the literature. However, it is clear that zeolite catalysis produces a very aromatic oil, high in single ring and PAH concentration. The alkene/alkane gas ratio data shown in Table 2 for the raw oil shale pyrolysis and Table 3 for the pyrolysis/catalysis experiments indicated that secondary reactions of the pyrolysis vapours were happening [8]. The PAH results show that the derived vapours had undergone signicant aromatisation, consistent with catalytic aromatisation reactions of alkanes and alkenes on zeolite catalysts. Table 7 shows the single ring nitrogen containing aromatic compounds and PANH in the pyrolysis oil and catalytically upgraded oils in relation to temperature. The role of the zeolite catalyst was to reduce the PANH concentration in the upgraded oils. The majority of the PANH in the benzene fraction were pyridine, quinoline, benzamines, indole and their alkylated derivatives. The concentrations inthe oils were much lower than the PAH shown in Table 6. PANH such as quinolines, carbazoles and their alkylated derivatives and amino-, cyano- and nitro-PANH have been
Table 7 Polycyclic aromatic nitrogen hydrocarbons (PANH) in pyrolysis and pyrolysis/catalysis oils (ppm) Compound Pyrolysis oil 520C Ethylpyridine Dimethylpyridines Methylbenzamines Dimethylbenzamines Aminoindane Quinoline Isoquinoline Indole Methylindoles Methylquinolines Methylisoquinolines Dimethylquinolines Phenylpyridine Benzoquinoline Phenanthridine Carbazole Hydroxyquinoline 17 107 19 11 13 150 183 86 174 186 279 186 31 132 33 221 230 Pyrolysis/catalysis oil 400C 14 46 B10 B10 B10 108 119 36 78 138 118 130 13 76 14 93 97 450C 13 36 B10 B10 B10 54 66 31 68 66 100 73 11 48 12 80 83 500C B10 28 B10 B10 B10 43 67 29 65 66 95 70 11 45 11 76 79 550C B10 23 B10 B10 B10 44 58 27 64 62 93 69 10 44 11 74 77

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Table 8 Polycyclic aromatic sulphur hydrocarbons (PASH) in pyrolysis and pyrolysis/catalysis oils (ppm) Compound Pyrolysis oil 520C Benzothiophene Methylbenzothiophenes Dimethylbenzothiophenes Dibenzothiophene Methyldibenzothiophenes Dimethyldibenzothiophenes Naphthothiophene Methylnaphthothiophenes Benzonaphthothiophene Phenanthrothiophene Methylphenanthrothiophene Pyrenothiophenes 63 181 66 111 160 436 13 419 147 175 111 175 Pyrolysis/catalysis oil 400C 29 107 30 125 74 204 B10 193 68 81 B10 81 450C 26 83 28 64 67 187 B10 176 62 74 B10 73 500C 24 71 25 44 61 170 B10 160 56 67 B10 66 550C 14 70 23 45 56 158 B10 147 51 61 B10 61

reported in raw shale oils before [34 38]. However, the role of zeolite catalysts at low pressure in reducing nitrogen aromatic compounds and PANH has not been demonstrated before. It has been shown that the majority of the nitrogen in shale oils is present as aromatic compound types [3], in addition, it has also been shown that for the petroleum oils, the nitrogen is concentrated in the higher molecular weight aromatic compounds [39]. Table 6 shows that for those PANH identied, the decrease in nitrogen does not correspond to the large reduction in total nitrogen shown in Table 4. Consequently, it may be concluded that much nitrogen containing material, most probably aromatic in nature is contained in the ethyl acetate and methanol fractions. There was further reduction in the concentration of PANH with increasing temperature of the zeolite catalyst. The single ring sulphur containing aromatic compounds and PASH in the pyrolysis oil and catalytically upgraded oils in relation to temperature are shown in Table 8. The majority of PASH found in the benzene fraction were benzothiophenes and dibenzothiophenes and their alkylated derivatives, and also naphtheno-, phenanthroand pyreno- thiophenes. A similar range of PASH have been reported in raw shale oils before [34 38]. The role of the catalyst was to markedly reduce the sulphur content of the shale oils as shown in Table 4 and this trend was also reected in the PASH contents of the upgraded oils. There was further decrease in the sulphur content of the upgraded oils with increasing catalyst temperature. 4. Conclusions On-line zeolite ZSM-5 catalytic upgrading of shale oils produces a marked reduction in the overall nitrogen and sulphur contents of the derived shale oils. However, there was a consequent decrease in the yield of oil of 50% at a catalyst temperature of 400C decreasing further to only 28% at 550C. There was also a

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consequent formation of coke on the catalyst and increased gas formation. The composition of the oil showed that PAH were markedly increased in concentration after catalysis compared to raw shale oil consistent with aromatisation reactions of zeolite catalysts. The reduction in overall sulphur and nitrogen contents of the derived catalytically upgraded shale oil was reected in a reduction in the PANH and PASH contents. Acknowledgements The authors would like to acknowledge the support of the University of Leeds technical staff, Peter Thompson, Chris Brear, Ed Woodhouse and Rod Holt. The award of a Pakistan Government Scholarship to H. Chisti is also gratefully acknowledged.

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