Journal of Analytical and Applied Pyrolysis 60 (2001) 187 203 www.elsevier.

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Inuence of residence time and catalyst regeneration on the pyrolysis zeolite catalysis of oil shale
Paul T. Williams *, Hafeez M. Chishti 1
Department of Fuel and Energy, The Uni6ersity of Leeds, Leeds LS2 9JT, UK Received 21 April 2000; accepted 20 October 2000

Abstract Oil shale from the Kark region of Pakistan has been pyrolysed in a xed bed batch reactor and the properties of the derived shale oil determined. The reactor system was then modied to incorporate a second reactor where the derived vapours from oil shale pyrolysis were passed directly to the second reactor containing zeolite ZSM-5 catalyst. The inuence of the process parameters of vapour residence time (VRT) over the catalyst and the regeneration of the catalyst were examined. The yield and composition of the derived gases before and after catalysis were determined. In addition, the yield and composition of the derived oil in terms of total nitrogen and sulphur content and the content of aromatic hydrocarbons in the oils was investigated. The results showed that the yield of oil after catalysis was reduced with a consequent higher yield of gases and formation of coke on the catalyst. The main gases from the pyrolysis of oil shales were CO2, CO, H2, CH4, C2H4, C2H6 and C3H6, C3H8 and minor concentrations of other hydrocarbon gases. The main role of catalysis was to convert the long chain alkanes and alkenes in the oil to lower molecular weight, short chain, alkyl substituted and iso species and high concentrations of aromatic hydrocarbons. Total nitrogen and sulphur contents in the oils were markedly reduced after catalysis. This reduction was reected in the reduced concentration of nitrogen and sulphur containing aromatic hydrocarbons. The inuence of longer VRTs was to increase the formation of aromatic hydrocarbons, reduce the nitrogen, and sulphur compounds in the oils. The inuence of catalyst regeneration, involving ve regenerations was not signicant on the yield and composition of the derived catalytically upgraded oils. 2001 Elsevier Science B.V. All rights reserved.
* Corresponding author. Tel.: + 44 1132 332 504; fax: + 44 1132 440 572. E -mail address: p.t.williams@leeds.ac.uk (P.T. Williams). 1 On leave from the Institute of Geology, Punjab University, Lahore, Pakistan. 0165-2370/01/$ - see front matter 2001 Elsevier Science B.V. All rights reserved. PII: S 0 1 6 5 - 2 3 7 0 ( 0 0 ) 0 0 1 9 8 - 4

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Keywords: Oil shale; Zeolite; Catalysis

1. Introduction Oil shales represent a long range potential source of liquid hydrocarbons as an alternative to petroleum. Although there are very large, reserves of oil shale their widespread development has not yet been realised due in part to the processing costs of oil shale retorting and the relatively high concentrations of nitrogen and sulphur in the derived shale oil [1,2]. It is essential to remove nitrogen and sulphur from the oils if transport grade fuels are to be produced due to the legislative requirements related to NOx and SOx emissions when such derived fuels are combusted in automotive engines. The process of nitrogen and sulphur removal from shale oils has almost exclusively concentrated on high pressure catalytic hydrotreatment since this is the conventional route used to treat heavy crude petroleum oils and renery residues in the petroleum industry [3 6]. Further rening of the oils in the petroleum industry involves low-pressure zeolite catalytic cracking to produce rened products [7]. In a recent paper, the authors reported on the coupling of the pyrolysis stage of processing and the nitrogen and sulphur removal/catalytic upgrading stage of processing [8]. The pyrolysis and on-line zeolite catalysis of oil shale produced an upgraded, low nitrogen and sulphur oil with a high aromatic content and reduced heavier end. The inuence of catalyst temperature between 400C and 550C on the yield and composition of the derived oils and gases was reported. In this paper, we report on the role of vapour residence time (VRT) of pyrolysis vapours over the catalyst and the inuence of the number of catalyst regenerations on the yield and composition of the derived oils from the same two-stage pyrolysis/catalysis of oil shales experimental system. Pyrolysis of the oil shales was also undertaken in the absence of catalysis to compare with the two-stage pyrolysis/catalysis results.

2. Experimental section The details of the experimental equipment and analytical methodologies have been described in a previous related paper [8]. Therefore, only a brief outline will be presented here.

2.1. Oil shale

The oil shale used was the Kark oil shale of Eocene age from the Kohat basin area of northern Pakistan and has been described in detail before [9]. The catalyst was of the high acidity, shape selective, zeolite ZSM-5 type and consisted of 2 mm , and the surface area diameter spheres. The catalyst pore size was a mean of 5.5 A was 300 m2g 1.

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2.2. Experimental
The reactor used for pyrolysis was a 200 cm3 xed bed gas purged type heated by an electric ring furnace. The weight of oil shale used throughout the experiments was 50 g and grain size 0.5 1 mm. The heating programme was a xed heating rate of 10C min 1 to the nal pyrolysis temperature of 520C and held at the nal temperature for 1 h. The liquid oil phase was trapped in a series of cold traps and the non-condensed gases were sampled and analysed off-line using packed column gas chromatography. Fig. 1 shows a schematic diagram of the pyrolysis reactor. The two-stage pyrolysis/catalysis reactor incorporated a second batch reactor containing the zeolite catalyst which was attached directly to the pyrolysis reactor so that the pyrolysis gases generated were passed directly over the xed catalyst bed. For the pyrolysis/catalysis experiments, the oil shale was heated at xed pyrolysis conditions of 10Cmin 1 to 520C and the catalyst temperature was 450C. The efuent from the reactor was passed to the condensation system described for the pyrolysis reactor to trap the derived oils and subsequent analysis of gases. Coke formation on the catalyst was determined by the difference in mass

Fig. 1. Schematic diagram of the pyrolysis reactor.

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

before and after catalytic regeneration. The VRT of pyrolysis vapours over the catalyst of 16.6, 10.9, 6.1 and 3.0 s and the number of catalyst regenerations using fresh catalyst and catalysts after 1, 3 and 5 regenerations were investigated. 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.

2.3. Analytical procedures

The non-condensable gases from the pyrolysis and pyrolysis/catalysis experiments were analysed for C4 hydrocarbons, CO2, CO, N2, H2, CH4, and O2 by packed column gas chromatography. In this work, the gas yield was calculated from the total individual gas concentrations rather than by difference. The derived oils from pyrolysis and pyrolysis/catalysis were analysed for their

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molecular weight distribution using size exclusion chromatography. The total nitrogen and sulphur content of the oils was carried out using a Perkin Elmer elemental analyser. It has been shown that the majority of nitrogen and sulphur present in shale oils is contained in the aromatic fraction of the oils [2,3,10]. Therefore, the aromatic fraction of the oils was isolated using chemical class fractionation using liquid column chromatography. Isolation was followed by analysis of the fractions using capillary gas chromatography with mass spectrometry and also with a variety of selective detectors. The liquid column chromatography used sequential elution of the column with pentane, benzene, ethyl acetate and methanol to produce chemical class fractionation in terms of increasing polarity, namely, aliphatic, aromatic, ester and polar fractions. The pentane fraction was analysed for aliphatic compounds using capillary column gas chromatography with ame ionisation detection. The benzene fraction was analysed for aromatic compounds including nitrogen and sulphur containing species. Aromatic nitrogen compounds were determined using capillary column gas chromatography with mass spectrometry (g.c./m.s.) and also using gas chromatography with alkali salt, nitrogen selective detection. Aromatic sulphur compounds were identied with the aid of the g.c./m.s., and the characteristic mass numbers of sulphur containing species and also using capillary column gas chromatography with ame photometric sulphur selective detection. Aromatic hydrocarbons containing no nitrogen or sulphur were analysed by capillary g.c./m.s. Extensive uses of retention indices were also used for identication throughout the analytical work. The ethyl acetate and methanol fractions could not be analysed using the available instrumentation.

3. Results and discussion

3.1. Product yield and gas composition

Table 1 shows the product yield and gas composition from the pyrolysis of oil shale at 520C and also the pyrolysis of oil shale with zeolite catalytic upgrading in relation to the pyrolysis VRT over the catalyst. The oil yield in the absence of the catalyst was 14.6 wt.% representing a signicant yield of oil. The main gases consisted of hydrogen, carbon monoxide, carbon dioxide, methane, ethane, ethene, propane, propene, with lower concentrations of iso -butane, butane and butene. Table 1 shows that the inuence of the zeolite catalyst was to signicantly reduce the yield of oil, there was a consequent increase in the production of gases and formation of coke on the catalyst. Water production was slightly decreased in the presence of the catalyst. The spent shale left after pyrolysis remained fairly constant, since the pyrolysis was undertaken at identical conditions for the catalyst

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experiments. As the residence time of the pyrolysis gases over the catalyst was reduced, the inuence of the catalyst was thereby reduced, and an increase in the yield of oil, coupled with a reduction in gas and water yields and coke formation on the catalyst was apparent. The formation of carbonaceous coke on the catalyst is an inevitable disadvantage of catalytic upgrading and under the conditions of xed bed, catalysis used in this work represents a signicant loss of organic material. The formation of coke is related to the interaction of the catalyst with the high concentrations of asphaltenes, aromatic compounds and alkenes found in the shale oil [7]. Table 1 shows that there was a marked increase in gases in the presence of the zeolite catalyst. The gas increase was due mainly to increases in carbon dioxide and the hydrocarbon gases. Both alkane and alkene gases were increased in the presence of the catalyst compared to the uncatalysed pyrolysis. As the VRT over the catalyst
Table 1 Inuence of VRT on the pyrolysis/catalysis of oil shale (wt.%) Product No catalyst VRT (s) 16.6 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 (C1C4) Sum of Alkenes (C1C4) Ethene/Ethane Propene/Propane Butene/Butane Alkenes/Alkanes 14.6 5.3 9.2 70.1 99.5 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 5.4 12.2 4.6 8.0 71.8 102.0 0.12 0.34 4.74 5.20 0.92 0.68 1.26 1.54 1.46 0.36 0.17 0.22 6.60 3.67 2.93 1.85 0.95 1.29 0.80 10.9 6.6 10.1 3.8 7.6 71.2 99.3 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 2.95 2.32 1.90 0.96 0.58 0.79 6.1 6.7 10.2 3.7 7.6 71.2 99.4 0.16 0.47 4.02 4.65 0.71 0.56 0.92 1.23 1.19 0.25 0.13 0.05 5.04 2.88 2.16 1.64 0.97 0.38 0.75 3.0 7.7 8.7 3.2 6.5 71.2 97.3 0.19 0.65 3.57 4.41 0.64 0.58 0.89 0.62 0.86 0.09 0.05 0.02 3.76 1.99 1.73 1.53 1.38 0.42 0.86

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was shortened, the inuence of the catalyst was reduced and the production of, in particular, carbon dioxide and the hydrocarbon gases were reduced. Also shown in Table 1 are the ratios of the C2 C4 alkanes and alkenes. The alkene/alkane ratios all showed a signicant increase after catalysis. Alkene/alkane gas ratios particularly ethene/ethane ratios in the evolved gases from oil shale pyrolysis have been used to indicate the degree of oil cracking reactions [9,11]. Higher alkene/alkane ratios indicating a higher degree of cracking. It has also been shown that the oil vapour cracking reactions, which produce increased ethene/ethane ratios, are linked to reduce yields of oil [12]. The alkene/alkane ratios of Table 1 show a clear increase after catalysis showing that indeed cracking reactions are as expected occurring. The reduced oil yield is also apparent. In addition, the ratios of ethene/ethane and butene/butane show a clear reduction as the VRT over the catalyst is reduced reecting a decreased time for the cracking reactions to occur and consequently a higher oil yield. There is also a reduced formation of coke on the catalyst. However, the relationship of the propene/propane ratio and total C2 C4 alkene/alkane ratios does not show such a clear relationship. Table 2 shows the product yield and gas composition for the pyrolysis/catalysis of oil shale in relation to the number of catalyst regenerations. Also shown are the results for pyrolysis of oil shale in the absence of the catalyst, discussed earlier, for comparison. It might be expected that fresh catalyst would be more active than regenerated catalyst and after each subsequent regeneration the effectiveness of the catalyst in cracking the oil may be reduced. This is shown by the fresh catalyst having a higher conversion of the pyrolysis vapours to gases and a higher coke formation on the catalyst compared to catalyst which had been regenerated a number of times. This was also reected in consequent lower oil yields. As before, the yield of all the gases and particularly carbon dioxide and the alkane and alkene gases dominate the gas produced after catalysis. The ethene/ethane ratios, which for the VRT experiments showed a clear link between the degree of catalyst cracking, in this case showed an increase with the number of catalyst regenerations. Fresh catalyst would be expected to be the most effective in cracking the oil and therefore a higher ethene/ethane ratio would be expected compared to a catalyst which had been regenerated several times. However, the opposite trend is shown in Table 2. Similarly, the propene/propane ratios also show no clear trend. Overall, the inuence of the number of catalyst regenerations appeared not to be signicant for the range of regenerations investigated. However, the range of 0 5 regenerations is very limited and industrial scale catalytic cracking may involve orders of magnitude higher numbers of regenerations.

3.2. Elemental composition of the oils

Table 3 shows the elemental composition of the uncatalysed pyrolysis oil and the pyrolysis/catalysis oils in relation to VRT and the number of catalyst regenerations. Initial nitrogen and sulphur contents in the pyrolysis shale oil were 0.4 and 1.5 wt.%, respectively. After catalysis, the oils showed signicant reductions in nitrogen and sulphur levels. There was evidence that with shorter residence times of the

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Table 2 Inuence of the number of catalyst regenerations on the pyrolysis/catalysis of oil shale (wt.%) Product No catalyst Number of regenerations 0 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 (C1C4) Sum of Alkenes (C1C4) Ethene/Ethane Propene/Propane Butene/Butane Alkenes/Alkanes 14.6 5.3 9.2 70.1 99.5 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 6.1 13.4 5.0 8.6 69.7 101.8 0.21 0.95 5.50 6.67 0.82 1.07 1.47 1.26 1.29 0.30 0.16 0.12 6.48 3.61 2.88 1.37 1.02 0.76 0.80 1 6.7 11.7 4.9 7.6 70.2 99.1 0.17 0.68 4.75 5.60 0.69 0.88 1.28 1.22 1.17 0.25 0.14 0.08 5.71 3.18 2.53 1.45 0.96 0.61 0.80 3 6.5 11.1 3.9 7.6 70.0 99.1 0.16 0.62 4.51 5.28 0.71 0.59 1.04 1.10 1.12 0.26 0.13 0.05 5.00 2.79 2.21 1.76 1.02 0.35 0.79 5 6.6 11.1 3.8 7.6 70.3 99.5 0.16 0.51 4.10 4.77 0.75 0.57 1.05 1.12 1.10 0.26 0.11 0.06 5.02 2.81 2.21 1.84 0.98 0.56 0.79

pyrolysis vapours over the catalyst the catalyst was less effective in removing the nitrogen and sulphur. However, the number of catalyst regenerations did not signicantly inuence the nitrogen and sulphur content of the derived oils. There are few data in the literature reporting the removal of nitrogen and sulphur from shale oils using zeolite catalysis. However, zeolite catalytic cracking of petroleum shows that nitrogen removal from petroleum oils is largely to form products on the coke and some formation of gaseous nitric oxide [12]. The removal of sulphur from petroleum oils is mostly through the production of hydrogen sulphide gas and only a small faction forms products on the coke [13,14].

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Table 3 Elemental composition of pyrolysis and pyrolysis/catalysis oils in relation to VRT and number of catalyst regenerations Process conditions Element (wt.%) Carbon Pyrolysis 520C Pyrolysis /Catalysis VRT 16.6 s 10.9 s 6.1 s 3.0 s Regenerations 0 1 3 5 Hydrogen Nitrogen Sulphur

79.2

10.1

0.4

1.5

88.5 87.9 84.3 82.7 89.3 88.6 87.9 87.9

9.1 9.3 9.6 9.8 9.2 9.2 9.3 9.3

0.1 0.2 0.2 0.2 0.1 0.1 0.1 0.2

0.7 0.7 0.8 0.9 0.6 0.7 0.7 0.7

Fig. 3. Molecular weight range of the oils derived from the pyrolysis and pyrolysis/catalysis of oil shale in relation to VRT.

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Fig. 4. Molecular weight range of the oils derived from the pyrolysis and pyrolysis/catalysis of oil shale in relation to the number of catalyst regenerations.

3.3. Molecular weight range of the oils

Fig. 3 shows the molecular weight range of the uncatalysed pyrolysis oil and the pyrolysis/catalysis oils in relation to the residence time of the pyrolysis vapours over the catalyst. Only the uncatalysed oil and 16.6 s and 3.0 s VRT results are shown for clarity. Fig. 4 shows the molecular weight range of the uncatalysed oil and the pyrolysis/catalysis oils in relation to the number of catalyst regenerations. Only the uncatalysed oil and 0 and 5 number of catalyst regeneration results are shown for clarity. The molecular weight range of the uncatalysed shale oil ranged from a nominal 60 to over 2300 Da with a peak at : 600 Da. After catalysis, there was a signicant decrease in the molecular weight range of the derived oils. The inuence of VRT showed a further reduction in the molecular weight range in relation to longer residence times of the vapours over the catalyst. Extended reaction times producing more catalytic cracking with a consequent lowering of the molecular weight of the oils, such that at 16.6 s residence time, the molecular weight range of the pyrolysis/catalysis oil was from a nominal 60 to : 800 Da and with a peak at about 200 Da. The inuence of the number of catalyst regenerations was not however, signicant. Although there was a clear reduction in molecular weight distribution after catalysis, the oils generated from the 0 5 number of regenerations were almost identical.

3.4. Detailed composition of the oils

Table 4 shows the chemical class fractionation of the oil derived from the uncatalysed pyrolysis of oil shale and the pyrolysis/catalysis of oil shale in relation

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to the residence time of the pyrolysis vapours over the catalyst and the number of catalyst regenerations. The pentane, benzene, ethyl acetate and methanol fractions representing, aliphatic, aromatic, ester and polar material respectively. The uncatalysed shale oil contained high concentrations of the more polar material. However, after catalysis the polar material fraction was markedly reduced with a consequent increase in the aliphatic and aromatic material of the pentane and benzene fractions. The inuence of VRT was that, as the residence time of the pyrolysis vapours over the catalyst was reduced, there was less time for reaction and consequently a progressive increase in more polar material and reduced production of aliphatic and aromatic material. The number of catalyst regenerations had a marginal effect on the chemical class fractionation of the pyrolysis/ catalysis oils. Detailed analysis of the pentane fraction of the uncatalysed pyrolysis oil showed that the aliphatic material consisted of mostly n -alkanes and 1-alkenes together with lower concentrations of branched chain compounds ranging from carbon number C10 to C35. After catalysis the pentane fraction had a much reduced carbon number distribution, the majority of the aliphatic material having a carbon number less than C15. In addition, the n -alkane and 1-alkene material had largely been converted to short chain, alkyl substituted and iso -aliphatic material. There has been a large volume of literature related to the petroleum industry regarding the cracking of pure n -alkanes and 1-alkenes and mixtures of these straight chain hydrocarbons over zeolite catalysts [15 20]. The cracking of these compounds produces a marked reduction in the carbon number range of the products and increased formation of aromatic material.
Table 4 Chemical class fractionation of pyrolysis and pyrolysis/catalysis oils in relation to VRT and number of catalyst regenerations Process conditions Chemical class fraction (wt.%) Pentane Pyrolysis 520C Pyrolysis /Catalysis VRT 16.6 s 10.9 s 6.1 s 3.0 s Regenerations 0 1 3 5 Benzene Ethyl acetate Methanol

19.1

28.7

34.7

8.8

26.4 24.8 23.5 21.2 25.9 25.0 24.8 24.8

42.6 41.4 34.6 33.4 43.0 41.8 41.5 41.2

13.8 15.9 21.7 24.2 13.2 13.8 15.7 15.9

1.2 2.1 3.4 4.1 1.7 2.0 1.9 2.1

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Table 5 Inuence of VRT on the nitrogen containing aromatic hydrocarbons in the oils from the pyrolysis and pyrolysis/catalysis of oil shale (ppm) Product No catalyst VRT (s) 16.6 Pyridines Quinolines Indoles Carbazole Total 125 1115 260 220 1720 35 370 90 65 560 10.9 50 460 100 80 690 6.1 50 500 105 90 745 3.0 55 755 160 150 1120

Table 5 shows the nitrogen containing aromatic hydrocarbons present in the benzene fraction of the uncatalysed shale oil and the pyrolysis/catalysis shale oils in relation to VRT. Table 6 shows the inuence of the number of catalyst regenerations on the nitrogen containing aromatic compounds found in the benzene fraction of the oils. The nitrogen containing compounds in the oils were dominated by pyridines, quinolines, indoles and carbazoles. After catalysis there was a signicant reduction in the nitrogen containing species, which was reected in the reduction in total nitrogen in the oils after catalysis, shown in Table 3. With shorter residence times of the pyrolysis vapours over the catalyst, the effectiveness of the catalyst in removing nitrogen compounds was seen with a progressive increase in their concentration in the oils. However, the inuence of the number of catalyst regenerations was less signicant. Although there was a noticeable increase in the concentration of the nitrogen compounds as the number of regenerations was

Table 6 Inuence of number of catalyst regenerations on the nitrogen containing aromatic hydrocarbons in the oils from the pyrolysis and pyrolysis/catalysis of oil shale (ppm) Product No catalyst Number of regenerations 0 Pyridines Quinolines Indoles Carbazole Total 125 1115 260 220 1720 30 300 70 50 450 1 35 360 80 60 535 3 40 395 90 70 595 5 50 410 90 70 620

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Table 7 Inuence of VRT on the sulphur containing aromatic hydrocarbons in the oils from the pyrolysis and pyrolysis/catalysis of oil shale (ppm) Product No catalyst VRT (s) 16.6 Benzothiophene Cn-Benzothiophenes Dibenzothiophene Cn-Dibenzothiophenes Total 65 245 110 595 1015 20 65 30 215 330 10.9 25 110 65 255 455 6.1 40 160 70 380 650 3.0 55 215 90 505 865

increased, thereby reducing the effectiveness of the catalyst in nitrogen compound removal. The total nitrogen content of the uncatalysed oil shown in Table 3 represented 4000 ppm, whilst those presented in Table 5 and Table 6 totalled much lower. However, the benzene fraction contained some higher molecular weight unidentied material and in addition, the ethyl acetate and methanol fractions are also likely to contain more polar nitrogen containing material. The benzene fractions of the oils were also analysed for sulphur containing aromatic hydrocarbons. Table 7 and Table 8 show the inuence of VRT over the catalyst and the number of catalyst regenerations on these compounds in the uncatalysed oil compared to the pyrolysis/catalysis oils. The majority of sulphur containing aromatic hydrocarbons is benzothiophene and dibenzothiophene and their alkylated derivatives. The role of the catalyst was to reduce the concentration of these compounds in the derived oils by signicant levels. As the VRT over the

Table 8 Inuence of number of catalyst regenerations on the sulphur containing aromatic hydrocarbons in the oils from the pyrolysis and pyrolysis/catalysis of oil shale (ppm) Product No catalyst Number of regenerations 0 Benzothiophene Cn-Benzothiophenes Dibenzothiophene Cn-Dibenzothiophenes Total 65 245 110 595 1015 20 100 55 210 385 1 25 120 60 230 335 3 25 95 65 240 425 5 30 90 65 250 435

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Table 9 Inuence of VRT on the aromatic hydrocarbons in the oils from the pyrolysis and pyrolysis/catalysis of oil shale (mg g1) Product No catalyst VRT (s) 16.6 1-Ring 2-Ring 3-Ring 4-Ring Total aromatic aromatic aromatic aromatic 1.33 32.55 2.81 1.73 38.42 33.58 79.46 5.43 2.28 120.75 10.9 37.82 73.90 4.94 2.07 118.73 6.1 23.60 57.62 3.90 1.64 86.76 3.0 15.89 52.02 3.89 1.90 73.70

catalyst was shortened, the catalyst was less effective in removing the sulphur containing compounds. The inuence of the number of catalyst regenerations was relatively less signicant, in some cases only reecting a marginal inuence on the extent of sulphur compound removal. As was the case for the nitrogen hydrocarbons, the ethyl acetate and methanol fractions are likely to also contain sulphur species of higher polarity and molecular weight. Table 9 shows the 1 4 ring aromatic hydrocarbons (non-hetero-atomic) present in the benzene fraction of the uncatalysed shale oil and the pyrolysis/catalysis shale oils in relation to VRT. Table 10 shows the inuence of the number of catalyst regenerations on the 1 4 ring aromatic compounds found in the benzene fraction of the oils. The 1-ring compounds present were mainly benzene, toluene and alkylated benzenes, the 2-ring compounds were mainly naphthalene and its alkylated derivatives, 3-ring compounds included, phenanthrene, anthracene and their alklylated compounds and 4-ring compounds included pyrene and chrysene. The uncatalysed oil contained signicant quantities of 2-ring hydrocarbons and lower concentrations of 1-, 3- and 4-ring compounds. However, after catalysis there was a marked increase in the 1-ring and 2-ring hydrocarbons present in the oils. The 3- and 4-ring
Table 10 Inuence of number of catalyst regenerations on the aromatic hydrocarbons in the oils from the pyrolysis and pyrolysis/catalysis of oil shale (mg g1) Product No catalyst Number of regenerations 0 1-Ring 2-Ring 3-Ring 4-Ring Total aromatic aromatic aromatic aromatic 1.33 32.55 2.81 1.73 38.42 34.82 85.33 5.78 2.43 128.36 1 32.56 79.50 5.38 2.26 119.70 3 31.27 75.40 5.20 2.18 114.05 5 30.08 72.93 4.94 2.07 110.02

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hydrocarbons showed a smaller increase. The inuence of VRT showed that longer residence times of pyrolysis vapours over the catalyst produce increased formation of 1- and 2-ring hydrocarbons. Ono et al. [17] and Sirokman et al. [18] have shown a similar relationship between residence time and aromatic production for hexane and pentane over ZSM-5 zeolite catalyst respectively. Table 10 shows that the inuence of the number of catalyst regenerations on the production of 1- and 2-ring hydrocarbons in the derived pyrolysis/catalysis oils was small but signicant. The increased number of regenerations reducing the effectiveness of the catalyst. It is clear that zeolite catalysis produces a very aromatic oil, high in 1- and 2-ring hydrocarbons. Thus indicating that the oils had undergone signicant formation of aromatic compounds consistent with catalytic aromatisation reactions of alkanes and alkenes on zeolite catalysts. The clear reduction in the more polar ethyl acetate and methanol fractions shown in Table 4 indicate that the catalyst is also effective in cracking these more polar compounds resulting in possibly aromatic hydrocarbon formation. In a previous paper by the authors [8] the inuence of catalyst temperature on the pyrolysis/catalysis of oil shale was investigated, using the same experimental system reported here. In that work, nitrogen and sulphur removal from the shale oil were similar to that reported here, with increasing catalyst temperature between 400C and 550C producing increased effectiveness of removal. Similar increases in the 1- and 2-ring aromatic compounds were observed. Consequently, it may be concluded that of the process parameters investigated for the pyrolysis/catalysis of oil shale to produce an upgraded oil, the important parameters with respect to nitrogen and sulphur removal and aromatic production are the VRT over the catalyst and the catalyst temperature. However, over the limited range of 0 5 regenerations, the effectiveness of the catalyst was not signicantly affected. In addition to the catalytic reactions of the shale oil, the potential of mere thermal cracking of the oil vapours should also be considered. Thermal cracking would produce increased gas and reduced oil production; a shift to lower molecular weight ranges for the oil and increased alkene/alkane ratios as was found here in the presence of the zeolite catalyst. However, whilst it is inevitable that thermal cracking reactions are occurring as the oil vapours pass through the hot bed of catalyst, there is also clear evidence for catalytic reactions occurring. For example, there is a marked decrease in oil yield and consequent increase in gas yield at a much higher level than would be expected with mere thermal cracking. Also, the nitrogen and sulphur contents are markedly reduced in the catalysed oil, if thermal cracking reactions were dominant, it would be expected that the heterocyclic compounds would be selectively concentrated in the oil and would show an increase rather than a decrease. Further, zeolite catalysts are known to promote the formation of single ring and two ring aromatic compounds due to their selective size and shape pore structure. The dramatic increase in single ring and two ring aromatic compounds shown in Table 9 and Table 10 conrm that catalytic reactions of the oil with the zeolite catalyst are indeed occurring.

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4. Conclusions Pyrolysis/catalysis of oil shales using a zeolite catalyst has shown that the process is effective in removing nitrogen and sulphur compounds from shale oils. The quality of the oil is improved by reducing the higher molecular weight material, reducing the alkene content and increasing the aromatic content of the oils. The gas yield consisting mainly of carbon dioxide and alkane and alkene gases was signicantly increased after catalysis compared to the uncatalysed pyrolysis. However, a disadvantage of the pyrolysis/catalysis process is the signicant formation of coke on the catalyst and the reduced yield of oil compared to pyrolysis with no catalysis. The reductions in total nitrogen and sulphur contents in the oils were reected in the reduced concentration of nitrogen and sulphur containing aromatic hydrocarbons. The inuence of longer VRTs was to increase the formation of aromatic hydrocarbons and reduce the nitrogen and sulphur compounds. The inuence of catalyst regeneration, involving ve regenerations was not signicant on the yield and composition of the derived catalytically upgraded oils.

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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