Organic Geochemistry 30 (1999) 15271534

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The scope for generating bio-oils with relatively low oxygen contents via hydropyrolysis
J. Dilcio Rocha a, b, Carlos A. Luengo b, Colin E. Snape a,*
a

University of Strathclyde, Department of Pure and Applied Chemistry, 295 Cathedral Street, Glasgow G1 1XL, Scotland, UK b Universidade Estadual de Campinas, Departmento. Fisica Aplicada, C.P. 6165, Campinas, SP, Brazil

Abstract The primary oils obtained in high yields from fast (uidised-bed) pyrolysis of biomass generally have high oxygen contents (ca. 40% w/w). The scope for using pyrolysis under hydrogen pressure (hydropyrolysis), to give oils with much lower oxygen contents compared to normal pyrolysis has been investigated. Fixed-bed hydropyrolysis tests have been conducted on cellulose, sugar cane bagasse and eucalyptus wood using hydrogen pressures up to 10 MPa, with heating rates of 5 and 300 C min1. A colloidal FeS catalyst was used in some tests (Fe loading of 5%, w/w) to increase overall conversions. Further, the attractive option of using a two-stage reactor in which the primary oil vapors are passed though a bed of hydrotreating catalyst is also described. Raising the hydrogen pressure from atmospheric to 10 MPa reduced the oxygen content of the primary oil by over 10% to below 20% w/w. The addition of a dispersed iron sulphide catalyst gave conversions close to 100% for all three biomass samples investigated at 10 MPa under conditions in the xed-bed reactor where signicant diusional resistances existed and reduced the oxygen content of the bio-oil by a further 10%. Although NMR indicated that the oils became increasingly aromatic as more oxygen was removed, the increase in hydrogen pressure decreased the extent of overall aromatisation that occurs primarily due to the lower char yields obtained. In two-stage tests for cellulose, using a commercial sulphided Ni/Mo g-Al2O3 catalyst at 400 C, increasing the hydrogen pressure from 2.5 to 10 MPa decreased the oxygen content of the oil by over 20% to 10% w/w. The H/C ratios were higher and O/C ratios smaller for the two-stage bio-oils compared to their single stage counterparts. However, the dierences in the O/C ratios between the single and two-stage bio-oils increase with pressure. # 1999 Elsevier Science Ltd. All rights reserved.
Keywords: Hydropyrolysis; Cellulose; Bio-oil; Catalysis; Hydrodeoxygenation; Aromatisation

1. Introduction There are a number of waste and biomass sources being considered as potential sources of fuels and chemical feedstocks (Sofer and Zaborsky, 1981). As a consequence, the yield and composition of liquid products obtained from the pyrolysis of cellulose and various forms of biomass at atmospheric pressure have received

* Corresponding author. Tel.: +44-141-548-2309; fax:+44141-548-4822. E-mail address: c.e.snape@strath.ac.uk (C.E. Snape).

considerable attention (e.g. Antal, 1983; Soltes, 1983). However, the primary oils produced in high yield by fast (uidised bed) pyrolysis generally have extremely high oxygen contents (ca >30% w/w) and contain a number of simple sugar derivatives, such as levoglucosan. The high oxygen contents, and the water present, make these oils hydrophilic to the extent that, without emulsifying agents, they do not blend readily with conventional petroleum products. For possible future use as replacements for hydrocarbon chemical feedstocks and fuels, the liquids will require considerable upgrading. To produce bio-oils with lower oxygen contents, pyrolysis under high hydrogen pressures (hydropyrolysis) can be

0146-6380/99/$ - see front matter # 1999 Elsevier Science Ltd. All rights reserved. PII: S0146-6380(99)00124-2

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used. Preliminary work (Gercel et al., 1993; Snape et al., 1994a) showed that, apart from obtaining the expected high oil yields in xed-bed hydropyrolysis for Euphorbia rigida (a plant that grows in abundance in arid regions), the oils have considerably lower oxygen contents than those from normal pyrolysis under inert atmospheres. Meier et al. (1994) have also shown that oils with relatively low oxygen contents can be produced from lignin by both batchwise and continuous hydropyrolysis, but a high concentration of a commercial Ni/Mo hydrotreating catalyst was required to achieve oxygen contents of about 10%. Although xed-bed reactors would clearly not be considered for scale-up to pilot plant operations, the information obtained is relevant, particularly to uidised-beds that have operated at pressures up to ca. 7 MPa for oil shales (Roberts et al., 1995). High conversions and oil selectivites are achieved in xed- and uidised-bed hydropyrolysis for coals and oil shales at relatively low temperatures (Roberts et al., 1995 and references therein) and pressures in excess of 5 MPa. These attributes have enabled the technique to be exploited analytically for specifying organic sulphur forms (Brown et al., 1997; Rocha et al., 1997) and quantifying covalently-bound biomarkers in sedimentary organic matter (Love et al., 1995, 1997; Rocha et al., 1997). Further, in hydropyrolysis, there is the attractive option of using a two-stage reactor in which the primary oil vapors can be passed though a bed of an appropriate hydrotreating catalyst. This approach has produced high yields of distillable oil directly from coal without the need for a separate hydrotreating reactor (Bolton et al., 1989). Two-stage reactors have also been employed at low pressures to improve the quality of oils from biomass where zeolites (primarliy HZSM-5) have been widely investigated (Diebold et al., 1994; Pindoria et al., 1998 and references therein). There is also a considerable literature on batchwise (liquid phase/revaporised oil) processing of bio-oils with both HZSM-5 and type Y zeolites and conventional hydrotreating catalysts (Churin et. al., 1988; Sharma and Bakhshi, 1993 and references therein; Samolada et al., 1998; Vitolo et al., 1999 and references therein). However, vapor phase treatments on the primary oils (two-stage reactors) are clearly benecial in terms of providing a simpler and probably more cost-eective process option to produce high quality oils. In this investigation, xed-bed hydropyrolysis experiments have been conducted on cellulose, sugar cane bagasse (from a Brazilian ethanol distillery) and eucalyptus wood (from a Brazilian cultivated forest) with the primary aim of producing bio-oils with low oxygen contents than can be readily utilised as hydrocarbon feedstocks. Sugar cane bagasse and eucaltpyus wood were selected for this investigation because they already make a signicant contribution to meet energy demand in Brazil (each providing 1011%, 2223 millions of

tons of oil equivalent-Mtoe) and larger quantities are available (La Rovere, 1995; Brito, 1997; De Freitas and Moreira, 1997). Single and two-stage tests have been carried out using hydrogen pressures up to 10 MPa and temperatures in the range 300520 C to thoroughly investigate the extent of hydrodeoxygenation during hydropyrolysis. A colloidal FeS catalyst has been used in some single stage tests (Fe loading of 5%, daf basis) to further increase conversions. For the two-stage tests, the primary oils were passed through a bed of a commercial Ni/Mo g-alumina-supported catalyst. Preliminary accounts of this investigation have been presented at the World Renewable Energy Congress IV (Rocha et al., 1996) and the 10th European Biomass Conference (Rocha et al., 1998).

2. Experimental 2.1. Feedstocks The feedstock compositions are summarised in Table 1. The wood and bagasse samples were ground to particle sizes between 75 and 250 mm and dried at 80 C for about 12 h in a vaccum oven. The commercial cellulose sample (Aldrich, <200 mm) was treated in a similar manner prior to the hydropyrolysis tests. 2.2. Hydropyrolysis tests The xed-bed hydropyrolysis experiments were carried out using hydrogen pressures up to 10 MPa and nal temperatures in the range 300520 C. The experimental procedures for the single and two-stage hydropyrolysis tests in the resistively-heated Incoloy reactor tube (0.8 cm i.d.) have been described previously (Bolton et al., 1989; Snape et al., 1994a, 1994b; Love et al., 1995, 1997; Roberts et al., 1995). The samples (5 g) were mixed with 15 g of sand supported with steel wool inside the reactor. The iron catalyst used for singlestage tests was prepared by bubbling H2S through FeSO4.solution for 15 min. following which the black
Table 1 Elemental and proximate analyses of the biomass samples used (wt%) Eucalyptus wood %C %H %N %AshTMa MoistureTM
a TM

Suger cane bagasse 49.1 6.2 0.4 3.5 1.3

49.4 5.9 0.3 <0.1 1.0

British standard (BS 1016, Part 3).

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iron sulphide precipitate was ltered and washed with water. It was then mixed with the cellulose powder in distilled water to give a nominal loading of 5% w/w Fe. Finally, the solution was ltered again and the iron sulphide-impregnated cellulose dryed in vacuo (Mastral et al., 1995). A set of single-stage tests on cellulose was carried out at temperatures of 300, 350, 400, 450 and 520 C with a pressure of 0.5 MPa, the residence time at the nal temperature and heating rate being 10 min and 300 C min1, respectively. The ow rate of 2 dm3 min1 corresponded to an empty tube (supercial) gas velocity at 520 C of 4.4 cm s1. To investigate the eect of pressure, experiments were conducted at 2.5, 5.0, 7.5 and 10 MPa with constant calculated gas velocity of 0.9 cm s1 (the ow rate measured at ambient temperature at 10 MPa being 10 dm3 min1). A test at 10 MPa was also carried out using a ow rate of 40 dm3 min1. Tests with and without the FeS catalyst at 520 C were conducted with heating rates, of 5 and 300 C min1. The liquid products (oil plus water) were collected in a trap cooled with dry-ice. The oil yields were then determined by correcting the total liquid product yields for the amount of water present which was measured by the Dean-Stark method. When the oil was required for analysis, it was recovered in dichloromethane (DCM) and the solution was then evaporated to dryness. For the two-stage tests (Bolton et al., 1989), the primary oils obtained from 5 g of cellulose were passed through a 1 g bed of commercial Ni/Mo g-aluminasupported catalyst (Criterion 424, containing 19.5 wt% MoO3, 4 wt% NiO and 8 wt% phosphorus oxide) at 400 C. This was sulphided prior to each run using a H2S/H2 gas mixture (9% v/v H2S) at 400 C by passing ve times the stoichiometric amount of sulphur required over the catalyst. Liquid products were of low viscosity and could be recovered directly from the trap to avoid the evaporative loss of low boiling constituents. 2.3. Product analysis Hydrocarbon gases were analysed by gas chromatography (Poraplot Q, 10 m0.53 mm capillary column). Chars were characterized by elemental analysis (Perkin Elmer II-2400 analyser) and the oils from the one and two-stage tests were subjected to elemental and solution state 1H NMR analyses to provide a simple assessment of bulk structural characteristics. 1H NMR was used to apportion the aromatic hydrogen to that in phenolic and polycyclic aromatic structures and the aliphatic hydrogen to that bound to carbons adjacent to oxygen (C-O, saccharide-type structures), adjacent to aromatic rings and types other than these. Spectra were recorded on a Bruker WM250 instrument with the oils being diluted in CDCl3.

3. Results and discussion 3.1. Single stage tests The yields of char, bio-oil and C1C4 hydrocarbon gases obtained for cellulose as a function of pyrolysis temperature at the relatively low hydrogen pressure of 0.5 MPa are presented in Fig. 1. The overall conversion (100 - % char) and bio-oil yield increase only very slowly above about 350 C, consistent with atmospheric pressure results (Antal, 1983; Soltes, 1983). However, although the bio-oil yield increases even less, the oxygen contents of the oils decrease markedly (Table 2) due to increased water formation. This trend is consistent with the general disappearance of OCHn groups from the cellulose observed by 1H NMR (Table 3). Fig. 2 shows the 1H NMR spectra of the bio-oil obtained at 400 C using a hydrogen pressure of 0.5 MPa. The spectrum contains many sharp resonances but, in terms of oxygen functionality, the key point to note is the intense band from aliphatic bound to oxygen (OCHn) at 36 ppm. This broad band merges into the aromatic hydrogen band (6.28 ppm). Peaks from aldehydes are also discernible (9.5 ppm), but these only account for a small proportion of the total hydrogen and have not been included in the overall hydrogen distributions (Table 3). As the oxygen contents of the bio-oils decrease, the intensities of the 36 ppm band decrease in relation to that of the other aliphatic hydrogen bands (02 ppm (Fig. 2). At 520 C, the conversion of 82% is less that would be obtained both in fast pyrolysis results (Antal, 1983; Soltes, 1983) and in xed-bed reactors where less sample and greater gas velocities are used (Pindoria et al., 1997). Thus, for the conditions for most of the tests in the xed-bed reactor used here, the volatile yields are limited to a signicant degree by inter-particle diusional eects. Further evidence is provided by the aromatic nature of the oils, especially at 450 and 520 C (Table 3). In fact, both the concentrations of phenolic and polycyclic groups containing predominately two

Fig. 1. Hydropyrolysis product yields for cellulose as a function of temperature with a hydrogen pressure of 0.5 MPa.

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rings increase with temperature (Table 3) although the increase for the latter is much more pronounced (Table 3). Although aromatisation reactions are symptomatic of conversions being limited by mass transfer, a benecial eect is that these are probably part of the sequence of reactions that result in oxygen removal with the oils obtained at 450 and 520 C having considerably lower oxygen contents than their counterparts from fast pyrolysis. Table 4 lists product yields as a function of pressure for the tests at 2.5, 5.0, 7.5 and 10 MPa. For purposes of comparison, the test conducted at 0.5 MPa with the much higher gas velocity is also included. It should be emphasised that not all the water is trapped with mass and oxygen balances both revealing that the water yields are lower than predicted. Raising the hydrogen pressure from 2.5 to 10 MPa, decreases the char yield by ca. 10%, but the oil yield rst decreases and then increases with the oil yields at 0.5 and 10 MPa being similar. Albeit relatively small, the hydrocarbon gas yields increase linearly with increasing pressure. Although carbon dioxide and carbon monoxide were not measured here, increasing hydrogen pressure is also likely to promote their formation through decarboxylation reactions. The apparently non-systematic trend in oil yield arises because any increase in oil yield in terms of greater carbon conversion (i.e. reduced char yield) is being countered by increased hydrodeoxygenation from the bio-oil. Indeed, the oxygen content of the primary oil was reduced by over 10% to below 20% as the

pressure was raised to 10 MPa (Table 4). In going from 2.5 to 10 MPa, it is estimated that the conversion expressed on the basis of the initial carbon increased by ca. 15%. This is roughly divided between 10% to the oil (note similar oil yields, but the carbon content of the 10 MPa oil is 74 compared to 64%, Tables 2 and 4) and 5% to the hydrocarbon gases. A lower char yield was obtained in the test at 0.5 MPa with the higher gas velocity compared to that at 2.5 MPa with the lower gas velocity (Table 4). This, and the fact that increasing the ow rate by a factor of 4 reduced the char yield from 18 to 13% provide further evidence that the yields are mass transfer limited to a signicant extent in the pressure series. However, as discussed earlier, this appears to have a benecial eect on oxygen removal. The iron sulphide catalyst decreased the char yield by between 9 and 15% (Tables 5 and 6) and at the highest pressure used (10 MPa), it approaches zero, corresponding to a conversion of 100% for both cellulose and the two biomass samples investigated. The catalyst also reduced the oxygen contents of the oils with the lowest content of 11% being achieved at 10 MPa with the faster heating rate (Table 2). However, there is still some oxygen remaining bound to aliphatic carbon (Table 3). As with hydrogen pressure alone, the catalyst counters the inuence of inter-particle mass transfer in reducing

Table 3 1 H NMR data for the cellulose bio-oils Hnon-a Hb 19 25 30 29 35 35 36 39 37 33 37 36 H-OCHnc 49 53 40 37 20 20 20 15 17 22 17 4 Hphd 8 7 9 10 13 13 14 14 12 9 10 10 16 7 Hare 4 2 4 5 12 7 12 12 17 10 12 14 13 7

Table 2 Elemental compositions of the cellulose bio-oils C (%) Temperature series 300 C 350 C 400 C 450 C 520 C Pressure series 2.5 MPa 5.0 MPa 7.5 MPa 10.0 MPa FeS catalyst 2.5 MPa 5.0 MPa 10.0 MPa H (%) O (%)a H/C atomic ratio 1.11 1.12 1.11 1.14 0.98 0.94 0.98 0.98 0.96 1.10 1.06 1.04 1.04 1.15 O/C atomic ratio 0.50 0.48 0.44 0.44 0.38 0.36 0.27 0.24 0.20 0.24 0.19 0.11 0.34 0.29

56.7 57.6 59.3 59.3 62.7 64.1 69.1 71.2 74.2 71.1 74.4 81.4

5.2 5.4 5.5 5.6 5.1 5.0 5.7 5.8 5.9 6.5 6.6 7.1

38 37 35 35 32 31 25 23 19.9 22 19 11.5

Temperature series 300 C 350 C 400 C 450 C 520 C Pressure series 2.5 MPa 5.0 MPa 7.5 MPa 10.0 MPa FeS catalyst 2.5 MPa 5.0 MPa 10.0

20 14 17 19 20 25 18 20 17 26 24 36

Slow heating rate (5 Cmin1) at 10 MPa Without FeS catalyst 10 40 21 With FeS catalyst 23 40 23
a b c d e

Slow heating rate (5 C min1), 10 MPa Without FeS catalyst 64.7 5.6 29.7 With FeS catalyst 67.2 6.4 26.4
a

Calculated by dierence.

Aliphatic H not adjacent to an aromatic ring or oxygen (CO single bond), 02.0 ppm. Other aliphatic H, 23.4 ppm. Aliphatic H adjacent to oxygen, 3.46.5 ppm. Aromatic H in single-rings including phenols, 6.57.3 ppm. Aromatic H in two or more aromatic rings, 7.39.0 ppm.

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conversions, but still promotes hydrodeoxygenation. When an extremely slow heating rate was employed (5 C min1), a conversion of 100% was achieved at 10 MPa with the catalyst (Table 5). However, the oxygen contents of the oils with and without catalyst were considerably higher than their counterparts obtained with the faster heating rate (Table 2). This was consistent with the oils obtained with slow heating still containing a high proportion of aliphatic carbon bound to oxygen (Table 3). Thus, it appears that volatiles can escape at considerably lower temperatures with slow heating that limits the level of hydrodeoxygenation that can be achieved in single stage hydropyrolysis. Table 6 indicates that the catalyst also decreased char yields for the eucalyptus wood and sugar can bagasse samples by comparable levels to the cellulose sample. Although 1H NMR indicated that the oils became increasing more aromatic as more oxygen was removed with increasing hydrogen pressure (Table 3 and Fig. 2), the increase in hydrogen pressure actually decreases the overall extent of aromatisation that occurs (Rocha et al., 1996, 1998). This is a consequence of the higher gas and lower char yields obtained (Table 1 and Fig. 1). 3.2. Two-stage tests Earlier studies for coals (Bolton et al., 1989) where two-stage hydropyrolysis with a commercial Ni/Mo

hydrotreating catalyst gave rise to light distillates with low heteroatom contents and this suggested that, although structurally quite dierent, a similar outcome in terms of oxygen removal could be achieved for biomass. A lightly coloured oil was obtained from cellulose at the highest pressure employed. Table 7 indicates that the oil obtained at 10 MPa contains about half the amount of oxygen as its single stage counterpart (noncatalysed). Although the oxygen content is not too dissimilar to that of the single stage oil obtained using the FeS catalyst. The two stage oil has a signicantly higher H/C ratio. In fact, under the second stage conditions used here with quite a low catalyst to oil ratio, it appears that the phenolic and the other more stable oxygen functionalities have only been partially removed. Therefore, the use of more catalyst in the second stage should give rise to oils with much lower oxygen contents as can be obtained in traditional hydroteating in the liquid phase and with revaporised oil (Churin et al., 1988). Reducing the pressure from 10 to 2.5 MPa gave rise to more highly coloured two-stage oils as their oxygen contents increased (Table 8). The comparisons presented in Table 8 indicate that, under the conditions employed here, the catalyst is only highly eective for hydrodeoxygenation at pressures above 5 MPa. FTIR has revealed qualitatively that concentrations of carbonyl/carboxyl groups were still high in the two-stage products obtained at 2.5 and 5.0 MPa (Rocha et al., 1998). Although the two-stage

Fig. 2. 1H NMR spectrum of the bio-oil obtained at 400 C using a hydrogen pressure of 0.5 MPa.

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products have not been extensively characterised, the major constituents identied by GCMS include cycloalkanes, alkylbenzenes with alkyl phenols in the material boiling above ca. 200 C. The level of carbon deposition on the catalyst (cf. 1 to >5% C on catalyst) was much less than found previously for coal tars that are much richer in polyaromatic species (Bolton et al., 1989). Thus, there is hardly any loss of carbon from the oil during the second stage. This is the major drawback with HZSM zeolite in that much of the carbon is deposited on the catalyst, albeit much as soluble high molecular mass species (Pindoria et al., 1998). Further, the improvements obtained in oil quality at moderate hydrogen pressures with HZSM-5 (up to 4 MPa) are much less pronounced than obtained here with the commerical hydrotreating catalyst where higher pressures (>7.5 MPa) are essential to achieve a signicant level of oxygen removal. 3.3. General considerations As mentioned in the introduction, xed-bed reactors would clearly not be considered for scale-up to pilot
Table 4 Product yields from cellulose as a function of pressure for the single-stage hydropyrolysis experiments at 520 C Pressure (MPa) 0.5 2.5 5.0 7.5 10.0
a b a

plant operations, but the information obtained is relevant particularly to uidised-beds that have operated at pressures up to ca. 7 MPa for oil shales (Roberts et al., 1995). Given that much more rapid heating occurs in uidised-beds, the same level of hydrodeoxygenation is anticipated to occur as achieved here in single stage hydropyrolysis (Roberts et al., 1995). Clearly, a

Table 6 Comparison of hydropyrolysis product yields for cellulose, eucalyptus wood and sugar cane bagasse at 520 C and 10 MPa Feedstock/heating rate ( C min1) Catalyst (Fe) Product distribution (% daf basis) Char Cellulose 5 300 5 300 Eucalyptus wood 5 300 5 300 Sugar cane bagasse 5 300 5 300 Bio-oil C1C4 gases 5 5 3 6 5 7 7 6 7 7 4 8

No No Yes Yes No No Yes Yes No No Yes Yes

16 13 <1 5 16 20 <1 17 15 21 <1 10

38 37 52 45 40 37 62 44 40 41 52 48

Char yield (%) 18 25 25 22 18

Bio-oil yield (%) 39 35 28 31 37

Water (%) 25 26 33 30 28

HC gas yield (C1C4) (%)b 1.0 2.8 2.4 2.7 5.2

Hydrogen gas velocity was greater by a factor of 5 than for the other experiments at the higher pressures (see Experimental). HC C1C4 hydrocarbons.

Table 7 1 H NMR data and elemental compositions for the cellulose bio-oils obtained at 10 MPa and 520 C Single-stage Single-stage Two-stage without with FeS with Ni-Mo catalyst catalyst catalyst Hnon- (02 ppm)d H (23.4 ppm)c H-OCHnc (3.46.5 ppm) Harl (6.57.3 ppm)a Har2 (7.39 ppm)b C (%) H (%) O (%) by di. Atomic H/C
a b c d

Table 5 Yields for the single stage hydropyrolysis tests on cellulose with the FeS catalyst Experimental conditions Char yield (%) Bio-oil yield (%) 57 55 45 Water (%) Gas yield (C1-C4) (%) 5 6 6 5 3

Fast heating rate with FeS 2.5 MPa 9 5.0 MPa 7 10.0 MPa 4

n.d.a 20 28

17 37 17 12 17 74.2 5.9 19.9 0.96

36 36 4 10 14 81.4 7.1 11.5 1.04

38 40 4 9 9 81.9 8.3 9.8 1.21

Slow heating rate (5 Cmin1) at 10 MPa Without FeS 16 37 21 With <1 52 21
a

n.d.=Not determined.

Har1=single-rings including phenols. Har2=two or more aromatic rings. H-OCHn=aliphatic adjacent to oxygen. H=aliphatic adjacent to aromatic ring. Hnon-=other aliphatic hydrogen not adjacent to an aromatic ring or an oxygen.

J. Dilcio Rocha et al. / Organic Geochemistry 30 (1999) 15271534 Table 8 Elemental compositions of the bio-oils from two-stage (TS) and single stage (SS) hydropyrolysis tests on cellulose at 520 C Pressure/MPa C TS 2.5 5.0 7.5 10.0
a

1533

% daf basis H SS 64.1 69.1 71.2 74.7 TS 6.3 7.0 7.7 8.3 SS 5.0 5.7 5.8 6.3 Oa TS 31.7 22.6 14.4 9.8 SS 30.9 25.0 23.0 19.0 Atomic H/C ratio TS 1.22 1.19 1.18 1.21 SS 0.94 0.99 0.98 0.95 Atomic O/C ratio TS 0.38 0.24 0.14 0.09 SS 0.36 0.27 0.24 0.20

62.0 70.4 77.9 81.9 By dierence.

drawback with hydropyrolysis is the need to generate the process hydrogen via steam gasication. However, even when oxygen can be removed hydrothermally, there are drawbacks in that much of the carbon is lost as carbon dioxide (30% yield in the Shell HTU process, Goudriaan and Peferoen, 1990). In terms of second stage upgrading, the performance of commercial hydrotreating catalysts with respect to giving greater oxygen removal and lower carbon losses as catalyst deposits would appear to be superior under hydrogen pressure to that of HZM-5 (Pindoria et al., 1998). Indeed, judging the performance of hydrotreating catalysts with coal tars (Bolton et al., 1989) and bio-oils (Churin et al., 1988), considerably higher levels of oxygen removal should be possible if higher catalyst to oil ratios are employed than used in this investigation.

Acknowledgements J.D.Rocha thanks FAPESP (026260/97) for a scholarship. The authors thank the CTC (Copersucar) and ESALQ in Brazil for providing the sugar cane bagasse and eucalyptus wood samples, respectively.

References
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4. Conclusions Single stage hydropyrolysis at relatively moderate pressures (ca. 10 MPa) is able to promote the hydrodeoxygenation of primary bio-oil to give oils containing about half the amount of oxygen as those from conventional pyrolysis. In a xed-bed, the extent of hydrodeoxygenation increases as the heating rate is raised from 5 to 300 C min1, but the overall conversion decreases. The combination of slow heating and an eective dispersed catalyst gives conversions of 100% for the biomass samples investigated at a pressure of 10 MPa. For the two-stage oils analysed, the H/C ratios were higher and O/C ratios smaller compared to their single stage counterparts with the reductions in oxygen contents becoming more pronounced with increasing pressure. This laboratory-scale assessment is useful for considering the design and operation of steady-state reactors, such as uidised-beds, that would have the capability to hydrotreat the primary bio-oils in the vapor phase to generate distillates compatible with existing hydrocarbon-based transportation fuels.

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