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Rapeseed residues utilization for energy and 2nd generation biofuels

A. Zabaniotou *, O. Ioannidou, V. Skoulou
Chemical Engineering Department, Aristotle University of Thessaloniki, Un. Box 455, 54124 Thessaloniki, Greece Received 24 June 2007; received in revised form 28 August 2007; accepted 4 September 2007 Available online 29 September 2007

Abstract Lignocellulosic biomass is an interesting and necessary enlargement of the biomass used for the production of renewable biofuels. It is expected that second generation biofuels are more energy ecient than the ones of rst generation, as a substrate that is able to completely transformed into energy. The present study is part of a research program aiming at the integrated utilization of rapeseed suitable to Greek conditions for biodiesel production and parallel use of its solid residues for energy and second generation biofuels production. In that context, fast pyrolysis at high temperature and xed bed air gasication of the rapeseed residues were studied. Thermogravimetric analysis and kinetic study were also carried out. The obtained results indicated that high temperature pyrolysis could produces higher yields of syngas and hydrogen production comparing to air xed bed gasication. 2007 Elsevier Ltd. All rights reserved.
Keywords: Rapeseed residues; Biofuels; Pyrolysis; Gasication; Kinetics

1. Introduction Directive 2003/30/EC of the European Parliament and the Council of 8 May 2003 aims at promoting the use of biofuels or other renewable fuels to replace diesel or gasoline for transport in each Member State, with a view to contributing to objectives such as meeting climate change commitments, as well as promoting environmental-friendly security of supply and renewable energy sources. In this context, Member States should ensure that a minimum share of biofuels or other renewable fuels is placed on their markets and, to that eect, they shall set national indicative targets. However, the rst generation biofuels seem to create some scepticism to scientists. There are concerns about environmental impacts and carbon balances, which set limits in the increasing production of biofuels of 1st generation. Additionally, both biodiesel and bioethanol are expensive

Corresponding author. Tel.: +30 2310 99 62 74; fax: +30 2310 99 62 E-mail address: sonia@cheng.auth.gr (A. Zabaniotou).

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options for climate mitigation as compared to biomass for heat and power generation. Bomb et al. [1] claimed that environmental impacts associated with energy crops require sustained investigation since the environmental impacts and carbon balances of biofuels depend on feedstocks and the way they are farmed, processed and distributed. Biodiesel and bioethanol in the EU has been calculated to result in 1570% greenhouse gas savings when compared to fossil fuels [2], while bioethanol from Brazil results in over 90% greenhouse gas savings [3]. Frondel et al. [4] based on a survey of recent empirical studies, found that the energy and greenhouse gas balances of rapeseed-based biodiesel is clearly positive but it appears to be unclear whether the overall environmental balance is also positive. Additionally, they claimed that biodiesel is not a cost-ecient emission abatement strategy. Thus, for the abatement of greenhouse gases, they recommend more ecient alternatives based on both renewable and conventional technologies. Besides, the agricultural rapeseed production capacities for example in Germany, which is the country with the highest rapeseed production, are almost exhausted

0016-2361/$ - see front matter 2007 Elsevier Ltd. All rights reserved. doi:10.1016/j.fuel.2007.09.003

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according to Bockey et al. [5]. During the recent years, Germany and Austria have been leading in the substitution of diesel with biodiesel and rapeseed-oil biofuels, while France, Spain and Sweden mainly substitute petrol with bioethanol. The market penetration of biofuels additionally has been driven by increasing costs for crude oil and fossil fuels. However, the increasing production clearly shows its rst limits. In Germany, during 2005, about 1 million of hectares were used for the cultivation of rapeseed for the production of biodiesel [6]. To a certain extend the increasing demand may be satised by importing feedstock or biodiesel but, in the long term, it is necessary to enhance the diversity of raw materials [6]. Therefore, it seems that energy crops are technically possible but that no single solution exists to cover every situation [7], pointed out that from a wider viewpoint, choices must maximize income, yield, quality characteristics, energy and technical tool savings, manpower, eects on soil, air and environment both at local and regional levels. In order to balance the cost of crops to biofuels options, it seems obvious that an aspect, which must be studied with particular care, is the economic exploitation of energy crops by-products determined by multi-functionality of many species [7] Electricity generation on the basis of crop residues for example, might be a relatively cheaper alternative in terms of abatement cost and an alternative income [4]. It seems then evident that an understanding of the relationship between production of grain and production of the biomass feedstock is important to support the emerging bioenergy technologies. Hoskinson et al. [8] have used a model the DSS4Ag in order to begin to understand the relationship between the production of grain and the production of biofeedstock, from the standpoint of the economics of simultaneously producing both. Many other computer models of bioenergy systems have been, also, developed. But none of them considered the economics of simultaneous production of an agricultural crop and its crop residue biomass. Summarising, it is obvious that: (1) Besides the biofuels derived from oil crops, grain and sugar crops, which are commonly called biofuels of the 1st generation, lignocellulosic feedstock can oer the potential to provide novel biofuels, the biofuels of the second generation (Table 1). (2) Electricity generation on the basis of crop residues, might be a relatively cheap alternative in terms of abatement costs and an additional alternative income source and employment support measure for the agricultural sector. In that respect, the present study being part of a research program aiming at the integrated utilization of rapeseed into Greece, attempting to contribute in the above problematic for the biodiesel production and parallel use of the residues for energy and 2nd generation biofuels produc-

Table 1 First and second generation biofuels from biomass First generation biofuels Type Bioethanol Biodiesel (FAME/ FAEE) Pure vegetable oils Biogas Bio-ETBE Method-Source Conventional From energy crops From waste Cold pressed Conventional From energy crops Second generation biofuels Type Bioethenol BTL Methanol DME Biodiesel Biohydrogen MethodSource Lignocellulosic Lignocellulosic Synthetic fuels Lignocellulosic NExBTL Lignocellulosic

tion. Experiments that took place in Mediterranean region (Greece, Italy, Spain) under the EU program during the last decades showed positive results [9]. In Greece, rapeseed can be cultivated as a winter or spring annual crop and at the moment, its cultivation has been conducted on experimental and demonstration scale, with the rst attempt of cultivation at real farmers level through the proposed research program. The ability to grow at low temperatures, compared to the other oleiferous crops grown in Greece, is the most important feature of rapeseed cultivation. The present research was conducted towards thermochemical conversion of rapeseed residues by means of high temperature pyrolysis and gasication for the production of a gas suitable for further energy production exploitation or syngas production for second generation biofuels production. Thermogravimetric analysis was also carried out for kinetic purposes. 2. Thermochemical conversion There are two basic procedures to transform solid biomass into liquid or gaseous biofuels for the second generation biofuels production (Fig. 1). One aims at the thermochemical conversion of the total biomass into a high caloric value synthesis gas with subsequent production of various liquid and gaseous fuels. The other is to transform

Fig. 1. Biofuels production from lignocellulosic feedstock.

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parts of the high moisture feedstock material into products (biogas) with a high content of energy by microbiological fermentation. This can be attributed to the specic conversion of the polysaccharides into alcohols, like bioethanol or biobutanol, or the conversion of digestible plant biomass into biogas, which can be puried to biomethane to be additionally supplied to the natural gas grid. As opposed to the biofuels of the rst generation, both pathways aim to complete integrate the utilization of biomass for energy production purposes. Large by-products quantities that are driven out of the process and left unexploited taking out of consideration of their attractive energy content (lignocellulosic biomass) could be an interesting and necessary unexploited energy container of the biomass used for the production of renewable biofuels. New technologies of releasing this spare energy content has not been applied or if so, just in pilot-plant scale. As no data are available for large-scale production, it is hard to get reliable cost estimates or to perform life cycle assessments for the various pathways [6]. Nevertheless, although a lot of eort has been focused into converting the lignocellulosic by-product materials to fermentable sugars and oils, this is unlikely to ever become a practical means of utilization of those materials due to the intractable and complex nature of lignocellulose, which contains relatively large amounts of biochemically resistant lignin. This gives the go-ahead to the thermochemical processes as the means of exploiting these materials. Converting the lignocellulosic by-products materials into energy through the thermochemical processes emerges as the best way, as it maximizes production of elemental carbon. The enormous increase in the production of rst generation biofuels such as ethanol starting with corn grain as a raw material and biodiesel from rapeseed, not only gives a little or no net production of energy overall from this approach, it is also causing distortions in the markets for supplying food products. Crop lignocellulosic by-products, on the other hand, produced in massive quantities worldwide and are readily obtained because it has to be handled anyway in the acquisition of grain [10]. Nevertheless, thermochemical processing of crop byproduct residues, found in massive amounts of lignocellulose material, has not received the attention that it deserves. There are few literature data concerning the exploitation of rapeseed residues for energy production purposes, although they present very high oileic content. Haykiri-Acma and Yaman [11] studied rapeseed through TG analysis under various dynamic atmospheres, showing the importance of the reactive atmosphere. Rapeseed stalks and straws were, also, studied from Karaosmanoglu et al. [12] using a slow pyrolysis, tubular reactor in order to study the liquid product. Additionally, Onay and Kockar [1315] studied rapeseed pyrolysis for bio-oil production in a xed bed reactor. Finally, Predel and Kaminsky [16] studied rapeseed in a uidized bed reactor in order to examine if the valuable contents of this grain can be obtained under an inexpensive and simpler way.

3. Experimental 3.1. Rapeseed residues The raw material used for experimentation was solid residues, remaining on elds from rapeseed cultivation in real elds being cultivated by Pioneer Hi-Bred Hellas S.A. in the region of Western Macedonia in Greece. Prior to use, samples washed from dust, grounded to desirable particle size (by a small laboratory scale mill) and sieved to powder of <1 mm diameter for enabling running the tests. A Thermonnigan, CHNS, EA 1112 elemental analyzer was used to estimate the ultimate analysis, while high heating value of rapeseed residues was calculated by the following equation [17]: HHV 0:3491 C 1:1783 H 0:1005 S 0:1034 0:0151 N 0:0211 A MJ kg1 1

The proximate analysis was performed by thermogravimetric analysis (TGA) while monitoring the weight change that occurs while the sample heating, the fraction of volatile components was determined. The moisture of rapeseed was also determined by an overnight heating at 105 C as ASTM methods. There were three main dierent steps in TGA: drying, devolatilization under an inert atmosphere and combustion in oxygen [18]. The measurement was carried out under air or inert atmosphere, such as helium or argon, and the weight is recorded as a function of increasing temperature. The instrument used in this study was a PerkinElmer thermogravimetric analyzer TGA 6, in which the sample was heated with air according to the following temperature prole: heating started at 30 C with a slow rate of 10 C min1 and stabilized at 100 C for 20 min. Then, with a rate of 20 C min1, the temperature increased up to 600 C and remained constant for other 20 min. And nally the temperature of 900 C was achieved with a rate of 20 C min1 t. From the TGA curve (Fig. 2) it is clear that there are three stages indicating the mass loss prole. The rst weight loss phase, up to 200 C maximum, during the preheating phase, was due to the water layer evaporation from minerals. During the second weight loss phase, lighter volatiles were burnt between 200 and 320 C. This step was identied as hemicellulose and cellulose decomposition. For temperature range of 400500 C, char oxidation was occurred. Lignin, which expresses the heavier volatiles, started decomposing at about 150 C and continued up to 900 C. So the char oxidation and the lignin decomposition happened simultaneously. The maximum peak of lignin formed at 450 C [19,20]. What remaining at the end of the char oxidation (900 C) phase is ash. The proximate and ultimate analysis of rapeseed residues is depicted in Table 2. Table 3 reports a comparison of rapeseeds HHV literature data with present study showing a good agreement.

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Fig. 2. Decreasing CO2 emissions in function to the C/H ratio in fuels.

Table 2 Ultimate and proximate analysis of rapeseed residues Proximate analysis (% w/w, dry) Rapeseed residues Moisture Ash Fixed carbon Volatiles Molar type
a

Ultimate analysis (% w/w) C H Oa N 44.52 5.53 49.37 0.58

placed after the solid carbon regarding the decrease of CO2 emissions as a function to C/H ratio of the fuel, even thought it advantages in all other environmental aspects. 3.2. Fast pyrolysis in a captive sample reactor The experimental apparatus for fast pyrolysis performance included a wire mesh sample reactor consisted of two electrodes, an electrical circuit, a water cooling coil, a trap for moisture, two lters for liquid hydrocarbons, a system for gas collection and a system of gas analyses (GC). The sample was weighted approximately $0.3 g and placed in an envelope of stainless steel 100 mesh. A thermocouple inside the sample, connected with a computer through program, provided the relation between tem-

5.86 3.95 23.04 73.01 C1H1.49O0.83N0.01

Calculated by dierence.

Chemical formula of the rapeseed solid residues was based on their ultimate analysis and was found to be: C1H1.49O0.83N0.01. Based on the chemical formula of rapeseed residues it can be seen at Fig. 3, rapeseed residues are

Table 3 Comparison of literature data over elemental analysis and HHV calculation of rapeseed residues (where daf:dry ash free) C 41.1 daf 45.17 df 44.52 df H 6 daf 5.15 df 5.53 df N 5.1 daf 0.75 df 0.58 df O 47.8 42.92 49.37 HHV (MJ kg1) 19.4 17.64 16.8 HHV calculation ASTM n.a. Calculation [17] Reference [11] [12] Present study

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was calculated by an external standard method. Gas composition and yields were resulted based on a linear relationship between the concentration and area measured by the program. The produced gas composed mainly by CO, CO2, H2, CH4, and less by light hydrocarbons (C2H4 and C2H6). The GC system comprised two detectors, where thermal conductivity detector (TCD) used for CO, CO2, H2, CH4, C2H4 and C2H6 analysis, and the ame ion detector (FID) for CH4, C2H4 and C2H6. 3.3. Gasication in a xed bed reactor The gasication experiments, with air as a gasication medium, performed in a batch, laboratory scale, xed bed reactor, as shown in Fig. 5. The experimental facility consisted of ve main parts: (a) the atmospheric downdraft xed bed reactor (b) the air providing section, (c) the gas cleaning and sampling section, (d) the temperature control section, and (e) a gas oine analysis section. The reactor was constructed from a 316-stainless steel tube and is surrounded by an individually controlled electric heater (heating rate $15 C min1) that aims at supplying heat for start up and counter heat losses during reactors operation. The volume of the reactor is 63 cm3 and biomass feeding is batch, performed by hand after appropriate dismantling of the reactor tube. The temperature is being controlled by a K-type thermocouple placed vertically inside the reactor. Air at ambient conditions is introduced into the reactor moving downwards to the xed biomass particles. During experimentation, produced gas exited the reactor from the top and passed through a cold trap (ice), a

Fig. 3. TGA of rapeseed residues.

perature and time (heating rate). Fig. 4 shows the experimental set up of fast pyrolysis [21]. The experiments were carried out in a temperature range of 480790 C, with a heating rate of 48 C s1, under atmospheric pressure and helium atmosphere. The reaction products included char, gas and volatile compounds. The produced gas was analyzed in a gas chromatograph (6890N, Agilent Technology). The two columns used were Plot Q and Molesieve, with helium as carrier gas. The temperature prole of the gas chromatograph was isothermal, at 40 C, and the retention time of the whole analysis was 38 min. The standard gas mixture used for the calibration of the method was CO, CO2, H2, CH4, C2H4 and C2H6 1% (v/v) balanced in helium and the volume concentration

Fig. 4. Schematic diagram of experimental set-up of the laboratory captive sample reactor.

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heating rate of 48 C s1. It was observed (Figs. 68) that by increasing the temperature of the reactor, released volatiles from biomass particles, and increased the yield of the gaseous products, while decreased char yield. This trend becomes more perceptible above 650 C. The higher gas yield in this study was 26.79 wt% at 790 C, while the maximum char yield reached 28.61 wt% at 480 C. Figs. 912 reveal the eect of temperature on pyrolysis gas composition. Imposing higher temperatures the H2 percentage increased and CO2 decreased. The amounts of CO

Fig. 5. Schematic diagram of experimental set-up of the laboratory xed bed gasier.

glass wool lter and a moisture trap (silica gel) and nally was collected in a bottle from were a sample was taken in order to proceed the gas composition analysis. At the start-up of each experimental run, a calculation of the air ow rate was simply determined using a chronometer and a volumetric cylinder. Reactor was placed vertically into the furnace and heating was turned on by setting the controllers at the selected operating temperatures of 750950 C in 50 C increments. After the reactor was placed inside the furnace, the bed temperature controller was set on and the air ow was, also, turned on. When the bed temperature reached the desired levels, the experiment stopped. Typically, it took almost 20 min for each test to reach the end. A gas sample was taken and when the reactor was cooled down the char residue was weighted. Under normal conditions each experiment was repeated two times, after thorough cleaning for eliminating possible memory eects and tar fouling dangers and the results showed a good agreement. After the experiment stopped clean and dry gas was sampled using airtight gas sampling bags and immediately analyzed on a gas chromatograph (Model 6890N, Agilent Technologies), with helium as carrier gas, to detect permanent gases (H2, CH4, CO, CO2, C2H4 and C2H6). 4. Results and discussion 4.1. Temperature eect 4.1.1. Fast pyrolysis experiments Pyrolysis products are gaseous, liquid and solid. Yields of these products are, generally, determined by dierent factors, among which temperature is of high importance. Pyrolysis experiments were carried out in a captive sample reactor under the temperature range of 480790 C and a

Fig. 6. Comparison of the produced char via pyrolysis and gasication.

Fig. 7. Comparison of the produced gas via pyrolysis and gasication.

Fig. 8. Comparison of the produced liquids via pyrolysis and gasication.

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Fig. 12. Comparison of the produced CO2 via pyrolysis and gasication. Fig. 9. Comparison of the produced CO via pyrolysis and gasication.

The low heating value of the gas was calculated by using the following equation [22,23]: LHV 30:0 CO 25:7 H2 85:4 CH4 151:3 Cn Hm 4:2 KJ MJ m3 2

Fig. 10. Comparison of the produced H2 via pyrolysis and gasication.

The LHV of the gaseous product was not really aected by temperature increases. It was uctuated around 14 MJ m3 (Fig. 13). The highest LHV observed at 620 C where CO and CH4 reached their maximum yield and at 790 C because of the high H2 content. According to Yang et al. [22] such gas belongs to the medium level gaseous fuels and could be directly used in engines, turbines and boilers for power production. Concerning char analysis, the amount of carbon did not show particular aection with temperature, while its hydrogen content decreased (Fig. 14) as temperature increased. The high and low heating values of char are depicted in Fig. 15. It is obvious that there is not much dierence between the two heating values and there are almost constant with temperature. According to the regulation norms for domestic briquettes [24] (Fig. 14), the pyrolysis char has a trend to fall in category B, which represents briquette production with carbon content 69% before agglomeration. As shown in Fig. 14, the maximum carbon content (65.63%) in pyrolysis experiments was found in char produced at 790 C.

Fig. 11. Comparison of the produced CH4 via pyrolysis and gasication.

and CH4 were not aected considerably with temperature ranges. The component with the highest yield in pyrolysis gas was carbon monoxide reaching 44.1% (v/v) at 620 C, while hydrogen reached 45.8% (v/v) at 790 C. Carbon dioxide reached $11% (v/v), while methane gave a percentage of 13.62% (v/v). Traces of ethylene and ethane were also determined but in very low quantities.

Fig. 13. LHV of pyrolysis and gasication gas.

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Fig. 14. Eect of temperature on the wt% C and wt% H of the pyrolytic char in the captive sample reactor, C/H ratio and categories A and B of regulation norms for xed carbon of charcoal according to Schenkel and Guyot [24].

4.1.2. Fixed bed gasication experiments The main gasication product was the producer gas. Pyrolysis experiments were carried out in a captive sample reactor under the temperature range of 750950 C and a

heating rate of $15 C s1. It was observed (Figs. 68) that by increasing the temperature of the reactor increased the yield of the gaseous products, while char, liquid yield decreased. The higher gas yield in this study was 27.19 wt% at 950 C, while the lower char and tar yield reached 20.06 and 27.54 wt% at 950 and 800 C, respectively. Temperature eect over the producer gas quality is also depicted in Figs. 912, under steady oxidizing conditions. Fig. 9 indicates that CO production reached a maximum, at the highest gasication temperature, of 24.48% (v/v). From Fig. 10, it can be clearly seen that H2 concentration increased with temperature and reached a maximum of 28.77% (v/v) at 900 C, while the content of CH4 (Fig. 11) showed an almost stable production trend of $8% (v/v). The above trends could be simply explained as it is widely known that high temperatures favour the reactants in exothermic gasication reactions, while in endothermic reactions favour the products, respectively. Therefore, as gasication is a complex process occurring through a number of endothermic and exothermic reactions that strengthened or became weaker, respectively, with increasing

Fig. 15. LHV of pyrolysis gas and char.

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temperature the evaluation of each gaseous component are explained. As it concerns LHV of gasication gas LHV (Eq. (2)) it increased with temperature as depicted in Fig. 13. LHV was estimated that follows a slight increasing trend as temperature increases reaching at high temperature 10.13 MJ m3.This could have a strong relationship to the fact that higher temperatures were more favourable for raising hydrogen and CO percentage in the gaseous mixture and as a result better heating value gas was produced. 4.1.3. Comparison of pyrolysis and gasication results Comparing the two thermochemical methods it can be said that high temperature fast pyrolysis showed generally better results than gasication. Although the gas yield was higher during the xed bed gasication (Fig. 7) the gas was classied as a low heating value gas, while the one obtained from the fast pyrolysis as a medium heating value gas (Fig. 13). This could be attributed to the fact that as air was used in the gasication, slight oxidizing reactions to CO2 and H2O products were inevitable, comparing to the completely inert atmosphere where high temperature pyrolysis took place and resulted in volatiles release. The lower amounts of CO and higher amount of CO2 in gasication producer gas, in comparison to pyrolysis gas, could be an also evidence of the fact that probably gasication at even lower oxidizing conditions would led to more CO production and even more reduced CO2 emissions. Temperature increase had an advantageous eect on syngas (CO + H2) yield, as well. At all gasication temperatures (% v/v) percentages of syngas was lower that that produced by high temperature pyrolysis (Fig. 16), but temperature increases generally seemed to maximize syngas production in both processes. Besides, a gas (from either pyrolysis or gasication) with a yield of (H2 + CO) (% v/v) >0.8 has a strong reducing power and could be used as a reducing medium in making iron sponge (porous iron), a raw material in electric arc fur-

Fig. 17. Comparison of the H2/CO and CO/CO2 ratios via pyrolysis and gasication.

Fig. 16. Comparison of the produced syngas via pyrolysis and gasication.

naces [25]. The produced syngas from pyrolysis, in the present study, showed a sum of (H2 + CO) varying around 0.8, which makes it appropriate for reduction medium on the contrary of gasication gas. Studying the eect of temperature on the H2/CO molar ratio (Fig. 17), it would also revealed that the ability to utilize such biogas (1 < (H2/CO) < 2) for chemical syntheses like methanol and pure naphtha production [25], Fisher Tropsh synthesis (ratio $ 2) and even oxo-synthesis processes (ratio $ 1) is evident [26]. In the present study the gasication produced gas showed an almost constant ratio of H2/CO $ 1.2 indicating that this biogas is good not only for Fisher Tropsh synthesis, methanol production, but also, for oxo-synthesis processes. In Fig. 17, the molar ratio CO/CO2 veries the occurrence of CO2 as the main product of oxidation reactions that embodied to gasication process, while in pyrolysis at high temperatures CO production is strongly favoured. The main conclusion from the comparison of the two methods (high temperature pyrolysis vs. gasication of rapeseed residues) is that hydrogen and syngas production are favoured through high temperature fast pyrolysis or alternatively gasication at very small oxidizing conditions, in order to be used in fuel cells and FT technologies, respectively.

A. Zabaniotou et al. / Fuel 87 (2008) 14921502 Table 4 Kinetic parameters of rapeseed pyrolysis T (K) 308373 473593 673773 E (kJ mol1) 12.74 58.50 15.31 k0 (s1) 0.87 64.1 103 2

1501

In the present study, the gasication produced gas showed an almost constant ratio of H2/CO $ 1.2 indicating that this biogas is good not only for Fisher Tropsh synthesis, methanol production, but also, for oxo-synthesis processes. Acknowledgments

5. Kinetics The kinetic parameters, activation energy and frequency factor could be predicted via non-isothermal thermogravimetric technique. Thermogravimetric data were used to derive DTG (derivative thermogravimetry) curve which was used to calculate the activation energy values of rapeseed residues by the method of CoatsRedfern [27]. The initial equation that many researchers use is by the following equation: da K i 1 an dt K i k 0i e
Ei RT

Authors are thankful to European Commission, Greek Ministry of Development-General Secretariat of Research & Technology and Pioneer Hi-Bred Hellas S.A. Company for funding this research under PABET2005 program. They also thank Mr. N. Mariolis and G. Zanakis from Pioneer Hi-Bred Hellas S.A. Company (www.pioneer.com) for providing the rapeseed residues and the laboratory of Chemical Process Engineering for hosting the gasication experiments. Special thanks to Dr. G. Stavropoulos. References

Assuming a single and a rst order reaction (n = 1) the method that Coats and Redfern suggest is expressed by Eq. (2) below      1a E 1 k0R log log log 4 2:303 R T qE T2 where a = (m0 mt)/m0, where m0 the initial mass of the sample and mt the current mass, and q is the heating rate. The Arrhenius kinetic parameters k0, E, were estimated by the slope and intercept of the line. The slope is the amount (E/2.303R) where the activation energy was estimated, and the intercept was the amount log (k0R/qE) where the pre-exponential factor was estimated. Table 4 shows the results of the kinetic parameters. 6. Conclusion In order to balance the cost of crops to biofuels options, it seems obvious that an aspect, which must be studied with particular care, is the economic exploitation of by-products. With respect to the sustainability, it has also to be proved if other pathways with higher energy eciency for the conversion of lignocellulosic biomass exist, e.g. heat and electricity production in heat and power plants. Within the energy sector biomass in stationary applications like power and heat oer best energy eciency and green house gases emission avoidance. The attempt to study thermochemical methods as a way of facing the rapeseed residues as an energy value product, lead to the conclusion that high temperature fast pyrolysis, compared to gasication, indicated the suitability of such thermochemical process in terms of syngas and hydrogen production.

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