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J. Anal. Appl. Pyrolysis 70 (2003) 1 Á/17 www.elsevier.

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Fluidized bed thermal degradation products of HDPE in an inert atmosphere and in airÁ nitrogen mixtures
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F.J. Mastral *, E. Esperanza, C. Berrueco, M. Juste, J. Ceamanos
Department of Chemical and Environmental Engineering, Centro Politecnico Superior, University of ´ Zaragoza, C/Marıa de Luna, 3, 50018 Zaragoza, Spain ´ Received 25 October 2001; received in revised form 17 January 2002; accepted 7 June 2002

Abstract Different processes involving thermal decomposition such as incineration, pyrolysis, gasification or co-combustion are becoming important for energy generation using plastic wastes as combustible materials. The thermal degradation of the material, the product distribution and consequently the economics of the process are strongly influenced by the experimental conditions used. In this work, the thermal degradation of high-density polyethylene (HDPE) has been carried out using a fluidized bed reactor under different temperature conditions. Two types of experiments have been performed, pyrolysis experiments, in which nitrogen has been used as inert gas, and gasification experiments, meaning that the thermal decomposition has been carried out in a nitrogen Á/air mixture with low oxygen concentration. The influence of the operating parameters on the product distribution and gas composition has been investigated using GC and MS/GC for the analysis of the gas, wax and oil fractions obtained. The results obtained show a widely differing product yield in both processes. The main objective of the paper is a comparison of pyrolysis and gasification in terms of the generation of products of high heating value, and the energy requirements for the thermal degradation and production of residues and polyaromatic compounds. An optimum interval of operation temperatures is suggested in order to obtain high yield to gases of high heating values and low yield to PAHs. # 2002 Elsevier B.V. All rights reserved.
Keywords: Polyolefins; Pyrolysis; Gasification; Fluidized bed; HDPE; Polyethylene

* Corresponding author. Tel.: '/34-976-76-2160; fax: '/34-976-76-1879. E-mail address: ceamanos@posta.unizar.es (F.J. Mastral). 0165-2370/03/$ - see front matter # 2002 Elsevier B.V. All rights reserved. doi:10.1016/S0165-2370(02)00068-2

the results of product yields from the degradation of HDPE obtained under pyrolysis and gasification conditions are shown. In other thermal degradation processes. In the latter case. plastics can be recycled for energy recovery. Laboratory scale pyrolysis plant The experimental system used in this work is shown in Fig. such as thermal decomposition kinetics [1 Á/4] or temperature influence on product yields [5 Á/8]. they can replace other fuels in different proportions. environmental activists. When mixed and incinerated with municipal solid wastes. political and social issue that has attracted the attention of researchers.1. [10]. Mastral et al. The bed temperature was measured by a K type thermocouple inside the bed. the energy necessary is supplied by partial combustion of the feed material or the gases produced.J. [12]. 730. Ranzi et al. Given their high calorific value. The HDPE pyrolysis and gasification runs were carried out at bed temperatures of 640. with an inert gas as fluidizing agent. [2]. Introduction The high consumption of polymeric materials means that they are a significant share of solid waste (either municipal or industrial). businessmen. business. and Savage et al. 1. Experimental 2.2 F. One of the materials present in significant quantities in municipal solid waste is polyethylene. The material bed was 0.25 Á/0. [9]. In this work. The pyrolysis of polyethylene has been the subject of numerous studies. The temperature interval used ranges from 640 to 850 8C. fluidized bed reactor 4. and in partial combustion conditions. Poutsma et al. saving primary fossil fuels. Anal. Williams and Williams [8].27 mm silica sand with a static bed depth of 80 mm. politicians. These experimental studies have been carried out in fluidized bed. Fuels derived from specific.8 cm in diameter and 23 cm in height. McCaffrey et al. The reactor was externally heated using an electrical ring furnace. separated plastics and combined with a lignocellulosic fraction can be an important substitute for coal in cement manufacture or for electricity generation in a power plant. Other studies using steam or pyrolysis gas as fluidizing agent have been carried out by Kaminsky et al. [11]. The reaction mechanisms that generate the different pyrolysis products have been considered by Bockhorn et al. . Appl. and the general public. using air and nitrogen as fluidizing agent. The main goal is the study of the influence of the atmosphere in which the thermal decomposition takes place and the temperature on the product distribution and heating value of the generated gas. The study was carried out using a stainless steel. plastics contribute to the safe combustion of the mixture and generate valuable energy. / J. Pyrolysis 70 (2003) 1 Á/17 1. it would be very interesting to compare the yields and the product distributions obtained both in strict pyrolysis conditions. using nitrogen as fluidizing agent. 700. The disposal of this waste has become a technological. In pyrolysis processes. 2. [3].

958 g cm (3.J. the mixtures were used to obtain a similar residential time and air ratio for all experiments. Two types of experiments were carried out. Since different gas yields are obtained depending on the temperature used. Mastral et al. gas flow for feeding was 50% of the total gas flow. HDPE manufactured by HOECHST (HOSTALEN GH 4765). / J. In order to obtain a continuous solid flow into the reactor. A flow of nitrogen was used as carrier gas and fluidizing agent in the pyrolysis experiments. 1. whilst for gas velocities five to seven times the Umf. an important fraction of the total gas flow used in the experiments was used in the feeding process. designated as pyrolysis and gasification experiments. Appl. 780 and 850 8C. Pyrolysis 70 (2003) 1 Á/17 3 Fig. with a density of 0. a softening point of 80 8C and a mean particle size of 0. Experimental system diagram. . For gas velocities three times the minimum fluidization velocity (Umf). gas flow for feeding amounted to 70% of the total gas flow.225 mm was used in this work. Anal. whilst air only was used in the gasification experiments carried out at higher temperatures. The air ratio imposed for all the experiments was in the range of 6Á/7% of the stoichiometric air for HDPE combustion. A flow of either air or air Á/nitrogen mixtures was used as the fluidizing gas in the gasification experiments.F. while the rest (either pure nitrogen in the pyrolysis experiments or a mixture of air and nitrogen in the gasification experiments) was preheated at the reactor temperature before entering the lower part of the fluidized bed. At low temperatures (640 and 700 8C) mixtures of nitrogen and air were used. Some preliminary experiments were carried out in order to determine the fraction of the gas flow necessary for the feeding and the fluidization. Polyethylene was fed continuously into the bed at a rate of 3Á/4 g min(1 using a pneumatic water-cooled feeder in order to avoid the melting of the material before entering the reactor.

Pyrolysis 70 (2003) 1 Á/17 The operation flows used provided a fluidizing gas velocity five to eight times the Umf. weighed and analyzed by GC/MS.J.53 mm )/15 mm. Samples of 1 ml were injected. 50 m)/0.2 cm s (1. Analysis The gas fraction was analyzed by gas chromatography using a HP 5890 series II.9 m)/3 mm packed with 45/60 mesh.4 F. The ion trap detector had a mass range from 32 to 800 amu and was linked to a computer with a Wiley library. Since no components were detected at temperatures over 330 8C. / J. CO and CO2 were determined by the TCD detector whilst the rest of hydrocarbon components from C1 to C6 were detected by the FID. the maximum oven temperature used was 350 8C. The product stream was passed through the cyclone to remove any particulate matter. Appl.32 mm )/0. The gas chromatography mass spectrometry consisted of an HT-5 aluminum clad column. and a molecular sieve 0. with a semi capillary column HPPLOT/Al2O3. using two detectors connected in series: a thermal conductivity detector (TCD) and a flame ionization detector (FID). Part of the flow from the condensers was collected online in a nylon bag for analysis during the experiment. The rest of the flow from the condensers was passed through a silica gel tube in order to retain the remains of waxes or oils. the oil and waxes were first dissolved in tetrahydrophurane (THF). . The residence time of the gas in the reactor had values between 0.1 mm (non polar) with a Tmax 450 8C. This flow was introduced into an online CO Á/CO2 detector and exited the system. where some heavy hydrocarbons were condensed (oil or waxes). 25 m)/0. Mastral et al. Anal. Waxes and oils were collected.81 and 1. The experiments lasted from 20 to 25 min. calculated in each experiment at the bed temperature. Helium was used as carrier gas with a flow rate of 1 ml min (1. the cyclone and the connections between the reactor and the cyclone and between the cyclone and the water condenser. For purposes of analysis. The temperature program was 40 8C for 2 min followed by a heating rate of 5 8C min (1 up to 180 8C. 2.2. with a split mode (20:1).45 s. N2. The high temperature column enabled oven temperatures of 400 8C to be reached ensuring that hydrocarbons up to C60 could be analyzed. The concentration of H2. The smaller fraction was passed through two ice Á/NaCl condensers at (/ 10 8C. and finally 10 min at 350 8C. then an increase up to 350 8C at a heating rate of 10 8C min (1. The exit flow was divided into two fractions: the largest one being passed through silica gel in order to retain the wax and oil carried by the gas in the form of aerosol. The resulting stream of vapors was passed through a cool water heat exchanger at 20 8C. The remaining lighter components were condensed using an ice Á/NaCl bath at (/ 10 8C. taking into account the total gas flow produced and considering the internal volume of the reactor (the sand bed and freeboard). The average Umf of the sand used in the bed was experimentally found to be 2.

5 to 91. for low temperatures the yield to gas increases as the temperature increases in both pyrolysis and gasification experiments.6% at 700 8C. relatively important in gasification experiments carried out at low temperatures.% in pyrolysis and from 54. As can be observed. so slight variations can be observed. yields to wax'/oil are slightly higher in pyrolysis. and for reactor temperatures ranging from 640 to 850 8C. the wax'/oil yields are very similar at the different temperatures studied except at 640 8C at which a higher yield is obtained under pyrolysis conditions.7 wt. The total yields over 100% observed in the gasification experiments are due to the fact that the oxygen fed appears as a part of the products obtained. Mastral et al. The carbon and hydrogen mass balances of the products. These compositions are measured at different moments during the experiment. oil and wax) with temperature is shown in Fig. the yield to gas reaches an approximately constant value in both processes. referring to the mass of HDPE fed.6% at 645 8C and 35. A small amount of char. quite close to 100%. Table 1 shows the yields to the different fractions obtained in the two types of experiments. Anal. the wax'/oil yield was 51. since the total gas flow exiting the system is not measured. this marked increase of the yield to gas ranges from 33.4% at 700 8C. Different observations can be noted: CO and CO2 are obviously not observed in the pyrolysis experiments and the yield to olefins decreases rapidly as the temperature increases. A high quantity of waxes and oils were found in the pyrolysis and gasification experiments carried out at 640 and 700 8C (real temperature). Yields to gas in gasification are higher than in pyrolysis in all temperature intervals studied. the yield to aromatic compounds increases as the temperature increases and similar values are obtained regardless of which gas is used in the experiments. appeared in waxes and oils. .2 to 104. olefins. 2. 3 shows the variation of the yields to the different fractions (gases except CO and CO2. oxygenated compounds and aromatics). The oxygenated fraction.1. Results and discussion 3. The variation of fraction yields (gas. slight variations from 100% are also observed. are also shown in Table 1. not quantified. Fig. Table 1 also shows the main experimental conditions used in the experiments performed: residence time. For higher temperatures. For temperatures in the range of 640 Á/730 8C. this fraction being more abundant in the pyrolysis experiments. For the rest of the temperatures studied. In the pyrolysis experiments. Appl. In the gasification experiments. Pyrolysis 70 (2003) 1 Á/17 5 3.F. decreases down to zero over 730 8C.J. CO Á/CO2.6 wt. / J.% in gasification. In the case of the pyrolysis experiments. Product yields The pyrolysis and gasification of HDPE were carried out in the experimental system previously described using different reactor temperatures. As can be observed. They can be explained taking into account that. As can be seen when comparing pyrolysis and gasification experiments. the yield was 68. in the range of 730Á/850 8C.5% at 640 8C and 39. air ratio and real temperature in the reactor. this mixture presenting a higher viscosity at 640 8C than at 700 8C. the balances are solved using the nitrogen balance and the composition of the different fractions.

% of feed) and component mass balances for pyrolysis and gasification of HDPE Temperature (8C) Process Residence time(s) Air factor Real temperature Gas yield Wax'/oil yield Aqueous phase Hydrogen mass balance Carbon mass balance 640 Pyrolysis 1.0 112 109 730 Pyrolysis 1.5 100 102 Gasification 1.9 6. Pyrolysis 70 (2003) 1 Á/17 Table 1 Product yields (wt.2 90 91 Gasification 0.8 106 101 .J.3 3.45 0 640 33.6 0.2 6.0 102 102 680 Pyrolysis 1.2 103 105 Gasification 1. / J.5 0.7 18 0.6 5.6 2.0 112 109 780 Pyrolysis 0.2 9.3 0 700 69. Anal.1 645 54.8 778 104.3 0 730 91.6 0 111 112 850 Pyrolysis 0.4 4.7 35.8 14.1 16.6 F.6 2.4 6. Mastral et al.1 730 104.81 0 780 102.0 11.2 852 103.6 14.4 39. Appl.2 0 112 104 Gasification 1.5 68.9 96 102 Gasification 1.0 5.85 0 850 89.03 6.2 51.9 700 86.

/ J. Influence of the experiment temperature on fraction yields.F. 3. Influence of the experiment temperature on product yields. the main difference observed between the gasification and pyrolysis experiments is the production of some gas species such as carbon dioxide. Anal. Mastral et al. Gas composition Table 2 shows the yields to the different gas species obtained in the pyrolysis and gasification processes. Appl. 3. The yield to hydrogen is Fig. carbon monoxide and water in gasification. As previously mentioned. Pyrolysis 70 (2003) 1 Á/17 7 Fig. due to the HDPE partial combustion and reduction reactions.2. 2.J. .

10 13.00 31.00 15.00 21.55 7.00 0.70 0.00 9.00 0.30 0.74 0.30 6.00 0.70 11.71 5.25 1.% of feed) for pyrolysis and gasification of HDPE Temperature (8C) Process H2 O2 CO CO2 CH4 C2H4 C2H6 C3 C4 Oxygenated Aromatic C5 Á/C8 C9 Á/C12 C13 Á/C19 C19 Á/C32 C33 Á/C60 640 Pyrolysis 0.65 11.50 0.00 F.00 Gasification 1.10 2.00 15.30 5.70 17.80 23.80 25.70 14. Pyrolysis 70 (2003) 1 Á/17 Gasification 0.05 0.60 20.30 4.00 0.00 0.70 0.30 0.00 2.22 0.60 11.07 1.20 2.73 5.00 0.00 11.40 Gasification 0. Anal.40 24.10 2.30 3.40 3.67 8.70 14.91 13.04 0.00 11.10 0.80 5.24 0.00 7.08 1.8 Table 2 Product yields (wt.00 4.00 0.60 3.33 0.20 12.00 29.00 13.40 23.90 2.00 0. Appl.00 0.90 7.00 0.03 0.41 0.13 6.00 4.09 0.00 2.40 6.00 0.40 17.20 7.40 32.40 17.00 730 Pyrolysis 0.27 Gasification 1.00 6.00 14.43 8.30 5.00 9.00 0.30 2.30 0.00 0.00 0.50 13.00 7.40 4.J.80 20.80 1.00 3.00 26.35 2.60 0.00 12.00 .70 34.90 1.14 1.00 0.80 0.00 9.00 0.28 4.60 0.00 0.50 0.60 0.50 5.00 850 Pyrolysis 1.00 0.10 5.80 7.00 0.00 0. / J.55 14.50 16.84 9.00 3.10 8.00 0.00 680 Pyrolysis 0.60 14.70 0.90 20.00 Gasification 2.80 17.00 780 Pyrolysis 0.86 31.80 0.70 10.50 2.00 3.62 13.23 3.00 14.80 8.00 0. Mastral et al.25 3.30 40.60 2.10 17.70 37.55 0.00 1.60 0.00 0.50 14.70 1.10 4.90 0.

For reactor temperatures up to 730 8C. as has been suggested by different authors [15. favored by the Boudouard and water shift reactions. As can be observed. Appl. obtaining similar values in both processes. up to 700 8C. propagation reactions generate hydrogen at low temperatures whilst the dehydrogenation reactions to generate aromatic compounds are responsible for H2 formation at high temperatures [10. The variation of the yields to CO and CO2 obtained in the gasification experiments and the CO/CO2 ratio with temperature are shown in Fig. Higher values are observed in the presence of oxygen. Under these experimental conditions a decrease of the yield to heavy hydrocarbons is also observed. At low temperatures. / J. given their endothermicity. 5. .16]. similar trends are observed for pyrolysis and gasification experiments although higher values are observed for gasification experiments at high temperatures. 4.J. The ethylene/ethane ratio increases in both processes with Fig. resulting in relatively low yields to CO and high yields to CO2. The variation of H2 and CH4 yields with temperature for pyrolysis and gasification experiments is shown in Fig. due to the above mentioned equilibria. As can be observed in Fig. Variation of CO and CO2 production and CO/CO2 ratio with gasification temperature. When comparing hydrogen production. Pyrolysis 70 (2003) 1 Á/17 9 relatively low and increases in both types of experiments as the temperature increases. the CO/CO2 ratio increases as the temperature increases. In the pyrolysis experiments carried out. the ethylene yield is higher in the pyrolysis process. Mastral et al. 6. 5. the yield to ethylene is higher in the gasification experiments. 4. The endothermic water gas and water shift reactions can also explain the higher yield to H2 observed at high temperatures in the gasification experiments.13 Á/15]. Methane is a stable product of the propagation reactions of the thermal decomposition of polyethylene. In the temperature interval from 730 to 850 8C. the combustion reaction is predominant. temperature strongly affects the yields to CH4. Anal.F. The yields to ethylene and ethane and their ratio is shown for both types of experiments and different temperatures in Fig.

Mastral et al. Anal. 10 Á/12 kcal mol (1). temperature. 5. playing a relevant role in the formation of ethylene.10 F. Variation of C2H4 production and C2H4/C2H6 ratio with pyrolysis and gasification temperature. . Fig. 6. / J. Variation of H2 and CH4 production with pyrolysis and gasification temperature. The difference between gasification and pyrolysis processes is mainly due to the presence of the hydroxyl and hydroperoxy radicals.5 vs. Pyrolysis 70 (2003) 1 Á/17 Fig. and is always higher in gasification than in pyrolysis. Appl. This would be explained by the more severe cracking conditions in the presence of oxygen. lowering the apparent activation energy of the overall process from 52 Á/55 to 43 Á/46 kcal mol (1 and explaining the higher reactivity observed in the gasification experiments. abstraction of H-atoms by OH radicals shows a lower activation energy than the H and CH3 radicals (3.J. In the presence of oxygen.

The heating value of gas products in pyrolysis and gasification processes is shown in Fig. these fractions react to generate aromatic compounds through Diels Alder reactions. 7. oxygenated compounds appear. 3. . Liquid composition An important amount of wax. including hydrocarbons of up to sixty carbon atoms is produced at low temperatures (645 8C). The heating value increases up to approximately 780 8C. favored under these conditions by condensation and dehydrogenation reactions. The heating value is lower for gasification than for pyrolysis due to the partial combustion of the HDPE fed. In the pyrolysis process these hydrocarbons are mainly olefins and diolefins. the latter fact coinciding with the increase in aromatic formation. / J. The maximum yields to these fractions are explained by the combined effect of cracking reactions and aromatic production reactions. Pyrolysis 70 (2003) 1 Á/17 11 The fractions C3 (mainly propylene) and C4 (mainly butadiene) show a maximum yield at 730 8C. also undergo further cracking leading to gas compounds of lighter molecular weight. The most important difference between the pyrolysis and gasification processes is observed at low temperatures. Appl. Mastral et al.3. 7. whilst decreasing slightly from 780 to 850 8C. paraffins appearing only in minor proportions. The yield to the olefinic fraction decreases as the temperature increases. produced by the cracking of heavy olefins. 8 and 9. In gasification. For temperatures above 730 8C. Heavier polyaromatic compounds are also generated. and falls to negligible values at temperatures over 780 8C. As the temperature increases a more intense cracking of heavy hydrocarbons occurs to produce gases and light fractions. The influence of the reactor temperature and the experiment type can be observed in Figs. 8.F. In Fig. their yield also increasing as the temperature increases. 9.J. and the olefinic Fig. some products have been lumped together for the sake of simplicity of data analysis. These fractions. The yield to aromatic compounds increases as the temperature increases. Anal. Heating value of gas products. The product chromatograms of the product distribution under different conditions are shown as examples in Fig.

more scissions in the polymer chain occur leading to a high number of short primary . At higher temperatures secondary reactions yield aromatic and polyaromatic compounds (also observed in Figs. Benzene and naphthalene production increases as the temperature increases.15 Á/18] and shown in Fig. As temperature is increased. 8.10 Á/13. 5 and 6). In Fig. being slightly higher in the case of gasification. 3). Mastral et al. 8Á/10). the polymer cracking reactions to yield smaller olefinic chains and gases (as experimentally observed in Fig. 11. CG/MS chromatograms of the liquid products of pyrolysis and gasification. Pyrolysis 70 (2003) 1 Á/17 Fig. The product distributions observed can be explained qualitatively taking into account the mechanisms of thermal degradation suggested by different authors [2.J. and at high temperatures. In all conditions benzene is the most abundant aromatic compound. with only very small amounts of alkanes and dialkenes being formed. where the substrate concentration is low.12 F. the RiceÁ/Kossiakoff mechanism [17] predicts the formation of mainly alkenes. Similar trends are shown in the experimental data obtained (Figs. At a given temperature. / J.3. fraction is smaller than that observed in pyrolysis. Appl. C2H4. CH4 and H2. the results show similar values in pyrolysis and gasification. In general. 3. For temperatures higher than 730 8C the liquid composition is similar in both pyrolysis and gasification experiments. In gas-phase. 10 aromatic compounds are detailed. Anal.

Appl. Pyrolysis 70 (2003) 1 Á/17 13 Fig. which undergo successive b-scission reactions and eliminate small molecules (this coincides with the results obtained. and the high production of ethylene). / J. Comparison of product distribution under pyrolysis and gasification conditions. Influence of temperature.F. Moreover. 9. Mastral et al. radicals. the higher radical concentration favors intermolecular hydrogen transfer (the higher concen- . Anal.J. with the gas yield increasing as the temperature increases.

Pyrolysis 70 (2003) 1 Á/17 Fig. as carried out in the gasification experiments. CH4. tration increases the bimolecular reaction probability). so that the difference observed with the pyrolysis experiments is more important at low temperatures. Influence of temperature. This fact coincides with a reduction of the average molecular weight of heavy products. Different mechanisms have been suggested for explaining the formation of benzene and other aromatic compounds such as the combination reactions between conjugated dienes and unsaturated compounds followed by dehydrogenation [5]. to generate alkanes (reaction V in Fig. 10. the system becomes more complex and a higher reactivity is observed. When considering the partial oxidation of the HDPE. The relative importance of the temperature (compared with that of the oxygen concentration) in the severity of the oxidation increases as the temperature increases. The products present in higher percentages are ethylene in gases and . Conclusions The operation temperature has an important influence on the product distribution and on the gas composition due to the secondary reactions occurring in the freeboard. 11). a higher production of light products (H2. / J. 4. Anal. A higher production of ethylene is noticed in the presence of oxygen at temperatures below 730 8C. Mastral et al. At low temperatures the presence of oxygen causes a more intense cracking effect. C2H4) and a decrease of the yield to heavy fractions is noticed.14 F. Comparison of aromatic product distribution under pyrolysis and gasification conditions. Appl. In HDPE fed basis. the gas production increases and the oil and wax production decreases in both pyrolysis and gasification processes. As the temperature increases.J.

Anal.J. 11.F. Appl. / J. Pyrolysis 70 (2003) 1 Á/17 15 Fig. Mastral et al. . General mechanism of the thermal degradation of polyethylene.

Aschawaller. 62 (1998) 513. Williams. Pyrol. Anal. 54 (2000) 5. Faravelli. A. Van Swaaij. Pyrol. J. If gasification is used.M. a suitable gas composition could be obtained for electricity generation at relatively low temperatures. [13] H.T.J.W. S. This temperature range also avoids a high production of heavy polyaromatic compounds. Montaudo. The low temperatures would also result in a reduction of heat losses and would decrease the wax fraction and the generation of oxygenated compounds (except CO and CO2). T. which can be problematic. A. 27 (2000) 99. Radlein. 24 (1995) 581. Stab. V. Ind. The product distribution can be qualitatively explained taking into account the mechanisms of thermal degradation of PE. References [1] J. Pyrol. Bockhorn. / J. Degrad. Appl. . Williams. U. R. [5] J. R. 51 (1999) 107. J. Stab.S. Anal. Acknowledgements The authors express their gratitude to CICYT (project QUI 98-0669) for providing financial support for this work. J. [7] D. Some of the experimental observations on the variation of the gas yield with the temperature.A. Bozzano. 40 Á/41 (1997) 305. In the presence of oxygen. Polym. a selfsustaining regime could be attained in order to avoid any additional combustible or external heating as required when the decomposition is carried out under pyrolysis conditions.P.M. Appl. Appl. Res. Marcilla. which favors the decomposition of heavy compounds. IV 3 (1993) 1543. Faravelli. Pyrol. Goldaniga. Marcilla. J. 36 (1997) 1955. Hornung. 54 (2000) 109. J. Energy Fuels 8 (1994) 1238. alkanes and dialkenes in the wax fraction and their dependence on the temperature variation corroborate the generally accepted mechanism.A. Piskorz. Kaminsky. R. Waanders. U. Pyrol. The increase in the formation of aromatics as the temperature increases is also explained. Bozzano. Appl. Hornung. the formation of alkenes. Simon. M. Appl. Kamal. the optimum being between 680 and 730 8C. Chem. Energy Fuels 11 (1997) 126. Appl. A. Eng. T. Ind.E.R. Anal. N. E. [4] R. B. D. 32 (1995) 19. Font. Schlesselmann. 50 (1999) 77.A. Anal. [11] W. Copper. Ranzi. Appl. J. although a slight increase in the reactivity is observed. the maximum production of these compounds appearing at 850 8C. Dev. Dente. 48 (1999) 93. Scott. [2] H. Cozzani. Conesa. C. [9] W. ´ [6] W. Kaminsky. Font. Sci. M. 33 (1991) 229. A. J. J. Proc. A. Pyrolysis 70 (2003) 1 Á/17 benzene in liquids. Conesa. W. G. D. Mastral et al. Kuipers. M. Des.C.L. Phys. D. Eng.J. the significant generation of ethylene. Chem.A. Hornung. Anal. J. Anal. Poutsma. J. [3] E. Polym. J. G. Bockhorn. Savage. the thermal decomposition process is similar to that observed under pyrolysis conditions. Pyrol.16 F. C. Hornung. [14] G. [15] E. [12] P. Degrad. McCaffrey. Dente. Garcıa. Appl. Fabini. Ranzi. Prog. Anal. Pyrol. [10] M. Westerhout. by using a correct proportion of air. Anal. The results obtained show that. Energy Comb. [8] P.G. Puglisi. Nava.

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