Converting of municipal solid wastes into valuable hydrocarbons by pyrolysis: the effect of the paper/plastic ratio and reaction

time
N. Miskolczi, A. Angyal, P.T. Williams, F. Buyong, L. Bartha
Abstract Municipal solid wastes from industrial plants (from
United Kingdom, Hungary and Malaysia) were pyrolyzed in a batch reactor to evaluate the influence of paper/plastic ratio and reaction time both on product quantity and quality. Raw materials have been pyrolyzed under nitrogen in a 3.0 dm3 autoclave at 450C for 20, 40, 60, 90 and 120 min reaction times. Results show considerable differences in yields and quality of products obtained by pyrolysis of wastes with different paper content. Light and heavy oils were mixtures of organic compounds containing valuable hydrocarbons and oxygenated chemicals, while chars were rather composed of inorganic compounds from the raw materials. Gases consisted of hydrocarbons together with CO and CO2, having middle-high calorific values and compositions were very depending on the paper/plastic ratio of raw materials. The reaction (pyrolysis) time had also a great influence on the product quantity and quality. Less reaction time was needed for complete pyrolysis of British RDF, but the product quality was the most favourable when Hungarian RDF had been decomposed. The storage stability, as one of the key points of the further product utilization, had been followed via formation of greater molecular agglomerates mainly from oxygenated hydrocarbons. Products had also been analyzed by GC, FTIR, EDXRFS and standardized methods.

Keywords bio-oil, pyrolysis, RDF, utilization. I. INTRODUCTION The global energy demand has been considerably increasing for 50 years and forecasts predicted same tendency in the future. Energy from renewable sources is the mostly investigated way for the problem solution, because wastes (municipal solid wastes (MSW), plastic wastes, etc.) should be the raw materials in waste to fuel (WTF) processes to generate e.g. bio-oils, hydrocarbons or energy. Only in the EU countries, more than 250 million tonnes of MSW are produced
N. Miskolczi is with the Chemical Engineering Institute, University of Pannonia, Veszprm, 10 Egyetem u., 8200, Hungary (corresponding author to provide phone: +36-88-624000; fax: +36-88-624520; e-mail: mnorbert@almos.uni-pannon.hu). A. Angyal is with Chemical Engineering Institute, University of Pannonia, Veszprm, 10 Egyetem u., 8200, Hungary (e-mail: angyala@almos.unipannon.hu). P. T. Williams is with Energy and Resources Research Institute, University of Leeds, Leeds, UK, LS2 9JT, UK (e-mail P.T.Williams@leeds.ac.uk). L. Bartha is with Chemical Engineering Institute, University of Pannonia, Veszprm, 10 Egyetem u., 8200, Hungary (e-mail: bartha@almos.unipannon.hu). F. Buyong is with Energy and Resources Research Institute, University of Leeds, Leeds, UK, LS2 9JT, UK (e-mail: eicha75@yahoo.com).

yearly, with an annual growth of 4%. MSW consists of plastic, paper and other organic wastes, but the most valuable components are plastics owing to their high energy content, favourable C/H ratio and oxygen free composition. By pyrolysis or chemical recycling of solid wastes considerable energy could be obtain in the form of hydrocarbons. Many researchers investigate the possible way of waste to fuel processes and numerous having prospective chance for industrial leading [1]-[5]. Quite a lot of processes are based on batch and semi-batch pyrolysis, in which gases, oils and solids have been produced. When MSW is heated in absence of air, the produced bio-oils containing water, hydrocarbons and oxygenated hydrocarbons. Both the water and oxygenated hydrocarbon content in bio-oils are undesirable because they easily can cause thermally instability, lower heating value, corrosion problems, storage difficulties, etc. One of the key parameters is the optimal reaction time of pyrolysis, because longer reaction time needs more operating costs, but the necessary pyrolysis time is affected by the composition of raw materials, too. Furthermore it had a considerable influence to both the products quantity and quality. Therefore it is important to know what correlation has been between the raw materials (e.g. paper/plastic ratio) and product properties. Due to the unfavourable high transporting cost of MSW, generally their pelletized form is applied, what special name is refuse derived fuels (RDF). In this work we have focused to determine the correlation between properties of raw materials and products quantity and quality in case of RDF pyrolysis. MSW samples from United Kingdom, Hungary and Malaysia were pyrolyzed in a 3.0 dm3 reactor under nitrogen at 450C for 20, 40, 60, 90 and 120 min having difference in plastic/paper ratio and plastic composition. We have tried to determine the optimal reaction time of pyrolysis process in relation product properties for further utilization. Thus mainly the product quantity, the composition, impurities level and the other fuel properties such as densitiy, heating value, pour point have been compared. II. EXPERIMENTAL A. Raw materials Three municipal solid wastes used in this experimental work, was represented by refused derived fuels and obtained from industrial companies in Great-Brittan (bRDF), Malaysia (mRDF) and Hungary (hRDF). First of all raw materials have

been great difference both in plastic/paper ratio and plastic composition. The main properties of the RDFs are reported in Table 1. Hungarian RDF had the highest (11.64) plastic/paper ratio, while British is the lowest (0.56). The composition of plastics in raw materials had been identified by FTIR spectrometer. Based on spectrum polyethylene, polypropylene, polystyrene, polyvinyl chloride and up to 8.6% other plastics were recognized. The polyethylene content followed the order of bRDF > mRDF > hRDF, while that of polypropylene bRDF < mRDF < hRDF. It is important to remark that the Hungarian RDF consisted of twice much polystyrene than the other two. Basically PET and PC mean the other plastics. The impurities were followed by EDXRFS, what indicate S, Cl, P, Br, Ca, Zn, etc. in raw materials. Both the high moisture (6.0%) and ash (16.1%) content of bRDF was caused by the vast paper content.
TABLE 1 MAIN PROPERTIES OF RDF Properties Country Plastic/paper ratio C/H ratio Paper, % Plastic, % Polyethylene, % Polypropylene, % Polystyrene, % PVC, % Other plastic, % Other, % Ash % Combustibles, % Impurities Moisture, % bRDF Great-Brittan 0.56 7.29 51.6 29.1 70.5 11.2 9.8 1.0 7.5 19.3 16.1 78.5 S, Cl, P, Pb, Br, Sb, Ca, Zn, Al, Ti, Fe 6.0 mRDF Malaysia 1.77 2.76 33.7 59.8 64.6 17.5 10.1 0.5 7.3 6.5 15.4 80.4 S, Cl, P, Pb, Br, Sb, Ca, Zn, Al, Ti, Fe 4.1 hRDF Hungary 11.64 1.37 7.6 88.5 49.8 18.1 23.5 8.6 3.9 5.8 92.9 S, Cl, Ti, Al, Br, Ca, Zn 1.3

where the condensable fraction transformed into liquid at 20C. The non condensable gases were measured with a gasflow meter and analyzed by GC. The water content of liquids was separated from the oil in a water/oil separator, which was followed by a dewatering unit. Final dewatering of oil used Na2SO4 for chemical absorption of water. Then Na2SO4XH2O was separated from light oil by filtration. Subsequent to the pyrolysis the remaining reactor content had been removed and the heavy oil separated from char by high temperature pressure filtration. During this procedure 130C temperature and 5 bar pressure had been applied.
C. Product analysis

The composition of gases was investigated by DANI gas chromatograph provided with a 50 m x 0.32 mm fused silica column with Al2O3/KCl coating, under isothermal conditions. While CO and CO2 were analyzed by thermal conductivity detector (TCD) with a 2m length by 2mm diameter column, packed with 80-100 mesh molecular sieve and isothermal conditions was used. Analysis of oils was done by TRACE gas-chromatograph fitted with a 30 m x 0.32 mm Rtx-11 (Crossbond1, 100% dimethyl polysiloxane) column and by a TENSOR 27 type Fourier transformed infrared spectrometer (resolution: 2 cm-1, illumination: SiC Globar light, monocromator: Littrow prism, detector: RT-DLaTGS (Deutero L- -Alanine Triglycin-Sulphate) type detector with KBr window). The average molecular weight of oils and residue had been measured by size exclusion chromatography. (Waters 1515 type pump, Waters 717 plus Autosampler unit and Waters 2414 differential refractometer). Samples were dissolved in tetrahydrofurane then filtered by a 0.2m Millipore (Millex filter) membrane and compounds were separated by three Ultrastyragel columns (7.8 x 300mm). Determination of density, heating value, viscosity, flash point, pour point, boiling points, nitrogen and sulphur content of fractions were performed by using standardized methods: MSZ EN ISO 12185:1996, MSZ 24000-5:1978, MSZ EN ISO 3104:1996, MSZ EN ISO 2719:2000, MSZ 11721:1964, MSZ EN ISO 3405:2000, ASTMD 6428 99 and ASTMD 6366 99, respectively. Contaminants in light oils, heavy oils and char were determined by X-ray analysis. PHILIPS MiniPal PW 4025/02 non-polarized EDXRFS (Philips Co., Alameno, Netherlands) was used, powered by PW 4051 MiniPal/MiniMate Software V 2.0A (rhodium-side window tube anode (power of 9W), SiPIN detector, integrated SPC (Statistical Process Control) module). III. RESULTS A. Product yields The yields of products obtained by pyrolysis of refuse derived fuels as function of reaction time are shown in Figs 24. As it results clearly demonstrate both the raw materials and

B. Cracking apparatus The pyrolysis of RDF was carried out for 20, 40, 60, 90 and 120 min in a batch reactor at 450C. The applied process layout is shown in Fig 1. For inert atmosphere nitrogen was introduced into the reactor with a constant flow rate (5dm3/h).

Fig 1 Pyrolysis process for oil recovery from RDF

(1-nitrogen, 2-flow meter, 3-reactor, 4-cooler, 5-separator, 6-gas flow meter, 7-water/oil separator, 8-dewatering 9-filter, 10-thermocouple, 11-motor)

The actual temperature has been controlled by PID controller and measured inside the reactor with thermocouple. Pyrolysis products in gas form were driven in a water cooler,

reaction time plays a major role to the product quantity. Longer reaction time of pyrolysis had produced higher noncondensable gas, water and light oil. Chars showed relatively constant yield as function of reaction time, 23.5-24.6%, 15.516.8% and 5.5-6.1% in case of bRDF, mRDF and hRDF, respectively. The lowest char amount was found when hRDF had been pyrolyzed with the lowest paper/plastic ratio, what refered that the solid char basically included compounds from papers residues.
40 35 30 Yield, % 25 20 15 10 5 0 0 10 20 30 40 Reaction time, min 50 60 70 Gases Water Light oil Char

Fig 2 Product yields obtained by pyrolysis of British RDF

35 30 25 Yield, % 20 15 10 5 0 0 20 40 60 Reaction time, min 80 100 Gases Water Light oil Char

Therefore the highest light oil and less water yield was given from pyrolysis of Hungarian RDF. It is also very important observation that the composition of products was notably affected by the reaction time. Generally the quantity of gases, water and light oils increased with the length of thermal effect, but the increasing function was different. The function curves were logarithmical fitted on the gas or water, yields and rather exponent that of light oil, but only in case of bRDF and mRDF. Hungarian RDF had given closely linear function in case of any products. The possible reason of that phenomenon may be linked to the different degradation characteristic of RDF constitutes. As it mentioned above, each RDF consisted of papers, organic wastes and plastics. Papers are decomposed in the temperature range of 250-350C, while plastics started to decompose only over 380C. Generally the gross thermal degradation of plastics is followed by first order kinetic that is the reason for the linear correlation. HRDF consisted of dominant plastics and only 5% papers. At higher values of reaction times the relatively constant water percentage also supported that the paper decomposition and transformation to water and oxygenated hydrocarbons was the first reaction step and nearly completed till the 40-50mins. Figs 2-4 also well demonstrated that different reaction time was necessary for nearly total decomposition. BRDF was needed 60min, mRDF was needed 90 min, while hRDF was needed 120min for recovery of all volatile products from the solid wastes. It is important data for industrial plants, because as longer was the reaction time as much operating costs was needed for pyrolysis. B. Gases Figs 5-7 show the composition of non-condensable gases at 20C. Gases contained CO, CO2 and hydrocarbons, but the concentrations were very function of reaction time and paper/plastic ratio.
60 50 Compositon, % 40 30 20 10 H2 CO CO2 CH4 C2 C3 C4 i-C4H10

Fig 3 Product yields obtained by pyrolysis of Malaysian RDF

80 70 60 Yield, % 50 40 30 20 10 0 0 20 40 60 80 Reaction time, min 100 120 140 Gases Water Light oil Char

0 0 10 20 30 40 50 60 70 Reaction time, min.

Fig 4 Product yields obtained by pyrolysis of Hungarian RDF

Gases were in the range of 4.9 and 25.4%, depending on the raw materials and the process parameters, but the highest gas amount could be measured when British RDF was used. For that phenomenon is the high paper content could be blamed. The maximum value of gas yield was 25.4% in case of bRDF and 18.9% that of hRDF. As seen from Figs 2-4 both the water and light oil content were significantly affected be the raw materials. The higher was the paper/plastic ratio, the higher was the water amount and lower was the light oil yield.

Fig 5 Gas composition obtained by British RDF pyrolysis

E.g. the CO and CO2 concentration changed in the range of 25.0-20.2% and 49.4-26.1% in case of bRDF pyrolysis, for what the decomposition of dominant paper constitutes in RDF via highly oxygenated compounds in raw materials (e.g. cellulose or hemicellulose from paper) can be blamed [3]-[4]. Similar results had been obtained by other researchers, who demonstrated dominant CO and CO2 in gases when paper

reach RDF was pyrolyzed. The total hydrocarbon concentration was the highest 72.2% at 20 min and risen to 94.9% at 120min in case of hRDF pyrolysis. Among hydrocarbons C2, C3 and C4 fractions were the dominants, for what the polyethylene and polypropylene decomposition would be blamed. As can be seen from figures the oxygenated compounds-hydrocarbons ratio could be significantly decreased, what can be attributed to both the concentration drop of CO and CO2 and increasing percentage of hydrocarbons with time due to the more significant chain scission of plastics constituents of solid waste.
40 35 30 Compositon, % 25 20 15 10 5 0 0 20 40 60 80 100 Reaction time, min. H2 CO CO2 CH4 C2 C3 C4 i-C4H10

contrast British only 29.1% with 9.8% polystyrene. The activation energy of plastic pyrolysis was followed the order of polystyrene < polypropylene < and polyethylene. That is the cause for the highest aromatic content had been measured in light oils from hRDF, and decreasing tendency in aromatic concentration was found in all cases. Firstly the polystyrene decomposed with highest yield then other plastics also could be converted into oils as function of their activation energy order.
Olefins 0 British RDF 10 Malaysian RDF Hungarian RDF 20 30 40 100 90 80 70 60 50 40
90 min 60 min 40 min 20 min

60 min 40 min 20 min

50 120 min 60 70 80 90 100 Aromatics 0 10 20 30 40 50 60 70

90 min 60 min 40 min 20 min

30 20 10 90 100 0 Paraffins

80

Fig 8 Composition of oils by pyrolysis

Fig 6 Gas composition obtained by Malaysian RDF pyrolysis

35 30 25 20 15 10 5 0 0 20 40 60 80 100 120 140 Reaction time, min. H2 CO CO2 CH4 C2 C3 C4 i-C4H10

Compositon, %

The concentrations of some individual oxygenated species found in light oils are shown in Table 2. It is noteworthy to mention that the highest concentration was found of acetic acid, but the lower was the paper/plastic ratio the lower were the concentration of oxygenated compounds. E.g. hRDF resulted only acetic acid, propionic acid, furane and phenol.
TABLE 2 MAIN OXYGENATED HYDROCARBONS IN LIGHT OILS (OBTAINED FROM RDF PYROLYSIS AT 40MIN IN EACH CASE) Acetic acid 2-propane, 1-hydroxy Propionic acid Furfuryl alcohol Furane Phenol Phenol 2-methyl Phenol 3-methyl Vanillin Dibenzothiophene bRDF 3.42 2.75 2.54 0.56 0.44 1.68 0.21 0.33 0.28 0.39 mRDF 1.23 0.74 0.38 0.09 0.21 0.22 0.14 0.17 0.11 0.09 hRDF 0.14 0.05 0.05 0.16 -

Fig 7 Gas composition obtained by Hungarian RDF pyrolysis

C. Light oil characterisation The triangular diagram in Figure 8 represents the hydrocarbon composition of light oils obtained by different RDF pyrolysis as function of reaction time. Both the raw materials and the reaction time had a significant effect to the structure of light oils, because the aromatic content notably decreased as function of the reaction time in all cases. The highest aromatic concentration was found when Hungarian RDF had been pyrolyzed: aromatics of 55.7%, aliphatic olefins of 24.1% and aliphatic paraffin of 20.2% were measured at 10min, while those of 25.8%, 39.0% and 35.2% at 120min, respectively. In contrast the aromatic, aliphatic olefin and aliphatic paraffin concentration were 26.6%, 38.8% and 34.6% at 10min in British RDF pyrolysis, while those of 15.0%, 45.7% and 39.3% at 60 min, respectively. For that phenomenon the difference of raw materials in paper/plastic ratio and polystyrene content could be blamed. Hungarian RDF consisted of 88.5% plastics with 23.5% polystyrene, in

To investigate the effect of the reaction time to the acidic properties and to know what correlation has been between acidic properties and oxygenated concentration, acid number and total oxygenated concentration have been measured as function of reaction time. Results are demonstrated at Fig 9. The oxygenated hydrocarbons are key components in waste derived bio-oils, owing to their undesirable properties, because they easily can cause thermally instability, lower heating value, corrosion problems, storage difficulties, etc. As seen the acidic characteristic had been affected by both the pyrolysis time and raw materials. Highest acid numbers had been measured in light oils from bRDF, while the less that of from hRDF. In each case both the acid numbers and the concentration of

oxygenated hydrocarbons could be decreased by using of longer reaction time. The cause of that phenomenon is given by the difference in energy requirement of decomposition of paper and plastic constituents. The activation energies of pyrolysis follows the order lignin < hemicelluloses < cellulose < polystyrene < polyproylene < polyethylene. It is also well known that paper constituents gave rather oxygenated hydrocarbons from e.g. cellulose decomposition therefore mainly products from paper decomposition could be blamed for acidic characteristic. Paper constitutes having lower activation energy requirement as that of plastics given more components in light oils at the beginning of pyrolysis. BRDF consisted of more paper consequently its acid number and concentration of oxygenated compounds must be the highest.
0.25 18 15 bRDF 12 0.15 9 0.1 mRDF 0.05 hRDF 0 20 40 60 Reaction time, min. 90 0 6 3

the boiling points below 150C must be positioned under those of the other two oils.
TABLE 3 MAIN PROPERTIES OF LIGHT OILS (OBTAINED FROM RDF PYROLYSIS AT 40MIN IN EACH CASE) Density, g/cm3 M, g/mol Viscosity, mm2/s Flash point, C Pour point, C Water content, ppm S, ppm N, ppm Cl, ppm P, ppm Br, ppm Boiling points, C IBP 10 30 50 70 90 FBP bRDF 0.789 157 2.85 69 -21 29 549 168 231 192 147 45 76 119 150 183 249 314 mRDF 0.786 151 3.02 68 -25 15 132 195 140 84 83 43 81 115 154 193 244 322 hRDF 0.791 158 2.94 71 -29 5 9 79 10 42 57 89 139 178 253 321

Acid number, mgKOH/g sample

0.2

Oxygenated hydrocarbons, %

Fig 9 Acid numbers and oxygenated hydrocarbons in light oils as function of pyrolysis time

Table 3 compares some fuel properties of light oils obtained from RDF pyrolysis. They have been characterized with boiling point ranges of 42-322 C. The water content was 15 and 29ppm in the oils from bRDF and mRDF, respectively, and no water can be determined in case of hRDF. Sulphur, nitrogen, phosphor, chlorine and bromine could be identified as impurities, but their quantity was affected by the raw materials, because the highest sulphur, phosphor bromine and chlorine level was measured in light oils from bRDF, while the less those of from hRDF. The low concentration of impurities in light oil products is a favourable property both from environmental and humanbiological aspects. According to densities (0.786-0.791g/cm3), viscosity (2.85-3.02mm2/s) and flash points (68-71C) of oils their showed similarities with heavy gasoline or light diesel oil from refinery. The pour point was the lowest of light oil from hRDF (-29C), what could be caused by its highest aromatic level. On the other hand the vast aromatics in that light oil from hRDF were the cause for difference in boiling points below 50%. Light oil obtained from hRDF consisted of relative lot of lighter hydrocarbons with lower boiling points than that of other two products. As it well known the lighter aromatics (benzene, toluene, styrene, ethyl-benzene, etc.) have boiling points below 150C therefore owing to the high lighter aromatic content of oils from hRDF,

Other important aspect regarding the longer usage of oils is the transporting and storage stability. Generally oils from biomass sources are quite instable during the storage. The cause of the problem is the relative high oxygenated hydrocarbon and water content in oils, because they are able to promote ageing and linking of hydrocarbons together into greater agglomerates with unfavourable pumping, corrosion and transporting properties. To investigate the mentioned problem the deposits and agglomerates from oils was measured as function of days (Fig 10). The best property has been oils from hRDF (up to 0.01%), and the worst from bRDF (up to 0.5%). Therefore the high paper content of the raw materials is unfavourable for longer storage of waste derived oils.
0,5 0,45 0,4 0,35 Precipitation,% 0,3 0,25 0,2 0,15 0,1 0,05 0 0 1 2 3 5 Days 10 15 20 30 bRDF mRDF hRDF

Fig 10 Storage stability of light oils

D. Heavy oils Heavy oils had been separated from char by high temperature pressure filtration. Their main properties are listed in Table 4. They were grease like in appearance heaving with dark brown colour with 57-69C melting points. The

highest melting point was found in case of hRDF, while the lowest in bRDF. Based on the average molecular weights, the average carbon number of compounds was about 69 formed in bRDF pyrolysis while, that of 96 from hRDF. It is important observation that the hydrocarbon composition was very similar: 7.4-8.9% aromatic, 51.8-55.4% aliphatic paraffins and 35.5-40.8% aliphatic olefins. No water can be determined in the heavy oils, but the levels of impurities (S, N, P, Cl and Br) were quite high apart from hRDF. Although the heating values of heavy oils per mass unit were lower than that of e.g. heating oils (41-42MJ/kg), those are enough high for energy production. These lower values are mainly due to the oxygen content in heavy oils.
TABLE 4 MAIN PROPERTIES OF HEAVY OILS (OBTAINED FROM RDF PYROLYSIS AT 40MIN IN EACH CASE) Paraffin, % Olefin, % Aromatic, % 3 Density, g/cm M, g/mol Flash point, C Melting point, C Caloric value MJ/kg S, ppm N, ppm P, ppm Cl, ppm Br, ppm Water, ppm Other impurities, ppm bRDF 55.4 35.7 8.9 0.834 970 191 57 38.2 16 125 6 252 98 mRDF 51.8 40.8 7.4 0.840 1125 205 62 39.0 11 182 2 101 55 hRDF 53.6 38.1 8.3 0.847 1350 217 69 39.1 9 6 53 6 -

time of pyrolysis had produced higher non-condensable gas, water and light oil. The lowest char amount was found when hRDF had been pyrolyzed with the lowest paper/plastic ratio. Gases contained CO, CO2 and hydrocarbons, but the concentrations were very function of reaction time and paper/plastic ratio. Both the raw materials and the reaction time had a significant effect to the structure of light oils, because the aromatic content decreased as function of the reaction time in all cases. The highest aromatic concentration was found when Hungarian RDF had been pyrolyzed, while the highest oxygenated concentration and acidic characteristic was found in case of bRDF. According to fuel properties of light and heavy oils their showed similarities with middle distillates and heavy oils in refinery, the high paper content of the raw materials was unfavourable for longer storage of waste derived oils ACKNOWLEDGMENT This study would like to acknowledge Malaysia Nuclear Agency for supplying the Malaysian RDF samples. We gratefully acknowledge the financial support for this work of the Chemical Engineering Institutes Cooperative Research Centre and Hungarian Academy of Sciences Jnos Bolyai Researching Foundation. REFERENCES [1] N. Merry M. Mitan, T. Bhaskar, W. J. Hall, A. Muto, P. T. Williams, Y. Sakata, Effect of decabromodiphenyl ether and antimony trioxide on controlled pyrolysis of high-impact polystyrene mixed with polyolefins, Chemosphere 72, 2008, 1073-1079 W. J. Hall, P. T. Williams Separation and recovery of materials from scrap printed circuit boards Resources, Conservation and Recycling 51, 2007, 691-709 G. Genon, E. Brizio Perspectives and limits for cement kilns as a destination for RDF Waste Management 28, 2008, 23752385 M. Garca-Prez, A. Chaala, H. Pakdel, D. Kretschmer, C. Roy Vacuum pyrolysis of softwood and hardwood biomass: comparison between product yields and biooil properties J. Anal. Appl. Pyrol. 78, 2007, 104116. N. Miskolczi, L. Bartha, Gy. Dek Thermal degradation of polyethylene and polystyrene from packaging industry over different catalysts into fuel-like feed stocks Polym. Degr. and Stab. 66, 2005, 235-245.

E. Char Table 5 demonstrates the properties of chars based on EDXRFS, what shows impurities of Ca, Ti, Fe, Al, Sb, Zn and Pb. In all probability their appearance forms were oxide-like in char. The heating values were about 32.0kJ per mass unit in case of char.
TABLE 5 PROPERTIES OF CHAR FROM RDF (OBTAINED FROM RDF PYROLYSIS AT 40MIN IN EACH CASE) bRDF Impurities, ppm Ca Ti Fe Al Sb Zn Pb Heating value, MJ/kg 5127 3492 926 3620 3055 273 720 31.8 mRDF 4834 2810 1530 2845 2948 846 664 32.9 hRDF 3095 2170 n.d. 246 n.d. 124 n.d. 32.5

[2] [3] [4]

[5]

IV. CONCLUSION Three municipal solid wastes from industrial plants were pyrolyzed in a batch reactor to evaluate the influence of paper/plastic ratio and reaction time both on product quantity and quality at 450C. Both the raw materials and reaction time plays a major role to the product quantity. Longer reaction