Pyrolysis and combustion of solid residues from olive oil processing was studied. The objective of the study was to identify the possible hazardous compounds present in incomplete combustion of this material. The thermal treatment was found to produce low amounts of pollutants, and in fact a small quantity of oxygen was enough to diminish the yields to extremely low levels.
Pyrolysis and combustion of solid residues from olive oil processing was studied. The objective of the study was to identify the possible hazardous compounds present in incomplete combustion of this material. The thermal treatment was found to produce low amounts of pollutants, and in fact a small quantity of oxygen was enough to diminish the yields to extremely low levels.
Pyrolysis and combustion of solid residues from olive oil processing was studied. The objective of the study was to identify the possible hazardous compounds present in incomplete combustion of this material. The thermal treatment was found to produce low amounts of pollutants, and in fact a small quantity of oxygen was enough to diminish the yields to extremely low levels.
Emissions from pyrolysis and combustion of olive oil solid waste
Jaakko Jauhiainen, Ignacio Martin-Gullon
* , Juan A. Conesa, Rafael Font Department of Chemical Engineering, University of Alicante, P.O. Box 99, E-03080 Alicante, Spain Received 14 June 2004; accepted 11 October 2004 Available online 25 December 2004 Abstract The pyrolysis and combustion of solid residues from olive oil processing was studied. The objective of the study was to identify the possible hazardous compounds present in incomplete combustion of this material. The study comprises the identication and quantication of the combustion pollutants produced in a laboratory horizontal furnace. The thermal treatment was found to produce lowamounts of pollutants, and in fact a small quantity of oxygen was enough to diminish the yields to extremely low levels, showing this way that the combustion efciency was high. The ashes contained a signicant quantity of potassium. No toxic or dangerous inorganic compounds were detected. # 2004 Elsevier B.V. All rights reserved. Keywords: Biomass; Waste; PAH; Emissions; Combustion 1. Introduction The world production of olive oil was estimated to be about 1.7 billion liters (statistics from year 2000) yearly. Spain is the world leader producer country with a share of approximately 30% [1,2]. The composition of the olives depends on the olive variety, soil and climate, dividing the olive content in stone (927%), seed (23%) and pulp, presenting the latter one oil content around 1825% [2]. In the olive oil production procedure, olives are rst processed invirgin olive oil plants, where thevirgin olive oil is separated from the rest (stones plus aqueous phase) by physical centrifugation. The virgin olive oil is then sent to either consumption or to rene treatments to reduce acidity. The solid cake (which contains the stones, pressed pulp and a high water content) still contains some amount of olive oil, so it is sent to extraction plants, where the cake is rst dried in rotary kilns, andafter that extracted with hexane, where the oil passes to the organic phase. The extracted oil is separated by solvent evaporation, meanwhile the hexane is recovered and recycled for the extraction process. On the other hand, there is a dry solid waste, formed mainly by exhausted stones and pulp, which forms the waste pomace or orujillo. Since this waste pomace is dry, it presents an energetic potential value and an auto-ignition risk. In fact, the traditional application of this waste pomace has been as a self-fuel for solid cake extraction plants, for the direct-red rotary kiln drier and for steam generators. As a consequence of this self-application, the waste pomace is usually accumulated at open air in the same plants until it is further used, frequently provoking autoring, emissions of which are nowadays cause of concern. Other minor applications are to use the pomace as a fertilizer, construction material and animal feed. Lately, the Spanish leading electricity company Endesa has built two power plants where this solid residue is used as the main fuel. Each plant has total power of 16 MW and is capable of handling 100,000 tons of pomace per year, 10% of the total amount produced in Spain. Masghouni and Hassairi [3] pointed out the suitability of pomace as combustible for brick manufacturing, as pomace lowers the emissions of sulphur oxides and nuisance of the inorganic ash in respect to heavy fuels. Armesto et al. [4] have studied the emissions from the co-ring of olive oil industry waste coming to conclusions that SO 2 and NO x emissions are not affected with the use of pomace in the fuel- mix. The combustion efciency was not affected either, while N 2 O quantity was increased with increasing pomace content. The pollution caused by combustion and pyrolysis can be divided into three major groups. All three product groups, www.elsevier.com/locate/jaap J. Anal. Appl. Pyrolysis 74 (2005) 512517 * Corresponding author. Tel.: +34 96 590 3400x2323; fax: +34 96 590 3826. E-mail address: gullon@ua.es (I. Martin-Gullon). 0165-2370/$ see front matter # 2004 Elsevier B.V. All rights reserved. doi:10.1016/j.jaap.2004.10.003 solid ash, liquid tars and organic gases can contain toxic or harmful components. The semivolatile tars hold among themselves many of the most harmful compounds formed in thermochemical processes. Such compounds are the polycyclic aromatic hydrocarbons (PAH) that can be the routed for the formation of polychlorodibenzodioxins (PCDD) and polychlorodibenzofurans (PCDF) [5]. The main objective of this study is to identify the possible hazardous emissions deriving fromuncontrolled combustion of pomace (as the auto-ignition in opened air). The gaseous emissions in the processes of pyrolysis and combustion were studied in a batch tubular laboratory reactor, in which the continuous combustion process can be simulated discon- tinuously. The effect of the temperature (7501050 8C) and the oxygen ratio were studied, working from conditions in oxygen absence (pyrolysis) and different rates of impover- ished air. The hot gases exiting from the reactor were caught in adsorbent resins (heavy semivolatile tars) as well as in Tedlar bags (volatiles), and later the compounds were analyzed with GC. 2. Experimental The pomace used in the present study was supplied by Espuny Castellar, a solid olive cake extraction company. As the solid was dried and hexane extracted, it presented a low humidity, 7.93wt.%. The residue was not very homogenous, and the olive stones were easy to detect amongst the dried pulp. To avoid heterogeneity when handling small amounts, the waste pomace was milled below 100 mm. The elemental analysis of the material (determined with a Carlo Erba EA 1108) and the proximate analysis are shown in Table 1, showing that the pomace has a high content of oxygen, which can be estimated by difference to over 40%, and nearly no sulfur content. The proximate analysis reveals that the pomace is partially carbonized due to its high value of xed carbon in respect to other biomasses, which explains its high oxygen content. The net caloric value (determined with a Leco Corp. AC-350 calorimetric bomb) was 17799 kJ/kg. The chemical analysis of the pomace was carried out according to standard procedures [6], attaining a lignin content of 45wt.%. and a holocellulose content of 44wt.%. This result of a higher lignin content than holocellulose reveals a biomass nature different to what it is usually common. A batch laboratory scale horizontal tubular reactor was used for the continuous simulations of pyrolysis and combustion at fuel-rich conditions. This equipment has been previously described in detail [7]. Basically, a given amount of solid pomace, placed in a quartz crucible, is introduced into the reactor at constant speed when the furnace is already at the nal temperature. The solid feeding system consists in a magnetic system moved by a small motor. The carrier gas (nitrogen for pyrolysis and air for combustion) was introduced parallel to the waste solid, with constant gas ows at around 250 ml/min. When the sample crucible is moving into the reactor, together with the gas ow, the continuous process is simulated respecting to the gas phase: a certain amount of volatiles will cross the reactor with the carrier gas, with oxygen-volatile reactions in the case of combustion runs. Consequently, the higher the sample mass, the higher the volatile concentration in gas phase. In combustion runs, the oxygen ratio (oxygen with respect to the oxygen necessary for combustion stoichio- metry) is varied changing the initial sample mass (from 25 to 100 mg). With these gas ow rates, the residence time in the furnace can be expected to be 57 s. The reactor outlet gas stream passes rst through a XAD- 2 resin xed bed, to retain semivolatile compounds, and nally the non-condensable gases are collected in a tedlar bag. Gas analysis was performed by GC technique: quantication of CO 2 and CO with GC-TCD (Shimadzu GC-14A) and light hydrocarbons C 1 C 6 together with benzene and toluene with GC-FID (Shimadzu GC-17A). A total of six different gas standards containing known amount of hydrocarbons C 1 C 6 together with CO 2 and CO, with the balance completed with N 2 , were used to calibrate the gas chromatographs. The semivolatile compounds were extracted with dichloromethane, and were determined by GC (Fisons GC8000) equipped with a mass spectrometer detector (Fisons MD8000), using a column DB-5 MS 30. The quantication was done with an internal standard of 6 deuterated PAHs (1,4-dichlorobenzene-D 4 , naphthalene-D 8 , acenaphthene-D 10 , phenanthrene-D 10 , chrysene-D 12 and perylene-D 12 ). Pyrolysis and combustion experiments were run with two variable conditions: the furnace temperature and oxygen ratio (l). The furnace temperatures studied were 750, 850, 950 and 1050 8C. On the other hand, the stoichometric oxygen ratios (l) studied were 0 (pyrolysis and nitrogen atmosphere), 0.1, 0.2 and 0.35, approximately (1 is the stoichiometric amount), giving a total of 16 different runs, which were replicated to assure reproducibility. 3. Results and discussion Tables 2 and 3 present the analysis of volatile gases and condensable compounds, respectively, of all the experiments carried out. Both tables are organized, in a main header, by J. Jauhiainen et al. / J. Anal. Appl. Pyrolysis 74 (2005) 512517 513 Table 1 The elemental and proximate analysis of pomace (dry basis) N 1.1 C 47.0 H 5.7 S 0.1 Ash 7.7 Volatiles 58.7 Fixed carbon 33.7 temperature, where each temperature has a sub-column for the different oxygen ratios. As mentioned in the experi- mental section, 4 different oxygen ratios were carried out for each temperature (nominal values of 0, 0.1, 0.2 and 0.35), although the real experimental value is placed in Tables 2 and 3. The values for each compound represent the emission factors expressed as mg compound resulting per kg of initial dried pomace. Table 3 only shows those compounds with appreciable amounts and which identication with the MS has a high condence level. 3.1. Effect of the temperature in pyrolysis In respect to Table 2, when considering pyrolysis runs at different temperatures (l = 0), results indicate high amounts of CO and CO 2 (above 30% in respect to initial pomace). As commented above, the initial oxygen content was very high respecting to other biomasses, indicative of a partial degradation in the industrial drying, with a high amount of oxygen complexes that are added to those of cellulose. There is no clear tendency in the carbon oxides emission versus temperature, and it can be considered constant. Table 2 also shows the emission of light hydrocarbons. The more abundant are, as expected, methane, unsaturated C 2 C 4 and benzene, presenting four different tendencies versus temperature. Fig. 1 shows clearly these behaviors. Methane, which presents the higher emission factors, presents rst a decrease in the emission at 850 and 950 8C and an increase at 1050 8C. The second behavior is a continuous decrease of the emission factor as shown by ethene and ethane in Fig. 1, where other compounds following this tendency are propane, propene, butane, butene, butadiene and hexane (present due to the solvent used in the extraction). The third behavior is an increase of J. Jauhiainen et al. / J. Anal. Appl. Pyrolysis 74 (2005) 512517 514 Table 2 Volatile emissions obtained from all the experiments, expressed by mg of compound per kg of pomace reacted (except CO/CO 2 ) Temperature (8C) 750 850 950 1050 l (oxygen ratio) 0 0.10 0.20 0.33 0 0.11 0.21 0.37 0 0.08 0.20 0.34 0 0.09 0.22 0.37 Methane 53682 17452 9101 3946 41824 22130 8577 5482 40885 18436 11961 7192 55321 31386 34405 7039 Ethane 6383 2357 642 151 3471 1268 418 61 428 172 42 100 172 73 123 n.d. Ethylene 40119 17164 8636 3362 31294 18603 8047 3454 23234 10149 6720 3722 9914 8028 6726 838 Propane 1225 311 37 n.d. 203 42 8 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. Propene 10207 3737 537 71 3820 1175 382 17 493 161 n.d. n.d. n.d. 63 n.d. n.d. Acetylene 3489 1950 1298 1068 3199 2593 2384 1287 6162 5205 4997 3363 13133 8369 7729 4313 n-Butane 722 180 11 n.d. 382 76 34 n.d. 79 46 n.d. n.d. n.d. n.d. n.d. n.d. 1-Butene 1315 258 28 n.d. 66 12 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. Isobutene 1149 350 14 n.d. 169 28 12 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. 1,3-Butadiene 7345 2822 365 71 3535 1098 260 n.d. 799 365 71 n.d. 499 264 262 n.d. 2-Butyne 379 181 146 n.d. 407 190 138 n.d. 316 143 81 n.d. 356 182 85 64 n-Hexane 2996 1145 543 73 1585 167 83 59 377 136 130 n.d. 86 n.d. 63 115 Benzene 5010 3996 2565 281 9095 3732 1833 762 9577 4444 2455 415 2540 1057 613 553 Toluene 2220 888 680 n.d. 2254 442 320 206 659 562 384 88 67 138 79 209 CO 2 a 16.5 90.1 99.1 145.0 15.4 70.8 77.7 143.6 13.5 86.7 135.1 153.3 17.4 113.8 148.8 178.9 CO a 14.4 9.12 8.61 3.15 12.9 8.93 4.51 3.69 9.40 8.19 5.81 3.25 15.5 13.8 12.5 4.41 a Expressed in g per 100 g of initial dried pomace. Fig. 1. Quantities of light hydrocarbons in pyrolysis at different tempera- tures. Fig. 2. Semivolatile compounds in pyrolysis runs which emissions increase vs. temperature. emission versus temperature, as ethyne, attaining an emission at around 1.3% at 1050 8C. Finally, benzene and toluene present the fourth behavior, a maximum yield at 850 8C and a further decrease. In respect to condensable compounds, either benzene- derived hydrocarbons (including oxygenated compounds) as PAH were determined in appreciable amounts (but much lower than volatile gases) and high condence level. Generally, at 750 8C the most emitted compounds are alkyl and alkenyl benzenes and naphtalenes. As far as the temperature is increased, the benzene-derived compounds disappear, increasing its presence PAH compounds (such as acephthylene, anthracene, pyrene, etc.). For monitoring the behavior of the different PAH compounds, the interest was focused on those considered the most harmful ones by EPA [8], where 12different PAHs fromthat ones were identied. In Fig. 2, it is possible to observe a clear increase in the yields of seven PAHs, with an elevation of the reaction temperature. All of these compounds have various aromatic rings, up to six [benzo(ghi)perylene], which makes them one of the latter stages before soot forming[9]. Onthe other hand, uorene and acenaphtene present the opposite behavior as can be observed in Table 3, which is the common one for the light hydrocarbons and monoaromatics (expect ethyne and methane) that is a clear sharp decrease of the yield when temperature is increased, to nearly nil emission. Both compounds are formed by two aromatic rings. The third type of semivolatile behavior towards increasing temperature corresponds to naphthalene and anthracene (stable double and triple aromatic rings). Their emissions at the lower temperature are already high (1000 mg/kg, as the other main compounds), and at 1050 8C their emissions have increased, but this increase is not so pronounced as the rst group of PAH. Consequently, these latter compounds are stable at any temperature and do not decompose easily. In summary, olive waste pomace yields in pyrolysis carbon oxides as main products (30%) regardless of temperature. At 750 8C, the pyrolysis treatment is soft, and there is little cracking reactions, yielding many volatile, benzene derived compounds, naphthalene and anthracene. As far as the pyrolysis temperature is increased, PAH emission increases, together with ethyne and methane. The latter is a stable product from aromatic condensation reaction, whereas ethyne must be a necessary intermediate for condensation with aromatic radicals [10]. The weight fraction of the elemental carbon that converted into hydrocarbons has been calculated at each temperature in pyrolysis, by means of carbon mass balance. Fig. 3 shows the total amount of elemental carbon converted to light hydrocarbons diminish versus temperature. Mean- while, the total amount of formed tars increases versus temperature, unless the combined amount of both volatile J. Jauhiainen et al. / J. Anal. Appl. Pyrolysis 74 (2005) 512517 515 Table 3 Emissions of major semivolatiles obtained from all the experiments, expressed by mg of compound per kg of pomace reacted Temperature (8C) 750 850 950 1050 l (oxygen ratio) 0 0.10 0.20 0.33 0 0.11 0.21 0.37 0 0.08 0.20 0.34 0 0.09 0.22 0.37 Xylene 479 n.d. n.d. n.d. n.d. n.d. n.d. n.d. 28 1 n.d. n.d. 4 20 13 82 Styrene 937 348 n.d. n.d. 919 406 193 83 307 100 48 n.d. 3 186 230 n.d. 2h-Cyclopenta-d-pyridazine 933 560 n.d. n.d. 473 471 115 n.d. 18 25 20 n.d. n.d. n.d. n.d. n.d. Benzene, 1-ethynyl-4-methyl- 617 467 67 n.d. 1487 607 179 n.d. 206 213 97 n.d. 261 281 726 n.d. Phenol, 2-methyl- 392 n.d. n.d. n.d. 113 n.d. n.d. n.d. n.d. n.d. n.d. n.d. 110 132 187 n.d. Benzene, 4-ethenyl-1,2-dimethyl- 664 65 n.d. n.d. n.d. 9 n.d. n.d. 7 n.d. n.d. n.d. n.d. 39 145 n.d. Naphthalene 973 458 76 359 2732 716 127 51 1152 390 122 116 2825 682 2147 300 Quinoline 27 30 28 n.d. 270 n.d. n.d. n.d. 128 51 30 n.d. 125 415 476 n.d. Naphtalene, 1-methyl- 415 133 40 n.d. 536 175 38 n.d. 249 28 10 n.d. 43 26 61 n.d. 1h-Indene, 1-ethylidene- 304 110 30 n.d. 396 111 22 n.d. 86 14 8 n.d. 30 15 42 n.d. Naphthalene, 2-ethenyl 61 66 36 n.d. 141 116 34 n.d. 162 52 34 n.d. 241 112 285 n.d. Dimethyl-naphthalene 475 39 13 n.d. 35 n.d. n.d. n.d. 112 18 7 55 90 35 64 n.d. Acenaphthylene 398 253 113 n.d. 961 482 123 n.d. 944 288 157 82 2614 476 1229 646 Acenaphthene 416 37 n.d. n.d. 206 38 n.d. n.d. 33 n.d. n.d. n.d. n.d. n.d. n.d. n.d. Dibenzofuran 60 36 29 n.d. 49 64 15 n.d. 33 12 11 n.d. 16 11 25 n.d. Fluorene 577 47 20 n.d. 359 94 24 n.d. 383 61 34 n.d. 190 90 162 n.d. 9h-Fluorene, 1-methyl- 259 29 3 154 336 n.d. n.d. n.d. 24 3 2 13 n.d. n.d. n.d. 78 Anthracene 554 236 234 70 1407 313 149 87 722 211 157 n.d. 2064 455 1354 n.d. 9h-Fluorene, 9-methylene- 37 63 n.d. n.d. 594 104 41 n.d. 238 40 11 n.d. 409 66 1791 n.d. Fluoranthene 12 43 22 n.d. 61 73 20 n.d. 211 88 53 n.d. 1154 323 902 n.d. Pyrene 21 59 27 n.d. 278 101 22 n.d. 247 108 55 n.d. 1307 616 1999 n.d. Benzo(ghi)uoranthene 156 n.d. n.d. n.d. n.d. n.d. n.d. n.d. 125 86 n.d. 59 555 106 606 n.d. Benzo(b)uoranthene 121 n.d. n.d. n.d. n.d. 27 n.d. n.d. 169 167 106 n.d. 326 300 998 n.d. Benzo(a)pyrene n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. 40 49 26 n.d. 108 97 362 n.d. Perylene 85 10 9 n.d. 33 21 13 n.d. 103 91 47 n.d. 229 234 1062 n.d. Indeno-1,2,3(cd)pyrene n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. 46 48 16 n.d. 105 88 558 n.d. Benzo(ghi)perylene n.d. n.d. n.d. n.d. 5 n.d. n.d. n.d. 42 42 n.d. n.d. 147 108 499 n.d. and condensable compounds, at 1050 8C, did not reach the same amount at 750 8C, which clearly indicates that an appreciable amount of soot was formed. Due to the high amount of oxygen present in the pomace, as the elemental analysis showed, the carbon oxide formation in pyrolysis is relatively high (up to 25% of the elemental carbon). A small increment can be noticed in the tendency to form more CO and less CO 2 , in the last increment of the temperature. The internal relation between the amounts of carbon resulting as the two oxides in the lower temperature increments is practically equal, with a little exception at 950 8C. 3.2. Effect of the oxygen ratio in combustion When introducing oxygen into the reactor, the behavior of most compounds is expectedinrespect topyrolysis conditions and oxygen ratio. The pyrolysis gases have a residence time of approximately 57 s in the reactor, which gives enough time to react with the limited amount of oxygen introduced in the reaction chamber. Table 2 shows that all volatile emissions, including carbon monoxide, diminish its values when increasing the oxygen ratio, regardless of temperature. Obviously, carbon dioxide increases when increasing the oxygen ratio, although it is important to point out that CO 2 values cannot be considered a simulation of a continuous process due to part of this, CO 2 may proceed fromthe oxygen gasication of the char (after devolatilization) until it is completely burnt out. 1,3-Butadiene is the most reactive compound (it is completely burnt at 0.35 oxygen ratio), whereas the rest of the volatile compounds seem to burn at similar rates. Moreover, the clear and expected results obtained with volatile gases were yielded for most of semivolatile compounds, with little exceptions. In general terms, the overall semivolatile emissions greatly decrease with only an oxygen ratio of 0.35. Only naphthalene and anthracenewere detectedat all temperatures with0.35oxygen ratio, with very little amounts. The yields of semivolatile compounds, at the highest experiment temperature 1050 8C, does include some marked results. The increased oxygen amount does not diminish some single components yields at 0.2 oxygen ratio. This could be related to possible puffs of incomplete combustion products in the reactor [11] or to a higher local temperature due to combustion of volatile gases. In all cases, the variations can be considered to be within reasonable limits. Practically no oxygenated compounds, excluding diben- zofuran and quinoleine in extremely small amounts, were detected in the 16 experiments. Even in this case, the oxygen may come fromthe waste pomace instead of fromthe air, due to the emitted amount already present at pyrolysis conditions. The behavior of the total hydrocarbonyield is shown in Fig. 4. As it can be seen, even a small amount of oxygen diminishes already clearly the total amount of the produced hydro- carbons. The total amount of carbon converted to semivo- latiles is relatively small even at pyrolytic conditions. At the highest studied oxygen relations (0.33 for experiments at 750 8C) the total amounts of incomplete combustion products are already extremely small. Due to the small amount of volatile hydrocarbons (around 23%) to start with from the pyrolysis, the combustion becomes effective alreadyat lowair factors. Consequently, it could be said that working at air rich conditions the incomplete combustion compounds would be negligible. 3.3. Comparison with other emissions found in the literature The pomace has similar amount of volatiles, approxi- mately 60%, as do the 10 different agricultural residues studied by Werther et al. [12]. In comparison with wood, peat and bituminous coal values from the same study, this amount is slightly higher as the respective values for these three compounds are around 40%. This would naturally result in higher incomplete combustion product yields, but in case of pomace the elevated oxygen content lowers the overall production as the carbon oxides yield in pyrolysis is J. Jauhiainen et al. / J. Anal. Appl. Pyrolysis 74 (2005) 512517 516 Fig. 3. Percentages of the converted elemental carbon as a function of the temperature. Fig. 4. Hydrocarbon production as a function of oxygen ratio at 750 8C. around 23%. Volatile gas composition at fuel-rich conditions is consistent with previous works with biomass (wood pellets), where the combustion efciency was easily attained, and the major hydrocarbon products were methane, ethyne, 1,3-butadiene and benzene [13,14]. Compared to other waste fuels, the biomasses in general have relatively low emissions. Fullana et al. [15] studied the pyrolysis of scrap tires coming to PAH emissions up to six times higher than in the present study. The total amount of volatiles is similar to pomace, but it has more tendency to form semivolatile tars, while the high oxygen content of pomace diminishes the emissions. Font et al. [16] studied the pyrolysis of polyethylene, practically completely volatile matter, detecting at lower temperatures high values of relatively long hydrocarbon chains (C 6 C 35 ), while at temperatures over 800 8C these compounds have practically disappeared, but with elevated amounts of PAHs. 3.4. Ash composition In general, the biomasses have reportedly high amounts of ash forming matter, although the values vary greatly between different materials. Werther et al. [12] studied the combustion of agricultural residues and found ash contents up to 25% in case of rice husks. The pomace was studied to have relatively high amount of ashes, 7.78%. These can be presented in the actual biomass, but a signicant part originates probably from dirt that has been mixed with the material. The pomace ash composition was studied and the results are shown in Table 4. The alkali oxides and salts have relatively low melting points, which can bring problems in the used furnaces. Slagging and fouling together with corrosion and bed material agglomeration occur when the components are volatilized in the high temperature zone of the oven and later condensate to surfaces with lower temperatures such as the heat transfer surfaces. The forming of high amount of potassium, as can be seen from Table 4, could result as a problem of eventual slagging and fouling in the furnaces. Other compounds that form low melting point complexes, Na, for example, have relatively low amount. On the other hand, there are no other traces of toxic or problematic ash forming, as the heavy metals do not appear. The elevated silicon quantity implies the presence of dirt in the pomace, as it was expected. Some inorganic compounds can be though present as silicates in the ash. The detected carbon is probably unburned material although the sample was kept in the furnace for a period of time, which was expected to be sufcient. The visual aspect of the ash did not raise any suspects of incomplete combustion. The temperature used in the procedure (800 8C) was sufciently high to exclude the presence of any carbonates in the ash. Werther et al. [12] had similar results in their study of combustion of various agricultural residues. Various types of different residues were studied and compared to other fuels. The potassium oxide and salt traces from the agricultural biomasses were signicantly higher than from bituminous coal, wood and peat. Nevertheless, the sodium content was more similar in all of the studied materials and the differences were within a reasonable range. The researchers suggest that the use of NPK- and NK-fertilizers (with high amount of potassium) in the agriculture could be the reason for the high amount of this element found in the study. Acknowledgements The study has received economical help from the Spanish Ministry of Science and Technology (MCYT) being a part of the projects PPQ 2002-00567 and PPQ2002-10548-E. Authors also thank Espuny Castellar Co. for kindly supplying the orujillo or pomace. References [1] http://www.aceitedeoliva.com. [2] http://www.oliveoilsource.com/olive_waste.htm. [3] M. Masghouni, M. Hassairi, Biomass Bioenergy 18 (2000) 257. [4] L. Armesto, A. Bahillo, A. Cabanillas, K. Veijonen, J. Otero, A. Plumed, L. Salvador, Fuel 82 (2003) 993. [5] B. Gullett, K. Bruce, L. Beach, A. Drago, Chemosphere 25 (1992) 1387. [6] B.L. Browning, Methods of Wood Chemistry, Wiley, New York, 1965. [7] J.A. Conesa, A. Fullana, R. Font, Envrion. Sci. Technol. 36 (2002) 263. [8] US EPA, Handbook For Air Toxic Emission Inventory Development, vol. I, Stationary Sources, OAQPS, 1998 (EPA-454/b-98-002). [9] S. Sidhu, A. Fullana, 225th ACS National Meeting, New Orleans, United States, 2327 March, 2003. [10] H. Hepp, K. Siegmann, K. Sattler, Chem. Phys. Lett. 233 (1995) 16. [11] T. Panagiotu, Y.A. Levendis, Combust. Sci. Technol. 112 (1996) 117. [12] J. Werther, M. Saenger, E.-U. Hartge, T. Ogada, Z. Siagi, Prog. Energy Combust. Sci. 26 (2000) 1. [13] M. Olsson, O. Ramnas, G. Petersson, J. Anal. Appl. Pyrol. 71 (2004). [14] G. Barrefors, G. Petersson, Chemosphere 30 (1995) 1551. [15] A. Fullana, R. Font, J.A. Conesa, P. Blasco, Envrion. Sci. Technol. 34 (2000) 2032. [16] R. Font, I. Aracil, A. Fullana, I. Mart n-Gullon, J.A. Conesa, J Anal. Appl. Pyrol. 6869 (2003) 599. J. Jauhiainen et al. / J. Anal. Appl. Pyrolysis 74 (2005) 512517 517 Table 4 Yields of inorganic material obtained from the pomace combustion Ashes mg/kg Dry weight K 18182 Si 5900 Ca 5640 O 32577 Al 2036 Mg 2554 P 1441 C 12550 S 834 Fe 2136 Na 334 Ti 55 Cl 258 Total 84499
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