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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.
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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