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Structural Changes of Sewage Sludge Char during Fixed-Bed Pyrolysis
Javier A#brego, Jesu#s Arauzo, Jose# Luis Sa#nchez, Alberto
Gonzalo, Toma#s Cordero, and Jose# Rodri#guez-Mirasol
Ind. Eng. Chem. Res., 2009, 48 (6), 3211-3221• DOI: 10.1021/ie801366t • Publication Date (Web): 05 February 2009
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Undigested dried sewage sludge from a wastewater treatment plant was pyrolyzed at temperatures between
300 and 900 °C, with an additional hold time at the highest temperature. A fixed-bed reactor was used with
a heating rate of 20 °C/min under an atmosphere of nitrogen. Pyrolysis product distribution, FTIR, XRD,
BET, SEM, and ultimate and proximate analyses were used to gain a better understanding of the structural
changes occurring during pyrolysis. At low to medium pyrolysis temperatures, major mass loss occurs, and
most of the gaseous and liquid products are released with little porous development, whereas at temperatures
between 700 and 900 °C, structural changes seem to be triggered by calcium carbonate decomposition. This
leads to a second stage of gas evolution, as CaO promotes gasification of the char in the presence of iron
sulfides. The subsequent release of CO runs parallel with an increase in the BET surface area. In addition, the
aromatic character of the char increases with temperature, and nanotube-like tubular structures can be detected
by SEM.
1. Introduction from sewage sludge can play a very effective role in the removal
of some contaminants generated in pyrolysis or gasification, such
Sewage sludge disposal is one of the major problems for
as hydrogen sulfide and sulfur or nitric oxides.6-15 It can also
wastewater treatment plants in the European Union.1 The
be used for the effective removal of metals, dyes, phenol, and
constant increase in its production is caused by the higher
chemical oxygen demand (COD) in aqueous solutions.16-22 If
constraints imposed on effluent treatments, so that disposal itself
necessary, adsorption properties can be improved by chemical
has become an environmental problem of the first magnitude.
or physical activation stages,10,14-24 as well as by mixing with
Conventional disposal routes such as landfilling, dumping, or
other materials.6,8,9,13,19
farmland application are subject to strict legislative constraints
To investigate the use of sewage sludge char as an adsorbent,
or are even banned in several countries, and therefore, alternative
the specific goal of this study was to investigate the structural
options need to be considered.
changes and the evolution of the char during low-heating-rate
One of the main characteristics of sewage sludge is the
pyrolysis on a fixed-bed reactor. Extensive analysis of the char
presence of high amounts of inorganic ash and low carbon
will provide useful knowledge about the processes that occur
contents when compared with other materials, such as wood or
during pyrolysis and will contribute to a better understanding
lignocellulosic char from agriculture. As a result, sewage sludge
of the thermochemical transformation pathways of sewage
has a relatively low energy value, but is sufficient for some
sludge.
kind of waste-to-energy process to be considered as feasible.
In addition, large amounts of sewage sludge are generated in
2. Experimental Section
every wastewater treatment plant, and as mentioned before,
appropriate disposal methods need to be found. Thermochemical 2.1. Sewage Sludge Analysis. A sample of dry sewage
processes seem to be a promising alternative pathway for this sludge was supplied as a granulated product from an urban
sewage sludge treatment.2,3 wastewater treatment plant. The sludge was undigested and had
Pyrolysis is a thermochemical process that consists of the previously undergone various physicochemical processes and
thermal decomposition of a material in the absence of air. thermal drying. Table 1 lists the results of proximate, ultimate,
Pyrolytic char can be considered as an adsorbent precursor if and ash analyses and and measurements of the low heating value
prepared under controlled pyrolysis conditions,4,5 so a large of the received sewage sludge, performed by the Instituto de
reduction in volume is achieved, together with the preparation Carboquı́mica (CSIC, Zaragoza, Spain).
of a valuable product. Thus, if one also considers energy The dried sewage sludge was crushed and sieved to provide
recovery from the gaseous and liquid products of pyrolysis, an a feed sample in the size range of 150-250 µm and kept at
integral sewage sludge valorization can be performed using this 105 °C for 24 h in an oven to remove the moisture prior to
technology. each experiment.
Pyrolytic char from sewage sludge has less surface area than 2.2. Laboratory-Scale Fixed-Bed Pyrolysis Installation.
commercial activated carbons. Reported Brunauer-Emmett- Pyrolysis of sewage sludge was carried out on a fixed-bed
Teller (BET) surface area values found in the literature are no reactor under an inert atmosphere. In each experiment, a sample
greater than 400 m2/g, whereas commercial activated carbon of 2.5 g of raw sewage sludge was pyrolyzed at a heating rate
can exhibit much higher surface areas. Nevertheless, adsorbents of 20 °C/min. The small sample amount minimized temperature
profiles during the experiments.
* To whom correspondence should be addressed. E-mail: javabr@
unizar.es. Figure 1 shows a diagram of the pyrolysis experimental
†
Aragón Institute for Engineering Research (I3A). system. The reactor was cylindrical with a diameter of 90 mm
‡
University of Málaga. and a height of 320 mm and was inside a 900-W furnace.
10.1021/ie801366t CCC: $40.75 2009 American Chemical Society
Published on Web 02/05/2009
3212 Ind. Eng. Chem. Res., Vol. 48, No. 6, 2009
Table 1. Analysis of Dried Sewage Sludge Sample Scanning electron microscopy (SEM) images were recorded
analytical using a JEOL JSM 6400 electronic microscope equipped with
standard/ an energy-dispersive X-ray (EDX) detector (eXL10 from Link
analysis instrument values Analytical).
proximate analysis wt %
moisture ISO-589-1981 0.7 3. Results and Discussion
ash ISO-1171-1976 26.0
volatiles ISO-5623-1974 64.6 3.1. Product Distribution. Figure 2 shows the weight
fixed carbon by difference 8.7 percentage evolution of solid, liquid, and gaseous products with
ultimate analysis wt % (dry) pyrolysis temperature (percentages related to initial weight of
(organic fraction)
carbon Carlo Erba 1108 41.7 sewage sludge). As can be observed, the sewage sludge weight
hydrogen Carlo Erba 1108 5.8 loss for 300 °C is low (6.5%), and thus, small quantities of
nitrogen Carlo Erba 1108 3.0 liquid and gaseous fractions are generated. In contrast, the next
sulfur Carlo Erba 1108 0.8 temperature range (up to 400 °C) exhibits a dramatic solid
oxygen by difference 22.7 fraction weight loss. Consequently, the major liquid and gaseous
ash analysis wt % in the ash
Al Horiba JY-2000 2.3 fractions are then generated. For higher temperatures, the weight
Ca Horiba JY-2000 13.6 loss slows to what seems like a small and almost constant
Fe Horiba JY-2000 8.3 descent from samples C700 to C900B. Gaseous and liquid
K Horiba JY-2000 0.6 products show opposite trends from 400 °C. Whereas liquids
Mg Horiba JY-2000 1.2
increase linearly up to 700 °C, gases show very little generation
Na Horiba JY-2000 0.3
Si Horiba JY-2000 9.7 in this range. At 700 °C, liquid release virtually stops, and an
Ti Horiba JY-2000 0.4 increase in gaseous products is detected.
heating value kJ/kg The evolution of the solid yield is very similar to that
LHVa ASTM D-3286-96 16400 observed in previous thermogravimetric studies carried out with
HHVb ASTM D-3286-96 17670
sewage sludges from various sources.25-30 The slight, initial
weight loss under 300 °C is thought to be caused mainly by
a
Lower heating value. b Higher heating value.
dehydration.31 The maximum rate of weight loss is in ac-
Sewage sludge pyrolysis took place in a steel basket hanging cordance with the literature. At high temperatures, a reduction
from the upper part of the reactor. Nitrogen, used as an inert in devolatilization rates has also been reported for sewage
carrier gas, entered the reactor at the top at a flow rate of 100 sludge.2 Regarding the liquid fraction, some authors have
mL/min. This value for the nitrogen flow rate was selected after observed very similar increases up to 650 °C, with more or less
preliminary gas analysis using the same experimental system. constant yields above this temperature.2 As a consequence, gases
The sample temperature was measured tith four type K evolve from char at high temperatures at approximately the same
thermocouples placed inside the steel basket. Outside the reactor, rate as occurs with devolatilization. High-temperature weight
the pyrolysis gases and nitrogen flowed through a gas cleaning loss has been attributed mainly to decomposition of inorganic
materials such as carbonates.26,27,32
system consisting of a condenser (cooled by a continuous flow
The sum of fixed carbon and ash (34.69% on a sludge basis,
of a mixture of water and ethylene glycol at -2 °C) and a cotton
as given by the proximate analysis) is higher than the final solid
filter. During the tests, gas composition was measured semi-
yield measured for C900B (32.4%). This suggests a loss of either
continuously by an Agilent 3000A gas chromatograph with a
mineral matter or fixed carbon during pyrolysis.
thermal conductivity detector (GC-TCD) connected online after 3.2. Gas Fraction. Evolution of the gaseous products was
the gas cleaning system. The chromatograph used a Porapak N measured by means of a chromatograph for all experiments.
column and a molecular sieve. The compounds analyzed were As no relevant differences were found between them, gas
H2, N2, CH4, CO, CO2, C2H6, C2H4, C2H2, and H2S. Gas mass evolution is presented for the longest experiment, which includes
yield was measured as a result of mass balances from chro- overall gas formation through all pyrolysis temperatures.
matographic data, taking nitrogen flow as the reference. Char Figure 3 presents the mass flow of released gases as a function
and condensate mass yields were measured gravimetrically. In of the extent of pyrolysis. The mass flow for each gas was
the following discussion, the char is referred to as C followed calculated from chromatographic measurements. As can be seen,
by a number representing the pyrolysis temperature (e.g., C700). the predominant gases formed are CO and CO2. CO evolves in
In the case of char pyrolyzed at 900 °C with a holding time of the first stage, with a maximum rate at 450 °C, and is released
2 h, the sample is referred to as C900B. Raw sewage sludge is in higher amounts from 700 °C until the final temperature. CO2
referred to as SS. forms mainly at temperatures around 425 °C, with a smaller
2.3. Char Analysis. Proximate and ultimate analyses of the second stage near 700 °C. The rest of the gases detected were
char were conducted using the same equipment and procedures present in much lower quantities, as shown in Figure 3b. H2
evolves significantly over a wide temperature range (500-900
as for the raw sewage sludge sample, detailed in Table 1. Fourier
°C), with a maximum near 625 °C. C2H4 and C2H6 show
transform infrared (FTIR) spectra were obtained in a Bruker
identical trends with a maximum at 550 °C, whereas CH4 is
Vertex 70 spectrometer, with KBr pellets and a resolution of 2 released in greater amounts with a maximum at 600 °C and
cm-1. X-ray diffraction (XRD) patterns were recorded in a continuing to 900 °C. Inguanzo et al.2 found almost identical
Bruker D8 Advance Series 2 diffractometer. Nitrogen adsorption trends for CO, CH4, C2H4, and C2H6, with H2 evolution
isotherms at 77 K were measured using a Micromeritics ASAP increasing even beyond 600 °C and CO2 without a second
2020 analyzer. Samples were degassed at 250 °C and 5 × 10-3 formation stage. Thipkhunthod et al.28 observed an additional
torr vacuum. Surface area was obtained by the BET method, intermediate step in CO2 formation at 500 °C and retarded H2
and t-plot external area, micropore area, and micropore volume evolution (with a maximum at 750 °C). CO was not determined,
were also calculated. and C2H4 and CH4 showed similar behaviors. Biagini et al.27
Ind. Eng. Chem. Res., Vol. 48, No. 6, 2009 3213
Figure 5. Ultimate analysis of sewage sludge and chars (based on the initial
weight of the sewage sludge).
Table 2. Comparison between Characteristic Absorptions (cm-1) Figure 8. Apparent aromaticity of chars.
from Cellulose and SS Sample
band this work Liu et al.44 Yang et al.45 Carrillo46
CsO stretch 1034 1030 1060 1035
1059 1064 1080 1055
1109 1114 1108 1111
1161 1161 1170 1155
Figure 10. Comparison of BET surface area, micropore surface area, and
evolved CO.
Figure 11. SEM image for C900 and EDX analyses for selected points.
to that of hydrogen, leading to minimal nitrogen content in fixed-bed sewage sludge pyrolysis. As the temperature increases,
C900B. Nevertheless, the weight loss for nitrogen takes place these aliphatic compounds undergo further cracking, thus leading
continuously from 400 to 900 °C, in contrast to hydrogen, which to lower-molar-weight aliphatic compounds as detected in the
has pronounced weight loss in the interval between C300 and chromatographic analyses. From 600 °C, hydrogen weight loss
C400. Finally, the weight loss curves for carbon and hydrogen is slower, indicating that the maximum formation of hydrogen-
show equivalent evolutions with temperature, which might be containing gaseous species has finished. At the same time, this
indicative of a close relationship regarding evolved or decom- relative decrease of the hydrogen release could indicate a
posed hydrocarbon products. predominance of aromatic compounds (rather than aliphatic
Comparing these results with gas evolution, it can be seen ones) in the liquid fraction at high temperatures, as has been
that the maximum hydrogen weight loss from char is located reported in several studies.2,35
between 300 and 400 °C. This does not correspond with the As previously mentioned, nitrogen suffers its maximum
maximum release of hydrogen-containing gases (H2, C2H6, C2H4, weight loss between 300 and 400 °C, which can be attributed
and CH4). Thus, the generated liquid fraction at this temperature to the decomposition of the less stable amino acid structures,
interval must contain most of this hydrogen. Such observation leading to ammonia formation. Further observations regarding
might indicate the formation of aliphatic compounds, which the amino acid content of sewage sludge will be discussed in
collect in the condensed fraction. Light hydrocarbons have been the next sections. According to Tian et al.,36 the low-heating-
identified as the major constituents of the condensate yield34 in rate pyrolysis of sewage sludge yields significant amounts of
3216 Ind. Eng. Chem. Res., Vol. 48, No. 6, 2009
obtained by calculating the aliphatic and aromatic hydrogen C900B. Oldhamite is a typical mineral phase formed under
mole fractions (determined from FTIR integrated areas for the extremely reducing conditions.65
aliphatic CsH region, 2700-2900 cm-1, and the aromatic CsH The total sulfur loss from the solid matrix at the final stage
region, 700-900 cm-1) and the atomic hydrogen/carbon ratio. of pyrolysis is 35%, as derived from ultimate analysis of C900B.
The results are shown in Figure 8. It is worth noting that this Hydrogen sulfide release in the gas product is below 6 wt %
calculated aromaticity cannot be considered an accurate mea- (based on the initial sulfur weight) and corresponds to the
surement of the aromatic content of chars. Nevertheless, it can interval between 300 and 400 °C. Consequently, some of the
serve as a useful parameter for comparative purposes between sulfur might also be forming tarry compounds in the condensate
chars. fraction. For high-temperature chars, the XRD spectra suggest
As was expected, a sharp increase in the aromatic character that sulfur from sewage sludge appears to be found mainly in
of the chars is observed up to 500 °C. At higher temperatures, calcium and iron sulfates. However, an occurrence of calcium
the aromaticity continues its increase at a lower rate. This is and iron sulfides at high temperatures appears to be much more
consistent with the FTIR interpretation above. Several authors significant than the initial sulfates detected by XRD for C300.
have also correlated an increasing pyrolysis temperature to an This suggests that most of the organic sulfur in the sewage
increase in the degree of aromatization of chars, based mainly sludge is reacting with inorganic cations to form sulfides during
on FTIR observations.5,47,56,63 pyrolysis.
3.3.3. XRD Spectra. XRD spectra of the chars are shown
Although not quantified, the phosphorus content in the sewage
in Figure 9. As can be seen at first glance, an increase in the
sludge seems to follow a similar trend, forming metal phosphides
pyrolysis time and temperature results in higher amounts of
that remain in the chars (especially barringerite) and tar
crystallographic phases, with sharper peaks appearing in the
compounds.
samples pyrolyzed at 900 °C. This could be a consequence of
the disappearance of amorphous organic phases and an increase Regarding iron phosphides and sulfides (detected only at the
in the ash percentage during pyrolysis, as well as the formation highest temperatures), sample C300 contains iron chloride
of new crystal structures by a combination of species released (FeCl3), which is one of the reagents used during the physico-
from decomposing material, under extreme temperature and chemical treatment of the original sludge. Thus, this compound
reduced atmosphere conditions. is bound to exist in sufficient amounts to provide most of the
As with the infrared spectra, detailed analysis of the XRD iron sulfides and phosphides at high temperature. Further
patterns becomes difficult because of the heterogeneous com- information about iron transformations could not be inferred
position of the chars. XRD spectra seem to be built up from a from XRD spectra, as iron compounds were not detected at
huge range of either crystal or amorphous structures. Thus, only significant levels at intermediate temperatures.
well-defined structures are identified in this section. In general, inorganic compounds in chars appear to be
Quartz is the most recognizable crystallographic structure for affected significantly by both pyrolysis temperature and time.
all temperatures. Thus, XRD spectra confirm FTIR observations Some inorganic phases were detected by XRD (especially those
regarding SisO structures. Calcite is detected for chars pyro- corresponding to the most abundant metals in sewage sludge
lyzed up to 700 °C. Beyond this temperature, carbonates undergo ashes, as showed in Table 1). Other dispersed phases might be
decomposition and therefore are not present in high-temperature present in minor amounts not detectable by this experimental
samples (C800 and C900), as indicated by FTIR spectroscopy. technique, but they might play an important role when consider-
Table 4 summarizes the crystallographic structures detected by ing these materials as potential adsorbent precursors.56
XRD analysis. 3.3.4. BET Surface Area. The evolution of the BET surface
For the C300 sample, the strongest peak at 2θ ) 22.6° might area of pyrolysis chars can be observed in Figure 10. As can
correspond to cellulose.64 It seems to have a low degree of be seen, the BET surface area is very small for chars pyrolyzed
crystallinity, probably because, at this point, partial depolym- under 600 °C, despite the major solid weight loss below this
erization has taken place. As mentioned earlier, cellulose temperature. This fact could be due to the blocking of pores
decomposition in pyrolysis takes place between 300 and 400 caused by volatile compounds from the char. As the temperature
°C,45 and thus, cellulose could not be detected at significant increases, these volatiles are further cracked and released from
levels in the C400 sample. The FTIR spectra are in agreement the solid. As confirmed by chromatographic analyses, products
with these observations. likely to result from volatile cracking (CH4, C2H6, and C2H4)
Phase identification allows carbonate decomposition to be reach their maximum generation rate between 500 and 600 °C.
confirmed, as concluded from the FTIR analysis discussed Cracking and subsequent release of gaseous species might partly
earlier. As seen in the gas evolution plots, near 700 °C, there is explain surface area development from these temperatures. Lu
a second stage of generation of CO2, which is one of the et al.4 found the lowest surface area for sewage sludge chars
decomposition products of carbonates. The other compound, pyrolyzed at 650 °C, and this fact was attributed to an
CaO, is detected the in XRD patterns for temperatures higher intermediate melt formation in addition to volatiles being
than 700 °C. evolved. A high increase in BET surface area was observed
For high-temperature chars, new phases become distinguish- after gases were released. In this work, the minimum BET
able, as mentioned before. Silicates, feldspars, and sulfides surface area was observed for sample C500. For higher
appear in these patterns. It is not only the temperature that causes temperatures, the surface area increased with increasing tem-
changes in the surface chemistry; the long isothermal pyrolysis perature, and thus, the maximum BET surface area (124 m2/g)
time (2 h for C900B) produces significant differences in the corresponds to char C900. Isothermal pyrolysis for 2 h at 900
diffraction pattern compared with that of the C900 char. For °C (C900B) causes only a very slight reduction in BET surface
instance, relatively high amounts of barringerite (iron phosphide) area. Nevertheless, the largest area of micropores is found at
are detected in the C900B char, whereas this phase is less lower stages of pyrolysis, near 800 °C. Beyond this temperature,
important in C900 and is not present in the lower-temperature micropore area production decreases. Thus, the observed
chars. Also, more oldhamite (calcium sulfide) is present for increase in BET surface area might be due to mesopore
Ind. Eng. Chem. Res., Vol. 48, No. 6, 2009 3219
formation from widening micropores. This effect has been toward desulfurization.13 However, no evidence has been found
observed in previous works for sewage sludge.4 for the presence of reduced iron. This is thought to be caused
An attempt was made to correlate the changes in BET surface by the immediate formation of barringerite (iron phosphide),
area with the observations derived from various analyses in the as detected clearly in XRD spectra. Probably, phosphide ions
present work. It was found that the BET surface area growth at have their origin in the high-temperature decomposition of
high temperatures seems to be closely linked with the CO phosphates, which were identified by FTIR spectra. In fact,
generation rate. The maximum generation rate for CO is located barringerite and oldhamite follow similarly increasing trends
at 900 °C, and 120 min of holding time produces a considerable in the XRD patterns. (3) As a result of this reaction, CO is
decrease in its evolution. This fact is also shown in Figure 10 evolved from chars. BET surface area is closely related to
and suggests that CO is released in proportion to newly forming evolved CO because it is proportional to char gasification. The
or widening pores. micropore surface area reduction at high temperatures could be
As previously mentioned, the micropore surface area reaches related to pore widening as CO continues being released.
its maximum value near 800 °C and then starts to decrease. 3.3.5. SEM/EDX Analysis. To confirm earlier observations,
This could be due to the high rates achieved at this temperature a series of SEM images were taken for raw sewage sludge and
for evolved CO. CO2 evolved at this temperature is thought to the C900 char. Figure 11 shows an SEM image of C900. The
be a product of direct carbonate decomposition, unlike CO diverse char particle shapes are a consequence of sewage sludge
formation, which could be a consequence of carbon removal heterogeneity. At some selected points, an EDX analysis was
from chars, i.e., char gasification. For coal and biomass, it has made to identify the predominant elements and their dispersion.
been found that the lower the rate of char gasification, the greater As can be seen, the main elements identified are C, O, Si, Ca,
the micropore development.66,67 Increasing rates of char gas- P, and Fe, and their relative amounts differ significantly from
ification would cause microporosity development to decelerate. one point to another. This indicates the heterogeneous composi-
Further decreases of microporosity can be attributed to pore tion of char.
widening, as mentioned earlier. A comparison of the SEM images of sewage sludge and the
According to these results, attention should be focused on C900 char is shown in Figure 12a,b. The images indicate a
CO formation, as it seems to be directly linked with surface significant reduction in volume for pyrolyzed particles and show
area evolution. the presence of fibrous structures formed as a result of pyrolysis.
The temperature range between 700 and 900 °C is the region More detailed SEM micrographs show structures resembling
of interest for BET surface area evolution. In this interval, the nanotube bundles or fibers, together with dispersed particles of
following facts were derived from experimental observations inorganic phases (Figure 13). Similar observations with evidence
and analyses made throughout this work: (1) The CO2 flow rate of such carbon structures have been reported for sewage sludge
decreases continually in the temperature range, whereas CO pyrolysis chars.7 The tubular structures found in our study seem
exhibits the opposite trend. (2) Calcium carbonate decomposition to be somewhat greater than those reported by Bandosz et al.
takes place at these temperatures and might explain the second-
stage CO2 formation. Consequently, CaO is formed, as revealed 4. Conclusions
by XRD. (3) The majority of sulfur is still forming part of the
char as a constituent of inorganic sulfides. Within this range, At low pyrolysis temperatures, CO2, CO, H2O, and tars are
some sulfur transfer reactions between metallic cations are evolved by means of devolatilization of sewage sludge fractions
observed by XRD. More precisely, sulfur tends to move from such as cellulose, long-chain fatty acids, and less stable proteins.
Fe compounds to Ca ions. (4) The latter is consistent with the NH3 is thought to be evolved as well. Most of the condensate
observed CaO decrease forming CaS. (5) At these temperatures, fraction and char weight loss is observed in the temperature
both char and carbon weight loss are still taking place, as shown range between 300 and 500 °C. At intermediate temperatures
by elementary analyses of chars and product distribution. (6) (400-700 °C), light hydrocarbons (CH4, C2H6, C2H4) are
The CO/CO2 ratio for this range does not fit with theoretical evolved as a consequence of thermal cracking of those volatiles
Boudouard equilibrium relationships. (7) The BET surface area remaining in the char as a product of low-temperature devola-
increases continuously with increasing temperature. (8) Taking tilization. This causes the development of a preliminary pore
into account these facts, this temperature region seems to be structure for chars, although the BET surface area development
the optimal for the development of adsorptive properties of is small. H2 evolution is prolonged even at 900 °C.
chars, especially regarding sulfur compound adsorption. Decomposition of carbonate (predominantly CaCO3) starts
Taking into account all of these factors, the following at 700 °C and produces a temperature-decreasing flow of CO2
hypotheses can be formulated: (1) Decomposition of carbonates (proportional to the remaining carbonate content). CaO is formed
(predominantly CaCO3) starts at 700 °C and produces a at the same time, which promotes char gasification and sulfur
temperature-decreasing flow of CO2 (proportional to the carbon- transfer within the inorganic constituents of the char ash
ate content). Simultaneously, CaO is formed, which promotes (specially Fe species). As a result, an increasing rate of CO
char gasification and sulfur transfer within the inorganic production is observed. BET surface area is closely related to
constituents of char ash. Calcium compounds have been the CO released and thus increases substantially. Over the entire
extensively studied as catalysts for char gasification of coal and temperature range, the aromatic character of the chars increases
desulfurization.68,69 (2) The aforementioned char gasification as pyrolysis advances.
occurs in the presence of iron sulfides. It is known that calcium Finally, the formation of filament-like carbon structures was
oxide can promote the decomposition of ferrous sulfide to form detected for high-temperature pyrolysis samples.
calcium sulfide.68 The proposed main reaction70 can be written
as Acknowledgment
FeS + C + CaO f Fe + CaS + CO The authors thank the Spanish Ministry of Science and
In accordance with this mechanism, calcium and iron have been Innovation (MICINN) for providing frame support for this work
identified as main factors governing the catalytic activity of chars (Project CTQ2007-66885).
3220 Ind. Eng. Chem. Res., Vol. 48, No. 6, 2009