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Article
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
Downloaded from http://pubs.acs.org on March 13, 2009

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 Ind. Eng. Chem. Res. 2009, 48, 3211–3221 3211

Structural Changes of Sewage Sludge Char during Fixed-Bed Pyrolysis

Javier Ábrego,*,† Jesús Arauzo,† José Luis Sánchez,† Alberto Gonzalo,† Tomàs Cordero,‡ and
José Rodrı́guez-Mirasol‡
Thermo-chemical Processes Group, Aragón Institute for Engineering Research (I3A), Marı́a de Luna 3, 50018
Zaragoza (Spain), and Chemical Engineering Department, School of Industrial Engineering, UniVersity of
Málaga, Campus de El Ejido s/n, 29013 Málaga (Spain)

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
Sewage sludge disposal is one of the major problems for
wastewater treatment plants in the European Union.1 The
constant increase in its production is caused by the higher
constraints imposed on effluent treatments, so that disposal itself
has become an environmental problem of the first magnitude.
Conventional disposal routes such as landfilling, dumping, or
farmland application are subject to strict legislative constraints
or are even banned in several countries, and therefore, alternative
options need to be considered.
One of the main characteristics of sewage sludge is the
presence of high amounts of inorganic ash and low carbon
contents when compared with other materials, such as wood or
lignocellulosic char from agriculture. As a result, sewage sludge
has a relatively low energy value, but is sufficient for some
kind of waste-to-energy process to be considered as feasible.
In addition, large amounts of sewage sludge are generated in
every wastewater treatment plant, and as mentioned before,
appropriate disposal methods need to be found. Thermochemical
processes seem to be a promising alternative pathway for this
sewage sludge treatment.2,3
Pyrolysis is a thermochemical process that consists of the
thermal decomposition of a material in the absence of air.
Pyrolytic char can be considered as an adsorbent precursor if
prepared under controlled pyrolysis conditions,4,5 so a large
reduction in volume is achieved, together with the preparation
of a valuable product. Thus, if one also considers energy
recovery from the gaseous and liquid products of pyrolysis, an
integral sewage sludge valorization can be performed using this
technology.
Pyrolytic char from sewage sludge has less surface area than
commercial activated carbons. Reported Brunauer-Emmett-
Teller (BET) surface area values found in the literature are no
greater than 400 m2/g, whereas commercial activated carbon
can exhibit much higher surface areas. Nevertheless, adsorbents
* To whom correspondence should be addressed. E-mail: javabr@
unizar.es.
†
Aragón Institute for Engineering Research (I3A).
‡
University of Málaga.
10.1021/ie801366t CCC: $40.75  2009 American Chemical Society
Published on Web 02/05/2009
from sewage sludge can play a very effective role in the removal
of some contaminants generated in pyrolysis or gasification, such
as hydrogen sulfide and sulfur or nitric oxides.6-15 It can also
be used for the effective removal of metals, dyes, phenol, and
chemical oxygen demand (COD) in aqueous solutions.16-22 If
necessary, adsorption properties can be improved by chemical
or physical activation stages,10,14-24 as well as by mixing with
other materials.6,8,9,13,19
To investigate the use of sewage sludge char as an adsorbent,
the specific goal of this study was to investigate the structural
changes and the evolution of the char during low-heating-rate
pyrolysis on a fixed-bed reactor. Extensive analysis of the char
will provide useful knowledge about the processes that occur
during pyrolysis and will contribute to a better understanding
of the thermochemical transformation pathways of sewage
sludge.
2. Experimental Section
2.1. Sewage Sludge Analysis. A sample of dry sewage
sludge was supplied as a granulated product from an urban
wastewater treatment plant. The sludge was undigested and had
previously undergone various physicochemical processes and
thermal drying. Table 1 lists the results of proximate, ultimate,
and ash analyses and and measurements of the low heating value
of the received sewage sludge, performed by the Instituto de
Carboquı́mica (CSIC, Zaragoza, Spain).
The dried sewage sludge was crushed and sieved to provide
a feed sample in the size range of 150-250 µm and kept at
105 °C for 24 h in an oven to remove the moisture prior to
each experiment.
2.2. Laboratory-Scale Fixed-Bed Pyrolysis Installation.
Pyrolysis of sewage sludge was carried out on a fixed-bed
reactor under an inert atmosphere. In each experiment, a sample
of 2.5 g of raw sewage sludge was pyrolyzed at a heating rate
of 20 °C/min. The small sample amount minimized temperature
profiles during the experiments.
Figure 1 shows a diagram of the pyrolysis experimental
system. The reactor was cylindrical with a diameter of 90 mm
and a height of 320 mm and was inside a 900-W furnace.
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

Figure 1. Schematic diagram of the laboratory-scale pyrolysis reactor.
Figure 2. Product distribution as a function of temperature or hold time.
Figure 3. Evolution of released gases as a function of pyrolysis temperature
and isothermal time.
also found a three-stage release of CO2. CO and H2 were not
reported, and the rest of the compounds showed similar
temperature dependencies. Conesa et al.33 described methane
formation in two stages, H2 evolution at lower temperatures,
and a greater second-stage CO2 formation at somewhat lower
temperatures (500-600 °C). Obviously, comparisons with other
Ind. Eng. Chem. Res., Vol. 48, No. 6, 2009 3213
Figure 4. Ultimate analysis of sewage sludge and chars.
Figure 5. Ultimate analysis of sewage sludge and chars (based on the initial
weight of the sewage sludge).
works do not take into account differences in heating rates,
sewage sludge composition, reactor type, and several other
factors.
According to the release rates (in grams per minute) given
by Figure 3, it is clear that most of the mass of the gas fraction
(more than 90 wt %) corresponds to carbon oxides. CO is
practically the only gas detected at the isothermal 900 °C stage
of the experiment. Even though it is being released at very low
rates at this point, it is generated continuously for 120 min and
thus contributes to a substantial percentage of the gas fraction.
3214 Ind. Eng. Chem. Res., Vol. 48, No. 6, 2009

Figure 6. FTIR spectrum of raw sewage sludge (SS).

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

3.3. Char Fraction. 3.3.1. Ultimate Analysis. Evolution of

the ultimate analysis of the char can provide useful information
about the transformations of pyrolytic char. Figure 4 shows
elementary compositions of chars. It can be observed that the
relative mass proportions of each element follow different trends
with pyrolysis. The relative percentage of carbon in the chars
shows little variation, with slight decreases between C400 and
C700. In contrast, the amounts of hydrogen and nitrogen in the
sample decrease at high temperatures. The sulfur percentage
shows a slight and constant increase, suggesting that most of
this element remains within the char regardless of the temper- Figure 9. XRD spectra of the chars.
ature or hold time.

Figure 10. Comparison of BET surface area, micropore surface area, and
evolved CO.

Figure 5 shows compositions calculated on a sewage sludge

Figure 7. Detailed evolution of FTIR spectra for selected wavenumber
intervals. basis. This seems a more convenient way to show mass loss
for each main char constituent, as it refers to the initial weight
Table 3. Wavenumber Shift of Initial 1642 cm-1 Band with of the sewage sludge and thus provides a more consistent
Temperature comparison. The total carbon content of the sewage sludge
band positiona (cm-1) sample decreases from more than 40% to about 10% in the final
1646 SS
experimental stage C900B. Thus, the carbon mass loss represents
1646 C300 more than 50% of the weight loss of the initial sludge. Hydrogen
1616 C400 is found in minimal amounts for this final sample, indicating
1601 C500 nearly 100% weight loss during pyrolysis. As mentioned before,
1578 C600 sulfur does not show any significant loss apart from a slight
a
Initially assigned to amide I. initial descent up to C400. Nitrogen exhibits a behavior similar
 Ind. Eng. Chem. Res., Vol. 48, No. 6, 2009 3215

Figure 11. SEM image for C900 and EDX analyses for selected points.

Table 4. Crystallographic Structures Identified by XRD

C300 C400 C500 C600 C700 C800 C900 C900B
cellulose
quartz SiO2 quartz SiO2 quartz SiO2 quartz SiO2 quartz SiO2 quartz SiO2 quartz SiO2 quartz SiO2
feldspars: albite, feldspars: albite, feldspars: albite,
anorthite anorthite anorthite
silicates: almandine silicates: almandine
calcite CaCO3 calcite CaCO3 calcite CaCO3 calcite CaCO3 calcite CaCO3
anhydrite CaSO4
calcium oxide CaO calcium oxide CaO calcium oxide CaO calcium oxide CaO
Portlandite Ca(OH)2
oldhamite CaS oldhamite CaS oldhamite CaS oldhamite CaS oldhamite CaS
iron sulfates
FeSO4, Fe2(SO4)3
FeCl3
troilite FeS troilite FeS troilite FeS
pyrrhotite Fe1-xS pyrrhotite Fe1-xS pyrrhotite Fe1-xS
(x ) 0-0.2) (x ) 0-0.2) (x ) 0-0.2)
barringerite Fe2P barringerite Fe2P

to that of hydrogen, leading to minimal nitrogen content in
C900B. Nevertheless, the weight loss for nitrogen takes place
continuously from 400 to 900 °C, in contrast to hydrogen, which
has pronounced weight loss in the interval between C300 and
C400. Finally, the weight loss curves for carbon and hydrogen
show equivalent evolutions with temperature, which might be
indicative of a close relationship regarding evolved or decom-
posed hydrocarbon products.
Comparing these results with gas evolution, it can be seen
that the maximum hydrogen weight loss from char is located
between 300 and 400 °C. This does not correspond with the
maximum release of hydrogen-containing gases (H2, C2H6, C2H4,
and CH4). Thus, the generated liquid fraction at this temperature
interval must contain most of this hydrogen. Such observation
might indicate the formation of aliphatic compounds, which
collect in the condensed fraction. Light hydrocarbons have been
identified as the major constituents of the condensate yield34 in
fixed-bed sewage sludge pyrolysis. As the temperature increases,
these aliphatic compounds undergo further cracking, thus leading
to lower-molar-weight aliphatic compounds as detected in the
chromatographic analyses. From 600 °C, hydrogen weight loss
is slower, indicating that the maximum formation of hydrogen-
containing gaseous species has finished. At the same time, this
relative decrease of the hydrogen release could indicate a
predominance of aromatic compounds (rather than aliphatic
ones) in the liquid fraction at high temperatures, as has been
reported in several studies.2,35
As previously mentioned, nitrogen suffers its maximum
weight loss between 300 and 400 °C, which can be attributed
to the decomposition of the less stable amino acid structures,
leading to ammonia formation. Further observations regarding
the amino acid content of sewage sludge will be discussed in
the next sections. According to Tian et al.,36 the low-heating-
rate pyrolysis of sewage sludge yields significant amounts of
3216 Ind. Eng. Chem. Res., Vol. 48, No. 6, 2009
Figure 12. SEM images of (a) sewage sludge and (b) C900 char.
Figure 13. Detailed SEM micrograph of C900 char.
ammonia between 300 and 500 °C and low yields of HCN at
higher temperatures (up to 900 °C), which is in good agreement
with the nitrogen loss in our study. Nevertheless, nitrogen
compounds are probably not limited to these two species. Some
minor amounts of other nitrogen compounds, such as cyano
compounds and those with heteroaromatic rings, are probably
incorporated in the liquid fraction throughout a wide temperature
range.34 Unfortunately, no measurements for any nitrogen
compounds were carried out in the present work.
Sulfur is assumed to be present mainly in organic forms in
sewage sludge, as will be discussed later. Only a minor weight
loss occurs before 400 °C, which corresponds to H2S formation,
as detected by chromatographic analysis. Further variations are
negligible, suggesting that sulfur persists in chars, probably
incorporated in inorganic structures.
3.3.2. FTIR Spectra. Spectral interpretation was done ac-
cording to the IR spectroscopy literature.37,38
3.3.2.1. FTIR Spectrum of Raw Sewage Sludge. Taking
into account its origin and undigested character, the sludge is
likely to be composed mainly of proteins and its constituents;
a cellulosic fraction, which includes cellulose, hemicellulose,
and lignin; and fatty acids.39 The sewage sludge should then
include most of the functional groups of these constituents:
alcoholic, carboxylic, amide, amine, aromatic, and methylene
groups. In fact, FTIR analysis confirms the predominance of
these functionalities, as shown in Figure 6.
A broad and intense band at 3200-3600 cm-1 corresponds
to OsH and NsH stretching vibrations. These functional groups
might indicate compounds such as alcohols, carboxylic acids,
and amides/amines present in the sample. Moving toward lower
wavenumbers, two peaks appear at 2926 and 2853 cm-1
corresponding to asymmetrical and symmetrical stretching,
respectively, of methylene groups forming predominantly
aliphatic structures.
Although very weak, a band at 2516 cm-1 provides the only
indication of organic sulfur in the sample, corresponding to SsH
stretching vibration. Other organic sulfur bands may be obscured
by stronger absorptions.
The peak at 1642 cm-1 is due to the amide I band.40 However,
other contributions cannot be excluded, such as the CdO
stretching vibrations from other functionalities (suggested by a
distinguishable shoulder at the left of the 1720 cm-1 peak,
assignable to fatty acid carboxylic groups).
The band at 1545 cm-1 might be due to NsH bending, which
is characteristic of the amide II band. CdC aromatic skeletal
vibrations can also be found between 1600 and 1500 cm-1 and
might be present in the sample because of lignin structures.41
In the interval between 1300 and 1500 cm-1, vibration of CH2
groups and OsH bending vibrations for alcohols and carboxylic
acids give rise to a variety of peaks. As a result, a broad band
around 1430 cm-1 is visible. This wavenumber has been said
to correspond to typical positions for CH2 scissoring for
cellulose42 and saturated fatty acids.43
In the fingerprint region of the spectrum (900-1300 cm-1),
the most remarkable feature is a combination of bands in
the interval between 1150 and 1000 cm-1 that has been
assigned by several authors to polysaccharides.39 More
precisely, this region of the spectrum consists of a broad band
with several shoulders, and it is almost identical to results
from several reported cellulose FTIR studies,44-46 as sum-
marized in Table 2.
Some inorganic structures in the sludge might also contribute
to the spectra. In fact, SisO structures generate bands around
1080 cm-1 that probably contribute to the mentioned band
combination above 1000 cm-1. Si has been identified in the
ash analysis (Table 1) as one of the major inorganic constituents
of sewage sludge. Also, a small but sharp peak at 873 cm-1
could be due to inorganic carbonates, especially calcium
carbonate (calcium is another major inorganic compound in the
ashes). A very sharp band at 1383 cm-1 can be attributed to
nitrates or phosphates.
Finally, the last portion of the spectrum below 900 cm-1 is
less representative for group determination purposes and could
be due to aromatic structures, skeletal vibrations, and amine
and amide groups.
The main absorption bands found for this particular sludge
donotdifferqualitativelyfromthosereportedpreviously,5,24,39,47-50

although marked discrepancies can be found among spectra
interpretation in the existing literature. Commonly, FTIR
analysis has been used as an additional technique to support
previous experimental observations. In the present work, an
attempt was made to detail the FTIR spectra of sewage sludge
and chars regarding the changes experienced by the solid fraction
during pyrolysis within the entire temperature range, while being
aware of its obvious limitations.
3.3.2.2. Changes in FTIR Spectrum during Pyrolysis. The
FTIR spectra exhibit visible changes during pyrolysis that are
related to the surface structure. Figure 7 shows detailed spectral
evolution with pyrolysis for selected wavenumber ranges. In
general, the organic functional groups found in sewage sludge
tend to decrease or even disappear as pyrolysis takes place. Upon
closer examination, some structural changes in the solid matrix
can be discerned.
For instance, pyrolytic decomposition of polysaccharides has
a marked effect in the strong decrease of the 1000-1200 cm-1
band.51 This band combination (as described in Table 2) is
clearly visible for the SS and C300 samples but is not present
at higher temperatures, thus confirming that the decomposition
of the cellulose fraction is complete at 400 °C.
Surprisingly, an increase of methylene stretching vibrations
for C300 shows that this functionality increases its concentration
compared to that found in sewage sludge. The partial decom-
position of cellulose, fatty acids, and polypeptides and subse-
quent formation of long aliphatic chains could explain this trend.
Also, Green et al.52 stated that cellulose depolymerization takes
place at low temperatures without significant mass loss or
generation of volatiles, as suggested by the negligible variation
of the 1000-1200 cm-1 band at 300 °C.
The weight loss of C300, compared to sewage sludge, is only
6.5%. The spectra of the two samples show few differences,
which seems to fit with the low weight loss. Apart from an
increase in the methylene stretching peak, a slight decrease in
the OsH stretch absorption can be observed. This could be
related to the dehydration of mineral matter. However, the most
prominent difference is found in the band previously assigned
to nitrates and/or phosphates at 1383 cm-1. This band is much
smaller at 300 °C and, thus, might indicate nitrate decomposi-
tion. The most likely predominant compound seems to be
ammonium nitrate, because of its low decomposition temper-
ature.53 Such decomposition would give NO2, H2O, and NH3
as the main products up to 300 °C.54 Persistence of other nitrates
and phosphates is suggested by the small remaining peak at
higher temperatures (C300-C500 samples). Also, minerals
absorbing at the same wavenumbers (such as quartz and albite)
might be present in the samples obtained at high temperatures.
A distinguishable change can be seen in what was previously
assigned to the amide I band (1642 cm-1). As the temperature
increases, this band gradually broadens and shifts toward lower
wavenumbers, although the intensity of the absorption remains
fairly constant up to 400 °C. This can be explained by a decrease
in amide groups and a simultaneous increase of amino acid
functionalities, due to hydrolysis of the polypeptides or protein
peptide bonds. Amine groups absorb near 1600 cm-1, overlap-
ping with the decreasing amide I band, thus causing a shift to
lower wavenumbers (Table 3). Amine functionalities also
manifest themselves between 1000 and 1200 cm-1, as might
be indicated by the broad shoulder at these wavenumbers for
C400. At the same time, carboxylic groups show increased
absorptions at the 1710 cm-1 band for the mentioned sample.
Additional formation of amino acid salts due to the sewage
sludge content of metals or halides cannot be ruled out. For
Ind. Eng. Chem. Res., Vol. 48, No. 6, 2009 3217
instance, carboxylate anions absorb strongly near 1600 and 1400
cm-1, which is in agreement with previous observations.43
Although it might seem unusual for amino acids to exist under
such conditions, a significant persistence of such structures at
these temperatures has been reported in previous pyrolysis
studies, without volatilization or sublimation,55 Furthermore,
interactions within the char matrix might enhance its stability.
The amide II band found at 1545 cm-1 disappears almost
completely at 400 °C. The band at 1430 cm-1 increases in
intensity from 300 to 400 °C and shows little change up to 500
°C. This could be due to several factors. One could be the
previously mentioned carboxylate salts formation. Aromatic
compounds might also be contributing.
For wavenumbers above 2800 cm-1, two visible changes
occur. First, the mentioned maximum of methylene stretching
decreases with increasing temperatures until it is almost
undetectable beyond 500 °C, thus indicating a loss of aliphatic
structures. Second, the OsH and NsH stretching bands become
broader with increasing temperatures, and their absorbance
decreases gradually from 300 to 500 °C. At higher carbonization
temperatures, thess bands undergo little change, suggesting
unchanged inorganic links with OsH.24
The spectral region below 900 cm-1 shows two main bands
that grow sharper up to a maximum at 500 °C. For the C600
and C700 chars, both bands are still significant. As the
temperature rises to 800 and 900 °C, the peaks gradually fade,
but still show some minor bands. This behavior could be related
to a gradual increase in the aromatic nature of the char, as
reported in some works.56,57 The maximum at 500 °C might
correspond to the maximum aromatic formation, and the
subsequent decrease at higher temperatures might be due to the
sequential release of aromatics that can be later found in
the condensate fraction. At 600 and 700 °C, these bands are
still prominent. Persistence of the band around 1420 cm-1 to
700 °C is also likely to be related to aromatics, as the carboxylic/
carboxylate groups seem to have disappeared earlier (as reflected
by the shoulder at 1710 cm-1, which is not present at
temperatures higher than 500 °C), and is in accordance with
the aforementioned spectral trends below 900 cm-1.
As can be seen, the main recognizable changes in the spectra
occur up to 500 °C and correspond to the breakdown of
polymeric structures and a huge range of reactions involving
the released products, which seem to lead to the gradual
formation of aromatic structures as the temperature increases.
This is in accordance with the maximum weight loss, observed
between 300 and 500 °C.
Two sharp but small peaks appearing near 876 and 712 cm-1
for dried sewage sludge remain almost unaltered until 700 °C
and suddenly disappear beyond 700 °C. This could indicate
calcium carbonate decomposition, as this compound has rec-
ognizable peaks at these wavenumbers. Another characteristic
band for calcium carbonate is located near 1420 cm-1. At low
temperatures, it is probably overlapped by other functionalities,
but as mentioned before, it disappears beyond 700 °C. XRD
analysis should confirm the presence of only calcium carbonate
for chars pyrolyzed up to 700 °C. The decomposition temper-
ature of calcium carbonate, as found in the literature, seems to
confirm this.58
At high temperatures, few spectral details are visible at first
glance. This is probably due to the strong background absorption
of amorphous carbon in the samples.
To provide further insight into functionality changes, apparent
aromaticity was calculated using the procedure proposed
elsewhere for coal chars.59-62 The apparent aromaticity, fa, is
3218 Ind. Eng. Chem. Res., Vol. 48, No. 6, 2009
obtained by calculating the aliphatic and aromatic hydrogen
mole fractions (determined from FTIR integrated areas for the
aliphatic CsH region, 2700-2900 cm-1, and the aromatic CsH
region, 700-900 cm-1) and the atomic hydrogen/carbon ratio.
The results are shown in Figure 8. It is worth noting that this
calculated aromaticity cannot be considered an accurate mea-
surement of the aromatic content of chars. Nevertheless, it can
serve as a useful parameter for comparative purposes between
chars.
As was expected, a sharp increase in the aromatic character
of the chars is observed up to 500 °C. At higher temperatures,
the aromaticity continues its increase at a lower rate. This is
consistent with the FTIR interpretation above. Several authors
have also correlated an increasing pyrolysis temperature to an
increase in the degree of aromatization of chars, based mainly
on FTIR observations.5,47,56,63
3.3.3. XRD Spectra. XRD spectra of the chars are shown
in Figure 9. As can be seen at first glance, an increase in the
pyrolysis time and temperature results in higher amounts of
crystallographic phases, with sharper peaks appearing in the
samples pyrolyzed at 900 °C. This could be a consequence of
the disappearance of amorphous organic phases and an increase
in the ash percentage during pyrolysis, as well as the formation
of new crystal structures by a combination of species released
from decomposing material, under extreme temperature and
reduced atmosphere conditions.
As with the infrared spectra, detailed analysis of the XRD
patterns becomes difficult because of the heterogeneous com-
position of the chars. XRD spectra seem to be built up from a
huge range of either crystal or amorphous structures. Thus, only
well-defined structures are identified in this section.
Quartz is the most recognizable crystallographic structure for
all temperatures. Thus, XRD spectra confirm FTIR observations
regarding SisO structures. Calcite is detected for chars pyro-
lyzed up to 700 °C. Beyond this temperature, carbonates undergo
decomposition and therefore are not present in high-temperature
samples (C800 and C900), as indicated by FTIR spectroscopy.
Table 4 summarizes the crystallographic structures detected by
XRD analysis.
For the C300 sample, the strongest peak at 2θ ) 22.6° might
correspond to cellulose.64 It seems to have a low degree of
crystallinity, probably because, at this point, partial depolym-
erization has taken place. As mentioned earlier, cellulose
decomposition in pyrolysis takes place between 300 and 400
°C,45 and thus, cellulose could not be detected at significant
levels in the C400 sample. The FTIR spectra are in agreement
with these observations.
Phase identification allows carbonate decomposition to be
confirmed, as concluded from the FTIR analysis discussed
earlier. As seen in the gas evolution plots, near 700 °C, there is
a second stage of generation of CO2, which is one of the
decomposition products of carbonates. The other compound,
CaO, is detected the in XRD patterns for temperatures higher
than 700 °C.
For high-temperature chars, new phases become distinguish-
able, as mentioned before. Silicates, feldspars, and sulfides
appear in these patterns. It is not only the temperature that causes
changes in the surface chemistry; the long isothermal pyrolysis
time (2 h for C900B) produces significant differences in the
diffraction pattern compared with that of the C900 char. For
instance, relatively high amounts of barringerite (iron phosphide)
are detected in the C900B char, whereas this phase is less
important in C900 and is not present in the lower-temperature
chars. Also, more oldhamite (calcium sulfide) is present for
C900B. Oldhamite is a typical mineral phase formed under
extremely reducing conditions.65
The total sulfur loss from the solid matrix at the final stage
of pyrolysis is 35%, as derived from ultimate analysis of C900B.
Hydrogen sulfide release in the gas product is below 6 wt %
(based on the initial sulfur weight) and corresponds to the
interval between 300 and 400 °C. Consequently, some of the
sulfur might also be forming tarry compounds in the condensate
fraction. For high-temperature chars, the XRD spectra suggest
that sulfur from sewage sludge appears to be found mainly in
calcium and iron sulfates. However, an occurrence of calcium
and iron sulfides at high temperatures appears to be much more
significant than the initial sulfates detected by XRD for C300.
This suggests that most of the organic sulfur in the sewage
sludge is reacting with inorganic cations to form sulfides during
pyrolysis.
Although not quantified, the phosphorus content in the sewage
sludge seems to follow a similar trend, forming metal phosphides
that remain in the chars (especially barringerite) and tar
compounds.
Regarding iron phosphides and sulfides (detected only at the
highest temperatures), sample C300 contains iron chloride
(FeCl3), which is one of the reagents used during the physico-
chemical treatment of the original sludge. Thus, this compound
is bound to exist in sufficient amounts to provide most of the
iron sulfides and phosphides at high temperature. Further
information about iron transformations could not be inferred
from XRD spectra, as iron compounds were not detected at
significant levels at intermediate temperatures.
In general, inorganic compounds in chars appear to be
affected significantly by both pyrolysis temperature and time.
Some inorganic phases were detected by XRD (especially those
corresponding to the most abundant metals in sewage sludge
ashes, as showed in Table 1). Other dispersed phases might be
present in minor amounts not detectable by this experimental
technique, but they might play an important role when consider-
ing these materials as potential adsorbent precursors.56
3.3.4. BET Surface Area. The evolution of the BET surface
area of pyrolysis chars can be observed in Figure 10. As can
be seen, the BET surface area is very small for chars pyrolyzed
under 600 °C, despite the major solid weight loss below this
temperature. This fact could be due to the blocking of pores
caused by volatile compounds from the char. As the temperature
increases, these volatiles are further cracked and released from
the solid. As confirmed by chromatographic analyses, products
likely to result from volatile cracking (CH4, C2H6, and C2H4)
reach their maximum generation rate between 500 and 600 °C.
Cracking and subsequent release of gaseous species might partly
explain surface area development from these temperatures. Lu
et al.4 found the lowest surface area for sewage sludge chars
pyrolyzed at 650 °C, and this fact was attributed to an
intermediate melt formation in addition to volatiles being
evolved. A high increase in BET surface area was observed
after gases were released. In this work, the minimum BET
surface area was observed for sample C500. For higher
temperatures, the surface area increased with increasing tem-
perature, and thus, the maximum BET surface area (124 m2/g)
corresponds to char C900. Isothermal pyrolysis for 2 h at 900
°C (C900B) causes only a very slight reduction in BET surface
area. Nevertheless, the largest area of micropores is found at
lower stages of pyrolysis, near 800 °C. Beyond this temperature,
micropore area production decreases. Thus, the observed
increase in BET surface area might be due to mesopore

formation from widening micropores. This effect has been
observed in previous works for sewage sludge.4
An attempt was made to correlate the changes in BET surface
area with the observations derived from various analyses in the
present work. It was found that the BET surface area growth at
high temperatures seems to be closely linked with the CO
generation rate. The maximum generation rate for CO is located
at 900 °C, and 120 min of holding time produces a considerable
decrease in its evolution. This fact is also shown in Figure 10
and suggests that CO is released in proportion to newly forming
or widening pores.
As previously mentioned, the micropore surface area reaches
its maximum value near 800 °C and then starts to decrease.
This could be due to the high rates achieved at this temperature
for evolved CO. CO2 evolved at this temperature is thought to
be a product of direct carbonate decomposition, unlike CO
formation, which could be a consequence of carbon removal
from chars, i.e., char gasification. For coal and biomass, it has
been found that the lower the rate of char gasification, the greater
the micropore development.66,67 Increasing rates of char gas-
ification would cause microporosity development to decelerate.
Further decreases of microporosity can be attributed to pore
widening, as mentioned earlier.
According to these results, attention should be focused on
CO formation, as it seems to be directly linked with surface
area evolution.
The temperature range between 700 and 900 °C is the region
of interest for BET surface area evolution. In this interval, the
following facts were derived from experimental observations
and analyses made throughout this work: (1) The CO2 flow rate
decreases continually in the temperature range, whereas CO
exhibits the opposite trend. (2) Calcium carbonate decomposition
takes place at these temperatures and might explain the second-
stage CO2 formation. Consequently, CaO is formed, as revealed
by XRD. (3) The majority of sulfur is still forming part of the
char as a constituent of inorganic sulfides. Within this range,
some sulfur transfer reactions between metallic cations are
observed by XRD. More precisely, sulfur tends to move from
Fe compounds to Ca ions. (4) The latter is consistent with the
observed CaO decrease forming CaS. (5) At these temperatures,
both char and carbon weight loss are still taking place, as shown
by elementary analyses of chars and product distribution. (6)
The CO/CO2 ratio for this range does not fit with theoretical
Boudouard equilibrium relationships. (7) The BET surface area
increases continuously with increasing temperature. (8) Taking
into account these facts, this temperature region seems to be
the optimal for the development of adsorptive properties of
chars, especially regarding sulfur compound adsorption.
Taking into account all of these factors, the following
hypotheses can be formulated: (1) Decomposition of carbonates
(predominantly CaCO3) starts at 700 °C and produces a
temperature-decreasing flow of CO2 (proportional to the carbon-
ate content). Simultaneously, CaO is formed, which promotes
char gasification and sulfur transfer within the inorganic
constituents of char ash. Calcium compounds have been
extensively studied as catalysts for char gasification of coal and
desulfurization.68,69 (2) The aforementioned char gasification
occurs in the presence of iron sulfides. It is known that calcium
oxide can promote the decomposition of ferrous sulfide to form
calcium sulfide.68 The proposed main reaction70 can be written
as
FeS + C + CaO f Fe + CaS + CO
In accordance with this mechanism, calcium and iron have been
identified as main factors governing the catalytic activity of chars
Ind. Eng. Chem. Res., Vol. 48, No. 6, 2009 3219
toward desulfurization.13 However, no evidence has been found
for the presence of reduced iron. This is thought to be caused
by the immediate formation of barringerite (iron phosphide),
as detected clearly in XRD spectra. Probably, phosphide ions
have their origin in the high-temperature decomposition of
phosphates, which were identified by FTIR spectra. In fact,
barringerite and oldhamite follow similarly increasing trends
in the XRD patterns. (3) As a result of this reaction, CO is
evolved from chars. BET surface area is closely related to
evolved CO because it is proportional to char gasification. The
micropore surface area reduction at high temperatures could be
related to pore widening as CO continues being released.
3.3.5. SEM/EDX Analysis. To confirm earlier observations,
a series of SEM images were taken for raw sewage sludge and
the C900 char. Figure 11 shows an SEM image of C900. The
diverse char particle shapes are a consequence of sewage sludge
heterogeneity. At some selected points, an EDX analysis was
made to identify the predominant elements and their dispersion.
As can be seen, the main elements identified are C, O, Si, Ca,
P, and Fe, and their relative amounts differ significantly from
one point to another. This indicates the heterogeneous composi-
tion of char.
A comparison of the SEM images of sewage sludge and the
C900 char is shown in Figure 12a,b. The images indicate a
significant reduction in volume for pyrolyzed particles and show
the presence of fibrous structures formed as a result of pyrolysis.
More detailed SEM micrographs show structures resembling
nanotube bundles or fibers, together with dispersed particles of
inorganic phases (Figure 13). Similar observations with evidence
of such carbon structures have been reported for sewage sludge
pyrolysis chars.7 The tubular structures found in our study seem
to be somewhat greater than those reported by Bandosz et al.
4. Conclusions
At low pyrolysis temperatures, CO2, CO, H2O, and tars are
evolved by means of devolatilization of sewage sludge fractions
such as cellulose, long-chain fatty acids, and less stable proteins.
NH3 is thought to be evolved as well. Most of the condensate
fraction and char weight loss is observed in the temperature
range between 300 and 500 °C. At intermediate temperatures
(400-700 °C), light hydrocarbons (CH4, C2H6, C2H4) are
evolved as a consequence of thermal cracking of those volatiles
remaining in the char as a product of low-temperature devola-
tilization. This causes the development of a preliminary pore
structure for chars, although the BET surface area development
is small. H2 evolution is prolonged even at 900 °C.
Decomposition of carbonate (predominantly CaCO3) starts
at 700 °C and produces a temperature-decreasing flow of CO2
(proportional to the remaining carbonate content). CaO is formed
at the same time, which promotes char gasification and sulfur
transfer within the inorganic constituents of the char ash
(specially Fe species). As a result, an increasing rate of CO
production is observed. BET surface area is closely related to
the CO released and thus increases substantially. Over the entire
temperature range, the aromatic character of the chars increases
as pyrolysis advances.
Finally, the formation of filament-like carbon structures was
detected for high-temperature pyrolysis samples.
Acknowledgment
The authors thank the Spanish Ministry of Science and
Innovation (MICINN) for providing frame support for this work
(Project CTQ2007-66885).
3220 Ind. Eng. Chem. Res., Vol. 48, No. 6, 2009
Abbreviations
BET ) Brunauer-Emmett-Teller
COD ) chemical oxygen demand
EDX ) energy-dispersive X-ray
FTIR ) Fourier transform infrared
GC ) gas chromatograph
HHV ) higher heating value
LHV ) lower heating value
SEM ) scanning electron microscopy
TCD ) thermal conductivity detector
XRD ) X-ray diffraction
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ReceiVed for reView September 10, 2008
ReVised manuscript receiVed December 16, 2008
Accepted December 18, 2008
IE801366T