Energy & Fuels 2006, 20, 1933-1940 1933
CO2 Sequestration by Direct Gas-Solid Carbonation of Air
Pollution Control (APC) Residues
Renato Baciocchi,*,† Alessandra Polettini,‡ Raffaella Pomi,‡ Valentina Prigiobbe,§
Viktoria Nikulshina Von Zedwitz,§ and Aldo Steinfeld§,|
Department of CiVil Engineering, UniVersity of Rome “Tor Vergata”, Via del Politecnico 1,
00133 Rome, Italy, Department of Hydraulics, Transportation and Roads, UniVersity of Rome
“La Sapienza”, Via Eudossiana 18, 00184 Rome, Italy, Department of Mechanical and Process
Engineering, ETH Zurich, 8092 Zurich, Switzerland, and Solar Technology Laboratory,
Paul Scherrer Institute, 5232 Villigen, Switzerland
ReceiVed March 30, 2006. ReVised Manuscript ReceiVed May 15, 2006
Direct gas-solid carbonation of alkaline residues from air pollution control (APC) systems was investigated
with the aim of evaluating its contribution as a CO2 storage option as well as its effect on the properties of the
residues, namely, the leaching behavior, which may affect the strategies for their disposal or reuse. APC residues
from a medical solid-waste incinerator located in the vicinity of Rome, Italy, were selected for performing
carbonation experiments with pure CO2 at reaction temperatures in the 200-500 °C range. The extent of
calcium conversion to the carbonate form was found to be negligible below 300 °C, whereas the maximum
conversion of 57% was already measured at 400 °C. This implies a storage capacity of 0.12 kg of CO2/kg of
dry solid. Considering that the APC residues production in the EU25 equals 1260 kiloton/year, this translates
in a CO2 storage potential for the European market of 0.15 megatons of CO2/year. On the basis of the ENV
12457-2 leaching test procedure performed after accelerated carbonation, the concentrations of Cd, Cu, and
Cr in the leachate were below the limits imposed by the Italian regulation for disposal in nonhazardous waste
landfills, whereas only the lead concentration still exceeded the corresponding limit value. These results indicate
that accelerated carbonation of alkaline residues could be suitable to address the issue of CO2 storage, especially
for niche applications such as at steel plants and solid-waste incinerators, where both the residues and the CO2
are present.
Introduction for sequestering the total CO2 emitted by the combustion of
the available fossil fuel reservoirs.2 However, capture of CO2
The rapid increase in the CO2 concentration in the atmosphere by mineral carbonation requires operation at high temperatures
from the pre-industrial values of 280 ppm to the current values (180 °C) and pressures (15 MPa).3 Although several other
of 370 ppm has forced the international community toward options have been proposed,2 it is worth noting that the current
adopting a series of actions, e.g., the Kyoto protocol, aimed at stage of process development is still at the lab scale.
reducing anthropogenic emissions of greenhouse gases. Fur- An alternative source of materials is represented by alkaline
thermore, because fossil fuels are projected to be a dominant wastes, which are available in relatively large amounts and are
energy resource in the 21st century,1 technologies for sequester- generally rich in Ca or Mg. Johnson4 proposed the use of several
ing emissions from fossil fuel combustion in a safe and definitive waste materials, including pulverized fuel ash (PFA) produced
manner are being developed and implemented. Among the by coal-fired power stations, ground granulated blast furnace,
different options, mineral carbonation has been proposed as a and stainless steel slags (SSG) from the steel manufacturer
possible way for CO2 sequestration. In this process, CO2 reacts industry, bottom and fly municipal solid-waste incineration ashes
with alkaline elements, namely, Ca and Mg, forming the (MSWI-b and MSWI-f), as well as deinking ash resulting from
corresponding thermodynamically stable carbonates.2 The large the waste produced during the recycling of paper. Carbonation
worldwide availability of minerals rich in alkaline earth silicates of these waste materials, previously mixed with water at
provides a source of alkaline materials that exceeds that required different water/solid (w/s) ratios, was carried out in a 100%
CO2 atmosphere at a pressure of 3 atm. The best performance
* To whom correspondence should be addressed. Telephone: +39-06-
72597022. Fax: +39-06-72597021. E-mail:
[email protected]. was obtained with SSG, with a maximum 20% weight gain upon
† University of Rome “Tor Vergata”. carbonation, achieved with a w/s ratio of 0.125. A lower but
‡ University of Rome “La Sapienza”.
still notable weight gain of 13% was also observed for MSWI-
§ ETH Zurich.
| Paul Scherrer Institute. f. More recently, Fernández Bertos et al.5 investigated more
(1) Fauth D. J.; Baltrus J. P.; Soong Y.; Knoer J. P.; Howard B. H.; specifically the carbonation behavior of bottom ash and air
Graham W. J.; Maroto-Valer M. M.; Andresen J. M. Carbon Storage and pollution control (APC) residues from different municipal solid-
Sequestration as Mineral Carbonates in EnVironmental Challenges and
Greenhouse Gas Control for Fossil Fuel Utilization in the 21st Century; (3) Wolf, G. H.; Chizmeshya, A. V. G.; Diefenbacher, J.; McKelvy, M.
Springer, Berlin, Germany, 2002. J. EnViron. Sci. Technol. 2004, 38, 932-936.
(2) Huijgen, W. J. J.; Comans, R. N. J. Carbon Dioxide Sequestration (4) Johnson, D. C. SCI Lect. Pap. Ser. 2000, 108, 1-10.
by Mineral Carbonation: Literature ReView; Report ECN SF ECN-C--03- (5) Fernández Bertos, M.; Li, X.; Simons, S. J. R.; Hills, C. D.; Carey,
016: Petten, The Netherlands, 2003. P. J. Green Chem. 2004, 6, 428-436.
10.1021/ef060135b CCC: $33.50 © 2006 American Chemical Society
Published on Web 07/07/2006
1934 Energy & Fuels, Vol. 20, No. 5, 2006 Baciocchi et al.
waste incinerators located in the U.K. The results from the up to 70% carbonation conversion was obtained for the fresh
experimental tests, performed at operating conditions very close material, but a reduction in the conversion yield was observed
to those reported by Johnson,4 resulted in a 7 and 3% weight after several carbonation-calcination cycles, required to recover
gain for APC residues and bottom ash, respectively. A quite the raw material from the process.
different approach was followed by Huijgen et al.,6,7 who The results obtained from direct gas-solid carbonation of
performed the carbonation of steel slag slurries at a 10:1 w/s natural alkaline oxides provide the basis for applying this route
ratio. A 70% Ca conversion was obtained operating at 20 bar to the carbonation of alkaline residues as well. Such materials
and 200 °C in a 100% CO2 atmosphere, on a solid fraction are mainly composed of calcium and magnesium oxides or
sieved below 106 µm. Stolaroff et al.8 assessed the feasibility hydroxides. The advantage of using alkaline residues rather than
of extracting free calcium from steel slag and concrete waste natural alkaline oxides is that, unlike the latter, they are not a
by dissolution experiments in aqueous solutions. According to raw material but a waste stream. Therefore, the process could
these authors, the solution containing free calcium could then be envisioned as a sequestration rather than a capture process.
be used in a carbonation process for capturing CO2 directly from Besides, the carbonation process could at the same time improve
air. the leaching properties of the waste material, potentially
Well before its exploitation as a process for CO2 storage, allowing for either utilization of the carbonated material for civil-
carbonation was investigated for its effects on the mechanical engineering application or mitigation of impacts at the final
properties of cementitious materials9-13 as well as on the disposal site. Relevant work dealing with direct gas/solid
leaching behavior of alkaline wastes14-20 and soils.17,21 Such carbonation of alkaline residues was performed by Jia et al.,25
studies assessed the effect of carbonation on the reduction of who performed pressurized thermogravimetric analysis (TGA)
the mobility of inorganic trace contaminants from raw and experiments of hydrated and nonhydrated fluidized bed combus-
solidified wastes as a result of pH changes and the formation tion (FBC) ash, achieving CaO conversion efficiencies up to
of stable carbonate forms or chemical interactions (including 60% when operating at temperatures above 400 °C and in a
sorption and coprecipitation) with the newly formed carbonate 100% CO2 atmosphere. Nevertheless, in this work, no further
species. independent evidence of the degree of carbonation was provided
An alternative to the direct wet route is represented by direct nor was any information given on the effect of the carbonation
gas-solid carbonation of alkaline residues. Such a carbonation reaction on metal-leaching behavior.
route has been traditionally applied for the carbonation of raw The objective of this work is to investigate the efficacy and
materials, such as calcium and magnesium oxides.22,23 Namely, efficiency of direct gas-solid carbonation of APC residues
Bhatia and Perlmutter22 investigated the kinetics of CaO collected from a medical waste incinerator located near Rome,
carbonation by modified TGA experiments performed in a CO2 Italy. Carbonation experiments performed under different
stream at different operating temperatures, obtaining 70% operating conditions in a modified muffle furnace are presented
calcium conversion at 500 °C but still a reasonably fast process and discussed. The carbonation degree is then evaluated on the
rate and high carbonation efficiency when operating at 400 °C. basis of different independent measurements (weight gain,
More recently, Abanades et al.24 proposed the use of CaO in a calcination tests, and TGA tests), made on the material before
fluidized bed to capture CO2 directly from combustion gases; and after carbonation. The leaching behavior of the tested
material prior and after the carbonation process is also inves-
(6) Huijgen W. J. J.; Witkamp, G.-J.; Comans, R. N. J. Mineral CO2 tigated to elucidate its influence on the mobility of trace metals.
Sequestration in Alkaline Solid Residues; Report ECN SF ECN-RX--04-
079: Petten, The Netherlands, 2004.
(7) Huijgen W. J. J.; Witkamp, G.-J.; Comans, R. N. J. EnViron. Sci. Experimental Section
Technol. 2005, 39, 9676-9682.
(8) Stolaroff, J. K.; Lowry, G. V.; Keith, D. W. Energy ConVers. Manage. APC ash was sampled at a medical solid-waste incinerator located
2005, 46, 687-699. in the vicinity of Rome from the baghouse section, following a
(9) Johnstone, J. R.; Glasser, F. P. Proc. 9th Int. Congr. Chem. Cem. contact reactor for acid gases and organic micropollutants abatement
1992, 5, 370-376. using Ca(OH)2 and activated carbon. When the fresh APC ash was
(10) Lange, L. C.; Hills, C. D.; Poole, A. B. EnViron. Sci. Technol. 1996, received at the laboratory, it was homogenized using a quartering
30, 25-30.
(11) Short, N. R.; Purnell, P.; Page, C. L. J. Mater. Sci. 2001, 36, 35-
procedure, oven-dried at 60 °C to constant weight, and finally
41. transferred into sealed containers, where it was kept until the time
(12) Shtepenko, O. L.; Hills, C. D.; Coleman, N. J.; Brough, A. EnViron. of testing to prevent contact with atmospheric CO2.
Sci. Technol. 2005, 39, 345-354. Characterization of APC ash involved the determination of
(13) van Gerven, T.; van Baelen, D.; Dutré, V.; Vandecasteele, C. Cem. element and major anion content, mineralogical composition, acid
Concr. Res. 2004, 34, 149-156. neutralization capacity (ANC), as well as leaching behavior. The
(14) Reddy, K. J.; Gloss, S. P.; Wang, L. Water Res. 1994, 28, 1377-
1382. elemental composition of APC ash was determined using an alkaline
(15) Meima, J. A.; van der Weijden, R. D.; Eighmy, T. T.; Comans, R. digestion procedure with Li2B4O7 in platinum melting pots at 1050
N. J. Appl. Geochem. 2002, 17, 1503-1513. °C, followed by dissolution of the molten material in a solution of
(16) Ecke, H.; Menad, N.; Lagerkvist, A. J. EnViron. Eng. 2003, 129, 10% (w/w) HNO3/nanopure water and measurement of element
435-440. concentrations by means of an atomic absorption spectrometer
(17) Fernández Bertos, M.; Simons, S. J. R.; Hills, C. D.; Carey, P. J. J. equipped with air-acetylene flame. The concentration of chloride
Hazard. Mater. 2004, B112, 193-205.
(18) Polettini, A.; Pomi, R. J. Hazard. Mater. 2004, B113, 209-215. and acid-soluble sulfate was determined using the standard Italian
(19) Rendek, E.; Ducom, G.; Germain, P. J. Hazard. Mater. 2006, B128, UNI 8520 test procedures, which involve dissolution with hot
73-79. deionized water and 3% HCl, respectively. The mineralogical
(20) van Gerven, T.; van Keer, E.; Arickx, S.; Jaspers, M.; Wauters, G.; composition of the material was evaluated by X-ray diffraction
Vandecasteele, C. Waste Manage. 2005, 25, 291-300. (XRD) analysis using Cu KR radiation, as well as by TGA and
(21) Perera, A. S. R.; Al-Tabbaa, A. Proceedings of the 4th BGA
GeoenVironmental Engineering Conference: Integrated Management of
differential thermogravimetry (DTG). The acid neutralization
Groundwater and Contaminated Land: Stratford-upon-Avon, U.K., June behavior of the material was evaluated through the ANC test as
28-30, 2004; pp 560-567.
(22) Bhatia, S. K.; Perlmutter, D. D.; AIChE J. 1983, 29, 79-86. (24) Abanades, J. C.; Anthony, E. J.; Lu, D. Y.; Salvador, C.; Alvarez,
(23) Butt, D. P.; Lackner, K. S.; Wendt, C. H.; Conzone, S. D.; Kung, D. AIChE J. 2004, 50, 1614-1622.
H.; Lu, Y.-C.; Bremser, J. J. Am. Ceram. Soc. 1996, 79, 1982-1898. (25) Jia L.; Anthony E. J. Fuel 2000, 79, 1109-1114.
CO2 Sequestration by Direct Gas-Solid Carbonation Energy & Fuels, Vol. 20, No. 5, 2006 1935
Table 1. Chemical Composition of APC Ash (Dry Weight Basis)
element concentration (mg/kg) anion concentration (g/kg)
Al 3195.0 Cl- 307.5
Ca 276 294 SO4-2 20.9
Cd 116.1
Cr 55.1
Cu 825.7
Fe 937.2
Mg 6187.0
Mn 29.0
Ni 42.0
Pb 707.9
Zn 5436.3
proposed by the Canadian Wastewater Technology Centre,26 which
involves contacting 11 subsamples of the material with HNO3
solutions with increasing acid concentration. The leaching behavior
was evaluated from the results of the ANC test reported as heavy-
metal-concentration-versus-pH curves, as well as by the ENV
12457-2 leaching test.
The accelerated carbonation treatment was applied as direct gas/
solid carbonation at different temperatures and contact times to
evaluate the ash susceptibility to the process and the optimal
operating conditions. The carbonation experiments were conducted
in a muffle furnace that was modified to allow for feeding a constant
100% CO2 flow and for distributing uniformly the gas flow within
the muffle chamber. Treatment temperature values of 200, 300,
400, and 500 °C were selected for the carbonation experiments,
and the treated samples were referred to as S2, S3, S4 and S5,
respectively. Residence time equal to 6 hours. Because of the
semibatch configuration of the carbonation reactor and the elevated
treatment temperature, no adjustment could be made to the moisture Figure 1. Results of TGA/DTG analysis for sample S0. (a) Sample
content of the material, and this, although recognized as an weight (s), derivative weight (gray line) (W0 ) 5.33 mg; heating rate
important parameter for carbonation,5,16,27 was not included among ) 10 °C/min), and (b) CO2 concentration (- - -) of gases leaving the
TGA furnace (W0 ) 38.83 mg; heating rate ) 20 °C/min; gas flow
the process variables. Before the onset of the experiments, the
rate ) 238 N mL min-1).
carbonation chamber was flushed with 100% CO2 for 10 min to
purge air out from inside. Control experiments were also performed as a result of volatile metal evaporation under the elevated
at the same operating conditions but using an inert gas (N2) flux. temperature conditions of the incinerator. Additional information
To evaluate the extent of carbonation, the treated material was on the mineralogical characteristics of APC ash was derived
characterized for weight gain upon carbonation and for final
from TGA/DTG analyses, which indicated the presence of two
carbonate content, which was measured by means of calcimetry.
This involved contacting the material with a standard volume of a peaks on the DTG curve at temperatures of about 500 and 650
HCl solution in a closed chamber and subsequently measuring the °C, respectively, with relatively large related weight losses. The
volume of CO2 evolved from the reaction between carbonate phases first DTG peak was associated to Ca(OH)2, with a weight loss
and HCl. Additional information on the production of major mineral of 5.0%, corresponding to a Ca(OH)2 content of 20.5%. The
phases as a result of carbonation was derived from TGA/DTG second peak, on the basis of the evidence from CO2 evolution
analyses as well as from a TGA technique coupled with an on-line measurements, was associated to CaCO3, the presence of which
gas chromatograph for the determination of CO2 in the gases in APC ash is presumably a result of a certain degree of
evolved from the sample. The influence of accelerated carbonation carbonation occurring before the time of testing, possibly in
on the leaching behavior of the material was evaluated through the the APC system. The total volume of CO2 measured for the
previously described ANC and ENV 12457-2 leaching tests.
second peak was 0.94 mL, which corresponds to a CaCO3
content of 10.8%, in very close agreement with the amount
Results and Discussion calculated from the weight loss associated to the second peak,
Characterization of APC Residues. Table 1 reports the which was equal to 10.6%.
chemical composition of APC ash, while Figure 1 depicts the Tentative partitioning of Ca among the different chemical
results from thermal analysis in terms of TGA and DTG curves species was calculated on the basis of the data discussed above,
as well as CO2 evolution as a function of the temperature. XRD measurements, as well as ENV 12457 leachate composi-
Chemical composition data reveal that the major constituents tion. The calculations were done to determine the amount of
of APC ash are by far calcium and chlorine, accounting for Ca available for the carbonation process [i.e, in the form of
more than 58% of the total mass of the residue. Relatively high Ca(OH)2/CaO] and the consequent Ca conversion yield. XRD
concentrations were also measured for volatile heavy metals, analysis of untreated APC ash (not reported here) revealed the
such as Zn, Pb, Cu, and Cd, which are present in APC residues presence of crystalline phases including chloride (halite, NaCl,
and sylvite, KCl) and sulfate minerals (anhydrite, CaSO4) in
(26) Stegemann, J. A.; Côté, P. L. InVestigation of Test Methods for addition to Ca(OH)2. Such species are formed during flue gas
Solidified Waste CharacterizationsA CooperatiVe Program, Appendix B: treatment as a consequence of acid gas neutralization reactions
Test Methods for Solidified Waste EValuation; Environment Canada, and are concentrated in the solid residue from the APC section.
unpublished Manuscript Series Document TS-15, 1991. It was assumed that chloride species were completely solubilized
(27) Fernández Bertos, M.; Scuzzarella, A.; Simons, S. J. R.; Hills, C.
D.; Carey, P. J. Proceedings of AIChE 2004 Annual Meeting; November during 24 h distilled water leaching. Under the hypothesis that
7-12, Austin, TX, 2004. Na and K in the eluate from the ENV 12457 leaching test were
1936 Energy & Fuels, Vol. 20, No. 5, 2006 Baciocchi et al.
Table 2. Calculated Ca Speciation in APC Ash
amount
species (% dry weight) measurement/assumption
Ca(OH)2 20.5 TGA/DTG analysis
CaCl2 32.0 indirect calculation based on Cl-
content and leaching results
CaCO3 10.8 TGA/DTG analysis
CaSO4 3.0 direct calculation based on
SO4-2 content
CaO 10.9 indirect calculation based on
residual Ca
in the form of the corresponding chloride salts, the amount of
NaCl and KCl in APC ash was calculated to be 16.8 and 0.2%,
respectively. The assumption was then made that the residual
chloride content (accounting for 20.5% of APC ash) was in the
form of CaCl2, while the entire sulfate content was present as
CaSO4. The amount of Ca remaining according to the above
calculations (which was equal to 7.8%) was finally assumed to
be in the form of CaO. Table 2 summarizes the speciation of
Ca determined, along with the hypotheses made for the
calculations. The amount of chemical forms available for
carbonation determined from Table 2 is thus 31.4% as Ca(OH)2
plus CaO or 18.9% as Ca. The presence of any Mg mineral
potentially liable to carbonation was not considered in the
present study because of the much lower Mg content (0.6%) in
APC ash as compared to Ca content (27.6%).
The ANC behavior of APC ash is shown in Figure 4. For
the untreated material, the ANC curve indicates the presence
of a very large plateau at a pH value of about 12.5 units, typical Figure 2. Results of TGA/DTG analysis for sample S3. (a) Sample
of solution pH control by Ca(OH)2, which was responsible for weight (s), derivative weight (gray line) (W0 ) 8.60 mg; heating rate
an acid neutralization capacity of about 8.8 milliequiv/g of dry ) 10 °C/min), and (b) CO2 concentration (- - -) of gases leaving the
TGA furnace (W0 ) 40.73 mg; heating rate ) 20 °C/min; gas flow
material. This corresponds to a Ca(OH)2 content of 17.6% rate ) 238 N mL min-1).
(expressed as Ca), which is reasonably close to the value of
18.9% determined using the approximate method described agreement with the undetectable weight gain observed at this
previously. From the ANC results, it is also evident that the temperature. In contrast, the CO2 content increased up to 18%
whole acid neutralization capacity of APC ash was dictated by at higher temperatures. Figure 6 compares the weight gain
Ca(OH)2; after solubilization of this phase, no additional plateau calculated from the difference in CO2 content after and before
was visible on the ANC curve reported in Figure 4, so that pH the carbonation treatment (derived from Figure 5b) with the
dropped steeply from 12.5 down to less than 1 unit upon the actual weight gain (reported in Figure 5a). Although the
addition of about 3 milliequiv of H+/g. quantitative agreement is not perfect, it is worth pointing out
Carbonation of APC Residues. The results of the carbon- that the two independent measurements suggest that the weight
ation experiments are reported in Figure 5a in terms of weight gain of the APC residue may be entirely attributed to the
gain observed at the different operating conditions tested. The increase in CO2 content. Besides, the trend line is respected,
results reported refer to samples S3, S4, and S5, whereas the with an increase in weight gain for samples S3 and S4 and
results for sample S2 are not shown because the weight gain almost no effect or a slightly negative one for sample S5.
was not detectable. The weight gain was found to be dependent The TGA/DTG curves relevant to sample S3, reported in
upon the operating temperature, increasing from 3.1% for sample Figure 2, show that the first DTG peak at 500 °C, associated to
S3 to slightly less than 10% for samples S4 and S5. Conversely, Ca(OH)2, was smaller than that observed for untreated APC
exposing the APC residues to a nitrogen flow resulted in a ash (sample S0, see Figure 1). Furthermore, a larger second
reduction in the sample weight that was slightly influenced by peak at 650 °C, associated to CaCO3, was observed, with an
the operating temperature, increasing from 1.2% at 300 °C to estimated calcium carbonate content of 25.7 wt % (11.3% CO2),
about 2.5% at 400 and 500 °C. Such a weight reduction was which is in agreement with the data obtained from the calcimetry
probably due to the dehydration process, involving the loss of test (Figure 5b) and discussed above. The data obtained from
both sample humidity and bound water (e.g., in calcium the GC analysis, also shown in Figure 2, confirmed that the
hydroxide). Because it is reasonable to assume that the dehydra- CO2 amount in the S3 sample was higher than for the untreated
tion process still takes place during accelerated carbonation and fly ash (sample S0), although the quantitative agreement between
that the extent of water loss is the same as under N2 and CO2 TGA/DTG and GC data was in this case rather poor, with the
atmosphere, the actual weight gain upon carbonation was latter measurements providing a CO2 amount of 18.1 wt %.
calculated using the principle of superimposition of the effects. The TGA curve for sample S4, depicted in Figure 3, showed
As shown in Figure 5a, the resulting actual weight change a different behavior than those curves for samples S0 and S3,
ranged from 4.4% at 300 °C to about 12% at 400 and 500 °C. displaying a sudden 20% weight loss at temperatures between
The CO2 content of the APC residues before and after 20 and 120 °C, ascribed to the loss of moisture that is probably
treatment in CO2 atmosphere, shown in Figure 5b, clearly more strongly retained in sample S4 because of a modification
confirmed the extent of the carbonation reactions. The CO2 of the material porosity. In addition, the DTG curve of Figure
content did not notably increase after carbonation at 200 °C, in 3 shows no peak at 500 °C, thus suggesting complete conversion
CO2 Sequestration by Direct Gas-Solid Carbonation Energy & Fuels, Vol. 20, No. 5, 2006 1937
Figure 4. ANC curves for untreated and carbonated APC residues.
powder of roughly 60-65%, depending upon the carbonation
conditions. Both figures are not far from that found for the APC
residues investigated in this work; this suggests that the
operating conditions adopted in the present work probably
allowed for the maximum conversion yield to be attained for
the investigated materials when applying carbonation as a gas-
solid reaction process.
The results commented above and derived from weight
change and calcimetric measurements as well as thermal analysis
were confirmed by the acid neutralization behavior of the
accelerated carbonated material, reported in Figure 4. It was
Figure 3. Results of TGA/DTG analysis for sample S4. (a) Sample found that the ANC of sample S2 was very similar to sample
weight (s), derivative weight (gray line) (W0 ) 9.06 mg; heating rate S0, as indicated by the presence of a plateau of comparable
) 10 °C/min), and (b) CO2 concentration (- - -) of gases leaving the width at a pH value of 12.5; considering that, as observed earlier,
TGA furnace (W0 ) 65.81 mg; heating rate ) 20 °C/min; gas flow such a pH plateau is the result of pH control by Ca(OH)2, this
rate ) 238 N mL min-1).
is an additional indication of the very poor carbonation degree
of sample S2. In the case of treatment at 300 °C, a large initial
of Ca(OH)2, while the CaCO3 peak corresponded to a higher pH plateau was still present, although with a lower width (6.4
associated weight loss when compared to the other samples. milliequiv of H+/g, as opposed to 8.8 milliequiv of H+/g for
The weight decrease at 650 °C was equal to 14.7%, assuming sample S0). This confirms that accelerated carbonation at 200
total water content of 20% on the basis of TGA observations, and 300 °C was not capable of producing any macroscopic
implying that the CO2 content of dry sample S4 was 18.4%, change in the mineralogical composition of APC ash. Con-
corresponding to 41.8% as CaCO3. Such figures are in close versely, the ANC behavior was dramatically modified by the
agreement with those obtained from the integration of the CO2 treatment at 400 °C, while for sample S4, the plateau at pH
evolution diagram, also reported in Figure 3, indicating a 20.1% 12.5 completely disappeared, indicating consumption of Ca-
CO2 content, i.e., a 45.6% CaCO3 content. Finally, it is worth (OH)2 as a consequence of the carbonation treatment; another
pointing out that even in this case the results obtained from large plateau at pH values in the range of 8.0-4.5 units (typical
TGA/DTG measurements provided similar values for the CO2 of the carbonate/bicarbonate buffer system) was visible on the
content if compared to those determined by the calcimetry ANC curve. The amount of acid required to overcome such a
experiments, reported in Figure 6. plateau was calculated to be 9.6 milliequiv of H+/g, corre-
On the basis of these results and relying on Ca speciation sponding to a carbonate content of 28.8% as CO3-2 or 48.0%
reported in Table 1, a 100 g APC residue sample contains as CaCO3. Considering the poor resolution of the titration curve
roughly 0.47 mol of Ca. Carbonation of APC ash at 400 °C as derived from the ANC test, this value is in reasonable
results in a 12% weight increase, which, as confirmed by agreement with that (43.5%) determined from TGA analysis.
different independent measurements, may be entirely attributed Carbonation is widely reported in the literature to be capable
to CO2 uptake as CaCO3. This corresponds to 12 g, i.e., 0.27 of affecting the release of trace metals from different types of
mol, of CO2. Therefore, the Ca conversion yield is equal to combustion ashes, likely because of the combination of different
57%. A similar yield was obtained at 500 °C, and a smaller mechanisms, such as pH changes, formation of metal carbonate
yield was obtained at 300 °C. As Bhatia and Perlmutter salts, reduction in permeability as a consequence of calcite
suggested,22 the occurrence of incomplete conversion in the precipitation in the pore spaces, as well as interaction (including
gas-solid reaction may be attributed to the closure of small sorption, surface precipitation, and complexation) with newly
pores, which are characterized by a higher specific surface area, formed solid phases. In particular, an immobilization effect of
so that only the larger slowly reacting pores are left. The carbonation was observed by several investigators14-16,19,20,29
maximum conversion yield attainable depends upon the cumula- for such metals as Cd, Cu, Pb, Mn, and Zn, while Cr, Mo, and
tive small pores volume, i.e., on the solid properties. The limit Sb were variously reported to be either mobilized or im-
conversion yield estimated by Bhatia and Perlmutter for CaO mobilized as a result of carbonation. However, the influence of
was found to be 71%. In a recent work, Abanades and Alvarez28
found an experimental maximum conversion yield for CaO (28) Abanades, J. C.; Alvarez D. Energy Fuels 2003, 17, 308-315.
1938 Energy & Fuels, Vol. 20, No. 5, 2006 Baciocchi et al.
Figure 7. Results from the ENV 12457 leaching test for untreated
and carbonated samples.
resulted in strongly reduced leachate concentration values. In
particular, for sample S0, Zn exceeded the limit concentration
of 5 mg/L prescribed for disposal in nonhazardous waste
landfills. After carbonation at 400 °C, the Zn concentration was
reduced to 1.1 mg/L, thus meeting the regulatory requirements.
In the case of Pb, the leachate concentration for sample S0 was
60.2 mg/L, thus even exceeding the limit value of 5 mg/L
prescribed for disposal in hazardous waste landfills. The strong
reduction in Pb release observed for sample S4 was such that
the eluate concentration (5.4 mg/L) complied with regulatory
Figure 5. Effect of carbonation. (a) Weight change under CO2 flux requirements for hazardous waste landfills but still exceeded
(light gray bars), weight change under N2 flux (gray bars), and net the threshold value of 1 mg/L imposed for nonhazardous waste
weight change (black bars). (b) CO2 content calculated from calcimetry landfills. A different behavior was observed for Cr, with an
tests.
increased leachate concentration of 0.41 mg/L for sample S4
as opposed to 0.12 mg/L for sample S0. However, for both
untreated and carbonated APC ash, Cr release during the ENV
12457 test was below the corresponding limit value of 1 mg/L
for disposal in nonhazardous waste landfills.
A better insight into the leaching behavior of untreated and
carbonated APC ash can be provided when complementing the
ENV 12457 leaching data with the overall leaching curve as a
function of pH as obtained from the ANC test (see Figure 8).
A first large difference in the solubility curve was observed for
Ca in the case of fully carbonated APC ash (sample S4): in
this case, the strongly reduced Ca leachate concentrations in
the whole pH range investigated suggest solubility control by
calcite, which is much less soluble than portlandite. Among the
trace metals, in the pH range of 10-12.5, the concentration of
Cd was found to be lower than the analytical detection limit of
Figure 6. Net weight gain for samples S3, S4, and S5 as calculated 20 µg/L (which was used to plot the leaching curves) for all of
from calcimetry tests (gray bars) and batch carbonation experiments the investigated samples, and for this reason, it was not possible
(black bars). to infer about the extent to which Cd leaching at the natural
pH of the material is affected by carbonation. Nevertheless, for
carbonation on the leaching characteristics of MSWI residues pH values below 8 units, all of the leaching curves for Cd were
has not been explained thus far. In the present study, the effect very similar, indicating no changes in solubility-controlling
of carbonation on metal leaching was investigated both at the minerals as a result of accelerated carbonation. Similarly, in
natural pH of the material and as a function of solution pH. the case of Cu, the shape of the leaching curves was not
Heavy-metal concentrations in the eluate from the ENV 12457 modified by carbonation. Although some investigators hypoth-
leaching test are depicted in Figure 7, which shows that in the esized the possibility of precipitation of malachite in leachates
case of Cu, Pb, and Zn accelerated carbonation at 400 °C from carbonated MSWI APC ash,16 other authors, when
characterizing the precipitate from MSWI bottom ash leachates,
(29) Bone, B. D.; Knox, K.; Picken, A.; Robinson, H. D. Proceedings stated that no evidence of Cu carbonate mineral formation could
of Sardinia 2003, Ninth International Waste Management and Landfill
Symposium; October 6-10, S. Margherita di Pula, Cagliari, Italy, 2003; be gained.15 As a consequence, the reduced Cu release from
session A10 (on CD ROM). sample S4 reported in Figure 7 was most likely a result of the
CO2 Sequestration by Direct Gas-Solid Carbonation Energy & Fuels, Vol. 20, No. 5, 2006 1939
Figure 8. Metal leaching as a function of pH (ANC test) for untreated and carbonated samples.
pH decrease toward the range of minimum solubility. In the reported to be capable of controlling Cr leaching by reducing
case of Pb, the leaching curve for sample S4 displayed lower Cr(VI) released from the material into the less soluble Cr(III).31
leachate concentrations in the pH range of 6-12.5 if compared It may be argued that calcite precipitated as a result of
to the other materials. The results from geochemical modeling carbonation forms a protective rim that coats the particles of
using Visual MINTEQ, a Windows version of the MINTEQA2 metallic aluminum, preventing it from reacting with Cr in
geochemical speciation code,30 indicated possible solubility solution, which is thus kept in the more soluble oxidized forms.
control by PbCO3 in the pH range of 6-12.5; nevertheless, at
lower pH values, Pb(OH)2 was still found to control the total Summary and Conclusions
Pb concentration in solution. The effect of accelerated carbon-
ation on Cr leaching could not be entirely resolved from the The carbonation of APC residues was shown to be a viable
leaching test results, because of some dispersion of the measured process for the storage of CO2, yielding almost 60% conversion
concentration values, particularly for sample S4. However, in of calcium available as calcium oxide or hydroxide and an
agreement with the findings from other authors,31 it appears that uptake of around 120 g of CO2/kg of residue. Considering that
carbonation lead to increased Cr leaching for different pH the estimated production of APC residues in the 25 countries
domains. The formation of any Cr carbonate species is excluded of the European Union (EU 25) from municipal, hazardous, and
at both the trivalent and hexavalent oxidation states of this metal; hospital solid-waste incinerators is approximately 1260 kilotons/
it is tempting to hypothesize that the carbonation process may year,34 the CO2 storage capacity would amount to about 0.15
have affected the availability of Al(0) in the material. Metallic megatons of CO2/year. This figure will be compared to the CO2
Al, which is commonly recognized in MSWI ash32,33 as small emission reduction expected from the application of the Kyoto
droplets condensed from evaporated metal, which can potentially
originate from aluminum foils used in food packaging, is (32) International Ash Working Group (IAWG: Chandler, A. J.; Eighmy,
T. T.; Hartlén, J.; Hjelmar, O.; Kosson, D.; Sawell, S. E.; van der Sloot, H.
(30) Allison, J. D.; Brown, D. S.; Novo-Gradac, K. J. MINTEQA2/ A.; Vehlow, J.), Municipal Solid Waste Incinerator Residues, Studies in
PRODEFA2. A Geochemical Assessment Model for EnVironmental Systems. Environmental Sciences 67, Elsevier Science: Amsterdam, The Netherlands,
Version 3.0 User’s Manual, U.S. Environmental Protection Agency: Athens, 1997.
GA, 1991. (33) Sabbas, T.; Polettini, A.; Pomi, R.; Astrup, T.; Hjelmar, O.;
(31) Astrup, T.; Rosenblad, C.; Trapp, S.; Christensen, T. H. EnViron. Mostbauer, P.; Cappai, G.; Magel, G.; Salhofer, S.; Speiser, C.; Heuss-
Sci. Technol. 2005, 39, 3321-3329. Assbichler, S.; Klein, R.; Lechner, P. Waste Manage. 2003, 23, 61-88.
1940 Energy & Fuels, Vol. 20, No. 5, 2006 Baciocchi et al.
protocol, about 8% of the 1990 CO2 emissions, i.e., about 350 as additional CO2 storage capacity. Furthermore, they could be
megatons of CO2/year, or to the more realistic 19.7% reduction suitable for niche applications, such as at steel plants and
effort with respect to the actual 2010 emission baseline, i.e., municipal solid-waste incinerators, where both the residues and
about 800 megatons of CO2/year. Thus, the APC residues the CO2 are present.2 Even though the ANC results did not show
produced from the existing incineration plants would cover only a major effect of the carbonation process on the leaching
0.02-0.05% of the total CO2 European storage capacity required behavior of the APC residues, Cd, Cu, and Cr concentrations
to comply with the Kyoto protocol objectives. Nevertheless, in the leachate of the ENV 12547 leaching test were below the
APC residues represent just a small fraction of alkaline residues limits imposed by the Italian regulation for disposal in nonhaz-
available in the European Union, and they could be effective ardous waste landfills, whereas only the Pb concentration still
exceeded the corresponding limit value. Thus, carbonation may
(34) European Commission. Study To Facilitate the Implementation of also represent an effective way to address the issues related to
Certain Waste Related ProVisions of the Regulation on Persistent Organic the disposal of these and other alkaline residues.
Pollutants (POPs). Synthesis Report ENV.A.2/ETU/2004/0044, Brussels,
Belgium, 2005. EF060135B
