Article

Cite This: Energy Fuels XXXX, XXX, XXX−XXX pubs.acs.org/EF

Fly Ash from Municipal Solid Waste Incineration as a Potential

Thermochemical Energy Storage Material
Saman Setoodeh Jahromy,*,† Christian Jordan,† Mudassar Azam,† Andreas Werner,‡ Michael Harasek,†
and Franz Winter†
†
Institute of Chemical, Environmental, & Bioscience Engineering, TU Wien, Getreidemarkt 9, 1060 Vienna, Austria
‡
Institute for Energy Systems and Thermodynamics, TU Wien, Getreidemarkt 9, 1060 Vienna, Austria

ABSTRACT: Each year, combustion at municipal solid waste incineration (MSWI) plants produces millions of tons of fly ash
globally. This ash is characterized as a hazardous material and is mostly placed in landfills after a stabilization process or stored
in hazardous waste sites. Thus, disposal of fly ash leaves a considerable social and environmental footprint and leads to high
waste management costs. Thermochemical energy storage (TCES) systems are considered to be outstanding because of their
high-energy density and near-zero energy loss over long periods of time. Calcium oxide (CaO), a main MSWI fly ash
component, is a promising candidate for TCES. In this study, we investigate the potential of fly ash as a TCES material. To do
from https://pubs.acs.org/doi/10.1021/acs.energyfuels.8b04106.

so, we analyzed representative samples from different MSWIs using simultaneous thermal analysis (STA) under N2, CO2, and
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CO2/H2O atmospheres. These analyses were supported by additional techniques such as X-ray fluorescence (XRF)
spectroscopy, inductively coupled plasma-optical emission spectroscopy (ICP-OES), and scanning electron microscopy (SEM).
The STA results illustrate fly ash reactivity under different atmospheres. All samples could store heat through endothermic
reactions and one sample was able to release stored heat under selected operating conditions. XRF analysis verified an average
fly ash composition of 27% CaO, ICP-OES analysis demonstrated the presence of different heavy metals, and SEM analysis
revealed the sintering and agglomeration of fly ash particles at high temperatures (1150 °C). This study shows that the use of fly
ash as a TCES material is promising and that further investigation in the field is needed to corroborate this application.

■ INTRODUCTION
The rising demand for energy, limited availability of fossil
fuels, growing environmental regulations, and increasing public
awareness are the main factors driving the investigation of
renewable energy sources. For example, using municipal solid
waste to produce renewable energy has recently attracted
significant attention because it is a good solution for energy
recovery; however, it generates some waste. Municipal solid
waste incineration (MSWI) improves disinfection, reduces the
waste volume by 90%, and has the additional advantage of
simultaneous energy recovery; however, MSWI still generates
bottom and fly ash that need disposal.1
Different combustion processes at MSWI plants in Vienna
produce approximately 48 000 tons of fly ash each year.2 The
disposal of fly ash poses significant environmental risks owing
to the presence of toxic metals and leaching of hazardous
pollutants. To minimize environmental impact, researchers
have investigated the recovery of metals and other materials
from fly ash as well as its use as a filling material or in cement
production.3−5 Although these research areas are beyond the
scope of this study, they offer two general approaches for fly
ash. The first approach involves the development of
technologies, such as the FLUWA process to recover heavy
metals from fly ash, to separate or reduce metals and toxic
materials.5 The second approach involves the investigation of
new fly ash applications.6,7 For example, Cherbanski et al.6
demonstrated the use of fly ash as a CO2 sorbent in a steam-
methane reforming process, and Gutierrez et al.7 discussed the
potential use of waste materials, such as MSWI fly ash, for
thermal energy storage. Ceramic materials produced after the
thermal treatment of fly ash was inert and had a thermal
capacity of 0.714−1.112 [kJ kg−1 K−1].7 Thermal energy
storage is used to store excess heat energy and positively
impacts the environment by reducing fossil fuel consumption,
thus mitigating global warming.8
Thermal energy storage falls into three categories: sensible,
latent, and thermochemical heat storage (TCES). Compared
with sensible and latent heat storage systems, TCES is
characterized by high energy density and zero energy loss.8−10
The preliminary requirement for any material for use in a
TCES system is its potential to store heat through
endothermic reactions. For example, material A decomposes
through an endothermic reaction into solid material B and gas
component C (eq 1).
The secondary requirement for a TCES material is the
possibility of an exothermic reaction of decomposed material
B with the gas component C (eq 1). Excess heat, such as that
from solar power plants (CSP), can be used in reactor 1 to
decompose the powder generated from fly ash (A(s)) into a
charged form (B(s)) and reactive gas (C(g)) by applying a
temperature higher than the forward reaction’s equilibrium
temperature (eq 1). Hence, the reaction energy ΔHR is stored
in products B(s) and C(g).
Special Issue: 27th International Conference on Impact of Fuel
Quality on Power Production and Environment
Received: November 26, 2018
Revised: January 26, 2019
Published: February 7, 2019

© XXXX American Chemical Society A DOI: 10.1021/acs.energyfuels.8b04106

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The charged form component (B(s)) of the initial material
(A(s)) can react with gas component C(g) in reactor 2 to
form the discharged form (A(s)) through the release of stored
heat ΔHR by applying a temperature lower than the back
reaction’s equilibrium temperature (eq 1). Then, the released
heat can be removed from the reactor using either a reactive or
inert gas. Further, this charging and discharging process can
take place in a single reactor; however, a storage system is
required in this case. Figure 1 shows a simplified
representation of procedures within a TCES system.11
A(s) + ΔHR ↔ B(s) + C(g) (1)
11
Figure 1. TCES system.
To illustrate the proposed concept, Figure 2 emphasizes a
suggested integrative consisting of a TCES system to a
combustion process. Fly ash is collected from the filter system,
Figure 2. Schematic of the TCES system connected to a combustion facility.
B DOI: 10.1021/acs.energyfuels.8b04106
Article
and heat can be provided and collected in the boiler’s heat
exchanger system. Additionally, flue gas may be introduced as
a CO2 source for discharging the TCES materials (fly ash).
The TCES system includes reactors for heat transfer and
storage facilities for charged and discharged material,
respectively. Aged energy storage material can be used in
the same way as the original fly ash.
A TCES system requires suitable materials for operation,
and previous studies have found that calcium oxide (CaO) is a
promising material for use in TCES systems.11−16 CaO is a
main component of fly ash, along with silicon oxide (SiO2)
and aluminum oxide (Al2O3).7 Two reversible exothermic and
endothermic reactions are possible with CaO: it can react with
water vapor (H2O(g)) and carbon dioxide (CO2) to produce
calcium hydroxide Ca(OH)2 (eq 2) and calcium carbonate
(CaCO3) (eq 3), respectively.
CaO(s) + H 2O(g) ↔ Ca(OH)2 (s) + ΔHR
ΔHR = −109 kJ/mol (2)
CaO(s) + CO2 (g) ↔ CaCO3(s) + ΔHR
ΔHR = −178 kJ/mol (3)
Additionally, owing to its chemical composition, MSWI fly
ash may have an alternative use as a TCES material. To
demonstrate this potential use, this study chemically
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characterized fly ash samples sourced from the grate furnaces Table 2 presents the ICP-OES analysis results and shows
of three MSWI plants in Austria. To achieve representative the different metals comprised in the fly ash samples. High
results, samples containing a mixture of seasonal collections
from each plant over the course of 4 years were used. We Table 2. Total Content of Nonmatrix Elements in the
analyzed these samples through X-ray fluorescence spectros- Different Fly Ash Samples Determined through Inductively
copy (XRF) and inductively coupled plasma-optical emission Coupled Plasma-Optical Emission Spectroscopy (mg/kg)19
spectroscopy (ICP-OES) to detect matrix and nonmatrix
fly ash sample A fly ash sample B fly ash sample C
elements and examined each sample’s reactivity under different
atmospheres through simultaneous thermal analysis (STA). In Sb 635 1316 302
addition, we performed a leachability test and scanning As 32 37 13
electron microscopy (SEM) analysis. Ba 984 1048 1745

■ MATERIALS AND METHODS

To detect matrix elements in our XRF analysis, we milled and
Pb
Cd
Cr
4394
321
259
7016
375
242
1100
38
276
grained the fly ash samples to a particle size of 250 μm. The Co 27 35 38
Cu 1004 1901 1009
samples were embedded in aqua regia in accordance with the
Mn 676 816 1050
standard EN 13657 (2002) and then analyzed via the ICP-
Mo 20 24 22
OES test in accordance with the standard EN 11885 (2009).
Ni 60 95 152
We used an STA 449 Jupiter instrument (Netzsch,
Hg 34.79 4.34 0.34
Germany) to conduct the STA of fly ash under different
atmospheres. We set a 30 K min−1 heating rate up to a sample Ag 44 47 14
Zn 18.371 21.613 5684
temperature of 1150 °C and used aluminum oxide crucibles of
Sn 835 865 177
125-μL volume for all the experiments. For each experimental
run, we measured a sample mass of approximately 30 mg. The
different gases used for STA had a minimum purity of levels (greater than 1 000 ppm) of barium, lead (Pb), copper,
99.999% (v/v). To identify the effect of thermal treatment in and zinc are noted, making fly ash a potential source of these
STA on the fly ash, we analyzed all the samples before and metals. Consequently, the FLUREC process has been used to
after the STA experiments through SEM analysis (FEI Quanta recycle zinc from fly ash in Switzerland on a large scale.20
250 FEG SEM). STA. To investigate the thermal activity of the samples, we
We performed a leachability test on the original samples in decomposed all the fly ash samples under an N2 atmosphere
accordance with the standard EN 12457-4 (2002) and using a heating rate of 30 K min−1 up to a sample temperature
analyzed leachates using ICP-OES in accordance with the of 1150 °C.
standard EN 11885 (2009).

■
In Figures 3−10, the green, blue, and dotted red lines show
the percentage of mass loss based on TG, DSC, and the
RESULTS AND DISCUSSION temperature profile, respectively. Three mass loss steps can be
XRF and ICP-OES. Table 1 presents XRF analysis results observed in the TG signals for fly ash samples A and B. The
for fly ash from the different plants. Fly ash samples A and B first mass loss (approximately 1.8%) occurs between 44 and
500 °C and is related to water and organic material
Table 1. Total Content of Matrix Elements in the Different evaporation. The second mass loss (greater than 4%) occurs
Fly Ash Samples As Determined through XRF Spectroscopy between 500 and 750 °C and is related to the dehydration of
(Mass Percent)19 metal hydroxides (e.g., calcium hydroxide or magnesium
hydroxide) in the fly ash. The third and final mass loss
fly ash sample A fly ash sample B fly ash sample C
(approximately 34% and 26% for fly ash samples A and B)
Na2O 11.2 10.7 1.9 occurs between 750 and 1150 °C and is related to
MgO 0.7 0.6 2.7 decarbonation and decomposition of sulfates and chloride.21,22
Al2O3 6.4 6.9 11.4 The endothermic DSC signals of fly ash samples A and B,
SiO2 11.8 13.0 27.4 which occur in the same temperature ranges as the mass
P2O5 0.5 0.6 0.7 losses, are depicted in Figures 3 and 4, respectively.
SO3 8.8 9.9 7.4 Figure 5 illustrates the decomposition of fly ash sample C
Cl 14.9 14.1 4.3 under an N2 atmosphere. Unlike fly ash samples A and B, fly
K2O 7.5 7.3 2.5 ash sample C exhibits four mass change steps in the relevant
CaO 26.6 25.0 32.3 endothermic DSC signals. Additionally, its total mass change is
TiO2 1.3 1.3 1.8 significantly lower (∼12%) than the mass changes of fly ash
Fe2O3 1 2.6 4.9 samples A (∼40%) and B (∼33%). A major reason for the
organic dry matter 4.9 2.8 0.9 reduced mass loss is the thermally inert behavior of Al2O3 and
SiO2, which are the main components of sand and in higher
concentrations in fly ash sample C.
exhibit similar elemental contents, with a maximum 2.1 mass Table 3 presents the results of thermal decomposition of fly
percent difference. However, fly ash sample C significantly ash samples A, B, and C, including information regarding the
differs in SiO2, Na2O, and Cl− content. Additionally, the CaO reaction type (exothermic or endothermic), based on mass
contents, where CaO exists freely or as part of compounds and DSC signals.
such as silicates, aluminates, sulfates, and carbonates,17,18 We obtained the fly ash energy content by integrating the
varies between 25 and 32.3 mass percent. endothermic peaks generated by the DSC signals (Figures
C DOI: 10.1021/acs.energyfuels.8b04106
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Table 3. Results of Decomposition of Fly Ash Samples in N2 Atmosphere (Mass Percent)

approximate temperature range mass change mass change endothermic/ temperature range mass change endothermic/
[°C] FA A FA B exothermic [°C] FA C exothermic
50−500 1.8 1.8 endothermic 46−309 0.4 endothermic
500−750 4.9 4.1 endothermic 309−448 1.2 endothermic
750−1150 34.1 26.5 endothermic 448−790 6.3 endothermic
790−1150 5.2 endothermic
sum 40.8 32.4 13.1

Figure 3. Thermal decomposition of fly ash sample A under an N2 atmosphere. The green, blue, and dotted red lines show the percentage of mass
loss based on TG, DSC, and temperature profile, respectively.

Figure 4. Thermal decomposition of fly ash sample B under an N2 atmosphere. The green, blue, and dotted red lines show the percentage of mass
loss based on TG, DSC, and the temperature profile, respectively.

3−5) calculated with linear baselines, and the results are Figures 6 and 7 illustrate the thermal reactivities of fly ash
summarized in Table 4. Fly ash sample C exhibits the highest samples A and C, respectively, under a CO2 atmosphere. Fly
energy content; it is approximately 4 times greater than those ash samples A and C have the same total mass change as that
under an N2 atmosphere; however, their DSC signals show
of fly ash samples A and B, which may be explained by higher significant differences. The reaction of fly ash samples with
free lime (Ca(OH)2) content in fly ash sample C (see CaO CO2 is clear, particularly for fly ash sample C (Figure 7). The
content in Table 1). mass of fly ash sample C increases by approximately 2.62% at a
D DOI: 10.1021/acs.energyfuels.8b04106
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Figure 11. SEM images showing particle changes before (left) and after (right) thermal treatment at 1150 °C for 30 min.
The preliminary requirement to qualify as a TCES material,
which is the ability to store heat (charging), was satisfied by all
three fly ash samples through endothermic decompositions
under an inert atmosphere during STA. We observed three
mass loss steps for fly ash samples A and B and four mass loss
steps for fly ash sample C. DSC signals indicated endothermic
reactions for each mass loss step. In the temperature range
between 30 and 1150 °C, fly ash samples A, B, and C achieved
total mass losses of 40%, 32%, and 13%, respectively. Through
thermal treatment up to a temperature of 1150 °C, fly ash
samples A, B, and C possessed energy contents of 90, 98, and
394 kJ/kg, respectively.
Exothermic reverse reactions (discharging) of fly ash sample
C with CO2 and CO2/H2O were demonstrated through STA.
The conversion of the reaction increased as temperature
decreased from 1150 to 880 °C and the cooling rate decreased
from 30 to 10 K min−1; however, complete conversion was not
achieved under these experimental conditions. The stored
H DOI: 10.1021/acs.energyfuels.8b04106
Article
energy of fly ash sample C up to 880 °C was 240 kJ/kg,
approximately 99 kJ/kg of which could be released under the
selected operational circumstances. This finding indicates that
fly ash sample C meets the second necessary requirement of
TCES materials: an exothermic reverse reaction of decom-
posed material (fly ash) with gaseous components such as
CO2 and H2O.
Although SEM analysis revealed the sintering and
agglomeration of particles in all the samples after STA, they
were all still in powder form and could easily be removed from
the crucibles. With respect to the potential applicability of fly
ash as a TCES material, this would provide a benefit to the
stability of its cycle; this issue will be part of further study.
Leaching test results indicated that some varieties of fly ash
may be considered as nonhazardous waste, making the use of
such material in TCES systems more feasible. Nevertheless,
further research is necessary to improve and demonstrate the
potential use of MSWI fly ash as a TCES material.
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Corresponding Author (11) Deutsch, M.; Müller, D.; Aumeyr, C.; Jordan, C.; Gierl-Mayer,
*E-mail: saman.setoodeh.jahromy@tuwien.ac.at. Phone: +431 C.; Weinberger, P.; Winter, F.; Werner, A. Systematic search
58801 166 368. algorithm for potential thermochemical energy storage systems.
ORCID Appl. Energy 2016, 183, 113−120.
Saman Setoodeh Jahromy: 0000-0003-4395-4181 (12) Criado, Y. A.; Alonso, M.; Abanades, J. C. Kinetics of the
Notes CaO/Ca(OH)2 hydration/dehydration reaction for thermochemical
The authors declare no competing financial interest. energy storage applications. Ind. Eng. Chem. Res. 2014, 53 (32),

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ACKNOWLEDGMENTS
The authors thank the Austrian Research Promotion Agency
(FFG) for its financial support of the project WASTE2-
STORAGE (No. 865100). Some of the data and experiments
presented in this paper are part of a large-scale research
initiative on anthropogenic resources (Christian Doppler
Laboratory for Anthropogenic Resources). The financial
support of this research initiative by the Federal Ministry of
Digital, Business, and Enterprise and the National Foundation
for Research, Technology, and Development is gratefully
acknowledged. The industry partners cofinancing the research
center on anthropogenic resources are Altstoff Recycling
Austria AG, Borealis AG, Voestalpine AG, Wien Energie
GmbH, Wiener Kommunal-Umweltschutzprojektgesellschaft
(WKU) GmbH, and Wiener Linien GmbH & Co. KG. In
particular, the authors would like to express their gratitude to
Municipal Department 48 of the City of Vienna not only for
cofinancing this project via its subsidiary WKU but also for its
essential contributions to the experiments in the form of
facilities and staff.
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I DOI: 10.1021/acs.energyfuels.8b04106
Energy Fuels XXXX, XXX, XXX−XXX