energies

Review
State-of-the-Art and Recent Advances in the Abatement of
Gaseous Pollutants from Waste-to-Energy
Marco Schiavon 1 , Marco Ravina 2, * , Mariachiara Zanetti 2 and Deborah Panepinto 2

1 Department of Agronomy, Food, Natural Resources, Animals and Environment (DAFNAE),

University of Padova, Viale dell’Università 16, 35020 Legnaro, Italy; [email protected]
2 Department of Environment, Land and Infrastructure Engineering (DIATI), Turin Polytechnic University,
Corso Duca Degli Abruzzi 24, 10129 Torino, Italy; [email protected] (M.Z.);
[email protected] (D.P.)
* Correspondence: [email protected]; Tel.: +39-0110907692

Abstract: Despite their key role in integrated waste management, direct (incineration) and indirect
(gasification/pyrolysis) waste combustion processes are still opposed by some of the general public
due to the past emission levels of air pollutants. In fact, although the release of air pollutants (espe-
cially dioxin) to the atmosphere from waste combustion processes has gradually decreased over the
years, thanks to the introduction of stricter regulations and more advanced removal technologies,
there is still an unsolved problem regarding the public acceptance of waste-to-energy facilities. The
aim of this paper is to provide an overview of the state-of-the-art air pollution control (APC) technolo-
gies used in waste combustion facilities. Air pollution control technologies are designed to reduce or
eliminate the emissions of harmful pollutants into the atmosphere. These technologies are important
for safeguarding public health, protecting ecosystems, complying with regulations, and promoting a
more sustainable and resilient future for both local and global communities. This paper will highlight
the complexity behind emission control and the efforts made by this sector over the years. This paper
will also propose suggested configurations based on the interactions/complementarity between
different APC technologies and recent findings to improve their performance.

Keywords: waste-to-energy; pollutant emissions; flue gas depuration; environmental compatibility;

Citation: Schiavon, M.; Ravina, M.; cleaning technologies; air pollution
Zanetti, M.; Panepinto, D. State-of-the-
Art and Recent Advances in the
Abatement of Gaseous Pollutants
from Waste-to-Energy. Energies 2024, 1. Introduction
17, 552. https://doi.org/10.3390/
Waste-to-energy (WtE) refers to all kinds of processes for recovering energy from
en17030552
waste. Among all types of WtE processes, combustion processes have historically attracted
Academic Editor: Frede Blaabjerg more attention by the population than others because of the past levels of emissions of
toxic compounds and because combustion processes take place in larger plants compared
Received: 29 December 2023
to other WtE processes due to the high investment costs that make small-scale plants
Revised: 18 January 2024
economically unfeasible.
Accepted: 19 January 2024
Published: 23 January 2024
Although the release of air pollutants (especially dioxin) to the atmosphere from waste
combustion processes has gradually decreased over the years [1], thanks to the introduction
of stricter regulations and more advanced removal technologies, there is still an unsolved
problem regarding the public acceptance of WtE facilities and the “not in my backyard”
Copyright: © 2024 by the authors. (NIMBY) syndrome [2]. Despite the chronic aversion to such processes, waste combustion
Licensee MDPI, Basel, Switzerland. still plays a key role in integrated waste management systems [3,4], responding to the
This article is an open access article fourth point of the Waste Hierarchy established by the European Union (“recovery”) and
distributed under the terms and allowing for the reduction of the amount of waste sent to municipal solid waste (MSW)
conditions of the Creative Commons landfills. Regarding this last point, a recent revision of the European Union (EU) Landfill
Attribution (CC BY) license (https:// Directive established that the amount of MSW that can be sent to landfills will be limited to
creativecommons.org/licenses/by/ 10% of the total MSW produced by 2035 [5]. Thus, during the transition towards ambitious
4.0/).

Energies 2024, 17, 552. https://doi.org/10.3390/en17030552 https://www.mdpi.com/journal/energies

Energies 2024, 17, 552 2 of 23

“zero waste” targets, WtE processes based on direct or indirect combustion cannot be
ruled out.
Waste combustion processes emit a large variety of air pollutants: dust and particulate
matter (PM), nitrogen oxides (NOx ), carbon monoxide (CO), volatile organic compounds
(VOCs), acid gases like sulfur oxides (SOx ), hydrochloric acid (HCl) and hydrofluoric acid
(HF), ammonia (NH3 ), heavy metals, polycyclic aromatic hydrocarbons (PAHs), dioxin
(PCDD/Fs) and polychlorinated biphenyls (PCBs). Besides channeled emissions, which
are the main emission sources of MSW combustion plants, diffuse emissions should also
be considered in environmental impact assessment procedures and environmental moni-
toring [6,7]. Diffuse emissions are mainly related to the discharge, storage, and handling
of waste and to operations related to the management of slags, bottom ashes, and fly
ashes intercepted by dry dust removal systems. Furthermore, channeled emissions can be
subdivided into two main categories: primary and secondary emissions. Primary emissions
refer to the main stack(s) of a waste incinerator, i.e., the stack(s) that release(s) the flue gas
coming from the combustion chamber and are treated by the air pollution control (APC)
technologies installed.
From this viewpoint, the following technologies are available: mechanical collectors,
such as cyclone separators and settling chambers, which use physical mechanisms to
remove particulate matter from the air; and electrostatic precipitators (ESPs), which use
an electric charge to attract and remove particulate matter from the air stream, for dust
and PM removal. Wet scrubbers use a liquid (usually water) to capture and remove
pollutants from the gas stream. Different types include venturi scrubbers, packed bed
scrubbers, spray towers, and dry scrubbers for acid gas removal. The selective noncatalytic
reduction (SNCR) and selective catalytic reduction (SCR) systems are used to convert
nitrogen oxides (NOx ) into nitrogen, water, and carbon dioxide. It is commonly used in
power plants and industrial facilities for the removal of NOx . The thermal oxidizers (these
devices combust VOCs at high temperatures, converting them into less harmful substances)
and the adsorption system (activated carbon or other adsorbents are used to capture and
remove VOCs from the air) are used for the removal of VOCs. It is important to note that
the effectiveness of these technologies depends on various factors, including the specific
pollutants targeted, the industry or source of emissions, and local environmental conditions.
Additionally, a comprehensive approach often involves a combination of these technologies
and measures to achieve optimal air quality outcomes.
Secondary emissions include all the remaining channeled emissions related to the
following main types of sources: the venting of silos containing ashes recovered by APC
systems or reagents and the discharge of the air from waste storage compartments or other
indoor environments. Secondary emissions have been recently estimated to account for up
to 29% and 10% of the total dust and organic carbon releases, respectively, from channeled
emissions [8]. Thus, their contribution is not negligible and should always be included
in environmental impact assessment procedures, especially considering that their type of
release may imply a weaker dispersion of air pollutants in the atmosphere.
In general, air pollution control technologies are crucial for several reasons, and their
importance is underscored by the numerous benefits they offer to human health, the envi-
ronment, and overall societal well-being. By analyzing the scientific literature, it is possible
to find key reasons why air pollution control technologies are important. Orach et al. [9]
highlight the importance of the protection of human health: air pollution is associated with
a range of adverse health effects, including respiratory diseases, cardiovascular problems,
and increased mortality rates. Implementing air pollution control technologies helps reduce
the levels of harmful pollutants in the air, directly benefiting public health.
Alterio et al. [10] focus on the preservation of the environment: air pollution has detri-
mental effects on ecosystems, water bodies, and vegetation. Acid rain, for example, results
from the release of sulfur dioxide and nitrogen oxides into the atmosphere, impacting
soil and water quality. By controlling air pollution, we can mitigate these environmental
impacts and protect biodiversity. Bianco et al. [11] highlight the necessity to improve air
Energies 2024, 17, 552 3 of 23

quality: the implementation of pollution control technologies contributes to improving

ambient air quality. Cleaner air enhances the quality of life for residents of urban and
industrial areas, reducing the risk of respiratory illnesses and other health problems. Raff
et al. [12] sharpen the necessity to meet regulatory standards: governments and environ-
mental agencies establish air quality standards and regulations to protect public health and
the environment. Air pollution control technologies are essential for industries to comply
with these standards and regulations, avoiding legal consequences and penalties [13].
Zhanga et al. [14] and Unegga et al. [15] addressed the necessity of improving the
global climate change phenomenon: some air pollutants, such as carbon dioxide (CO2 ) and
methane (CH4 ), contribute to climate change. Technologies that reduce greenhouse gas
emissions play a crucial role in addressing global warming and mitigating the impacts of
climate change. Other important points in this field are the benefits coming from waste
source separation and the coupling between recycling and incineration.
Knox et al. [16] underline the question of sustainable development: implementing
cleaner technologies aligns with the principles of sustainable development. By adopting
more environmentally friendly practices, industries can reduce their ecological footprint
and contribute to a more sustainable and resilient future. Panepinto and Zanetti [17] and
Konga et al. [18] highlight the necessity of enhancing energy efficiency; many air pollution
control technologies also contribute to increasing energy efficiency. For instance, technolo-
gies like combined heat and power (CHP) systems can simultaneously generate electricity
and useful heat, reducing overall energy consumption and associated emissions. Dong
et al. [19] promote the point of innovation and research: the development and deployment
of air pollution control technologies drive innovation and research in environmental sci-
ence and engineering. This fosters the creation of new, more efficient technologies and
encourages continuous improvement in pollution control measures. Yang et al. [20] point
out the aspect of public awareness and education: the existence and implementation of
air pollution control technologies contribute to public awareness about the importance
of environmental protection. This awareness, in turn, can lead to a more informed and
engaged citizenry advocating for cleaner air and sustainable practices. Li et al. [21] and Ge
et al. [22] underline the importance of global collaboration: air pollution is often a trans-
boundary issue requiring international collaboration to address it effectively. By adopting
and sharing best practices in pollution control technologies, countries can work together to
tackle regional and global air quality challenges.
In summary, air pollution control technologies are designed to reduce or eliminate the
emissions of harmful pollutants into the atmosphere. These technologies are important
for safeguarding public health, protecting ecosystems, complying with regulations, and
promoting a more sustainable and resilient future for both local and global communities.
The aim of this paper is to provide an overview of the APC technologies conventionally
adopted in waste combustion plants (including incineration, gasification, and pyrolysis)
and believed to guarantee the lowest environmental impacts at present. In addition, some
novel APC options for the WtE sector will be discussed based on recent literature studies,
and this is the real novelty of the paper, from which it is possible to draw some innovative
measures within the topic covered.

2. Materials and Methods

The best available techniques (BATs) identified by the European Commission for waste
incineration were considered a starting point for this work [23]. The BATs were reviewed
to depict the current standard for APC technologies in waste incineration plants and to
differentiate between consolidated techniques and novel processes/technologies/reagents
that may represent advances in this field and opportunities to improve the abatement of
emissions from the WtE sector.
To keep track of the publications on novel processes for advanced APC in waste incin-
eration plants, the Preferred Reporting Items for Systematic Reviews and Meta-Analyses
(PRISMA) was used. This methodology has been widely used to ensure transparency
Energies 2024, 17, x FOR PEER REVIEW 4 of 23

Energies 2024, 17, 552 To keep track of the publications on novel processes for advanced APC in waste 4 ofin-
23
cineration plants, the Preferred Reporting Items for Systematic Reviews and Meta-Anal-
yses (PRISMA) was used. This methodology has been widely used to ensure transparency
and completeness in reporting the results of bibliographic
bibliographic research
research and
and literature
literature reviews.
reviews.
PRISMA helps the reader reconstruct the process followed by researchers to include or
replicate the
exclude scientific articles and replicate the analysis.
analysis.
publications were preliminarily selected based on the following search
In total, 52 publications
logical operators
keywords, separated by logical operators “AND”
“AND” and “OR”:
• waste AND incineration AND (air pollution control) control) AND NOxx;
• waste AND incineration
waste incineration AND (air pollution control)
control) AND ((acid gases) OR (HCl) OR
(HF) OR
(HF) OR (SO
(SO22) OR (SOxx));
));
• waste
waste AND
AND incineration
incinerationANDAND(air(airpollution
pollutioncontrol)
control)ANDAND VOCs, respectively,
VOCs, for the
respectively, for
research on the
the research on removal of NO
the removal , acid
of xNO gases,
x, acid andand
gases, VOCs.
VOCs.
The PRISMA flow diagram is presented in Figure Figure 1.1. The apparent low number of
publications is due to the specificity
specificity of this
this topic
topic (i.e.,
(i.e., waste
waste incineration)
incineration) and the choice
of limiting the
the search
search toto novel
novel strategies/techniques
strategies/techniques in in a relatively
relatively narrow field (i.e., the
abatement of gaseous pollutants).
pollutants).

Figure 1.
Figure 1. Flow
Flowchart
chartofof
the PRISMA
the PRISMAprocess forfor
process thethe
selection of scientific
selection publications
of scientific on novel
publications tech-
on novel
niques for the abatement of gaseous pollutants in waste incineration processes.
techniques for the abatement of gaseous pollutants in waste incineration processes.

The publications
The publications selected
selected by
by the
the authors
authors were
were identified
identified in
in the
the Scopus database. Only
Scopus database. Only
publications written
publications writtenininEnglish
English
andand published
published in 2013
in 2013 werewere considered.
considered. The choice
The choice of
of limit-
ing the research to recent publications is due to the need to identify novel options available
for the abatement of gaseous pollutants. During this research, 15 publications were soon
excluded as irrelevant to the topic. Thus, the publications considered to be eligible for read-
Energies 2024, 17, x FOR PEER REVIEW 5 of 23

limiting the research to recent publications is due to the need to identify novel options
Energies 2024, 17, 552 available for the abatement of gaseous pollutants. During this research, 15 publications 5 of 23
were soon excluded as irrelevant to the topic. Thus, the publications considered to be eli-
gible for reading became 37. Seven publications were discarded after reading them be-
cause they were
ing became considered
37. Seven only marginally
publications relevantafter
were discarded to the research
reading themtopic. The 30they
because remain-
were
ing publications
considered were considered
only marginally andtocited
relevant in this paper
the research topic. because they deal publications
The 30 remaining with either
were considered
novel and cited
APC technologies forin this paper
gaseous becauseinthey
pollutants wastedeal with eitherplants,
incineration novel modifications
APC technolo-
gies
of for gaseous APC
conventional pollutants in waste incineration
technologies, plants,used
or novel reagents modifications of conventional
in the abatement APC
of gaseous
technologies, or novel reagents used in the abatement of gaseous pollutants.
pollutants.
The publications
The publicationswere
wereconsidered
consideredeligible
eligiblefor
forreading
readingprimarily
primarilybecause
becauseofofthetherele-
rele-
vance of their
vance their titles
titlesand,
and,secondly,
secondly, their abstracts.
their Finally,
abstracts. the selected
Finally, papers
the selected were were
papers arrangedar-
into theinto
ranged following topic categories:
the following (1) abatement
topic categories: of acid gases,
(1) abatement (2)gases,
of acid abatement of NOx , and
(2) abatement of
(3) xabatement
NO of VOCs. of
, and (3) abatement Figure
VOCs. 2 shows
Figurethe trend of
2 shows thepublication year for the
trend of publication papers
year on
for the
novel abatement
papers techniquestechniques
on novel abatement cited in this work.
cited in this work.

Figure
Figure2.
2.Distribution
Distributionof
ofthe
thecited
citedpapers
papersaccording
according to
to their
their topic
topic and
and year
year of
of publication.
publication.

The
The literature
literature review
review allowed
allowed for
for the
the evaluation
evaluation of
of the
the possible
possible adoption
adoption of
of novel
novel
techniques and their implementation in APC systems for waste incineration.
techniques and their implementation in APC systems for waste incineration.

3.Air
3. AirPollution
PollutionControl
ControlTechnologies
Technologies
3.1.BATs
3.1. BATs
BATs are
BATs aredefined
definedasas“the
“themost
mosteffective
effectiveand
and advanced
advanced stage
stage in in
thethe development
development of
of activities
activities andand
theirtheir methods
methods of operation,
of operation, which which indicates
indicates the practical
the practical suitability
suitability of
of par-
particular techniques for providing the basis for emission limit values and other
ticular techniques for providing the basis for emission limit values and other permit con- permit
conditions
ditions designed
designed to prevent
to prevent and,and,
wherewhere
that that
is notis practicable,
not practicable, to reduce
to reduce emissions
emissions and
and the impact on the environment as a whole” [24]. The concept of BAT was introduced
the impact on the environment as a whole” [24]. The concept of BAT was introduced by
by the European Council in 1996 when the directive on Integrated Pollution Prevention
the European Council in 1996 when the directive on Integrated Pollution Prevention and
and Control (IPPC) was issued [25]. In 2010, the Industrial Emission Directive (IED) was
Control (IPPC) was issued [25]. In 2010, the Industrial Emission Directive (IED) was pub-
published, updating and reinforcing the above concept [24]. Since their introduction, BATs
lished, updating and reinforcing the above concept [24]. Since their introduction, BATs
have become a reference for industry. Operators and local environmental agencies are
have become a reference for industry. Operators and local environmental agencies are
pushed to compare their installation performance with the specifications reported in these
pushed to compare their installation performance with the specifications reported in these
reference documents.
reference documents.
Three aspects are enclosed in the concept of BATs: the word “Technique” includes
Three aspects are enclosed in the concept of BATs: the word “Technique” includes
the “technology used and the way in which the installation is designed, built, maintained,
the “technology used and the way in which the installation is designed, built, maintained,
operated, and decommissioned” [24]. This means that not only pollution abatement instal-
lations are considered, but also the environmental management of the whole production
process. The term “Availability” indicates that the technique considered is “developed
on a scale that allows implementation in the industrial sector under economically and
Energies 2024, 17, 552 6 of 23

technically viable conditions” [24]. This definition implies that the technique is present on
the market under accessible economic conditions. Finally, “Best” means that the technique
considered is the “most effective for achieving a high general level of protection of the
environment as a whole” [24]. The reference documents known as BREFs (Best Reference
Documents) [26] analyze and describe BATs. The BAT-associated emissions limits, or BAT-
AELs, are also listed in these publications. The procedure by which these BREFs are created
and revised is known as the Sevilla Process, and it is governed by a specific Commission
decision [27]. This method has been developed throughout the years, reaching a three-year
revision process for BREFs. The determination of BATs is usually achieved through the
identification of representative installations, data collection, performance analysis and
comparison, and selection of the most appropriate solutions [28].
The original BREF on waste incineration was adopted by the European Commission in
2006. The review commenced in May 2014. The updated version was adopted by the Euro-
pean Commission in 2019, and the BAT Conclusions (BATC) were published on 3 December
2019. The Commission, EU Member States, the relevant industries, and non-governmental
organizations that support environmental protection collaborated to produce the BREF
document. The methods to prevent or (in cases where it is not feasible) limit the environ-
mental impact of installations in this sector are described in Chapter 4 of this document.
When applicable, this material also contains the environmental performance levels (such
as emission and consumption levels) that can be attained through the application of the
techniques, the costs and associated monitoring, as well as any cross-media effects. The BAT
conclusions, as outlined in Directive Article 3(12), are presented in Chapter 5. Information
on “emerging techniques”, as specified in Directive Article 3(14), is provided in Chapter 6.
Chapter 7 reports concluding remarks and recommendations for future work [23,24].
The BATC for the waste incineration sector has been defined through an iterative
process starting from the identification of the key environmental issues and the examination
of the most relevant techniques to address these key issues. The next step in the analysis
was to look at the circumstances that led to the achievement of significant environmental
performance levels. Other important aspects, such as costs, cross-media impacts, and
the positive/negative drivers for putting the strategies into practice, were also taken into
account. The process terminated with the selection of BATs and their associated BAT-AELs.
The main sources of information for the review process were [23]:
• scientific and technical literature;
• more than 300 questionnaires from operators of waste incineration and incineration
bottom ash treatment plants;
• additional information from the technical working group (TWG) members;
• about 2900 comments on Draft 1 of the revised BREF;
• information gathered from site visits;
• outcomes of workshops and webinars.
BATs on flue gas control (FGC) in waste incineration systems are based on a combina-
tion of primary and secondary techniques [29]. Primary measures are defined as pollution
prevention techniques to reduce or eliminate the generation of pollutants. Secondary
measures are pollution control techniques. These methods do not eliminate the generation
of contaminants but serve as a means to contain and prevent emissions. These techniques
must be integrated to provide an efficient system for the reduction of the pollutants present
in the flue gases. To this end, multiple components and design approaches can be combined.
In general, primary techniques include both optimization of the incineration process (e.g.,
advanced control systems or optimization of the furnace design) and optimization of the
temperature, flow rates, and sites of injection for the primary and secondary combustion
air, as well as the waste feed rate and composition, in order to efficiently oxidize organic
compounds while lowering NOx production. Although not listed as a BAT, the use of
fluidized bed combustion technologies and rotary kilns is often mentioned in the BREF
document for waste incineration as virtuous combustion technologies that enable lower
contents of total organic carbon in slags and bottom ashes. Fluidized beds, in particular,
Energies 2024, 17, 552 7 of 23

can accept various fuels, allowing for different co-incineration strategies, and also show
relatively low NOx and SOx emissions [30,31]. The fluidized bed technology has also been
conveniently employed for oxy-fuel combustion, i.e., by using oxygen instead of air [30].
Secondary techniques include a wide set of end-of-pipe technologies, which can be applied
differently depending on the composition and features of the flue gas [32].

3.1.1. BATs for Acid Gas Reduction

For the neutralization of acid gases, three types of processes can be used individually
or combined: wet systems, semi-dry systems, or dry systems. The main technologies
are reported in Table 1. Each of the methods has its own advantages and disadvantages,
depending on the conditions of the process and installations [33].

Table 1. Acid gas abatement technologies [34].

Technology Principle Advantages Disadvantages

A dry sorbent powder is
dispersed by injecting it into
the effluent gas stream (or Simple technology; minimum Major consumption of sorbent;
Boiler/Inline injection of
combustion chamber). The amount of auxiliary higher amount of residuals;
sorbent (or duct sorbent
sorbent reacts with the acid equipment; low operating possible dust pollution of heat
injection, DSI)
gas to form a solid, which is costs exchange surfaces
subsequently removed with
dust suppression systems.
Separation of the pollutants is
ameliorated by a hydrate shell,
which is formed around the
lime particles and results from Flue gas must be conditioned
Higher efficiency than no
Conditioned dry sorption the water contained in the flue to achieve higher relative
conditioned dry sorption
gas. The separation is humidity
governed by the dissolution
rate of the pollutants in
aqueous solution.
A spray dryer is used to inject
a suspension of lime and
water (lime slurry) into the
Worse use of sorbent in comp.
flue gas stream. When the 50% less water consumption
to wet methods; Higher
Semi-dry scrubbing suspension is injected into the than wet methods; dry
investment costs comp. to dry
flue gas stream, the water residuals
method
component evaporates, and
only the solid lime particles
remain in the flue gas.
Makes use of a liquid such as
Higher complexity; higher
water or an aqueous solution Low consumption of sorbents;
corrosion; drop in flue gas
Wet scrubbing capable of absorbing the low sensitivity to fluctuation
temperature; large area
acidic compounds present in in flows
needed
the gaseous effluent.
Wet non-regenerative type
that makes use of the natural No waste is formed; no
Flue gas desulphurization alkalinity of seawater to reagents or additional
Low efficiency; wet residues.
(FGD) with seawater absorb the acidic chemicals; lower capital and
contaminants present in the operating costs.
gaseous effluent.

Wet systems are based on absorption through an aqueous solution containing alkaline
reagents. The reaction products are in the aqueous phase; therefore, the system generates
liquid effluents. The main wet technologies used include [23]:
• jet scrubbers;
Energies 2024, 17, 552 8 of 23

• rotation scrubbers;
• venturi scrubbers;
• spray scrubbers;
• packed tower scrubbers.
The choice of the neutralizing agent is of fundamental importance. If milk of lime
or limestone (CaCO3 ) is used, water-insoluble residues such as sulfates, carbonates, and
fluorides may form. On the contrary, the use of sodium hydroxide (NaOH) does not cause
this problem since the products obtained are soluble. The use of NaOH, however, can
lead to the accumulation of CaCO3 inside the scrubber [35]. Efficiencies vary depending
on the type of scrubber used. For example, a single-stage venturi scrubber can achieve
HCl removal efficiency of up to 95%, while a counter-current packed tower can deliver
exceptionally high efficiency, up to 99.9%, and it is widely preferred in waste incineration
plants [33].
In semi-dry systems, the absorbent is introduced into the gas stream in the form of a
highly concentrated aqueous suspension or solution. When this solution comes into contact
with acid gases, the water present in it evaporates. As a result, the reaction products are dry.
Dry systems are based on adsorption by means of an adsorbent agent, which is injected
in the form of a powder. The dosage of the reagent depends on the temperature of the
gases, the ratio between gaseous species, and the type of reagent. The reaction products are
dry. These chemicals can then be collected along with the residual fly ash at the boiler exit
using a baghouse filter or an electrostatic precipitator. Dry systems are mainly made up
of two elements: a device for injecting absorbent material into the gas flow and a particle
filtration device to remove reaction products [36]. The main technologies are:
• Techniques for injecting sorbent into the boiler: This approach involves introducing a
dry sorbent into the combustion chamber or adding calcium- or magnesium-based
sorbents to the bed of a fluidized bed boiler. The sorbent particles react with the acid
gas present in the boiler effluents. Often, this technique is combined with a particulate
emission control system;
• Circulating fluidized bed (CFB) dry purifier: the gaseous effluents coming from the
air pre-heater in the boiler enter the lower part of the purifier and rise vertically
through a venturi section, where a solid absorbent and water are injected separately.
Also, in this case, this solution is usually associated with a technique for reducing
suspended particles;
• Inline sorbent injection (DSI): This technique involves dispersing a dry powdered
sorbent into the flue gas stream. The sorbent reacts with acid gases to form a solid,
which is subsequently removed through particulate emission control systems. Usually,
the use of bag filters is preferred;
• Atomizer, spray dryer absorber (SDA): a suspension or solution of alkaline reagent is
introduced and dispersed in the flue gas flow. The material in contact with the gaseous
contaminant reacts to form a solid, which is subsequently removed downstream
through a particulate emission control system.
Dry systems are categorized as either sodium-based or calcium-based systems, de-
pending on the additive employed. Table 2 lists the reactions that take place during the
process of removing acid gas. The reaction process of calcium-based sorbents is explained
by Equations (1)–(3). The reaction process of sodium-based sorbents is explained by
Equations (4)–(6) [37].
The efficiency of adsorption processes is affected by the specific surface area of the
solid (m2 /kg reagent), the degree of gas mixing, the concentration of the gas to be adsorbed,
the temperature and humidity of the flow, and the concentration of the reagent (usually
expressed in terms of stoichiometric ratio). Dry scrubbing systems need substantially
more reagents than wet systems, requiring at least a partial recirculation of the separated
solids in order to attain the same yields as wet systems [38]. Besides their higher cost,
sodium-based sorbents generally provide higher collection efficiency than calcium-based
sorbents. Regarding the latter, the substantial amount of additives that these processes
Energies 2024, 17, 552 9 of 23

require is offset by their relatively low cost, which makes these processes appealing from
an economic perspective. Furthermore, compared to single-stage bicarbonate-fed systems,
calcium-based materials can result in significant operating cost savings when employed in
efficient two-stage systems [39].

Table 2. Adsorption reactions for acid gases.

Calcium Hydroxide Sodium Bicarbonate

Ca(OH)2 ⇄ Ca2+
+ 2OH− 2NaHCO3 → 2Na+ + HCO3 −
HCl → H+ + Cl− (1) HCO3 − ⇄ CO3 2− + 2H+ ⇄ CO2 + H2 O (4)
Ca(OH)2 + 2HCl → CaCl2 + 2H2 O 2NaHCO3 → Na2 CO3 + CO2 + H2 O
Na2 CO3 → 2Na+ + CO3 2−
Ca(OH)2 ⇄ Ca2+ + 2OH−
HCl → H+ + Cl−
SO2 + 2OH− → SO4 2− + 2H+ (2) − (5)
CO3 + 2H+ ⇄ CO2 + H2 O
2
Ca(OH)2 + SO2 + ½O2 → CaSO4 + H2 O
Na2 CO3 + 2HCl → 2NaCl + CO2 + H2 O
Ca(OH)2 ⇄ Ca2+ + 2OH− Na2 CO3 → 2Na+ + CO3 2−
CO2 + OH− → HCO3 − ⇄ CO3 2− + H+ (3) SO2 + 2OH− → SO4 2− + 2H+ (6)
Ca(OH)2 + CO2 → CaCO3 + H2O Na2 CO3 + SO2 ½O2 → Na2 SO4 + CO2

Technologies or techniques designed for the abatement of other pollutants can also be
used to remove acid compounds. For example, SCR and SNCR technologies were originally
developed for the removal of nitrogen oxides in exhaust gases. Despite this, in SNCR, the
ammonia used to reduce NOx can also react with the HCl and HF present in the flying
particles, forming ammonium chloride and fluoride [40].

3.1.2. BATs for NOx Reduction

In this study, nitrogen oxides (NOx ) refer to the sum of nitrogen dioxide (NO2 ) and
nitrogen monoxide (NO). NOx may be formed in three ways [23]:
• Thermal NOx : generated during combustion due to the oxidation of nitrogen contained
in the air. This reaction is significantly triggered at temperatures above 1300 ◦ C, and
the rate of conversion depends exponentially on the temperature.
• Fuel NOx : part of the nitrogen contained in the burning waste is oxidized to nitro-
gen oxides.
• Prompt NOx : formation of NOx via radical reaction; although this reaction cannot be
stopped or mitigated, this mechanism has minor importance in waste incineration.
The average concentration of NOx at the stack of European waste incineration plants,
collected during the BREF revision process and based on continuous measurements, is
reported in Figure 3.
For the reduction of NOx emissions, primary techniques are of great importance.
However, to reach an acceptable emission level, combinations of primary and secondary
techniques are generally applied [41]. Considering primary techniques, NOx production
can be limited using measures that control the combustion process, preventing the oversup-
ply of air or unnecessarily high combustion temperatures, and optimizing the control of the
process for more homogeneous conditions. One widely used and significant primary strat-
egy for reducing NOx generation is the use of a well-distributed primary and secondary air
supply to prevent uneven temperature gradients that lead to high-temperature zones and,
consequently, higher NOx production [42].
To this end, the control of gas mixing and temperature are important elements. Flue
gas recirculation (FGR) is also a commonly used technique. With FGR, around 10–20% of
the secondary combustion air is replaced with recirculated flue gases. The recirculated flue
gases have a lower oxygen concentration, resulting in lower nitrogen oxide production. The
injection of either pure oxygen or oxygen-enriched air also avoids the supply of additional
nitrogen that may increase NOx production [43]. Staged combustion is based on reducing
the oxygen supply in the phase of the primary reaction and increasing the air supply in later
Energies 2024,
Energies 2024, 17,
17, 552
x FOR PEER REVIEW 10 of 23
10 of 23

The average
combustion zonesconcentration of NO
to complete the x at theof
oxidation stack of European
the gases. waste incineration
This approach plants,
requires effective
collectedmixing
air/gas duringinthe
the BREF revision
secondary zoneprocess andthat
to ensure based on continuous
incomplete measurements,
combustion products areis
maintained
reported in at low levels.
Figure 3.

Figure 3.
3. Continuously
Continuouslymonitored
monitoredNO
NOx emissions into the air from reference lines incinerating pre-
Figure x emissions into the air from reference lines incinerating
dominantly MSW [23].
predominantly MSW [23].

For the reduction

Advanced control of NOx emissions,
options can also be primary
appliedtechniques
to mitigate areNO ofx great importance.
production. For
example, in existing installations, the detection of NOx precursors and their placesecondary
However, to reach an acceptable emission level, combinations of primary and of origin
techniques
in are generally
the combustion chamber applied [41]. Considering
established the chanceprimary to reduce techniques,
the oxidation NOx of production
nitrogen
can be limited
compounds using in
present measures
the fuelthat to NOcontrol the combustion
by local control of the process,
air flowpreventing
[44]. A the over-
primary
supply ofbased
measure air or onunnecessarily
these findings high is combustion
the Very Low temperatures,
NOx (VLN™) and optimizing
process. theprocess,
In this control
of the process
combustion gasfor
is more
drawnhomogeneous
off from above conditions.
the fuel bed One at widely
the rearusedof the and significant
grate. pri-
It is mixed
mary strategy for reducing NO generation is the
with the secondary air and reduces the demand for combustion air [40].
x use of a well-distributed primary and
secondary air supply
To regulate NOxtoemissions
prevent uneven
from the temperature
combustor,gradients
natural thatgas lead to high-temper-
can also be injected
aturethe
into zones and, consequently,
over-grate region of the higher
furnace.NOxTwoproduction
methods [42].
can be used: methane de-NOx
(i.e., To
by this end, the
injecting control
natural gasofdirectly
gas mixing intoandthe temperature are important
primary combustion unit)elements. Flue
or reburning
gas recirculation
(i.e., by injecting(FGR)natural is also
gas ainto
commonly
a separate used technique.
reburn zone With
situatedFGR,above
around the10–20%
primaryof
combustion zone). Lastly, another option is to introduce water
the secondary combustion air is replaced with recirculated flue gases. The recirculated into the furnace. The hot
spot temperatures
flue gases have a lowerin theoxygen
primary combustionresulting
concentration, zone caninbelower lowered with oxide
nitrogen the use of an
produc-
injection
tion. The system
injectionthat is correctly
of either designed
pure oxygen or and operated [23].airOne
oxygen-enriched alsoor more the
avoids of the above
supply of
primary
additional techniques
nitrogen is implemented
that may increase in the
NOdesign of low-NO
x production burners.
[43]. xStaged These burners
combustion are
is based
designed
on reducing to delay but improve
the oxygen supply in combustion
the phase ofand theincrease
primary heat transfer.
reaction The conversion
and increasing the air
of fuel-bound nitrogen
supply in later combustion zones to NO x and the production of thermal
to complete the oxidation of the gases. NO x can be reduced
This approach by
regulating the air/fuel mixing. In this way, the peak flame
requires effective air/gas mixing in the secondary zone to ensure that incomplete combus- temperature and oxygen
availability
tion products canare
bemaintained
reduced while at lowmaintaining
levels. high combustion efficiency.
As mentioned
Advanced above,
control secondary
options can alsotechniques
be appliedare frequently
to mitigate NOneeded to achieve
x production. com-
For exam-
pliance with NO
ple, in existing x emission limits.
installations, For most
the detection of NO processes, the application
x precursors and their place of ammonia
of origin orin
compounds releasing ammonia (e.g., urea) as a reduction agent
the combustion chamber established the chance to reduce the oxidation of nitrogen com- is the proven standard
method. The nitrogen
pounds present oxides
in the fuel in the
to NO flue gas
by local are reduced
control of the airtoflowN2 [44].
and water vapor
A primary by the
measure
Energies 2024, 17, 552 11 of 23

reduction agent. Both NH3 and urea are applied as aqueous solutions. For safety reasons,
NH3 is normally supplied as a 25% solution. Urea can also be applied in its pure, solid
form. Two processes are important for the removal of nitrogen from flue gases: SNCR and
SCR [45].
In SCR, an ammonia–air mixture (the reduction agent) is added to the flue gas and
passed over a catalyst, usually a mesh (e.g., platinum, rhodium, TiO2 , zeolites). The most
common SCR reactions, which are catalyzed, are reported in Equations (7)–(10):

4NO + 4NH3 + O2 −→ 4N2 + 6H2 O (7)

NO + NO2 + 2NH3 −→ 2N2 + 3H2 O (8)

2NO2 + 4NH3 + O2 −→ 3N2 + 6H2 O (9)
6NO2 + 8NH3 −→ 7N2 + 12H2 O (10)
SCR systems are frequently installed in low-dust positions (i.e., at the tail end, after
de-dusting). However, in a few WtE plants, the SCR catalyst is installed as a so-called high
dust catalyst directly downstream of the boiler [23]. Such an installation has the advantage,
compared to a tail-end SCR, that it prevents energy losses by reheating the flue gas after
the chemical gas cleaning stages. Nevertheless, the lifetime of the catalysts seems shorter
compared to those in backend installations [40].
Most catalysts used in waste incineration processes operate in the range of 180–250 ◦ C
to limit the need for flue gas reheating. Lower operating temperatures, however, correspond
to a larger catalyst surface. Also, a greater risk of fouling and catalyst poisoning is found
at lower temperatures [46]. SCR allows high NOx reduction rates (usually over 90%)
considering stoichiometric (or close to stoichiometric) injections of the reduction agent. In
waste incineration applications, SCR is mostly used in the low-dust configuration, that
is, following the removal of acid gas and de-dusting stages. Zones of higher and lower
response rates can be found within the 900–1000 ◦ C temperature range where the SNCR
process takes place. Using SNCR to reduce NOx levels by more than 60–80% implies adding
more of the reducing agent. Ammonia emissions, sometimes referred to as ammonia slip,
may result from this. Recorded NH3 slip data are typically in the order of a few mg/m3 [44].
In SCR/SNCR systems, the operating temperature is a critical parameter. In SNCR,
the temperature should be higher than 900–1000 ◦ C and the residence times should be at
least 0.2–0.5 s to keep the undesired nitrous oxide (N2 O) emissions within the acceptable
limits [47]. Conversely, it should be kept below 1050 ◦ C to prevent the oxidation of NH3
and the formation of thermal NOx . In SCR, low-temperature catalysts reached 90% removal
efficiency already at 160 ◦ C [48].
Another secondary alternative to BAT for NOx abatement is catalytic filter bags. In
order to produce the fibers utilized as the filter medium, either a catalyst is mixed directly
with organic material or the catalyst is impregnated into filter bags. These filters have the
ability to lower emissions of PCDD/F as well as NOx when used in conjunction with an
NH3 source [49].

3.1.3. BATs for the Removal of Organic Pollutants

Flue gas from waste incineration plants can contain trace quantities of a very wide
range of organic species, including halogenated aromatic hydrocarbons, PAHs, benzene,
toluene, and xylene (BTX), and PCDD/Fs [23].
As for NOx , the limitation of organic pollutants is based on a combination of primary
and secondary technologies. A well-controlled combustion process that prevents the
formation of precursors is key to preventing incomplete combustion products in waste
incinerators [50]. The primary techniques involve operational techniques, including the
control and preparation of the waste before it is incinerated. Knowledge of the incoming
waste, in fact, allows for better combustion control. Well-controlled combustion also aids
in the destruction of PCDD/Fs and its precursors, which may already be in the waste.
Energies 2024, 17, 552 12 of 23

In the energy recovery section of the process, the reformation of undesired by-products
(PCDD/Fs in particular) must be prevented. Reducing the residence time of dust-laden gas
in the 450 ◦ C to 200 ◦ C temperature zone reduces the risk of the formation of PCDD/Fs and
similar compounds [51]. The potential for PCDD/F production is increased by dust removal
devices (such as electrostatic precipitators and bag filters) operating at temperatures higher
than 200 ◦ C in high dust zones. As a result, temperatures at the dust removal stage should
be kept below 200 ◦ C. The ideal conditions for flue gas incineration, including the oxygen
content, waste agitation, flue gas and waste residence time, and flue gas temperature and
turbulence, allow a high destruction efficiency of the precursor compounds [52].
Regarding secondary techniques, adsorption on activated carbon reagents is one of
the most commonly adopted processes. In an entrained flow system, activated carbon is
injected into the gas flow. The carbon is filtered from the gas flow using bag filters. Acti-
vated carbon shows a high adsorption efficiency for many organic compounds, including
PCDD/Fs [53]. Static or moving bed filters are also commonly used. These filter beds can
be very efficient at adsorbing pollutants at low concentrations. In carbon-based systems, the
spent carbon can be sent into the furnace, which will reburn the adsorbed pollutants [54].
The total pressure drop connected to the FGC system can restrict its use. Lack of space
may limit the application in the case of existing plants [53]. The adsorption efficiency of
different kinds of activated carbon varies. This has to do with the unique characteristics of
the carbon particles, which are affected by the production process [55].
SCR systems that are commonly applied for NOx reduction can also destroy gaseous
organic pollutants through catalytic oxidation. Abatement efficiencies of up to 99% can be
reached for PCDD/Fs. In this case, the SCR system requires a deeper and multi-layered
catalyst with respect to the de-NOx -only configuration.
As an alternative, catalytic filter bags can also be employed. Emissions of organic
hydrocarbons can also be limited through the dust treatment stage since these pollutants
tend to adsorb on fine particles. The same results can also be obtained by forced flue gas
cooling (condensation) [56].
The BREF document on waste incineration also highlights some emerging techniques
that could be considered for the removal of organic carbon pollutants. If wet scrubbing
systems are used, oil instead of water (or other solvents) could be used as scrubbing liquor
to absorb organic compounds. Some organic pollutants have low solubility in water, and
therefore, they are not efficiently removed by water-wet scrubbers. If such pollutants
(like PCDD/Fs) are more lipophilic, a high-boiling, partly unsaturated oil or an oil–water
emulsion of such oil could provide suitable scrubbing media [23].

3.1.4. Recommendations for Future Work

The intense knowledge exchange held during the BREF revisions revealed a num-
ber of issues that should be addressed in the future. The recommendations include the
following [20]:
• More information and technology assessments of gasification, plasma, and pyrolysis
plants incinerating waste should be included;
• More information on the incineration process of hazardous waste or sewage sludge
should be collected, in particular for the characterization of the boiler efficiency and
its variation depending, for example, on the use of auxiliary fuels or on the type and
extent of sludge pretreatment in the case of the incineration of sewage sludge;
• With regard to the monitoring method for PCDD/F emissions, more information on
PCDD/F emissions measured on the basis of short-term versus long-term sampling
should be collected.

3.2. Novel Options for APC

3.2.1. Acid Gas Removal
In the USA, Hunt et al. [57] studied the role of dry sorbent injection in the abatement
of SO2 , both as a retrofitting system and as a replacement of flue gas desulphurization
Energies 2024, 17, 552 13 of 23

systems relying on wet and semi-wet systems that generate slurry products. The authors
focused on the improvements in sorbents that have been achieved in the last two decades,
specifically involving the production of enhanced hydrated lime sorbents with increased
pore volume and surface area and with the addition of chemical treatment. The resulting
material allows for lower reagent usage (about 50%) to obtain the same removal efficiency
as conventional high-quality hydrated lime.
A wet scrubber combined with an ESP was studied by Park et al. [58] as a solution for
the simultaneous removal of NO and SO2 from the exhaust gas of thermal plants. Specifi-
cally, the wet scrubber used sodium chlorite (NaClO2 ) aerosol particles. Negatively charged
aerosol particles obtained by the reaction of NO and SO2 with NaClO2 aerosol particles in
an acidic solution (pH = 2) were collected at the anode of the ESP. Acidic conditions (pH = 2)
were obtained by dosing an HCl solution onto the wet scrubber. The authors obtained a
100% SO2 removal efficiency at an initial concentration of 500 mg/Nm3 , an airflow rate of
60 Nm3 /h, a contact time of 1.25 s, a NaClO2 molar flow rate of 50 mmol/min, and an ESP
power consumption of 68.8 W.
The simultaneous removal of NOx and SOx was also the subject of a recent study
carried out in China by Zhu et al. [59]. In their work, 75% and 95% removal efficiencies
were obtained for NOx and SOx , respectively, through the injection of de-NOx and desulfu-
rization agents (respectively 0.4 g/Nm3 and 0.6 g/Nm3 ) directly into the furnace, allowing
for respective NOx and SO2 stack concentrations of 80 mg/Nm3 and 10 mg/Nm3 . The
de-NOx sorbent consists of urea, polypropylene, and sodium salt, while the desulfurization
sorbent is made of sodium hydroxide and polypropylene. According to the authors, a shift
from conventional desulfurization and de-NOx processes to sorbent injection would more
than halve the operational costs and would reduce the investment costs by 21 times.
Wet technologies represent the majority (87%) of desulphurization systems world-
wide [60] due to their low operational costs, high removal efficiency, and CaCO3 , which is
used as an absorbent. However, they are characterized by high investment costs, high space
occupation, the production of waste sludge, and related treatment costs [38]. In contrast,
semi-wet technologies like spray drying absorption may overcome many drawbacks of
wet technologies in spite of disadvantages like the use of calcium hydroxide (Ca(OH)2 ) or
sodium-based sorbents, which are more expensive than limestone, higher reagent rates
required, and a higher exhaust gas temperature needed, which decreases the efficiency of
the boiler. To reduce these drawbacks, alternative sorbents have been studied, like zeolites
and silicates [38]. Zeolites and other clay minerals have been proven to be effective in terms
of mercury removal from exhaust gas [61]. The addition of salts to Ca(OH)2 may reduce
water evaporation from the droplets due to their hydroscopic properties and, thus, increase
the retention time of SO2 on the droplet and its contact with Ca(OH)2 [38].
A way to improve the removal of acid gases in dry sorbent injection systems is to
optimize the residence time and the contact between the sorbent and the exhaust gas.
For the removal of HCl in a real-scale reactor in the Republic of Korea, Kim et al. [62]
studied a dry sorbent reaction accelerator, i.e., a reactor characterized by a peculiar layout:
the exhaust gas enters the reactor from the bottom and comes into contact with Ca(OH)2
particles, injected at a high speed in a narrow region of the reaction column; the column
section then enlarges with a conic profile; sorbent particles fall by gravity laterally and
are resuspended by the high-speed vertical flow of the exhaust gas at the center of the
reaction column, to recreate the typical conditions of a fluidized bed. However, in spite of
the improved contact between sorbent and exhaust gas, no quantitative comparison with a
conventional dry sorbent injection system is made by the authors.
The removal of acid gases in dry sorbent injection and their cost-effectiveness may be
improved by the use of two-stage dry systems, where Ca(OH)2 and sodium bicarbonate
(NaHCO3 ) are used, respectively, as sorbents in the first and second stages [36]. Both
stages should be combined with bag filters to continue the reactions on the filter cake and
to remove reacted sorbent particles, unreacted sorbent particles, and ashes. Unreacted
sorbent particles can be reused in the adsorption processes, while calcium-based waste (e.g.,
Energies 2024, 17, 552 14 of 23

gypsum) and sodium-based waste (e.g., sodium chloride and sodium sulfate brine) can
be recycled in cement and sodium carbonate (Na2 CO3 ) production processes, respectively.
Conversely, other calcium-based waste and ashes are usually disposed of. Dal Pozzo
et al. [36] found that a two-stage calcium- and sodium-based dry sorbent injection process
is more cost-effective than single-stage processes and may respond better to fluctuations in
the composition of the input waste.
To improve the environmental sustainability of the thermal WtE sector, Kumar and
Jana [33] suggested the use of marble waste as a substitute for limestone, recalling the
work of Davini [63], who found that the Ca(OH)2 synthesized by calcination and hydration
of white-marble waste was more reactive than the Ca(OH)2 obtained by processing com-
mercial limestone because of its higher surface area. The use of marble waste would not
require significant changes in the desulfurization systems using limestone, which cover
most of the applications of acid gas removal technologies worldwide and allow for the
recovery of gypsum from the reaction between limestone and SO2 . However, Kumar and
Jana [33] suggest that also magnesium-based sorbents (specifically, magnesium hydroxide)
in semi-wet processes could play an important role in SO2 abatement, thanks to the easy
separation and drying of magnesium sulfite (the reaction product) for the generation of
magnesium oxide (MgO) and the possibility of using the released SO2 for sulfuric acid
production (H2 SO4 ) with no production of waste.

3.2.2. NOx Removal

Improved flue gas recirculation, flue gas mixing, and heat recovery are considered
preparatory steps to avoid NOx formation in waste combustion processes [64–66]. Waldner
et al. [44] stressed the importance of a correct design of furnaces to improve flue gas
mixing, avoid regions where the flue gas is separated by secondary air, and thus reduce
the air supply to reduce NOx formation. The authors developed a model to optimize the
gas flow and introduced a dynamic SNCR system in a real-scale grate combustion plant
located in Switzerland, which is capable of injecting NH3 at different levels depending
on the temperature of the flue gas. Indeed, to avoid NH3 slip, SNCR must be operated at
temperatures > 850 ◦ C. Improved distribution and dosing of primary and secondary air
reduced the NOx concentration upstream of the SNCR from 340 mg/Nm3 to <190 mg/Nm3 .
The use of the dynamic NH3 injection system reduced NH3 slip by a factor of 2–8. Under
such conditions, the stack concentration of NOx was 140 mg/Nm3 . A higher NH3 yield
further reduced the NOx stack concentration to 100 mg/Nm3 , with only a slight increase in
the NH3 slip.
Park et al. [58] previously mentioned SO2 abatement with an ESP combined with a wet
scrubber and NaClO2 aerosol particles and obtained a 94.4% NO removal efficiency under
the same conditions as the experiment carried out on SO2 abatement. Thus, an interesting
NO removal efficiency was obtained without using conventional de-NOx systems like
SNCR or SCR.
Focusing on the simultaneous removal of NOx and PCDD/Fs, Lin et al. [67] studied
an SNCR process with the injection of thiourea in addition to NH3 in a 2.9 volumetric
ratio. This study focused on a real-scale MSW incinerator in China. Besides a 91% removal
efficiency of PCDD/Fs, the use of thiourea reduced the NOx concentration in the flue gas
from 140 mg/Nm3 (NH3 injection only) to 80 mg/Nm3 .
Wang et al. [68] focused on the way to optimize the concurrent removal of PCDD/Fs
and NOx using NH3 -based SCR. Indeed, the removal of both types of pollutants with the
same technology is limited by their competition in the catalytic reactions they are involved
in and by the different optimal ranges of temperature for their removal (200–300 ◦ C for
PCDD/Fs and 300–400 ◦ C for NOx ). The authors investigated the benefits achievable
from the use of manganese oxides–ceria oxides (MnOx -CeO2 ) composite catalysts modified
by titanium oxide-based carbon nanotubes (TiO2 -CNTs). The authors set a Mn/Ti and a
Ce/Ti ratio of 0.15 and 0.10, respectively, based on a previous study that focused on the
simultaneous removal of dichlorobenzene and NOx [69]. The larger surface area and the
Energies 2024, 17, 552 15 of 23

higher ability to capture active components obtained with this modification seem to be
the reasons behind the enhanced abatement of both pollutants. The removal efficiencies
of ortho-dichlorobenzene (a substitute for PCDD/Fs) and NO increased from 27.9% and
51.3%, respectively, to >70% after the introduction of 20% wt. TiO2 -CNTs.
Catalysis was also at the center of a study by Zhang et al. [70], but this time, it was
used for the simultaneous abatement of NOx and dust. The aim is to understand if both
categories of pollutants can be abated in one single stage since this would reduce the space
occupied by the APC technologies in an MSW incinerator. The authors studied a modified
PTFE bag filter with the addition of a cheap catalyst (V2 O5 -WO3 supported on TiO2 ) fixated
on PTFE by a very simple method: immersion. The catalytic bag filter, preceded by NH3
injection, would act as a catalyst for the SCR process and as a dust removal step at the
same time. Based on a pilot-scale experiment on a real flue gas exiting the furnace of an
MSW incinerator, the authors obtained simultaneous NO and dust removal efficiencies of
>70.0% and 99.8%, respectively, starting from initial respective NO and dust concentrations
of 150–180 ppm and 1800–2100 mg/Nm3 , an NH3 injection rate of 6–10 g/min, a gas
flow rate of 25 Nm3 /min, and a gas temperature of 180–195 ◦ C. In their pilot-scale study,
the authors used 48 bags with a filtration area of 24.4 m2 and a catalyst loading of 16%
wt. Two previous experiments carried out at lower temperatures (115–180 ◦ C) showed
better results in terms of NO removal (>80%) and similar results in terms of dust removal
(>99.97%). In the first experiment, Pan et al. [71] used a MnOx catalyst on a TiO2 sol–gel
transition layer applied to a silicon carbide ceramic membrane to abate initial NO and dust
concentrations of 300 ppm and 100–400 mg/Nm3 , respectively, using an NH3 concentration
of 300 ppm. In the second experiment, Luo et al. [72] used a FeOx −MnOx catalyst applied
to a PTFE/PPS membrane through hydrothermal methods, starting from 500 ppm and
800 mg/Nm3 concentrations for NO and dust, respectively, and using NH3 (500 ppm) as
the reducing agent. At a higher temperature (200 ◦ C), better results in terms of NO removal
(95.3%) were obtained by Yang et al. [73], who used a Mn–Ce–Nb-Ox catalyst deposited on
a P84 felt by foam coating. However, higher initial concentrations of NO and NH3 were
used (600 ppm in both cases).
As mentioned in Section 3.2.1, NOx and SOx could be simultaneously removed by
direct injection of polymer-based sorbents in the furnace [59]. This would save space
and reduce the investment and operational costs compared to dedicated SCR/SNCR and
desulfurization units.
A life cycle assessment was undertaken by Wen et al. [74] to evaluate different scenarios
for APC schemes in MSW incinerators. The authors compared three configurations: (1) a
semi-wet adsorber, followed by activated carbon injection and filter bags; (2) a semi-wet
adsorber, followed by dry alkaline sorbent injection, activated carbon injection, and filter
bags; (3) an SNCR, followed by a semi-wet adsorber, dry alkaline sorbent injection, activated
carbon injection, and filter bags. From the point of view of environmental impacts, the third
scenario is preferable for NOx reduction. However, this configuration would lead to higher
SOx stack concentrations (though below the limits set by many regulations worldwide)
and, especially, to higher chromium emissions, for which concerns were raised in a recent
study [75].

3.2.3. VOC Removal

As mentioned in Section 3.1.3, organic compounds, including VOCs, can be abated by
different techniques, especially the optimization of the combustion process and the waste
feed, dry sorbent injection, adsorption, and SCR. Alternative methods for VOC abatement
were recently reviewed by Corbasson et al. [76]. One possible alternative is the use of
membranes for the separation of VOCs from the gas flow. However, the operating tempera-
ture is an important factor influencing material resistance, VOC selectivity, and separation.
Different materials behave differently with increasing or decreasing temperature, and this
aspect should be considered when selecting membrane characteristics [77].
Energies 2024, 17, 552 16 of 23

Non-thermal plasma has also been studied as a method to remove VOCs from gaseous
effluents, but its application is still limited by the high energy consumption involved
when dealing with high airflow rates [78] and the potential generation of unwanted by-
products [79].
Zhang et al. [53] recently studied the use of biochar as an adsorber for VOCs and
found that ball-milled biochar doped with hydrogen peroxide and ammonium hydroxide
can capture 3 to 4 more times benzene and xylenes compared to pristine biochar, achieving
high levels of reusability after thermal desorption. However, the ability of biochar to
perform well at high temperatures was not proved because the authors tested biochar only
at ambient temperature (25 ◦ C).
SCR systems usually employ catalysts based on transition metals like vanadium (V),
manganese (Mn), cerium (Ce), copper, and iron. Specifically, V-based catalysts (V2 O5 -
WO3 /TiO2 ) have shown the best catalytic activity in the temperature range of 300–400 ◦ C.
However, the usual operating temperature of SCR systems is lower than this range. Thus,
there is a need to improve the conversion efficiency of catalysts at lower temperatures,
possibly ensuring the simultaneous removal of NOx and VOCs. The same problem exists
for the simultaneous removal of NOx and PCDD/Fs, as mentioned in Section 3.2.2. In
recent experiments, Xu et al. [80] showed that V2 O5 -WO3 /TiO2 doped with tungsten (W)
and praseodymium (Pr) is capable of increasing the conversion efficiency of both NOx and
chlorobenzene significantly at lower temperatures (200–300 ◦ C) compared to the undoped
catalyst. In another recent study [81], different degrees of interaction (impregnation, physi-
cal mixing, co-precipitation, and sol–gel) between Mn- and Ce-based oxides were evaluated
in terms of the removal capability of NO and dichlorobenzene. Co-precipitation and sol–gel
resulted in the best formulations, enabling relatively high NO and dichlorobenzene removal
rates (>80% and 60%, respectively) in the 200–300 ◦ C temperature range.
When selecting catalysts for an SCR system, possible mechanisms of catalyst deactiva-
tion should be considered. In a recent review, Zheng et al. [82] discussed the potential risks
involved in catalytic processes applied to industrial furnaces. For instance, heavy metals
in the flue gas could clog active sites, preventing adsorption, or may induce electronic
effects that reduce the adsorption of specific compounds. The presence of SO2 in the flue
gas and of NH3 in SCR systems may form ammonium sulfites and sulfates, which may
poison the catalysts. Finally, dissociated chlorine may react with ammonium to form am-
monium chloride, which may deposit on the surface of catalysts, reducing the availability
of active sites.

3.3. Suggested Configurations for an APC System, including Novel Removal Techniques
The tendency of the sector is to prefer dry removal technologies because of their easier
management and absence of liquid waste streams [83]. However, wet removal technologies
are preferable for the removal of NOx (via SNCR or SCR) or specific substances that may
induce environmental and/or health risks that are not compatible with the local context
where the plant is located. For instance, Rada et al. [75] highlighted the potential impacts
related to chromium (Cr) VI emissions from waste combustion plants, suggesting that wet
removal technologies are more appropriate to reduce the emissions of Cr VI due to its
relatively high water solubility.
In addition to these considerations, the possible location of the novel removal pro-
cesses reviewed in Section 3.2 must be decided according to general rules adopted by
current waste incinerators and related both to the technical and economic convenience
of specific abatement processes and to the emission limits that waste incinerators must
comply with. The choice of the location of novel abatement technologies/processes for
gaseous pollutants must then consider the presence of other processes that are necessary to
abate other regulated air pollutants, like PCDD/Fs, PCBs, PAHs, total suspended particles,
and heavy metals.
More in detail, Peng et al. [84] suggest that specific operating conditions of the com-
bustion chamber (e.g., high flue gas turbulence, flue gas temperature > 1000 ◦ C for at least
Energies 2024, 17, 552 17 of 23

1 s or temperature > 850 ◦ C for at least 2 s, excess oxygen volume content of 3–6%) should
be adopted to guarantee satisfying removal of PCDD/Fs formed during waste combustion.
The choice of the de-NOx system also influences the location of other APC technologies; for
example, if an SNCR is selected, it should be placed as close as possible to the combustion
chamber to take advantage of the high temperature of the flue gas. Temperatures > 850 ◦ C
are necessary to carry out NOx reduction without the aid of catalysts and prevent NH3 slip.
If SNCR is not considered the de-NOx technology for a WtE plant, rapid quenching of
the flue gas should be guaranteed through an appropriate design of the quenching tower
and of the heat exchanger to avoid de novo formation of PCDD/Fs, which are formed by
metal chlorides, fly ashes, and organochlorinated precursors that act as catalysts [85]. De
novo formation of PCDD/Fs can be minimized by performing a rapid cooling of the flue
gas to temperatures < 200 ◦ C and optimizing the design of the heat exchanger to reduce
the chance of deposition of fly ashes on its surfaces [86]. The use of an SNCR system does
not rule out the introduction of a downstream SCR system to abate NH3 that may slip
from the SNCR stage. In this case, the quenching stage should be placed soon after the
SNCR stage. If SCR is used alone as a de-NOx process, this should be located preferably
downstream of other abatement systems to avoid poisoning of the active catalyst sites by
other pollutants [87] and, in any case, in a position where the flue gas temperature is low
enough to ensure a satisfying removal efficiency of NOx . To avoid catalyst poisoning, SCR
systems must be preceded by an efficient dust abatement technology, i.e., bag filters. The
latter should be operated at relatively low temperatures, like SCR systems, to avoid moving
the partition equilibrium of air pollutants to the gas phase rather than the particle phase.
Indeed, high temperatures reduce the efficiency of bag filters. It is known that particle-
phase pollutants may be generated from gas-phase pollutants undergoing nucleation,
condensation, and coagulation, with gas temperature playing a key role in gas-to-particle
conversion [88]. For instance, PCDD/Fs, originally formed in the gas phase, show the
tendency to convert into particles with decreasing temperature and increasing the degree
of chlorination [89]. As a result, the abatement of gas-phase contaminants may prevent
the formation of particle-phase pollutants. Bag filters were found to give the best results
at an operating temperature of 160 ◦ C [90]. In addition, to make bag filters effective for
the removal of heavy metals, PCDD/Fs, PCBs, and PAHs, they should be preceded by dry
sorbent injection if dry abatement technologies are adopted for acid gas removal.
In light of the previous considerations, it is possible to suggest the introduction of the
novel processes or materials reviewed in Section 3.2 within typical APC schemes for waste
incinerators. Different possibilities for the implementation of novel techniques are proposed
in Figure 4. The configuration proposed by Zhu et al. [59] was included in the scheme for
completeness. However, such configuration does not include any techniques reported in
the BAT Reference Document for Waste Incineration [23]. Thus, the applicability of this
process should be further verified and evaluated case by case, depending on the country.
Similar configurations, with some minor changes, may be adopted for other thermal
WtE processes like gasification or pyrolysis, i.e., indirect waste combustion processes.
Indeed, both the air pollutants generated by syngas combustion and their emission rates
are comparable with the typical emissions from waste incineration. The main difference
is related to the lower emission rates of NOx and PCDD/Fs, which are generally lower
because gasification and pyrolysis operate, respectively, with defects and the absence of
oxygen [91,92].
 novel processes or materials reviewed in Section 3.2 within typical APC schemes for waste
incinerators. Different possibilities for the implementation of novel techniques are pro-
posed in Figure 4. The configuration proposed by Zhu et al. [59] was included in the
scheme for completeness. However, such configuration does not include any techniques
Energies 2024, 17, 552 reported in the BAT Reference Document for Waste Incineration [23]. Thus, the applica-
18 of 23
bility of this process should be further verified and evaluated case by case, depending on
the country.

Figure 4. Proposed configurations for the implementation of the novel techniques reviewed for the
Figure 4. Proposed
abatement configurations
of gaseous for the
pollutants from implementation
waste incinerationofplants
the novel techniques reviewed for the
[33,36,38,44,57–59,62,64–68,70–
abatement of gaseous
73,80,81]. Paths pollutants
specifically from for
intended waste incineration with
configurations plants [33,36,38,44,57–59,62,64–68,70–73,80,81].
SNCR and SCR are represented in red
Paths specifically
and blue, intended for configurations with SNCR and SCR are represented in red and blue,
respectively.
respectively.
Similar configurations, with some minor changes, may be adopted for other thermal
4.WtE
Conclusions
processes like gasification or pyrolysis, i.e., indirect waste combustion processes. In-
deed,The present
both the airpaper provides
pollutants a review
generated of treatments
by syngas and APC
combustion technologies
and their emissionapplicable
rates are
tocomparable
direct (incineration) and indirect
with the typical emissions(gasification
from waste andincineration.
pyrolysis) waste combustion
The main difference plants
is
for the removal
related of gaseous
to the lower emission pollutants,
rates of i.e.,
NOxacid
andgases (SOx , which
PCDD/Fs, HCl, andare HF), NOx , lower
generally and VOCs.be-
State-of-the-art
cause gasificationAPC andtechnologies were identified
pyrolysis operate, andwith
respectively, reviewed
defectsaccording to the of
and the absence BREFs
ox-
drafted by the
ygen [91,92]. European Commission for waste incineration. In addition, recent advances
in the field were presented and discussed to suggest processes and technologies that go
4. Conclusions
beyond the BATs presented in the BREFs. The focus on novel techniques aims to highlight
the technological effortsprovides
The present paper that theaWtE sector
review has madeand
of treatments in the
APClast decades toapplicable
technologies reduce the
potential environmental and health impacts of high-temperature processes.
to direct (incineration) and indirect (gasification and pyrolysis) waste combustion plants
APC
for the technologies
removal allowpollutants,
of gaseous for abatingi.e.,
toxic and
acid carcinogenic
gases (SOx, HCl,airand
pollutants
HF), NO(e.g., PCCD/Fs,
x, and VOCs.
PCBs, PAHs, VOCs, NO ,
State-of-the-art APC technologies
x SO x , CO, PM, and heavy metals) that may directly
were identified and reviewed according to the BREFs impact
human health. Reducing HCl, HF,
drafted by the European Commission for waste and NH 3 emissions, as well as NO and SO x would
,
incineration. In addition,x recent advances
prevent acid were
in the field rains presented
and soil acidification,
and discussed which may negatively
to suggest processesaffect ecosystems. For
and technologies thatthese
go
reasons, investing in research on novel abatement technologies is extremely important to
continuously reduce the impact of the WtE sector and to go beyond the adoption of BATs,
which already ensure high environmental standards.
The present paper showed the complexity behind the choice of optimal APC schemes
due to the interactions between air pollutants, different APC technologies, and flue gas
parameters (especially temperature). Suggested configurations were proposed based on
recently published peer-reviewed papers and on the multi-year experience gained by
this sector. As a matter of fact, such configurations include both well-known abatement
technologies (e.g., ESPs, bag filters, SCR, and SNCR) and many of the new techniques
reviewed in this paper.
Energies 2024, 17, 552 19 of 23

Given the contribution of this sector to the emission of greenhouse gases (mainly due
to the presence of waste with a non-biogenic origin), carbon capture technologies should
be considered more insistently in the future, especially in reference documents like the
BREFs. Such technologies are out of the scope of the present paper, which focuses on local
air pollutants. However, reducing the carbon footprint of WtE technologies might help
decrease the level of aversion and skepticism to such processes in public opinion.

Author Contributions: Conceptualization, M.S., M.R., M.Z. and D.P.; methodology, M.S., M.R., M.Z.
and D.P.; investigation, M.S. and M.R.; writing—original draft preparation, M.S., M.R. and D.P.;
writing—review and editing, M.S. and M.R.; supervision, M.Z. and D.P. All authors have read and
agreed to the published version of the manuscript.
Funding: This research received no external funding.
Data Availability Statement: No new data were created or analyzed in this study. Data sharing is
not applicable to this article.
Conflicts of Interest: The authors declare no conflicts of interest.

Nomenclature

APC Air pollution control MgO Magnesium oxide

BATs Best available techniques MSW Municipal solid waste
BAT-AELs BAT-associated emission limits Na2 CO3 Sodium carbonate
BREFs BAT Reference Documents NaClO2 Sodium chlorite
BTX Benzene, toluene, and xylene NaHCO3 Sodium bicarbonate
CaCO3 Limestone NaOH Sodium hydroxide
Ca(OH)2 Calcium hydroxide NH3 Ammonia
CFB Circulating fluidized bed NO Nitrogen oxide
CH4 Methane NO2 Nitrogen dioxide
CHP Combined heat and power NOx Nitrogen oxides
CO Carbon monoxide PAHs Polycyclic aromatic hydrocarbons
CO2 Carbon dioxide PCBs Polychlorinated biphenyls
DSI Duct sorbent injection PCDD/Fs Polychlorinated dibenzo-p-dioxin and dibenzofurans
ESP Electrostatic precipitator PM Particulate matter
FGC Flue gas control SCR Selective catalytic reduction
FGD Flue gas desulfurization SDA Spray dryer absorber
FGR Flue gas recirculation SNCR Selective noncatalytic reduction
H2 SO4 Sulfuric acid SO2 Sulfur dioxide
HCl Hydrochloric acid SOx Sulfur oxides
HF Hydrofluoric acid VOCs Volatile organic compounds
IED Industrial Emission Directive WtE Waste-to-energy
IPPC Integrated Pollution Prevention and Control

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