Progress in Energy and Combustion Science 79 (2020) 100844

Contents lists available at ScienceDirect

Progress in Energy and Combustion Science

journal homepage: www.elsevier.com/locate/pecs

Reaction mechanisms and chemical kinetics of mercury

transformation during coal combustion
Yingju Yang, Jing Liu∗, Zhen Wang
State Key Laboratory of Coal Combustion, School of Energy and Power Engineering, Huazhong University of Science and Technology, Wuhan 430074, China

a r t i c l e i n f o a b s t r a c t

Article history: Mercury (Hg) emission from coal combustion has attracted considerable public concern because of its
Received 15 September 2019 harmful effects on human health and the ecosystem. The fundamental understanding of the reaction
Accepted 8 March 2020
mechanisms and chemical kinetics that govern the transformation of Hg0 to Hg2+ and Hgp in coal-fired
Available online 18 March 2020
flue gas is crucial for mercury emission control. Kinetic calculations with quantitative predictability are
Keywords: critical to scaling up laboratory experiments to pilot- or full-scale tests. Despite extensive research over
Mercury the last two decades, there remain many unresolved issues that can limit our ability to make useful en-
Reaction mechanism gineering predictions and hence the potential for mercury emission control. This review discusses recent
Chemical kinetics progress in the study of reaction mechanisms and kinetics of mercury oxidation over a wide temperature
Kinetic model range, with a specific focus on the heterogeneous reaction mechanism of mercury adsorption, conver-
Coal combustion sion and desorption on solid surfaces. Thermochemical properties of relevant mercury species are the
basis of thermodynamic predictions. They are reviewed and provided first. Various methods and theories
for evaluating and estimating kinetic rate parameters of elementary reactions are surveyed from existing
experiments and theoretical studies. Further, the chemical reaction kinetics of mercury oxidation is dis-
cussed with an emphasis on two primary aspects of the problem: (i) the development of homogeneous
reaction mechanisms using quantum chemistry calculations and (ii) the advancement of heterogeneous
reaction mechanisms in which kinetic parameters of surface reactions are fitted to experimental data.
Various kinetic models are tested against selected experimental data, the corresponding performance of
each kinetic model is compared and evaluated. Finally, we provide an outlook on the reaction mecha-
nisms and kinetics of mercury transformation during coal combustion.
© 2020 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
1.1. Mercury emissions and current policy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
1.2. Scope of this review. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2. Thermodynamics of mercury transformation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2.1. Thermochemical properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2.2. Equilibrium calculations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
3. Methods of kinetic studies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
3.1. Experimental techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
3.1.1. Laser induced fluorescence . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
3.1.2. Fast flow-discharge . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
3.1.3. Relative kinetic measurements. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
3.1.4. Absolute rate measurements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
3.2. Theoretical methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
4. Homogeneous reaction kinetics of mercury transformation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
4.1. Historical perspective . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7

∗
Corresponding author.
E-mail address: liujing27@mail.hust.edu.cn (J. Liu).

https://doi.org/10.1016/j.pecs.2020.100844
0360-1285/© 2020 Elsevier Ltd. All rights reserved.
2 Y. Yang, J. Liu and Z. Wang / Progress in Energy and Combustion Science 79 (2020) 100844

4.2.Hg/Cl reaction system . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. ... . ... . . . . . . . . .. . .. . .. . . . . . 8

4.2.1. Hg/Cl reaction mechanism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. ... . ... . . . . . . . . .. . .. . .. . . . . . 8
4.2.2. Kinetic modeling of Hg/Cl reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. ... . ... . . . . . . . . .. . .. . .. . . . . . 9
4.3. Hg/Br reaction system . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. ... . ... . . . . . . . . .. . .. . .. . . . . . 9
4.3.1. Hg/Br reaction mechanism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. ... . ... . . . . . . . . .. . .. . .. . . . . . 10
4.3.2. Kinetic modeling of Hg/Br reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. ... . ... . . . . . . . . .. . .. . .. . . . . . 11
4.4. Hg/I reaction system . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. ... . ... . . . . . . . . .. . .. . .. . . . . . 12
4.4.1. Hg/I reaction mechanism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. ... . ... . . . . . . . . .. . .. . .. . . . . . 12
4.4.2. Kinetic modeling of Hg/I reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. ... . ... . . . . . . . . .. . .. . .. . . . . . 12
4.5. Hg/O reaction system . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. ... . ... . . . . . . . . .. . .. . .. . . . . . 12
4.5.1. Hg/O reaction mechanism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. ... . ... . . . . . . . . .. . .. . .. . . . . . 13
4.5.2. Kinetic modeling of Hg/O reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. ... . ... . . . . . . . . .. . .. . .. . . . . . 13
4.6. Hg/N reaction system . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. ... . ... . . . . . . . . .. . .. . .. . . . . . 14
4.7. Hg/S reaction system . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. ... . ... . . . . . . . . .. . .. . .. . . . . . 14
5. Heterogeneous reaction kinetics of mercury transformation . . . . . . . . . . . . . . . . . . . . . . . . . . . .. ... . ... . . . . . . . . .. . .. . .. . . . . . 14
5.1. Historical perspective . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. ... . ... . . . . . . . . .. . .. . .. . . . . . 14
5.2. Reaction chemistry over unburned carbon within fly ash . . . . . . . . . . . . . . . . . . . . . . . . .. ... . ... . . . . . . . . .. . .. . .. . . . . . 15
5.2.1. Heterogeneous Hg/Cl mechanism and kinetic model over unburned carbon . . . .. ... . ... . . . . . . . . .. . .. . .. . . . . . 15
5.2.2. Heterogeneous Hg/Cl/Br mechanism and kinetic model over unburned carbon .. ... . ... . . . . . . . . .. . .. . .. . . . . . 16
5.3. Reaction chemistry over transition metal oxides within fly ash . . . . . . . . . . . . . . . . . . . .. ... . ... . . . . . . . . .. . .. . .. . . . . . 17
5.3.1. Mechanism and kinetic model of mercury oxidation over Fe2 O3 . . . . . . . . . . . . .. ... . ... . . . . . . . . .. . .. . .. . . . . . 17
5.3.2. Mechanism of mercury oxidation over CuO. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. ... . ... . . . . . . . . .. . .. . .. . . . . . 18
6. Mechanism of Hg oxidation over SCR catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. ... . ... . . . . . . . . .. . .. . .. . . . . . 19
6.1. V2 O5 -based catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. ... . ... . . . . . . . . .. . .. . .. . . . . . 19
6.1.1. Experimental studies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. ... . ... . . . . . . . . .. . .. . .. . . . . . 19
6.1.2. Quantum chemistry calculations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. ... . ... . . . . . . . . .. . .. . .. . . . . . 20
6.1.3. Numerical simulation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. ... . ... . . . . . . . . .. . .. . .. . . . . . 20
6.2. MnO2 -based catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. ... . ... . . . . . . . . .. . .. . .. . . . . . 22
6.2.1. Experimental studies. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. ... . ... . . . . . . . . .. . .. . .. . . . . . 22
6.2.2. Quantum chemistry calculations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. ... . ... . . . . . . . . .. . .. . .. . . . . . 24
6.2.3. Numerical simulation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. ... . ... . . . . . . . . .. . .. . .. . . . . . 24
6.3. CeO2 -based catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. ... . ... . . . . . . . . .. . .. . .. . . . . . 25
6.3.1. Experimental studies. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. ... . ... . . . . . . . . .. . .. . .. . . . . . 25
6.3.2. Quantum chemistry calculations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. ... . ... . . . . . . . . .. . .. . .. . . . . . 25
6.3.3. Numerical simulation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. ... . ... . . . . . . . . .. . .. . .. . . . . . 26
7. Mechanism of Hg oxidation over noble metal catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. ... . ... . . . . . . . . .. . .. . .. . . . . . 27
7.1. Au-based catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. ... . ... . . . . . . . . .. . .. . .. . . . . . 27
7.1.1. Experimental studies. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. ... . ... . . . . . . . . .. . .. . .. . . . . . 27
7.1.2. Quantum chemistry calculations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. ... . ... . . . . . . . . .. . .. . .. . . . . . 27
7.2. Pd-based catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. ... . ... . . . . . . . . .. . .. . .. . . . . . 28
7.2.1. Experimental studies. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. ... . ... . . . . . . . . .. . .. . .. . . . . . 28
7.2.2. Quantum chemistry calculations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. ... . ... . . . . . . . . .. . .. . .. . . . . . 28
7.3. Pt-based catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. ... . ... . . . . . . . . .. . .. . .. . . . . . 28
7.3.1. Experimental studies. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. ... . ... . . . . . . . . .. . .. . .. . . . . . 28
7.3.2. Quantum chemistry calculations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. ... . ... . . . . . . . . .. . .. . .. . . . . . 28
7.4. Ru-based catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. ... . ... . . . . . . . . .. . .. . .. . . . . . 29
7.4.1. Experimental studies. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. ... . ... . . . . . . . . .. . .. . .. . . . . . 29
7.4.2. Quantum chemistry calculations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. ... . ... . . . . . . . . .. . .. . .. . . . . . 29
7.5. Ag-based catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. ... . ... . . . . . . . . .. . .. . .. . . . . . 29
7.5.1. Experimental studies. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. ... . ... . . . . . . . . .. . .. . .. . . . . . 29
7.5.2. Quantum chemistry calculations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. ... . ... . . . . . . . . .. . .. . .. . . . . . 30
8. Challenges and future prospects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. ... . ... . . . . . . . . .. . .. . .. . . . . . 30
9. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. ... . ... . . . . . . . . .. . .. . .. . . . . . 31
Declaration of Competing Interest . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. ... . ... . . . . . . . . .. . .. . .. . . . . . 31
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. ... . ... . . . . . . . . .. . .. . .. . . . . . 31
Supplementary materials. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. ... . ... . . . . . . . . .. . .. . .. . . . . . 32
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. ... . ... . . . . . . . . .. . .. . .. . . . . . 32

1. Introduction
1.1. Mercury emissions and current policy
Mercury (Hg) is a global hazardous pollutant released from ge-
ological reservoirs into the atmosphere by anthropogenic activ-
ities including fossil fuel combustion, cement production, metal
smelting, and other activities. The Global Mercury Assessment 2018
[1] found that a new global inventory of mercury emissions from
anthropogenic sources quantified global emissions into the air at
approximately 2220 tonnes. The total atmospheric mercury con-
centration increases by approximately 450% compared with the
natural levels due to human activities [2]. Stationary combus-
tion of fossil fuels contributes approximately 24% of the total an-
 Y. Yang, J. Liu and Z. Wang / Progress in Energy and Combustion Science 79 (2020) 100844
thropogenic mercury emissions, primarily from coal combustion
(21%) [1]. Therefore, coal combustion (particularly coal-fired power
plants) is one of the main sources of anthropogenic mercury emis-
sions [3]. Some policies or standards with stringent emission lim-
its have been issued to reduce mercury emission from coal-fired
power plants [4–7].
In the United States, a national standard (Mercury and Air Tox-
ics Standards, MATS) was proposed in 2011 by the US Environmen-
tal Protection Agency (EPA) to reduce mercury emissions [8]. This
standard requires 91% mercury removal from the existing coal-fired
power plants. Subsequently, an updated limit value (1.4–4.1 μg/m3 )
for mercury emissions from power plants was adopted by MATS
[4]. In the meantime, activated carbon injection technology was
widely implemented to reduce mercury emissions from coal-fired
power plants. The current emission level of mercury from coal
combustion in North America is approximately 27 tonnes [1]. In
Europe, the Industrial Emissions Directive (IED) is the main legisla-
tive instrument for regulating mercury emissions from coal-fired
power plants [9]. The new limit value of the IED is 1–10 μg/m3
[10]. The current level of mercury emissions from coal combus-
tion in Europe is approximately 46.5 tonnes [1]. In China, the
Ministry of Environmental Protection issued the emission standard
(GB13223-2011) for air pollutants from coal-fired power plants in
2011 [5]. The limit value for mercury emissions is 30 μg/m3 . Un-
der the national regulation, ultra-low emission control devices are
widely used in coal-fired power plants. The current mercury emis-
sion level is approximately 3.3 μg/m3 [11]. The projected level of
mercury emissions is expected to further decline due to the ag-
gressive measures in the United States, Europe, and China [7,11,12].
In addition, the Minamata Convention on Mercury, which aims
to reduce global Hg pollution, came into force in August 2017.
A modest decrease in mercury emissions from coal-fired power
plants in the United States, Europe, and China has been recorded
owing to concerted efforts by these countries. Nevertheless, mer-
cury pollution is still identified as a key environmental problem in
the context of global change [13–16]. Therefore, more efforts are
required to reduce Hg emission from coal-fired power plants.
1.2. Scope of this review
During pulverized coal combustion (>1400 °C), mercury is va-
porized and released into flue gas in its elemental mercury (Hg0 )
[17]. As the flue gas cools in the complex post-combustion envi-
ronment, Hg0 can be converted to oxidized mercury (Hg2+ ) and
particulate bound mercury (Hgp ) via a series of homogeneous and
heterogeneous reactions [18]. Finally, the mercury species in flue
gas include Hg0 , Hg2+ , and Hgp [19]. HgCl2 is commonly regarded
as the main form of oxidized mercury [20]. Hg2+ can be easily
removed using a wet flue gas desulfurization (WFGD) system, or
adsorbed on fly ash particles as Hgp and subsequently captured
with high efficiency using air pollution control devices (APCDs)
[21]. However, Hg0 is difficult to capture and remove using APCDs
because of its water insolubility and chemical inertness. As a re-
sult, mercury emission control in coal-fired power plants relies on
mercury speciation [22,23]. Therefore, a fundamental understand-
ing of the chemical reaction mechanisms and kinetics that govern
the transformation of Hg0 to Hg2+ and Hgp is crucial to control
mercury emissions from coal-fired power plants.
A large number of works have been devoted to the understand-
ing of the elementary reactions in mercury transformation chem-
istry and to the development of homogeneous-heterogeneous ki-
netic models to predict the mercury speciation distribution in coal-
fired flue gas. However, these kinetic models are still challenging
for the quantitative engineering predictions [24]. Therefore, there
is still a motivation to deeply understand the complex mercury
transformation chemistry and develop reliable and versatile chem-
3
ical kinetic models. A state-of-the-art review of the chemical re-
action kinetics of mercury transformation is necessary to high-
light recent advances, remaining difficulties, and future outlook.
To date, most review papers mainly focused on thermodynamic
behaviors [25], deposition chemistry [26], catalytic oxidation pro-
cesses [23,27,28], and control technologies [29,30]. However, there
is a lack of a comprehensive and systematic review in the field of
the elementary reaction kinetics governing mercury transformation
and a comparison of different kinetic models in terms of accuracy
and performance.
The objective of this work is to provide an overview of the re-
action mechanisms and kinetics of mercury transformation in coal-
fired flue gas. This rest of this paper is organized in the follow-
ing manner. Section 2 briefly discusses the knowledge of thermo-
chemistry, and explains mercury speciation distribution in a chem-
ically complex post-combustion environment through thermody-
namic equilibrium calculations. Section 3 reviews the experimen-
tal techniques and theoretical methods used to achieve elementary
reaction rates. Sections 4 and 5 summarize the progress on ho-
mogeneous and heterogeneous reaction kinetics related to mercury
transformation over a wide temperature range, respectively. Vari-
ous subsets of the kinetic models are tested against experimental
data and the predictive capability of the mechanism is assessed.
In Sections 6 and 7, experimental and density functional theory
(DFT)-derived Hg0 oxidation mechanisms over different catalysts
are critically reviewed for mercury transformation at low and mod-
erate temperatures. Finally, a lot of recommendations are given for
the future work.
2. Thermodynamics of mercury transformation
Chemical thermodynamics is closely related to the descrip-
tion of the equilibrium states of multicomponent reaction systems.
Thermodynamic calculation allows us to determine the thermal
and compositional properties of products when the reaction sys-
tem reaches an equilibrium state. Moreover, thermodynamics plays
an important role in clarifying reaction kinetics as thermodynamic
data is used to calculate the reaction equilibrium constants. More
importantly, the thermochemical properties can be used to bench-
mark theoretical calculations. Thermochemical data can serve as
excellent benchmarks for theoretical model predictions if kinetic
measurements are not available in the literature. Mercury transfor-
mation during coal combustion is regarded as a multicomponent
reaction system as different gaseous species (HCl, SOx , NOx , O2 ,
etc.) participate in this complex conversion process [31]. Therefore,
specific aspects of the thermodynamics of mercury transformation
are discussed in this section.
2.1. Thermochemical properties
The thermochemistry of Hg-containing chemical species is a
subject of active research interest in combustion chemistry [32].
The thermochemical properties (enthalpy of formation, standard
entropy, and heat capacity) of different mercury species are given
in Table 1. The NIST-JANAF Thermochemical Tables [33] can pro-
vide the thermodynamic data for most of mercury species (Hg0 ,
HgCl, HgCl2 , HgBr, HgBr2 , HgI, HgI2 , HgF, HgF2 , HgH). The gas-
phase enthalpy of formation (61.38 kJ/mol) of Hg0 is derived from
the vapor pressure study conducted at different temperatures [34–
38]. This value is virtually adopted by the subsequent thermo-
chemical tables [39]. The enthalpy of formation for HgCl, HgBr, HgI,
HgF and HgH is based on the dissociation energy of molecule into
gaseous atoms (D0 ) [40,41]. Moreover, the gas-phase enthalpy of
formation can also be calculated from the enthalpy of formation of
crystal (National Bureau of Standards [42]) and the 3rd law heat
4 Y. Yang, J. Liu and Z. Wang / Progress in Energy and Combustion Science 79 (2020) 100844

Table 1
Thermochemical properties of different mercury species. Enthalpy of formation (f H0298 ), standard entropy
(S0298 ), and heat capacity (Cp ) are given in kJ/mol, J/(mol K), and J/(mol K), respectively.

Species f H0298 S0298 Cp Ref.

300 400 500 600 800 1000 1500

Hg0 61.38 174.97 20.80 20.78 20.77 20.77 20.78 20.79 20.80 [33]
HgCl 78.45 260.00 36.43 37.03 37.36 37.58 37.87 38.10 38.58 [33]
HgCl2 −146.29 294.78 58.11 59.89 60.72 61.19 61.66 61.89 62.15 [33]
HgBr 104.18 271.54 37.22 37.56 37.78 37.96 38.24 38.50 39.09 [33]
HgBr2 −85.45 320.22 60.29 61.18 61.59 61.81 62.04 62.15 62.27 [33]
HgI 133.47 280.75 37.93 38.28 38.59 38.86 39.39 39.91 41.18 [33]
HgI2 −16.13 336.21 61.13 61.65 61.90 62.04 62.18 62.24 62.31 [33]
HgF 2.93 248.36 34.63 35.93 36.58 36.58 37.46 37.78 38.34 [33]
HgF2 −293.65 271.74 54.04 56.96 58.65 59.68 60.79 61.33 61.89 [33]
HgO 16.72 239.13 32.78 34.65 35.57 36.11 36.75 37.14 37.74 [47]
HgH 238.49 219.71 30.06 31.42 32.81 34.05 35.94 37.23 39.31 [33]
CH3 Hg 188.10 131.00 23.23 26.72 29.91 32.68 36.89 40.25 45.66 [48]
HgOH 39.21 258.30 42.85 43.91 44.91 45.84 47.53 49.00 51.87 [49]
HgNO 183.63 298.33 41.47 41.76 42.26 42.97 44.48 44.48 47.57 [49]
HgNO2 124.10 340.29 53.17 56.10 58.98 61.53 65.50 68.09 71.39 [49]
HgONO 157.59 302.51 52.92 57.22 60.65 63.33 67.05 69.30 72.06 [49]
ClHgOH −152.61 311.42 70.05 71.01 71.90 72.74 74.24 75.55 78.04 [49]
BrHgOH −160.60 318.75 73.27 73.79 74.27 74.72 75.51 76.16 77.35 [49]
HgSO 153.57 296.36 42.01 43.51 44.81 45.90 47.28 48.07 48.99 [49]
ClHgSO −60.11 311.66 55.51 58.60 60.65 62.07 63.75 64.62 65.58 [49]
BrHgSO −250.01 320.61 56.43 59.15 60.99 62.28 63.87 64.71 65.63 [49]
ClHgSO2 −41.55 344.06 70.60 75.24 78.83 81.51 85.02 86.99 89.28 [49]

of sublimation at 298 K [43]. Examples include the gas-phase en-
thalpy of formation of HgCl2 , HgBr2 and HgI2 . For HgF2 , the en-
thalpy of formation (−293.65 kJ/mol) at 298 K is estimated through
comparing with other gas-phase mercuric halides and the crystal
mercuric fluorides [33]. The heat capacity and entropy of these
abovementioned species are based on the predicted electronic en-
ergy levels and quantum weights [44], and complemented by the
results of spectroscopic data (vibrational and rotational constants)
[45,46].
In low-chlorine coal-fired flue gas, HgO is one of the main
oxidized mercury species [50]. The thermochemical properties of
HgO molecule have received substantial attention from combustion
community, and theoretical and atmospheric physical chemistry
community [51–57]. However, there is a disagreement between dif-
ferent communities about the evaluation of the thermochemistry
of HgO molecule. In combustion community, the gas-phase ther-
mochemistry data of HgO molecule mainly comes from the NIST
Chemistry WebBook [47]. The often-cited enthalpy of formation is
41.84 kJ/mol, which is obtained from the quantity of gaseous PbO
[33]. However, a smaller bond dissociation energy of ∼4.0 kcal/mol
(16.72 kJ/mol) of HgO molecule can be obtained from the high-
level ab initio calculations [51–53]. This value is calculated from
the X0+ ground state of HgO molecule with the consideration of
the spin-orbit coupling effects, and is much smaller than the NIST
value (41.84 kJ/mol) [47]. The difference is attributed to the differ-
ent methods that are used to obtain the enthalpy of formation. The
theoretical value is widely accepted in theoretical and atmospheric
physical chemistry community. Thus, the enthalpy of formation
(16.72 kJ/mol) listed in Table 1 for HgO molecule is taken from the
theoretical calculations [51]. The heat capacity and entropy of HgO
molecule are taken from the NIST Chemistry WebBook [47]. Dur-
ing the calculation of heat capacity and entropy, the equilibrium
inter-nuclear separation of gaseous HgO is derived from the related
value of PbO molecule. The ground state structure of HgO is based
on the analogy with BeO [33]. It should be stressed here that the
thermodynamic data of HgO need to be taken with caution.
OH is a very important and reactive radical in combustion
chemistry [38,58,59]. Moreover, NOx also exists in coal-fired flue
gas. Therefore, some mercury species with oxygen moieties (such
as HgOH, HgNO, HgNO2 , HgONO, ClHgOH, and BrHgOH) may be
important in combustion chemistry of Hg. The thermochemical
properties (see Table 1) of these mercury species are taken from
the ab initio calculations using different work reactions [38,49,60–
64]. The template work reaction scheme (including the isogyric
and isodesmic reactions) is a good method to calculate the stan-
dard enthalpy of formation of mercury species [38]. The accuracy
of this method highly depends on the well-established enthalpy of
formation of reference species.
SOx is the acid flue gas species produced from coal combustion.
SOx can react with mercury species to form a lot of complex com-
pounds (such as HgSO, ClHgSO, BrHgSO, and ClHgSO2 ) [49]. The
presence of these compounds can alter the reaction pathways of
mercury transformation in coal-fired flue gas. The enthalpy of for-
mation of HgSO is much higher than those of ClHgSO, BrHgSO, and
ClHgSO2 species (see Table 1). This is attributed to the stronger
Hg-S bond dissociation energy of HgSO species [49]. Moreover, Br
addition leads to a more negative enthalpy of formation of XHgSO
compared with Cl addition.
To date, the thermochemical properties of other gaseous inor-
ganic mercury species (HgSO4 , Hg2 SO4 , Hg2 (NO3 )2 , Hg(NO3 )2 ) can-
not be found in the published works and highly-cited databases,
such as the Active Thermochemical Tables (ATcT) [65–67], NIST
Chemistry WebBook [47], NIST-JANAF Thermochemical Tables [33],
Ideal Gas Thermochemical Database [48], and National Bureau of
Standards [42]. In the future works, the thermochemical properties
of these gaseous inorganic mercury species need to be determined
by experiments or quantum chemistry calculations at the different
levels of theory. The NASA-polynomial expressions can be used to
fit the calculated results in two different temperature intervals.
Mercury transformation in coal-fired flue gas also involves C-
, H-, O-, N-, S-, Cl-, and Br-containing species. The thermochem-
ical properties of these species can be obtained from the Active
Thermochemical Tables (ATcT) [65–67], THERM program [67], high-
level ab initio calculations [68], and CHEMKIN database [69]. The
thermochemistry of Cl- and Br-containing species is mainly pro-
vided by Pelucchi et al.’s [70] and Dixon-Lewis et al.’s [71] works.
2.2. Equilibrium calculations
In the high-temperature combustion region (>1400 °C) of coal-
fired boilers, mercury within coal decomposes to form the thermo-
 Y. Yang, J. Liu and Z. Wang / Progress in Energy and Combustion Science 79 (2020) 100844
Fig. 1. Equilibrium mercury speciation as a function of temperature in (a) Hg/O/Cl/C/H/N/S and (b) Hg/O/C/H/N/S systems. The air excess number (λ) and mercury content
of subbituminous coal combustion are 1.2 and 0.2 ppmv, respectively (Reprinted from [25] with permission of Elsevier).
dynamically favored Hg0 . As the flue gas cools in the post-furnace
region, oxidation reactions occur for the transformation of Hg0 to
Hg2+ and Hgp . The transformation efficiency is affected by many
factors such as chlorine content of coal, combustion environment
(air- and oxy-fuel combustion), fly ash compositions, and operat-
ing conditions [29]. Thermodynamic equilibrium calculations can
provide some useful information on the possible mercury specia-
tion and the corresponding equilibrium concentration [72]. There
have been numerous studies involved in mercury speciation distri-
bution in pulverized coal combustion systems through equilibrium
calculations [25,72–119].
Chlorine is the most important species for mercury transfor-
mation in the post-combustion gasses [109]. The transformation
of Hg0 to HgCl2 occurs at the temperatures below about 950 K
[25,111], as shown in Fig. 1(a). All of the mercury species exist
as HgCl2 in the temperature window of 40 0–70 0 K [109]. At the
temperatures above 950 K, mercury species exist in the forms of
Hg0 and HgO. Hg0 and HgO account for 99% and 1% of the to-
tal mercury, respectively. HgCl2 formation in the temperature win-
dow of 70 0–90 0 K is determined by the chlorine content of coal.
The crossover temperature between Hg0 and HgCl2 increases from
803 K to 1013 K when HCl concentration increases from 50 ppmv
to 30 0 0 ppmv [111]. The trend is consistent with other studies
[88,92,96]. HgSO4 condensation is observed when the temperature
decreases to about 380 K [25,109,120,121]. In the oxidative system
without chlorine, HgSO4 and HgO are the stable oxidized mercury
species, as shown in Fig. 1(b). HgSO4 (cr) is the only stable mercury
species at the temperatures below about 540 K. Hg0 and HgO exist
in the region where the temperature is higher than 590 K.
Oxy-fuel combustion is a promising carbon capture and sepa-
ration technology [122,123]. Compared with air-firing conditions,
oxy-fuel combustion environment modifies the behavior and fate
of mercury because of the CO2 -rich flue gas re-circulation to the
boiler [73,124–127]. The stable temperature range of HgCl2 under
oxy-fuel conditions is much wider than that of HgCl2 under air-
firing conditions [74], because some Cl2 molecules can be formed
from the reactions between CO2 and alkali chlorides [128,129].
Moreover, oxy-fuel combustion environment is favorable for HgO
formation [73,77,80,84]. Mercury concentration in oxy-fuel com-
bustion case with 72.1% flue gas recycle is approximately two times
higher than that in air-firing case [84]. The increase in mercury
concentration is attributed to Hg-containing flue gas recirculation
[86]. During flue gas recirculation, the high-concentration SO2 in-
hibits the transformation of Hg0 to Hg2+ and Hgp [79].
Some fly ash compositions (such as CaO) affect the mercury
speciation distribution in coal-fired flue gas [81,92,101,113]. The
presence of CaO leads to the decrease of Hg0 /HgCl2 transforma-
5
tion temperature as CaO inhibits mercury chlorination through the
consumption of HCl [81]. A part of CaO can be rapidly converted
to CaCl2 via the reaction CaO + 2HCl = CaCl2 + H2 O at the tempera-
tures below 850 K, leading to the consumption of HCl. As the tem-
perature further decreases to 700 K, HCl is thoroughly depleted for
CaCl2 formation. Hg0 /HgCl2 transformation temperature decreases
from 750 to 550 K when the mole ratio of CaO/HCl increases from
1 to 10 0 0 [92].
The operating conditions (such as stoichiometric ratio, SR)
of coal-fired boilers impact the flue gas compositions and the
transformation behavior of heavy metals [76,117]. All mercury
species exist in its elemental form under the conditions of
950 K < T < 1050 K and SR = 0.6 (reducing condition) [101]. How-
ever, HgCl2 and HgO exist in the equilibrium reaction system when
stoichiometry increases from 0.6 to 1.3 (oxidizing condition). Mer-
cury transformation in coal-fired flue gas is significantly dominated
by Cl-species. It should be noted that the change in stoichiome-
try affects Cl-species distribution in flue gas [81]. Under the re-
ducing condition, HCl is the dominated chlorine species, whereas
under the oxidizing condition, HCl is the main species with mi-
nor amounts of Cl radicals (< 1.5%) at higher temperatures [101].
The small amounts of Cl radicals are important for HgCl2 formation
during mercury transformation.
3. Methods of kinetic studies
Although thermodynamics links the initial state to the final and
equilibrium states of a reaction system, it cannot provide the in-
formation about the pathway dominating reaction process and the
time approaching to chemical equilibrium [32]. Thermodynamic
equilibrium calculations are subject to several limitations. The ma-
jor one is that only the information of thermodynamic equilib-
rium can be predicted by these calculations. The assumption of
gas-phase thermodynamic equilibrium for mercury species in coal-
fired flue gas is not valid at the temperatures below about 800 K
[109]. Mercury transformation in coal-fired flue gas is kinetically
limited as the flue gas rapidly cools [20,22,130]. The rates ap-
proaching to thermodynamic equilibrium (chemical kinetics) rep-
resent a significant problem which must be generally studied by
experiments [118]. Kinetic calculation has the ability to distin-
guish between reactions which can and cannot take place under
the specified conditions of temperature, pressure and composition.
Moreover, since mercury transformation has some finite and char-
acteristic times defining the related phenomena, chemical kinet-
ics is necessary for understanding the pathways and rates through
which reactions proceed during such times [29].
6 Y. Yang, J. Liu and Z. Wang / Progress in Energy and Combustion Science 79 (2020) 100844
The measurement of kinetics and branching fractions for mer-
cury transformation reactions is experimentally challenging be-
cause of its toxicity, high volatility, and ultra-low concentration (<
10 ppb) in flue gas. Moreover, the mercury speciation measure-
ment (Hg2+ = HgT - Hg0 ) has an inherent difficulty to distinguish
the different oxidation states of mercury. The determination of the
accurate reaction rate coefficients for a specific reaction mecha-
nism is an intricate task, because this process involves parameter
calculation procedures for a dynamical model stated in a form of
differential equations [131]. Over the past decades, substantial ef-
forts have been made to improve the experimental methods for
the investigation of mercury reaction kinetics. More crucially, the
state-of-the-art quantum chemistry and theoretical kinetics have
been exploited to relate the fundamental properties of potential
energy surface (PES) to experimental measurement. The most pow-
erful combination of theoretical and experimental studies working
in consistency has proven to be a successful approach, yielding a
framework to develop optimized chemical kinetic model that can
rationally guide the design of new experiments. This section aims
to review and compare the various methods that are capable of
providing accurate rate constants of elementary reactions.
3.1. Experimental techniques
The accurate measurements of rate constants of mercury trans-
formation reactions depend on the development of advanced ex-
perimental techniques. The developed experimental techniques can
be grouped into four classes: laser induced fluorescence, fast flow-
discharge, relative kinetic measurements, and absolute rate mea-
surements. The briefly basic principle, advantages, disadvantages,
and the utilization of these experimental techniques are presented
below.
3.1.1. Laser induced fluorescence
Laser induced fluorescence (LIF) is the spontaneous emission
from atoms or molecules that are electronically stimulated through
photon adsorption typically in the ultraviolet or visible spectral
range. A molecule will be excited by the laser source to an upper
electronic state when a photon with energy of hv is absorbed. The
excited molecule is unstable and will spontaneously undergo radia-
tive decay from the electronically excited state, emitting another
photon with energy of hv. The spontaneous emission (fluorescence)
from the excited molecule can be detected and represented as the
concentration of corresponding molecule. The detailed basic prin-
ciple, fluorescence theory, and the related knowledge of LIF can be
found in the Refs. [132,133].
LIF is a quantitative in-situ measurement technique of funda-
mental reaction kinetics [132,134]. LIF technique can preciously de-
tect gas-phase mercury [135–138]. This technique possesses the
following advantages [139,140]: (1) This technique without essen-
tial perturbation of the environment possesses high sensitivity and
ultra-low detection limit (parts-per-quadrillion). (2) LIF can pro-
duce relatively strong fluorescence signal intensity with high tem-
poral and spatial resolutions. The wavelength of the fluorescence
produced from the excited molecule can be easily discriminated.
(3) The disturbance of heterogeneous reaction can be neglected
due to the little contact time of flow system. (4) LIF application
cannot be limited by the pressure of reaction system. This feature
allows the remote measurements of the local concentration espe-
cially under the high-temperature and high-pressure conditions,
such as internal combustion engines [133,141,142]. (5) This tech-
nique shows good performance for the measurement of the fast
reactions, because the time is only limited by electrons and laser.
(6) The monochromatic laser with narrow band can be tuned to
specific electronic transitions to increase the sensitivity and selec-
tivity [143,144].
Most of elementary reactions of mercury transformation involve
the participation of active radicals. During the reaction rate mea-
surements, the interested radicals are first produced by the pulsed
laser photolysis (PLP) of precursor. Therefore, LIF is usually com-
bined with PLP during the kinetic measurements. The pulsed laser
photolysis-pulsed laser induced fluorescence (PLP-PLIF) technique
has been frequently used to study the kinetics of the reaction be-
tween Hg0 and radicals, such as Hg0 + Cl [145], Hg0 + Br [146] and
Hg0 + OH [140] reactions.
3.1.2. Fast flow-discharge
Fast flow-discharge (FFD) technique makes a contribution to the
high-precise measurement of the rate constants of elementary re-
actions involved in the complicated processes, such as combus-
tion [147–149], atmospheric chemistry [150,151] and photochemi-
cal reactions [152]. A typical FFD system essentially includes [153]:
(1) Discharge tube, (2) Flow tube, (3) Measuring system of atoms
and radicals concentrations, (4) Flowmeters and vacuum valves,
and (5) An independent high-vacuum line for gas handling. In
the FFD system, the atoms produced from the discharge tube are
rapidly pumped into the flow tube under the steady state condi-
tions. Meanwhile, the time-dependent concentrations of radicals
are determined by the measurements at different distances along
the axis of the flow tube.
In the FFD technique, the atoms or radicals of elementary re-
actions are usually produced from the radiofrequency discharge
[154], microwave discharge [155] or silent discharge [156,157] at
low pressure. The utilization of radiofrequency discharge can ef-
fectively provide a highly stable and pure source of atomic species,
and eliminate a major source of contaminants in the discharge
products. The successful utilization of FFD technique includes the
kinetic measurements of Hg0 + nitrate radicals [155,158], Hg0 + O3
[156], Hg0 + I [157] and HgH + NO [154] reactions.
3.1.3. Relative kinetic measurements
Relative kinetic measurement (RKM) technique is an indirect
method for determining the rate constant of elementary reactions.
In this method, the kinetics of the interested reaction is investi-
gated relative to the known rate constant of a well-established re-
action. This technique can be highlighted by its two main advan-
tages [159]: (1) The kinetic experiments can be readily performed
under the simulated reaction conditions. (2) The reaction cham-
bers can connect with several state-of-the-art instruments for de-
tailed product analysis and rate constant determination. However,
there are some disadvantages [160]: (1) The relative reaction rate
constant is highly dependent upon the availability of the reaction
rate constant of the reference molecule. (2) The calculation of the
accurate rate constant may be hindered by the complexity of the
reactants or the enhanced potential of side reactions. Thus, RKM
technique is appropriate for the pseudo-first order reactions.
Most relative kinetic studies include several reference molecules
as the accuracy of measured rate constant highly depends on the
referenced rate constants [161–164]. Experimental measurements
of relative rates for different elementary reactions should produce
the straight lines with near zero intercept. An example of RKM
technique utilization is the kinetic measurements of the Hg0 + OH
reaction [165]. Cyclohexane, 2-methyl propane, and n-butane were
used as the reference molecules. There is a good linear relationship
between Hg0 and different reference molecules.
3.1.4. Absolute rate measurements
Absolute rate measurement (ARM) technique is a direct method
which can quantitatively observe the time evolution of chemical
species during a complicated or simple reaction. Obviously, com-
pared with the RKM technique, no reference molecules are needed
 Y. Yang, J. Liu and Z. Wang / Progress in Energy and Combustion Science 79 (2020) 100844
for the kinetic studies using the ARM technique. There is no re-
lated experimental error caused by the introduction of reference
molecules. Moreover, ARM technique is a better choice for the ki-
netic studies if there is no known rate constant of reference reac-
tion. However, the utilization of the ARM technique in many cases
may lead to the kinetic uncertainties during the calculations of
gas-phase rate constant. For example, it is difficult to maintain a
constant concentration of reactant when a pseudo rate constant is
calculated [159]. Furthermore, some absolute rate studies are con-
ducted under the conditions of higher reactant concentration and
lower pressure. The rate constant obtained under these conditions
must be properly corrected or extrapolated for its utilization under
the conditions of coal combustion [160]. In general, ARM technique
shows a much wider application range for the kinetic studies of
mercury transformation than the RKM technique.
The accuracy of rate constants obtained by the ARM technique
highly depends on the detection instruments. The widely used de-
tection instruments include cold vapor atomic absorption spec-
trophotometer (CVAAS) [166–169], kinetic absorption spectroscopy
(KAS) [170], and mass spectrometry (MS) [171]. CVAAS can only
detect the Hg0 concentration, the intermediates and oxidized mer-
cury species cannot be detected by the CVAAS technology. The
ARM technique connecting with CVAAS is generally used for the
kinetic measurements of overall reactions, such as Hg0 + Cl2 [166],
Hg0 + Br2 [167], Hg0 + ICl [168], and Hg0 + S2 Br2 [169]. Since KAS
and MS can detect the intermediates and oxidized mercury species,
the ARM technique connecting with KAS and MS is capable of
measuring the rate constants of elementary reactions.
3.2. Theoretical methods
Computational chemistry and theoretical studies have been
widely regarded as the indispensable parts of elementary reac-
tion kinetics over the past decades due to the significant advances
in both quantum chemistry and reaction rate theory [147]. As a
consequence, the accurate electronic structure calculations based
on quantum chemistry have revolutionized our understanding of
chemical reaction kinetics. It is unrealistic to experimentally mea-
sure the rate coefficients of elementary reactions over the whole
pressure-temperature parameter space. The rate coefficients of el-
ementary reactions that are difficultly investigated by experiments
can be obtained by using the advanced theoretical methods [172–
174], which can extrapolate the calculated kinetic parameters to
the whole pressure and temperature conditions of practical com-
bustion process. A series of theoretical studies based on quantum
chemistry have been performed for determining the kinetic infor-
mation of these elementary reactions [50,175–185].
The quantum chemistry calculations are often performed using
different theoretical schemes (the level of theory and the selection
of basis set). They mainly include two important features [147]:
(1) The ability evaluating the system errors caused by the unavoid-
able simplifications and neglected effects, and (2) The prediction of
the simplest and computationally cheapest modification with the
largest improvement in accuracy. However, some quantum chem-
istry calculations involving multi-electron systems like mercury re-
main challenging, because relativistic effects become important in
the core electrons. Additionally, the valence electrons of the multi-
electron atoms also encounter the relativistic effects due to their
interactions with core electrons.
In order to improve the calculation accuracy of heavy ele-
ments, some efforts have been made to provide the reliable so-
lutions treating the relativistic effects [159]. These solutions can be
mainly classified into two groups: all-electron and pseudopoten-
tial methods. The all-electron method is very difficult for the quan-
tum chemistry calculations of mercury atoms, because the 80 elec-
trons of mercury make the electronic structure calculations com-
7
putationally intensive. Thus, the pseudopotential method consid-
ering the relativistic effects and the core-valence electron corre-
lation is necessary for the mercury-related quantum mechanical
calculations. In the pseudopotential method, the relativistic effect
of inner core electrons is replaced by an effective core potential
(ECP) [186,187]. The basis sets incorporating the relativistic effects
of the mercury inner electrons mainly include: RCEP28DVZ and
RCEP60VDZ [188], ECP28MWB [189], ECP60MDF [190], LANL2DZ
[191], Aug-cc-pVTZ-PP [192]. RCEP28DVZ and RCEP60VDZ use a
relativistic compact effective potential to replace 28 and 60 core
electrons of mercury atom, respectively. In the Hg/Cl reaction sys-
tem, the combination of QCISD/RCEP28DVZ can provide the most
accurate results [176,182], whereas in the Hg/Br reaction system,
the most accurate predictions for the bond lengths of mercury-
bromine compounds are provided by the CCSD(T)/AVTZ level of
theory [180].
After the validation of theoretical methods and basis sets, reac-
tion rate coefficients can be calculated using the selected scheme.
The accuracy of rate coefficients highly depends on the accurate
potential energy surface (PES) of a reaction, because the crucial PES
can provide some important parameters (such as activation ener-
gies). Transition state theory (TST) and Rice-Rampsberger-Kassel-
Marcus (RRKM) theory are the extensively used methods to de-
termine the rate coefficients of elementary reactions. In the RRKM
theory [193,194], a thermal average incorporating collisional effect
is included in its original form. The microcanonical ensemble of
unimolecular reactions can be well described by the RRKM the-
ory. TST method is mainly used for the kinetic investigation of bi-
molecular reactions [179,181,182,195], whereas RRKM theory tradi-
tionally focuses on the rate coefficients of unimolecular reactions
[177,178] including dissociation and recombination. A complete re-
action mechanism of mercury transformation in coal-fired flue gas
simultaneously includes a series of bimolecular and unimolecular
reactions. Thus, both TST and RRKM theories are necessary for the
development of a kinetic model predicting mercury transformation
in coal-fired flue gas. The detailed knowledge of transition state
theory and RRKM theory can be found in references [196,197].
4. Homogeneous reaction kinetics of mercury transformation
A complete kinetic model consists of the reaction mechanism,
thermochemical data, and transport data of the species [198,199].
Reaction mechanisms consisting of a series of elementary reac-
tions provide possible pathways for the molecular-level trans-
formation of reactants into products. Moreover, reaction mecha-
nisms are coupled with the thermochemical data of the species
to determine the chemical reaction rates based on the princi-
ple of microscopic reversibility. In certain cases in which dif-
fusion is the rate-controlling process, the transport data of the
species involved is also needed to simulate the chemical reac-
tion process (such as non-premixed combustion). Numerous mass-
, energy-, momentum- and species-conservation differential equa-
tions are numerically integrated based on the principle of kinetics
to calculate the target task, such as the dominant reaction path-
way, concentration, and heat release profiles. The thermochemical
properties of mercury-containing species have been discussed in
Section 2. The homogeneous reaction mechanism and the corre-
sponding kinetic modeling are presented in this section. The sum-
marized rate coefficients reflect the current level of knowledge of
the gas-phase chemical kinetics of mercury transformation in coal-
fired flue gas.
4.1. Historical perspective
Mercury reaction chemistry through detailed kinetic modeling
started from the frameworks of Widmer et al. [200], Senior et al.
8 Y. Yang, J. Liu and Z. Wang / Progress in Energy and Combustion Science 79 (2020) 100844
Table 2
Rate coefficients of Hg/Cl mechanism in Arrhenius form k = ATn exp(−Ea /RT).
No. Reaction
1 Hg0 + Cl + M = HgCl + Ma
2 Hg0 + Cl2 = HgCl + Clb
3 Hg0 + HCl = HgCl + Hb
4 Hg0 + HOCl = HgCl + OHb
5 HgCl + Cl + M = HgCl2 + Ma
6 HgCl + Cl2 = HgCl2 + Clb
7 HgCl + HCl = HgCl2 + Hb
8 HgCl + HOCl = HgCl2 + OHb
a
The unit of pre-exponential factor is cm6 /mol2 -s.
b
The unit of pre-exponential factor is cm3 /mol-s.
[109] and Sliger et al. [111] in 20 0 0, though studies that used the
global reaction rates to understand the chemistry of mercury trans-
formation in flue gas started much earlier (e.g., Ref. [201]). The ear-
lier successful works have encouraged a large number of studies in
more recent years into the reaction chemistry of mercury transfor-
mation in coal-fired flue gas [24]. Since then, many homogeneous
reaction kinetic models have been proposed to predict mercury
transformation in simulated flue gas [17,22,50,78,87,88,96,109,176–
182,202–227]. Moreover, some theoretical studies have also been
performed in persistent efforts to update rate coefficients through
the state-of-the-art quantum chemistry calculations [176–182].
Evaluation of chemical kinetic models depends on the accuracy
of the existing experimental data. The accuracy of experimental
data published prior to 2008 has been called into question [228],
because the utilization of the Ontario Hydro method for measuring
the extent of homogeneous mercury oxidation is subject to bias in
the presence of chlorine and absence of SO2 [229]. It is clear that
uncertainties exist in the accuracy of the developed models which
are tested by the earlier experimental data during the early stage
of kinetic mechanism studies [205]. In order to provide the system-
atic validation for the homogeneous kinetic model, the experimen-
tal data of homogeneous mercury oxidation was updated by the
modified Ontario Hydro method [130,228,230–232]. The updated
efficiency of homogeneous mercury oxidation is much lower than
the earlier experimental data. The updated data has been widely
used for the systematic evaluation of homogeneous reaction kinetic
models [18,78,217,219,220,222].
4.2. Hg/Cl reaction system
Hg/Cl reaction is the most extensively studied class of mer-
cury transformation in coal-fired flue gas, because chlorine species
are the most important oxidants responsible for mercury oxida-
tion [109]. The extensive investigation of Hg/Cl reaction system has
resulted in a high fidelity of chemical kinetic models which are
readily adopted into kinetic modeling studies of mercury trans-
formation. The kinetics of Hg/Cl reaction system is well under-
stood. Hg/Cl reaction is mainly initiated by Cl radicals produced
from the decomposition of HCl, and typically followed by the fur-
ther oxidation of HgCl into HgCl2 [22,87]. In the following sections,
an overview of Hg/Cl reaction kinetics important for homogeneous
mercury oxidation in coal-fired flue gas is presented.
4.2.1. Hg/Cl reaction mechanism
Although there are several Hg/Cl mechanisms for the descrip-
tion of mercury oxidation by chlorine species, the framework of
Widmer et al. [200] is more comprehensive from the theoretical
perspective. Therefore, the elementary reaction steps of most of
Hg/Cl mechanisms published after the year 20 0 0 come from Wid-
mer et al.’s [200] framework. An example of Hg/Cl mechanism
is given in Table 2. This Hg/Cl mechanism can be used to pre-
A (cm3 /mol-s) n Ea (kcal/mol) Ref.
9.00 × 1015 0.0 0.00 [220]
4.52 × 1013 0.0 36.03 [227]
1.69 × 1014 0.0 89.06 [182]
1.14 × 1014 0.0 14.88 [182]
1.16 × 1015 0.5 0.00 [22]
1.39 × 1014 0.0 −1.00 [220]
3.11 × 1011 0.0 31.22 [176]
3.28 × 105 2.4 0.29 [227]
dict mercury transformation in the chemical reaction environment
(N2 , 4–6% O2 , 10–16% CO2 , 5–12% H2 O, 10 0–20 0 0 ppm SOx , 10 0–
10 0 0 ppm NOx , 1–10 0 ppm HCl) of the post-combustion flue gas.
HCl and O2 which are present in the reaction system are impor-
tant for the experimental oxidation data. Hg0 oxidation can be ini-
tiated by Cl, Cl2 , HCl and HOCl species. HgCl produced from the
initiating steps can be further oxidized by these chlorine species,
forming the stable product HgCl2 . The kinetic parameters of el-
ementary reactions are improved based on the collision theory
[22,202,203] and the state-of-the-art quantum chemistry calcula-
tion [176–179,181,182,233,234].
The rate parameters displayed in Table 2 for the Hg0 + Cl + M
and HgCl + Cl2 reactions are based on the assembly of different
kinetic parameters [220]. For example, the pre-exponential factor
was directly obtained from Ref. [22]. The temperature exponent of
Ref. [18] was used for the determination of rate constants. The ac-
tivation energies of the Hg0 + Cl + M and HgCl + Cl2 reactions were
taken from Refs. [22] and [227], respectively. The rate constant of
the Hg0 + Cl + M reaction is comparable to the hard sphere colli-
sion limit [22,202,203]. The assembled rate parameters have been
adopted by a series of works [220–222].
Regarding the Hg0 + Cl2 and HgCl + HOCl reactions, the rate pa-
rameters are taken from the theoretical calculation results [227].
The utilization of different levels of theory leads to a large dif-
ference in rate coefficients. The rate coefficients calculated at
the QCISD/CEP-121G level of theory [227] are much lower than
those calculated at the B3LYP/RCEP60VDZ level of theory [179,195].
Therefore, the different combinations of the quantum mechan-
ical methods and basis sets need to be tested before the uti-
lization. QCISD/RCEP28DVZ provides the most accurate results for
the electronic structure calculations of different mercury species
[181,182]. In addition, the combinations of B3PW91/RCEP28DVZ
and B3LYP/ECP28MWB can provide reasonably theoretical results.
As a result, the rate constants of the Hg0 + HCl and Hg0 + HOCl
reactions were determined using transition state theory at the
QCISD/RCEP28DVZ level of theory [181,182].
The rate constant of the HgCl + Cl + M reaction is taken from
the collision-limited value [22], because the experimental mea-
surements for the rate of this reaction are scarce. The collision-
limited value is three orders of magnitude greater than the the-
oretical rate constant calculated at the MP4/SDD level of theory
[227]. Although uncertainties persist in the collision-limited value,
this value has been adopted by different mechanisms [18,220,226].
The rate constant of the HgCl + HCl reaction is based on the
theoretical work of Wilcox et al. [176–179,195,235]. The Hg0 + HOCl
reaction is faster than the Hg0 + Cl2 and Hg0 + HCl reactions,
as shown in Fig. 2. However, Hg0 + HOCl and Hg0 + Cl2 reac-
tions compete with each other at high temperatures. HOCl and
Cl2 are likely to play a major role in mercury oxidation, but
atomic chlorine is more likely involved in the dominant oxidation
pathway.
 Y. Yang, J. Liu and Z. Wang / Progress in Energy and Combustion Science 79 (2020) 100844
Fig. 2. Forward rate constants of different elementary reactions as a function of
temperature (Reprinted from [179] with permission of ACS).
4.2.2. Kinetic modeling of Hg/Cl reactions
Mercury concentration in coal-fired flue gas is typically less
than 10 ppbv. However, the reaction that does not involve Hg can
exhibit an indirect effect on mercury oxidation, because these re-
actions determine the concentrations of important flue gas species
(HCl, Cl, Cl2 , HOCl, and O) responsible for mercury oxidation.
Therefore, a complete kinetic model not only includes the Hg/Cl
sub-mechanism, but also involves other sub-mechanisms such as
C/H/O/N/S/Cl chemistry, NOx chemistry and SOx chemistry. These
reaction sub-mechanisms simultaneously control mercury transfor-
mation in coal-fired flue gas.
Although some homogeneous Hg/Cl mechanisms have provided
important insight into the qualitative behavior, their quantitative
accuracy has been called into question [228]. Errors may stem from
the utilization of aqueous chemistry methods which are usually
used to determine the extent of mercury speciation [18]. More-
over, some kinetic parameters of elementary reactions of mercury
and oxidized species have been estimated rather than based on
the direct experimental measurements. Ideally, a reliable model
should be tested by comparison to accurate data with the possibil-
ity of systematic error elimination. Moreover, a good kinetic model
can well reproduce the experimental data and predict the experi-
mental phenomenon under the harsh conditions (high temperature
and pressure). As shown in Fig. 3(a), a reasonably good agreement
is found between the experimental measurements and the recent
model predictions. The temperature histories of flue gas are shown
in Fig. S1. The developed model is tested by comparison to the
well-characterized data [210] that is unbiased by mercury oxida-
tion in the impinge solutions of aqueous chemistry methods. The
experimental data can be reasonably reproduced by this kinetic
model [220], although the kinetic calculation results show an en-
hanced sensitivity of mercury oxidation to the temperature quench
rate and straddle the experimental data. Moreover, the effects of
HCl concentration and quench rate on mercury oxidation can be
successfully described by the updated kinetic model. Compared
with other previous modeling efforts, Yang et al.’s [220] mecha-
nism has a relatively better performance to predict homogeneous
mercury oxidation in coal-fired flue gas, as shown in Fig. 3(b).
The rate of production analysis and sensitivity analysis are the
powerful tools to analyze the dominant reaction pathway of mer-
cury oxidation in coal-fired flue gas. Homogeneous Hg0 oxidation
proceeds mainly through two reactions Hg0 + Cl + M = HgCl + M
and HgCl + Cl2 = HgCl2 + Cl [22]. The dominant reaction path-
way of homogeneous mercury oxidation is a two-step process
(Hg0 → HgCl → HgCl2 ) [87]. Hg0 reacts with Cl atoms to form in-
termediate HgCl. Subsequently, HgCl is further oxidized into HgCl2 .
Mercury oxidation process in different reaction stages is controlled
9
by different elementary reactions. Homogeneous mercury oxida-
tion process in the isothermal stage is mainly determined by the
reaction rate of HgCl + Cl2 = HgCl2 + Cl, whereas mercury oxida-
tion in the cooling stage is determined by the reaction rate of
Hg0 + Cl + M = HgCl + M [22].
Homogeneous mercury oxidation occurs in the quench region
and begins at temperatures of around 800 K [18]. The quench
rate of flue gas shows significant effects on mercury oxidation.
Thus, a typical time-temperature history of coal-fired power plant
should be considered during the kinetic prediction of mercury
speciation [17]. Most of experiments [130,205,227] and kinetic
modeling [18,206,220] suggested that high quench rate is favor-
able for mercury oxidation. Mercury conversion at high quench
rate (−440 K/s) is much higher than that at low quench rate
(−210 K/s) [205]. As mentioned above, Hg0 + Cl + M = HgCl + M and
HgCl + Cl2 = HgCl2 + Cl were found to be responsible for mercury
oxidation [22,111]. The recombination reaction (2Cl + M = Cl2 + M)
of Cl radicals is regarded as the most sensitive reaction [18], be-
cause this reaction dominates the concentration of Cl radicals.
Moreover, high quench rate is favorable for the formation of Cl
radicals [236]. The rapid quench rate of flue gas and the kinetic
constraints of Cl radicals recombination lead to a significant su-
perequilibirium concentration of Cl radicals. Therefore, the higher
mercury oxidation at high quench rate is attributed to the longer
residence time at low temperature region and to the higher con-
centrations of Cl radicals. These can explain the entire oxidation of
mercury in the temperature quench environment of sample probe.
The Cl/Hg ratio of feed coal is an important factor of homo-
geneous mercury oxidation in coal-fired flue gas. Mercury oxida-
tion increases with increasing the Cl/Hg molar ratio. This trend can
be verified by the mercury speciation distribution of five different
coal-fired power plants [215]. However, a saturation limitation can
be observed for mercury oxidation efficiency when the HCl/Hg ra-
tio is larger than 40 0 0 [111], the further increase of HCl concentra-
tion does not lead to the increase of mercury oxidation. This be-
havior can be explained by the reason that mercury concentration
is low enough to limit the reaction rate of Hg oxidation [22]. The
addition of Cl2 and HCl leads to a near-equal conversion of Hg0 in
the presence of oxygen [214].
Mercury transformation in coal-fired flue gas is also affected by
the interactions between Cl-species and other species. The com-
plex interactions can be well understood by kinetic analysis. Dur-
ing hydrocarbons combustion, the surplus hydrogen and H2 O re-
act with Cl radicals to form HCl, thereby inhibiting mercury oxida-
tion [214]. However, the inhibitory effect of H2 O is much weaker
than that of hydrogen. Oxygen plays an important role in mercury
oxidation, because it can tie up hydrogen as H2 O. The addition
of high-concentration NOx inhibits mercury oxidation by chlorine
[25,214], because several exothermic and catalytic cycles lead to
the loss of Cl radicals. However, the presence of low-concentration
NOx promotes mercury oxidation [22]. This is consistent with the
experimental observations of the flow reactor [130]. SO2 shows an
inhibitory effect on homogeneous mercury oxidation, which is at-
tributed to an irreversible reaction SO2 + Cl2 → SO2 Cl2 [95].
4.3. Hg/Br reaction system
Bromine addition can effectively promote the transformation of
Hg0 into Hg2+ in low-rank coal-fired flue gas with low HCl con-
centration [237–240]. Bromine compounds can be applied at very
lower concentrations. The presence of bromine adds a new di-
mension to the already complex chemistry and kinetics of mer-
cury transformations in post-furnace regions of coal-fired boil-
ers, which can significantly alter branching fractions and open
up new pathways for mercury oxidation in coal-fired flue gas.
Many efforts have been made to investigate Hg/Br reaction chem-
10 Y. Yang, J. Liu and Z. Wang / Progress in Energy and Combustion Science 79 (2020) 100844

Fig. 3. Comparison of measured and predicted mercury oxidation efficiency. (a) Model predictions of Ref. [220]. (b) Model predictions of Ref. [223]. The symbols denote
experimental data [130]. Solid and dashed lines denote model predictions at 440 K/s and 210 K/s, respectively. The legend below the figures corresponds to the right figure
(Reprinted from [220,223] with permission of Elsevier). Hg/Cl sub-mechanisms were taken from Yang et al. 2016 [220], Gharebaghi et al. 2011 [18], Helble et al. 2007 [206],
Bhopatkar et al. 2006 [204], Xu et al. 2003 [50], Wilcox et al. 2003 [176], Edwards et al. 2001 [17], Niksa et al. 2001 [22].

Table 3
Rate coefficients of Hg/Br mechanism in Arrhenius form k = ATn exp(−Ea /RT).

No. Reaction A n Ea (kcal/mol) Ref.

1 Hg0 + Br = HgBra 4.00 × 1011 0.859 – [180]

2 Hg0 + Br + M = HgBr + Mb 6.94 × 1014 0.5 0.0 [213]
3 Hg0 + Br2 = HgBr + Brc 1.15 × 1015 0.0 30.08 [180]
4 Hg0 + HBr = HgBr + Hc 1.86 × 1013 0.0 71.58 [180]
5 Hg0 + Br2 = HgBr2 c 2.83 × 1010 1.06 40.44 [216]
6 HgBr + Br = HgBr2 a 2.00 × 1012 9.18 – [180]
7 HgBr + Br2 = HgBr2 + Brc 4.02 × 1011 0.0 0.87 [180]
8 HgBr + HBr = HgBr2 + Hc 9.41 × 1012 0.0 18.68 [180]
a
The temperature-dependent rate expression is k = A(T/298)−n .
b
The unit of pre-exponential factor is cm6 /mol2 -s.
c
The unit of pre-exponential factor is cm3 /mol-s.

istry. The related elementary reactions have been studied in some ory. The rate constant agrees well with the previously theoretical
depth by theoretical methods [55,63,64,180,184,185,216,241–247] results [247,249], and is in good agreement with the experimental
and experimental techniques [144,146,161,167,248]. Some homo- measurements [161].
geneous Hg/Br kinetic models have been developed to understand The three-body collision reaction (Hg0 + Br + M = HgBr + M)
the kinetics of mercury transformation in coal-fired flue gas with provides another channel to form HgBr. The kinetic parameters
bromine addition [78,210–213,217,222–225,232]. of this elementary reaction are taken from the reaction-rate
adjustments based on the hard sphere collision limit [213],
although there are experimental measurements (including a PLP-
4.3.1. Hg/Br reaction mechanism
PLIF study at low temperatures [146]) and theoretical studies
The reaction paths converting Hg0 to HgBr2 are initiated by the
(including a RRKM calculation with a master equation anal-
combination of elemental mercury with atomic bromine (Hg0 + Br)
ysis in the temperature range of 180–400 K [246]). The mea-
[64,180,184,241–243,246,247], molecular bromine (Hg0 + Br2 )
sured rate constant from the PLP-PLIF study is expressed as
[180,184,216,242,243,245], or hydrogen bromide (Hg0 + HBr)
(1.46 ± 0.34) × 10−32 × (T/298)−(1.86±1.49) cm6 molecule−2 s−1
[180,242,243], and followed by the further oxidation of mercury-
[146]. However, based on the B3LYP/CEP-121G quan-
containing intermediates to HgBr2 . Table 3 lists eight elementary
tum chemistry, the calculated rate constant is
reactions among six reactive species (Hg0 , HgBr, HgBr2 , Br, Br2 ,
1.1 × 10−12 × (T/298)−2.37 cm3 molecule−1 s−1 [246]. Reaction-rate
and HBr).
adjustments are periodically proposed as more accurate experi-
The Hg0 + Br reaction has received substantial attention includ-
mental data become available [250]. Recently, many efforts have
ing experimental measurements [161,248] and theoretical calcula-
been made to improve the predictive capabilities of kinetic model
tions [55,180,242,243,246,247]. However, these kinetic experiments
under the conditions of coal combustion [222,224].
are mainly performed at the room temperature, and thus cannot
For the Hg0 + Br2 (R3), Hg0 + HBr (R4), HgBr + Br2 (R7) and
accurately understand the high-temperature chemistry of mercury
HgBr + HBr (R8) reactions, there are no experimental data available
transformation in coal-fired flue gas. The rate coefficients listed in
for the rate determination of these elementary reactions. However,
Table 3 for the Hg0 + Br reaction are based on the theoretical work
these reactions have been theoretically investigated at different
conducted by Wilcox et al. [180] at the CCSD(T)/AVTZ level of the-
 Y. Yang, J. Liu and Z. Wang / Progress in Energy and Combustion Science 79 (2020) 100844
levels of theory (such as CCSD(T)/AVQZ [245], CCSD(T)/CBS [184],
B3LYP/RCEP60VDZ [180,242], and QCISD(T)/SDD [243]). The rate
constants of the four elementary reactions are based on the kinetic
analysis using transition state theory over the 298–20 0 0 K temper-
ature range [180,242]. During the kinetic analysis, the tunneling
correction factor should be considered for the HgBr + HBr (R8) re-
action. Moreover, the rate constant of the Hg0 + Br2 (R3) reaction
can also be determined from its reverse rate coefficient [184]. The
global potential energy surface of HgBr + Br = Hg0 + Br2 includes
three smooth regions: abstraction reaction HgBr + Br → Hg + Br2 ,
insertion reaction Hg +Br2 → HgBr2 and recombination reaction
Br + HgBr → HgBr2 . The calculated reaction enthalpy with smaller
errors (∼1 kcal/mol) is within the experimental uncertainties.
Hg0 + Br2 = HgBr2 is an insertion reaction to accomplish the
one-step oxidation of Hg0 into HgBr2 . Although several experimen-
tal studies focus on the rate measurements of this insertion reac-
tion at low temperatures [167], there are accumulative uncertain-
ties in the final kinetic data due to the errors from least-squares
fits (5-20%), concentration measurements (<5%) and reactor sur-
face adsorption (<6%) [161]. Moreover, the high-temperature ex-
perimental measurements for the rate of this insertion reaction are
scarce. Therefore, the high-level theoretical calculation appears to
be a more accurate representation of the insertion reaction rate
[55,184,216,247]. The temperature- and pressure-dependent rate
constant obtained from the master equation analysis is therefore
selected for this insertion reaction in Table 3. The insertion reac-
tion has a higher activation energy barrier and a very small rate
constant. The rate constant increases with increasing pressure.
For the HgBr + Br = HgBr2 reaction, the experimental studies
focused on the rate constant determination are scarce. How-
ever, the room-temperature reaction rate can be estimated from
a time-resolved study of HgBr2 dissociation [144]. Neverthe-
less, the reaction rate is known less well at the combustion-
related temperatures. Thus, the high-temperature reaction rate of
HgBr + Br = HgBr2 is supplemented by a series of definitive ab ini-
tio quantum chemistry calculations [55,180,184,242,246,247]. A no-
table one is the work of Wilcox et al. [180] who provide the
more accurate rate predictions over the 298–20 0 0 K tempera-
ture range. Therefore, the rate coefficients given in Table 3 for
HgBr + Br = HgBr2 are taken from their work.
4.3.2. Kinetic modeling of Hg/Br reactions
There are some kinetic models to predict homoge-
neous mercury oxidation by bromine species [78,210–
213,217,219,222,225,232]. The most comprehensive experimental
studies on homogeneous mercury oxidation by bromine species
come from Silcox and coworkers [130,230,231,251]. The exper-
imental data from the flow reactor is often very reliable, in
particular under the conditions using the improved wet condition-
ing system coupled with an online mercury analyzer. Concerns
include the accuracy of the measured mercury oxidation efficiency,
time-temperature profile, and the possible interactions with re-
actor surface. No heterogeneous mercury oxidation over reactor
surface and additional oxidation in impinge solution were found
during these experiments.
HBr dissociates into the most reactive radicals for mercury ox-
idation in the typical post-furnace region [212,213]. At high tem-
peratures (≥10 0 0 K), Br radicals formation is controlled by the in-
teraction between HBr and OH [219]. As the temperature decreases
below 10 0 0 K, the interaction of HBr with BrO dominates Br radi-
cals formation. Mercury oxidation by bromine begins at high tem-
peratures of around 1100 K [219]. The dominant channel of ho-
mogeneous mercury oxidation by HBr is identified as a two-step
process Hg0 → HgBr → HgBr2 [212,213], whereby Hg0 is first oxi-
dized by Br radicals into HgBr, which is subsequently oxidized by
Br2 into HgBr2 . At the temperatures below 800 K, the HgBr + Br re-
11
Fig. 4. Comparison between experimental data and model predictions for homoge-
neous mercury oxidation by HBr in a flow reactor (Courtesy of dr. Paula A. Buitrago
[232]). The symbols denote experimental data [130], while the lines denote model
predictions [232]. The homogeneous Hg/Br mechanisms are taken from Bozzelli
et al. [216,217,252] and Niksa et al. [212,213].
action competes with the HgBr + Br2 reaction for HgBr2 formation
[219]. However, the HgBr + Br2 reaction is dominant for mercury
oxidation when the temperature further decreases.
The role of quench rate in mercury oxidation by bromine is
different from that envisioned in Hg/Cl reaction system. The low
quench rate is favorable for mercury oxidation in the presence of
bromine [130], whereas the high quench rate leads to more mer-
cury oxidation in the Hg/Cl reaction system [205]. The drastically
different halogen chemistry can explain the different effects of the
quench rate seen with HBr versus HCl [130]. Although some ki-
netic models have been developed to predict homogeneous mer-
cury oxidation in the presence of bromine, most of them cannot
accurately describe the effects of quench rate, as shown in Fig. 4.
Many efforts have been made to enhance the predictive capabil-
ity of kinetic model [217]. However, the dependence of model pre-
dictions on quench rate needs to be further improved. These may
imply mechanistic or parametric uncertainties (e.g., deficiencies in
kinetic parameters or insufficient reaction paths), because some
Hg/Br mechanisms are developed by analogy with Hg/Cl mecha-
nism [212,213].
The changes in the combustion environment affect the chem-
istry and behavior of mercury oxidation by bromine in coal-fired
flue gas. The different behaviors of mercury transformation in oxy-
fuel and air-firing combustion environments have been demon-
strated by a series of homogeneous experiments [230,253] and ki-
netic modeling [78]. Oxy-fuel combustion is much more effective
for mercury oxidation than air-firing conditions. The primary rea-
son is that CO2 as a third body is much more effective than N2 in
the rate-controlling reaction Hg0 + Br + M = HgBr + M [230]. Under
the oxy-fuel combustion conditions, the presence of NO and SO2
shows little or no effects on mercury oxidation by bromine.
Besides the abovementioned kinetic modeling, there are re-
cently persistent efforts to develop reliable and versatile chemical
kinetic model for the description of mercury oxidation by bromine
[222,223]. The updated experimental data used for model evalu-
ation is taken from Silcox and coworkers [230]. Model predictions
are generally in satisfactory agreement with the measured mercury
oxidation efficiency, as shown in Fig. 5. The temperature histories
of flue gas are similar to their previous works [130], as shown in
Fig. S1. Mercury oxidation increases with increasing HBr concentra-
tion. Kinetic model captures the mercury oxidation trend well. The
small deviation between model predictions and experimental data
is observed under the condition of low HBr concentration (10 and
12 Y. Yang, J. Liu and Z. Wang / Progress in Energy and Combustion Science 79 (2020) 100844

Fig. 5. Comparison of experimental data and model predictions. The symbols de-
note experimental data [230], the line denotes model predictions [230] (Reprinted
from [222] with permission of Elsevier).
Table 4
Rate coefficients of Hg/I mechanism in Arrhenius form k = ATn exp(−Ea /RT).
No. Reaction A (cm3 /mol-s) n Ea (cal/mol)
1 Hg0 + I = HgI 2.41 × 1011 −2.38 0.0
2 HgI + I2 = HgI2 + I 1.48 × 1016 0.0 0.0
3 Hg0 + I2 = HgI + I 8.68 × 1018 0.0 27,796
4 HgI + I = HgI2 3.66 × 1010 0.0 0.0
5 Hg0 + I2 = HgI2 2.37 × 1010 1.06 38,020
20 ppmv). However, the deviation decreases with increasing HBr
concentration. Nevertheless, as mentioned above, there is a signifi-
cant difficulty in capturing the dependence of mercury oxidation
on quench rate. Therefore, this kinetic model should be further
evaluated by the experimental data obtained at different quench
rates.
4.4. Hg/I reaction system
Iodine species addition can promote Hg0 oxidation in coal-fired
flue gas [254,255]. Iodine species reacts with Hg0 to form HgI2 via
a series of elementary reactions. Many efforts have focused on the
thermochemistry and kinetics of Hg0 oxidation by iodine species,
including experimental measurements [157,168,256] and theoreti-
cal calculations [63,216,244]. The Hg/I kinetic model can reason-
ably predict mercury transformation in flue gas with iodine species
[217].
4.4.1. Hg/I reaction mechanism
Currently, Hg/I reaction mechanism includes five elementary re-
actions, as shown in Table 4. Hg0 oxidation by iodine species is ini-
tiated by HgI formation (the Hg0 + I and Hg0 + I2 reactions). Subse-
quently, HgI is further oxidized into HgI2 species (the HgI + I2 and
HgI + I reactions). Moreover, Hg0 can be directly oxidized into HgI2
species via an insertion reaction (Hg0 + I2 = HgI2 ).
HgI species produced from the Hg0 + I reaction can be observed
by the kinetic absorption spectroscopy experiments [256]. Since
the combination reaction of Hg0 with I radicals is much slower
than the combination reaction of I radicals, it is difficult to ob-
tain an accurate concentration of the transient HgI species [256].
Therefore, little kinetic experiments can be found to measure the
reaction rate of the Hg0 + I reaction. However, the rate constant of
the Hg0 + I reaction can be taken from the theoretical calculations
at the B3LYP/CEP-121G level of theory [246]. The combination reac-
tion of Hg0 with I radicals is a factor of 3-4 times slower than that
of Hg0 with Br radicals, which is attributed to the smaller binding
energy of HgI.
The rate constants of the HgI + I2 , Hg0 + I2 , and HgI + I re-
actions are mainly characterized by the theoretical calculations
[216,244]. The calculated enthalpy of the Hg0 + I2 reaction is
27.47 kcal/mol [244], which is consistent with the calculation re-
sults (27.83 kcal/mol) of Auzmendi-Murua et al. [216]. The slight
difference between the calculated enthalpies is related to the dif-
ferent levels of theory. Since the rate constant of the HgI + I2 re-
action is much larger than that of the HgI + I reaction, the HgI + I2
reaction makes a significant contribution to HgI2 formation.
There are a lot of experimental measurements [157,168] and
theoretical calculations [216,244] to determine the rate constant of
the insertion reaction (Hg0 + I2 = HgI2 ). These experimental mea-
surements cannot provide the consistent results. Therefore, the
rate coefficient listed in Table 4 for this insertion reaction is
taken from the theoretical calculations [216]. The reaction en-
thalpy (−32.96 kcal/mol) obtained at the M06-2X/aug-cc-pVTZ-
PP level of theory is consistent with the experimental results
(−33.45 kcal/mol) [33]. Pressure shows a significant effect on the
reaction rate of Hg0 + I2 = HgI2 . Activation energy and temperature
exponent increase with increasing pressure. The pre-exponential
factor decreases when the pressure increases from 1 atm to 100
Ref. atm.
[246]
[216]
[216]
4.4.2. Kinetic modeling of Hg/I reactions
[216] There is a kinetic model including the Hg/I reaction mecha-
[216] nism [217]. This kinetic model is tested by the Hg/Cl and Hg/Br
oxidation experiments [130]. However, this kinetic model needs to
be further evaluated by the Hg/I oxidation experiments. The bond
energy (71.3 kcal/mol) of HI is much lower than those (87.6 and
103.1 kcal/mol) of HBr and HCl [217]. HI easily dissociates into I
radicals for Hg0 oxidation. Therefore, iodine shows higher reactiv-
ity for Hg0 oxidation than bromine and chlorine. Under gas-phase
reaction condition, 30 ppmv iodine leads to >90% mercury oxida-
tion.
The quench rate of flue gas shows a significant effect on mer-
cury transformation [220]. Compared with the low quench rate,
the high quench rate is favorable for Hg0 oxidation by iodine
species [217]. The effect of quench rate is closely associated with
the thermochemical properties of iodine and mercury species. The
high temperature region (140 0−160 0 K) is necessary for the for-
mation of I radicals, which react with Hg0 to form the unstable in-
termediate HgI. During the high quench rate process, the flue gas
has a longer residence time at the lower temperatures, which are
necessary for the existence of the unstable HgI species. Thus, more
HgI species can further react with iodine to form the stable HgI2
species.
4.5. Hg/O reaction system
Halogen species are the most important species for mercury ox-
idation in coal-fired flue gas. However, oxygen species are also im-
portant for mercury oxidation as oxygen is necessary for HCl con-
version into chlorine radicals [101]. Some experiments [26,121,257]
and equilibrium calculations [79,84,109] have shown that HgO
species can be formed through mercury-oxygen interaction. HgO
in gas phase is stable with respect to Hg0 and ground state O by
4 kcal/mol [51], which is about 0.43 times lower than the Hg–O
bond energy of HgOH. Based on the weak Hg–O bond of the-
ory, the lifetime (3.01 ms) of gas-phase HgO is estimated from the
lifetime of HgOH. Moreover, HgO production may be important
for mercury transformation in low-rank coal-fired flue gas with
low HCl content [17]. Therefore, a complete homogeneous kinetic
 Y. Yang, J. Liu and Z. Wang / Progress in Energy and Combustion Science 79 (2020) 100844
Table 5
Rate coefficients of Hg/O mechanism.
No. Reaction A (cm3 /mol-s)
1 Hg0 + O = HgOa 5.62 × 105
2 Hg0 + O2 = HgO + Ob 2.41 × 101
3 Hg0 + O3 = HgO + O2 b 1.44 × 1014
4 Hg0 + OH = HgOHb 1.21 × 1015
a
The temperature-dependent rate expression is k = A(T/298)−n .
b
The temperature-dependent rate expression is k = ATn exp(−Ea /RT).
model should include the Hg/O reaction chemistry. Most of the ki-
netic studies mainly focused on the reactions between mercury
and halogen species. Relatively fewer systematic studies have fo-
cused on the mechanism and kinetics of the Hg/O reaction system,
as discussed below.
4.5.1. Hg/O reaction mechanism
There are several Hg/O reaction subsets that describe the
mercury-oxygen interaction [17,50,201]. The widely used mecha-
nism of Hg0 oxidation by oxygen mainly includes different ele-
mentary reactions, as presented in Table 5. Flame deposition ex-
periments have shown that mercury is mainly deposited as HgO
species in chlorine-free flue gas [121]. Moreover, little oxidized
mercury species can be found under fuel-rich condition [101].
Therefore, these pathways and oxygen species are important for
mercury oxidation in low-chlorine or chlorine-free flue gas. Hg0
oxidation can be initiated by atomic O and molecular O2 . More-
over, ozone injection is a promising technology for multiple pollu-
tants emission control [258]. Thus, Hg/O reaction mechanism also
includes the O3 -initiated reaction.
There are some experiments [156,171,201,259–261] and theo-
retical calculations [50,55,88,181,182,195,243,244] to determine the
rate constants of the abovementioned elementary reactions. Even
though rate constants and product channels are well established
for the Hg0 + O2 and Hg0 + O3 reactions, little experimental mea-
surements are available for the Hg0 + O reaction. Only an estima-
tion [17] and quantum chemistry calculation [195] can be found
for determining the rate constant of this reaction. The rate coeffi-
cients given in Table 5 for the Hg0 + O reaction are taken from the
theoretical calculations [195]. The reaction rate of Hg0 with O is
very slow, and should be used with caution for model evaluation
purposes. The energy barrier (7.51 kcal/mol) of HgO dissociation is
much lower than that (79.32 kcal/mol) of HgCl2 dissociation.
The rate constant of the Hg0 + O2 reaction is mainly character-
ized by experimental measurements in the stopped and continuous
flow reactors [201,261]. No significant reaction between Hg0 and
O2 was observed in these experiments due to the smaller rate con-
stant. Thus, only an upper limit of the second-order rate constant
can be obtained (see Table 5). Activation energy (116 kcal/mol) was
estimated from the O=O bond dissociation energy (120 kcal/mol)
and Hg-O bond formation energy (4 kcal/mol) [262]. The correc-
tion in the rate constant may affect the model prediction re-
sults (such as oxidation efficiency, reaction channels, and HgO
production rate). The enthalpy of reaction (Hreaction ) was cal-
culated from the enthalpies of formation of reactants and prod-
ucts. The Hg0 + O2 reaction is endothermic, since Hreaction is a
positive value (48.93 kcal/mol) and is much higher than those of
other three reactions. Clearly, more extensive experimental mea-
surements and high-level theoretical studies would be needed for
a more accurate assessment of the rate coefficient of this reaction.
For the Hg0 + O3 reaction, the rate constant is derived from
a lot of experimental measurements [165,171,259,260] and the-
oretical calculations [50,88,181,182,243]. Fig. 6 shows an Arrhe-
nius plot for the rate constant of the Hg0 + O3 reaction. The ex-
perimental measurements of the high-temperature reaction rate
13
n Ea (cal/mol) Hreaction (kcal/mol) Ref.
3.04 – –70.29 [195]
0.0 116,000 48.93 [261]
0.0 32,310 –44.82 [182]
0.0 85.53 –14.62 [262]
Fig. 6. Arrhenius plot for the reaction Hg0 + O3 = HgO + O2 . The symbols denote ex-
perimental measurements, while the lines denote theoretical calculations. The data
are taken from Snider et al. 2008 [171], Hall et al. 1995 [260], 1998 [259], Pal et al.
2004 [156], Xu et al. 2003 [50], 2008 [88], Zheng et al. 2005 [181], Liu et al. 2010
[182], and Gao et al. 2015 [243].
are scarce. Although the methods used in these theoretical works
have been tested by comparing the calculated geometries, vibra-
tional frequencies, and reaction enthalpies to experimental data,
all theoretical calculations underpredict the experimentally mea-
sured rate constant. The deviation may be attributed to the uncer-
tainties of experimental measurements or/and theoretical calcula-
tions, e.g., the difficulties associated with mercury measurement,
the surface-induced reactions on reactor wall, and the selection of
methods/basis sets. In these theoretical works, the utilization of
different methods leads to substantial differences for the calculated
rate constants. Compared with Xu et al.’s [50,88] and Gao et al.’s
[243] works, Zheng and Liu et al.’s [181,182] works give a relatively
more accurate rate constant for the Hg0 + O3 reaction.
The Hg0 + OH reaction that is observed in atmospheric chem-
istry may play an important role in mercury transformation in
coal-fired flue gas. Although experimental and theoretical studies
have focused on the Hg0 + OH reaction [49,140,163,165,246,263],
there is a disagreement about the rate constant of this reaction
[264]. The utilization of different reference molecules is responsi-
ble for the differences of experimental measurements. The struc-
ture of HgOH species is very sensitive to the method and basis set
during theoretical calculations. Conceivably, the ab initio calcula-
tions of rate constants need to be performed at the high level of
theory. The rate coefficients listed in Table 5 for the Hg0 + OH reac-
tion are taken from the theoretically updated value of Dibble et al.
[262].
4.5.2. Kinetic modeling of Hg/O reactions
The kinetic understanding of HgO formation pathway depends
on the development of Hg/O chemical reaction model. The perfor-
mance of some kinetic models is sensitive to temperature [17]. At
the higher temperatures, model predictions are in good agreement
with experimental data. At the lower temperatures below 630°C,
14 Y. Yang, J. Liu and Z. Wang / Progress in Energy and Combustion Science 79 (2020) 100844
Table 6
Rate coefficients of Hg/N mechanism in Arrhenius form k = ATn exp(−Ea /RT).
No. Reaction
1 Hg0 + NO = HgNO
2 Hg0 + NO2 = HgNO2
3 Hg0 + NO2 = HgONO
4 HgNO + NO = Hg(NO)2
5 HgNO + NO2 = NOHgNO2
6 HgNO2 + NO = NOHgNO2
7 HgNO2 + NO2 = Hg(NO2 )2
the kinetic model underpredicts the experimental data. A lot of
uncertainties exist in the kinetic model due to the deficiency of
performance test [208]. In addition, uncertainties also exist in the
accuracy of previous kinetics and thermochemistry of HgO. There-
fore, the Hg/O reaction mechanism needs to be re-run with the
corrected kinetics and thermochemistry of HgO. The performance
of Hg/O reaction mechanism should be further tested by updated
experimental data of mercury oxidation by oxygen.
The contribution of oxygen species to mercury oxidation in
coal-fired flue gas can be analyzed by kinetic modeling. O2 weakly
enhances homogeneous mercury oxidation [50], especially under
the conditions of low chlorine concentration. HgO contributes
approximately 1.5–6.0% of the total oxidized mercury species.
Hg0 + ClO = HgO + Cl provides an important channel for HgO pro-
duction. Moreover, kinetic modeling can be used to predict the
amount of ozone injection. During the low-temperature reaction
process of mercury oxidation by ozone [218], mercury oxidation
efficiency increases with increasing O3 /NO mole ratio. Mercury ox-
idation efficiency increases from 5% to 30% when the O3 /NO mole
ratio increases from 1.0 to 2.0.
4.6. Hg/N reaction system
The reactions of mercury species with nitrogen oxides (NO2 and
NO) are widely observed in the field of atmospheric chemistry
[60,61,63,64,185,265]. Nitrogen oxides can be formed during the
high-temperature combustion process [266,267]. Obviously, mer-
cury transformation in coal-fired flue gas also involves the reac-
tions of mercury with nitrogen oxides [49], as shown in Table 6.
Different N-containing mercury species (such as HgNO, HgNO2 ,
HgONO) can be produced via these elementary reactions. Experi-
mental studies cannot provide accurate rate constants of these ele-
mentary reactions due to the limitation of the used CVAAS method
[201]. The reaction enthalpies of the elementary reactions can be
obtained from the theoretical calculations [49].
The Hg/N reaction mechanism can be used to explain the for-
mation of N-containing mercury species in coal-fired flue gas.
Moreover, the kinetic model containing the Hg/N reaction mech-
anism can also predict the effects of NOx species on mercury oxi-
dation. For example, the Hg/N reaction mechanism has been incor-
porated into a kinetic model to predict the effects of NO on Hg0
oxidation by halogen species [217]. NO shows an inhibitory effect
on Hg0 oxidation because of the consumption of halogen species.
Hg0 oxidation by halogen species can be reasonably predicted by
this kinetic model. However, the predictive capability of this ki-
netic model needs to be further improved under the condition of
low quench rate. Moreover, this kinetic model should be tested by
the formation of the N-containing mercury species.
4.7. Hg/S reaction system
Sulfur dioxides (SOx ) are the main products of sulfur oxidation
during coal combustion. HgSO4 is one of the main oxidized mer-
cury species in chlorine-free flue gas [25,109,120,121]. Some reac-
tion intermediates (such as HgSO and HgSO2 ) play an important
A (cm3 /mol-s) n Ea (cal/mol) Ref.
1.0 × 1011 0.0 6000 [49]
1.0 × 1011 0.0 6000 [49]
1.0 × 1011 0.0 6000 [49]
1.0 × 1011 0.0 48,700 [49]
1.0 × 1011 0.0 19,600 [49]
1.0 × 1011 0.0 15,000 [49]
2.0 × 1014 –3.68 3000 [49]
role in HgSO4 formation. Two elementary reactions are responsible
for HgSO and HgSO2 formation, as shown in Table S1. SO is a reac-
tive radical and can react with Hg0 to form HgSO. Moreover, Hg0
can also react with SO2 to produce HgSO2 species. The reaction en-
thalpies of the Hg0 + SO and Hg0 + SO2 reactions are 20.9 kcal/mol
and −3.0 kcal/mol, respectively. These values are obtained from the
ab initio calculations at the M06-2X/AVTZ level of theory [49].
The Hg/S reaction mechanism can be incorporated into kinetic
model to explain the effects of SOx species on mercury oxidation
in coal-fired flue gas. The interaction between Hg0 and SOx can be
elucidated by the Hg/S reaction mechanism. To date, there is a ki-
netic model including the Hg/S reaction mechanism [217]. SO2 in-
hibits mercury oxidation in the presence of chlorine species. How-
ever, SO2 shows little effects on mercury oxidation in the presence
of bromine and iodine species. This is associated with the lower
bond dissociation enthalpies of BrSO2 and ISO2 species.
5. Heterogeneous reaction kinetics of mercury transformation
It is well-known that a large amount of fly ash exists in coal-
fired flue gas. Fly ash particles are believed to exhibit catalytic ox-
idation activity for mercury transformation [18,27,130,268]. Con-
sequently, the mercury transformation routes include homoge-
neous gas-phase reactions and heterogeneous gas-solid interac-
tions [24,220]. It has been reported that the mercury transforma-
tion process is dominated by heterogeneous chemistry in practical
combustion systems [20,130,257]. As a result, the quantitative ac-
curacy of model prediction using the homogeneous reaction mech-
anism has been called into question under realistic flue gas condi-
tions [24,224]. Therefore, a complete and reliable chemical kinetic
model should consider the homogeneous/heterogeneous chemistry
coupling. The homogeneous kinetic model has been reviewed in
Section 4. In the following sections, the development of the het-
erogeneous mechanism of mercury oxidation over different active
components within fly ash is outlined. The predictive capability
of homogeneous-heterogeneous kinetic models is evaluated. The
rate constants specified in this section represent the current state
of knowledge of heterogeneous oxidation mechanism for mercury
transformation in coal-fired flue gas.
5.1. Historical perspective
Over the past two decades, many heterogeneous mechanisms
have been proposed to describe the reaction chemistry of mer-
cury transformation in the actual coal-fired flue gas. The first het-
erogeneous Hg/Cl mechanism for mercury oxidation by HCl over
unburned carbon (UBC) within coal-derived fly ash was proposed
by Nikas et al. [202,203], and was evaluated by comparison to
lab-scale and pilot-scale experimental data (pulverized coal com-
bustion). Since then, more attentions have been devoted to the
deeper understanding of heterogeneous mercury oxidation chem-
istry on UBC surface, including quantum chemistry calculations
[269–276] and kinetic modeling [18,204,212,277]. The community
has also realized that the inorganic components (such as iron ox-
ides) within fly ash exhibit the catalytic activity for mercury oxi-
 Y. Yang, J. Liu and Z. Wang / Progress in Energy and Combustion Science 79 (2020) 100844
dation in coal-fired flue gas [278–280]. Moreover, it is widely ac-
cepted that mercury transformation is significantly affected by the
surface reaction chemistry of competitive adsorption among differ-
ent flue gas species (such as SOx , NOx , HCl, and H2 O) on fly ash
surface [281–283]. Therefore, the first attempt to investigate the
catalytic reaction chemistry of Fe2 O3 and the competitive adsorp-
tion mechanism of flue gas species was made by Yang et al. [220–
224] to improve the predictive capability of kinetic model.
The above historical perspective highlights the data-driven
method to develop state-of-the-art kinetic models for a compre-
hensive understanding of mercury transformation in the actual
coal-fired flue gas. As previously mentioned, the mercury trans-
formation behavior over a wide temperature range can be suc-
cessfully predicted without the need to adjust the kinetic param-
eters. Nevertheless, most of the experimental data used for model
evaluation are mainly obtained using atomic absorption spectrom-
etry or atomic fluorescence spectrometry. However, these mer-
cury concentration measurement techniques cannot be used to di-
rectly measure the oxidized mercury species and reaction interme-
diates. Moreover, different oxidized mercury species cannot be dis-
tinguished by these measurement techniques. Therefore, uncertain-
ties exist in the experimental measurements of mercury oxidation
efficiency, which implies that the experimental results should be
used with caution for model evaluation purposes.
The following sections will further discuss the details of het-
erogeneous mercury oxidation chemistry, including the surface re-
action mechanism and kinetic model development. The fundamen-
tal understanding of the reaction mechanism serves as the basis
for developing the heterogeneous kinetic model. Consequently, the
kinetic modeling efforts will be discussed in the following order:
mechanistic investigation, model development, and kinetic model-
ing.
5.2. Reaction chemistry over unburned carbon within fly ash
It is well known that unburned carbon within fly ash shows the
highest catalytic reaction activity for mercury oxidation compared
to other inorganic components [27,278,284–294]. Therefore, most
of the heterogeneous kinetic models were mainly developed based
on the surface reaction mechanism of mercury oxidation over un-
burned carbon.
5.2.1. Heterogeneous Hg/Cl mechanism and kinetic model over
unburned carbon
Experiments and quantum chemistry calculations [269–
276,282,295–299] can provide insights into the interaction
between Hg0 and unburned carbon surface. The structure of
unburned carbon within fly ash is similar to that of graphene
[300]. During the quantum chemistry calculations, the single-layer
graphene structure is commonly used to represent the unburned
carbon [301–304]. As a result, theoretical calculations based on
graphene surface can provide a fundamental understanding of
heterogeneous reaction mechanism of mercury oxidation over
unburned carbon.
The amount and types of active sites provide the important
information for the development of heterogeneous kinetic model.
The unsaturated carbon atoms are the active sites of Hg0 adsorp-
tion on unburned carbon surface [270]. The physisorption mech-
anism is responsible for Hg0 adsorption over unburned carbon
[275,295], the adsorption energy of Hg0 on unburned carbon sur-
face ranges from −18.07 kJ/mol to −44.60 kJ/mol. The presence
of carbon vacancy enhances the activity of its neighboring sites,
thereby promoting Hg0 adsorption on unburned carbon surface
[298]. The adsorption energy of Hg0 on defective surface is much
higher than that of Hg0 on perfective surface. Moreover, the exis-
tence of oxygen functional groups also affects mercury adsorption
15
or oxidation on unburned carbon surface [274,295]. For example,
lactone, carbonyl and semiquinone groups promote mercury ad-
sorption. Conversely, phenol and carboxyl groups are unfavorable
for mercury adsorption due to the repulsive interaction.
Chlorine is the most important species for mercury transfor-
mation in coal-fired flue gas, and plays a promotional effect on
Hg0 adsorption over unburned carbon [270,295]. Hg0 adsorption
is enhanced by the pre-adsorption of Cl atom on unburned car-
bon surface. The chemical adsorption mechanism is responsible for
the strong interaction between oxidized mercury species (i.e., HgCl
and HgCl2 ) and unburned carbon surface [270], including dissocia-
tive and non-dissociative adsorption. HgCl can stably exist on the
unburned carbon surface and serve as an important intermediate
for mercury oxidation by HCl. Moreover, HgCl can react with the
pre-adsorbed Cl atom to form HgCl2 . The formed HgCl2 molecule
easily desorbs from unburned carbon surface due to its unstability.
Additionally, other flue gas species produced from coal combus-
tion exhibit inhibitory or promotional effects on mercury adsorp-
tion. For example, SO2 promotes Hg0 adsorption on unburned car-
bon surface by increasing the activity of its neighbor sites [282].
However, the high-concentration SO2 inhibits Hg0 adsorption be-
cause of the competitive adsorption between Hg0 and SO2 . SO3
also shows inhibitory effects on Hg0 adsorption over unburned car-
bon [297], because SO3 broadens the LUMO-HOMO energy gap of
the carbonaceous surface.
The abovementioned theoretical studies mainly focused on the
comparison of adsorption energy, the more important kinetic pa-
rameters (such as activation energy and pre-exponential factor)
of elementary reactions of mercury oxidation on unburned car-
bon surface are still unknown for the development of heteroge-
neous kinetic model. The available adsorption energy cannot pro-
vide the deeper kinetic understanding for the reaction mechanism
of mercury oxidation over unburned carbon. The oxidation reac-
tivity of unburned carbon may not just rely on the adsorption
energy calculations. The activation energy barrier and rate con-
stant can be found in an extended study [276]. The activation en-
ergy barrier of Hg0 oxidation into HgCl over unburned carbon is
in the range of 38.89–55.76 kcal/mol. The rate constant increases
from 1.64 × 10−17 s−1 to 2.73 × 10−8 s−1 when the tempera-
ture increases from 298 K to 433 K. The oxidation step of HgCl
into HgCl2 presents a relatively higher activation energy barrier of
85.80 kcal/mol.
The heterogeneous mechanism should be combined
with the homogeneous mechanism to develop a homoge-
neous/heterogeneous kinetic model [18,305]. In most of kinetic
models [202,203,212,213,220–222], the rate coefficients of hetero-
geneous reactions are based on the sticking coefficients. Sticking
coefficient represents the probability that a certain process takes
place when a collision between a given gas-species occurs with
the surface [220]. Physically, sticking coefficient denotes the
probability that a specific collision will generate the products in
a particular reaction channel. In some kinetic models [204,277],
the rate coefficients of heterogeneous reactions are based on the
Arrhenius parameters. Although the reaction-rate parameters of
several specific heterogeneous reactions have been provided by
the abovementioned quantum chemistry calculations [276], most
of them are obtained by fitting to the experimental data. An
updated heterogeneous mechanism of mercury oxidation by HCl
over unburned carbon is given in Table S2.
After the development of homogeneous/heterogeneous kinetic
model, the predictive capability should be evaluated by experimen-
tal data. The kinetic parameters of some elementary reactions are
obtained by fitting to the experimental data. However, only us-
ing the parameter-fitting experimental data to evaluate the pre-
dictive capability of the kinetic model is not reasonable. Thus,
the developed homogeneous/heterogeneous kinetic model should
16 Y. Yang, J. Liu and Z. Wang / Progress in Energy and Combustion Science 79 (2020) 100844
Fig. 7. (a) Comparison between model predictions and experimental data (Reprinted from [220] with permission of Elsevier). (b) Rate of production analysis for mercury
oxidation in coal-fired flue gas (Reprinted from [220] with permission of Elsevier).
be assessed by the different sets of experimental data. For exam-
ple, the kinetic model of Niksa et al. [202,203] was tested by dif-
ferent experimental data from 1-MWt and 29-MWt furnace, and
subsequently used to predict the mercury emission from different
coal-fired power plants [306–308]. Another comprehensive kinetic
model was also evaluated by different experimental data and suc-
cessfully predicted the mercury speciation distribution in a 1-MWt
semi-industrial-scale coal-fired furnace [85], as shown in Fig. 7(a).
Mercury oxidation in coal-fired flue gas is mainly controlled by
unburned carbon (UBC) content and HCl concentration [220]. At
low UBC level, the availability of UBC active sites determines mer-
cury oxidation, whereas at high UBC level, HCl availability becomes
dominant for mercury oxidation. Mercury oxidation under the con-
ditions of higher UBC level is much more sensitive to HCl con-
centration variations than that under the conditions of lower UBC
level.
Compared with homogeneous reaction, heterogeneous reac-
tion makes a significant contribution to mercury oxidation (see
Fig. 7(b)). StCl(s) + Hg0 → StHgCl(s) provides an important chan-
nel to oxidize Hg0 at the highest rate, and produces 64% of
the total oxidized mercury. Moreover, 24.6% of oxidized mercury
is produced via StCl(s) + Hg0 → StSA(s) + HgCl. As a result, 88.6%
of oxidized mercury is generated on unburned carbon surface.
StHgCl(s) + HCl → StSA(s) + HgCl2 + H is the main production chan-
nel of HgCl2 . In addition, 4.5% of oxidized mercury is generated
from the Hg0 + Cl + M→ HgCl + M. Therefore, the dominant path-
way of mercury transformation in coal-fired flue gas is a two-step
process: Hg0 → StHgCl(s) → HgCl2 .
5.2.2. Heterogeneous Hg/Cl/Br mechanism and kinetic model over
unburned carbon
Bromine addition can significantly enhance mercury oxidation
in coal-fired flue gas, because bromine is much more effective than
chlorine in mercury oxidation [130]. Moreover, bromine addition
remarkably alters the reaction chemistry of mercury transforma-
tion in coal-fired flue gas. The existence of some cross-reactions
makes the heterogeneous reaction mechanisms and kinetics more
complicated for the understanding of mercury transformation. The
development of heterogeneous kinetic model highly depends on
the accurate understanding of surface reaction chemistry of mer-
cury oxidation over unburned carbon. Some experiments [271–
273], quantum chemistry calculations [275,276] and kinetic studies
[212,213,222] have been undertaken to understand the heteroge-
neous reaction mechanisms and kinetics of mercury oxidation over
unburned carbon in the presence of bromine species.
Hg0 adsorption on unburned carbon surface is mainly related
to the adsorbed Br atoms. Bromine shows an effective effect on
Hg0 adsorption over unburned carbon due to the charge transfer
[275,295]. The adsorbed mercury has an oxidation state of Hg2+
and coordinates with two Br atoms, which can be confirmed by
the X-ray photoelectron spectroscopy (XPS) and extended X-ray
absorption fine structure (EXAFS) spectroscopy studies [271,272].
HgBr is stably adsorbed on the edge carbon sites through the inter-
action between Br and C atoms [272], and serves as an important
intermediate for mercury oxidation [275]. The existence of NOx
species promotes mercury oxidation on brominated carbon surface,
while SO2 shows inhibitory effects on Hg oxidation [273].
Hg0 oxidation by bromine species on unburned carbon sur-
face is kinetically controlled [272]. The energy barrier and rate
constant of Ref. [276] can provide the important kinetic informa-
tion for Hg0 oxidation by bromine over unburned carbon. During
the heterogeneous mercury oxidation, the first step (Hg0 → HgBr)
is activated by 47.88 kcal/mol. The further oxidation of HgBr into
HgBr2 presents a relatively higher activation energy barrier of
75.21 kcal/mol. The rate constant of HgBr formation during hetero-
geneous Hg0 oxidation at 298 K is 4.26 × 10−12 s−1 . The second
oxidation step (HgBr →HgBr2 ) is the rate-determining step of mer-
cury oxidation by bromine species.
The heterogeneous reaction scheme of mercury oxidation by
bromine species over unburned carbon is more complex than
the heterogeneous Hg/Cl reaction scheme, because HBr is much
more dissociative than HCl under the typical postflame condi-
tions [212,213]. Molecular Br2 produced from Br radicals recom-
bination exists in the concentrations that are comparable to HBr
levels. Given the roles of Br2 and Br in heterogeneous mercury
oxidation, the reactions between mercury and bromine species
(Br2 and Br) should be included in the heterogeneous Hg/Br
mechanism, as shown in Table S3. Since chorine species ex-
ist in coal-fired flue gas, the heterogeneous Hg/Br mechanism
should be combined with the aforementioned Hg/Cl mechanism
to form a combined homogeneous/heterogeneous Hg/Cl/Br kinetic
model.
The evaluation of the combined Hg/Cl/Br kinetic model relies on
the availability of experimental data. For example, the experimen-
tal data of bromine-addition field tests in three different coal-fired
power plants have been used to evaluate the predictive capabil-
ity of the combined Hg/Cl/Br kinetic model [212,213], as shown in
Fig. 8. The developed kinetic model can reasonably predict the ef-
fects of bromine addition on mercury removal. Mercury removal
efficiency increases with increasing bromine addition, because Hg0
 Y. Yang, J. Liu and Z. Wang / Progress in Energy and Combustion Science 79 (2020) 100844 17

Fig. 8. Comparison between field test data and model predictions. (a) Monticello Unit #3 and Milton R. Young Unit #2 (Reprinted from [213] with permission of ACS), (b)
Miller Unit #4 (Reprinted from [213] with permission of ACS). The symbols denote experimental measurements [309–311], while the lines denote theoretical calculation.

can be efficiently oxidized into HgBr2 . At high temperatures, most

of HgBr2 is formed heterogeneously on unburned carbon surface.
The heterogeneous recombination reaction of Br radicals over un-
burned carbon maintains a relatively small population of adsorbed
Hg-Br species, inhibiting the formation of particulate bound mer-
cury. As a result, bromine addition can significantly promote Hg0
oxidation in coal-fired flue gas, but cannot enhance the formation
of additional particulate bound mercury.
The accuracy of a kinetic model needs to be further assessed
when new and more accurate experimental data are available. Fol-
lowing such a process, the predictive capability of a kinetic model
can be improved as the excellent agreement is obtained between
experimental data and model predictions. For example, the latest
Hg/Cl/Br kinetic model of Ref. [222] was assessed by the well-
characterized measurements from a slipstream reactor [239], and
tested by 793-MWt full-scale experimental data [311]. The com-
bined homogeneous/heterogeneous model accurately predicts mer-
cury oxidation at different HBr concentrations. HBr concentration
has a major impact on mercury oxidation. In coal-fired power
plants, about 150 ppmw Br loading on coal (approximately 3.5
ppmv HBr in flue gas) leads to a Hg0 oxidation efficiency of >90%.
Therefore, the utilization of bromine addition at low concentration
can achieve 90% mercury emission control.
As mentioned previously, mercury transformation in coal-fired
flue gas is dominated by chlorine-related reactions. However,
bromine addition alters the dominant reaction pathway of mer-
cury transformation in coal-fired flue gas. Reaction path analysis
is a powerful tool to provide a visual representation of complex
reaction system, and has been successfully used to analyze the
reaction path diagram of mercury transformation (see Fig. 9)
[222] and NO reduction [312,313]. During mercury transformation,
about 79.2% of consumed Hg0 is oxidized into gaseous HgBr via
StBr(s) + Hg0 → StSA(s) + HgBr. However, most of the gaseous HgBr
decomposes into Hg0 via the homogeneous reactions at high
temperatures. StBr(s) + Hg0 → StHgBr(s) provides another pathway
for Hg0 oxidation. Most of StHgBr(s) is further oxidized into HgBr2
via StHgBr(s) + HBr → StSA(s) + HgBr2 + H. The dominant channel
of mercury transformation in coal-fired flue gas with bromine
addition is controlled by two reactions: StBr(s) + Hg0 → StHgBr(s)
and StHgBr(s) + HBr → StSA(s) + HgBr2 + H. Hg0 oxidation in
flue gas mainly occurs through the Br-containing reactions.
Therefore, HBr is much more active than HCl in mercury
oxidation.
Fig. 9. Reaction path analysis for mercury transformation in coal-fired flue gas with
bromine addition (Reprinted from [222] with permission of Elsevier).
5.3. Reaction chemistry over transition metal oxides within fly ash
Fly ash plays an important role in mercury transformation due
to its catalytic oxidation activity. The chemical compositions of fly
ash are suggested to be an important factor with respect to mer-
cury oxidation. Some inorganic components within fly ash are ex-
pected to show catalytic oxidation activity for Hg0 oxidation. Some
experiments have demonstrated that ferric oxide (Fe2 O3 ) and cop-
per oxide (CuO) within fly ash exhibit catalytic activity for mer-
cury oxidation in the presence of HCl [278,279,284,289,314–319].
To develop the heterogeneous kinetic model involving the catalytic
activity of Fe2 O3 and CuO within fly ash, the corresponding reac-
tion mechanism of mercury oxidation should be first investigated.
Moreover, the kinetic parameters of the reactions and the thermo-
chemical properties of involved species should be provided.
5.3.1. Mechanism and kinetic model of mercury oxidation over Fe2 O3
Fe2 O3 content of fly ash typically ranges from 4% to 40% [320].
The heterogeneous reaction mechanism of mercury oxidation on
Fe2 O3 surface has been extensively investigated by experiments
and theoretical calculations. The reported experimental work in-
cludes data from fixed-bed reactor [221,278,279,289,321,322] and
flow reactor [227,280,323,324]. Most of the theoretical calculations
are based on density functional theory (DFT) [325–333]. On the
basis of the mechanistic studies, the heterogeneous kinetic model
has been developed to quantitatively describe mercury oxidation
on Fe2 O3 surface [220–224].
18 Y. Yang, J. Liu and Z. Wang / Progress in Energy and Combustion Science 79 (2020) 100844
Mercury oxidation by HCl on Fe2 O3 surface follows either the
Deacon process [279] or the Eley-Rideal mechanism [221]. In the
Deacon process, molecular chlorine (Cl2 ) is formed from the cat-
alytic oxidation of HCl and reacts with gaseous Hg0 . However, mer-
cury oxidation through the Deacon process is not likely to happen
[20], because the gas-phase reaction between Hg0 and Cl2 is very
slow. Therefore, the Eley-Rideal mechanism is mainly responsible
for Hg0 oxidation by HCl on Fe2 O3 surface [221]. In the Eley-Rideal
mechanism, gas-phase Hg0 reacts with the adsorbed Cl species
produced from HCl dissociation on Fe2 O3 surface. The Eley-Rideal
mechanism can be further confirmed by the pretreatment experi-
ments [221] and Mössbauer spectroscopy study [321].
Although the Eley-Rideal mechanism has been known for Hg0
oxidation by HCl on Fe2 O3 surface, it is difficult to get the im-
portant kinetic information (such as elementary reactions and
rate constants) from experimental works. The elementary reactions
and activation energy barriers can be supplemented by density
functional theory calculations [325–327,329]. The adsorption en-
ergy of Hg0 on Fe2 O3 (001) surface ranges from −17.10 kJ/mol to
−46.46 kJ/mol [325,329,334]. The physical adsorption mechanism is
associated with Hg0 adsorption on Fe2 O3 (001) surface. HCl decom-
poses on Fe2 O3 surface [327], generating active chlorine species for
Hg0 oxidation. Hg0 is first oxidized by the adsorbed Cl atoms into
HgCl, which is subsequently oxidized into HgCl2 . The energy barri-
ers of the oxidation steps are 139.47 kJ/mol and 81.76 kJ/mol.
Fe2 O3 can expose different surfaces for the occurrence of het-
erogeneous mercury oxidation. Different surfaces show different
catalytic activity for mercury oxidation. Fe2 O3 (11̄02) is a ther-
modynamically stable, well-ordered, and catalytically active sur-
face [335,336]. The adsorption energy of Hg0 on Fe2 O3 (11̄02) sur-
face is in the range of −85.20 ∼ −91.73 kJ/mol [224]. Hg0 ad-
sorption on Fe2 O3 (11̄02) surface is controlled by the chemisorp-
tion mechanism. The existence of Cl atoms promotes Hg0 oxidation
on Fe2 O3 (11̄02) surface [328]. Compared with Fe2 O3 (001) surface,
Fe2 O3 (11̄02) surface is much more active for Hg0 oxidation.
Since the difference of halogens (such as HCl and HBr) and sur-
faces (such as (001) and (11̄02)), the reaction mechanisms of mer-
cury oxidation over Fe2 O3 are different. Heterogeneous mercury
reaction with HBr on Fe2 O3 (11̄02) surface follows the Langmuir-
Hinshelwood mechanism [224], in which adsorbed Hg0 reacts with
active bromine species to form gaseous HgBr2 . Two possible re-
action channels (four-step and three-step processes) are responsi-
ble for Hg0 oxidation by HBr on Fe2 O3 (11̄02) surface. Compared
with the three-step process with higher energy barrier, the four-
step process (Hg0 → Hg(s) → HgBr(s) → HgBr2 (s) → HgBr2 ) is much
more kinetically and thermodynamically favorable. The third step
HgBr(s) → HgBr2 (s) is the rate-determining step.
Based on the available mechanistic studies and kinetic informa-
tion, the heterogeneous kinetic model can be developed to predict
mercury oxidation over Fe2 O3 . For example, the development of
heterogeneous Hg/Cl reaction model is based on the Eley-Rideal
mechanism [221]. The heterogeneous Hg/Cl reaction subset in-
cludes eleven elementary reactions (see Table S4), and provides
another channel for Hg0 oxidation over fly ash. This reaction sub-
set involves the competitive adsorption among HCl, SOx and H2 O
on Fe2 O3 surface. This kinetic model is able to reasonably predict
mercury oxidation in the flow reactor [227,280] and fixed-bed re-
actor [221]. The HCl concentration and Fe2 O3 particle loading de-
pendences can be reproduced over the wide temperature range,
but the improvements in quantitative agreement are needed.
Although both bromine and chlorine are the halogen species,
Hg/Br chemistry differs from Hg/Cl chemistry. The heterogeneous
Hg/Br kinetic model over Fe2 O3 is more complex than the Hg/Cl
kinetic model, as shown in Table S5. The heterogeneous Hg/Br ki-
netic model well reproduces the experimentally measured mercury
oxidation efficiency [224] (see Fig. 10). The experimental measure-
Fig. 10. Comparison between the measured and simulated mercury conversion on
Fe2 O3 surface in the presence of HBr. The symbol denotes experimental measure-
ments, while the line denotes model predictions (Reprinted from [224] with per-
mission of Elsevier).
ments were performed in a fixed-bed reactor. Nevertheless, fur-
ther assessment of this kinetic model needs to be performed us-
ing more experimental data. Mercury oxidation efficiency initially
increases to a maximum value and subsequently decreases as the
reaction temperature increases. This trend is associated with the
temperature-dependent reaction chemistry [224].
Mercury oxidation process over Fe2 O3 in the presence of
HBr is governed by a delicate interplay of elementary reac-
tions. Mercury oxidation is strongly promoted by the adsorption
reaction Hg0 + Fe(s) → Hg(s) and the chain propagating reaction
Hg(s) + Br(s) → HgBr(s) + Fe(s), as shown in Fig. 11(a). The disso-
ciation reaction of HBr on Fe2 O3 surface also significantly pro-
motes mercury oxidation, because the surface coverage of active
bromine atoms is controlled by this reaction. The desorption reac-
tion Hg(s) → Hg0 + Fe(s) inhibits mercury oxidation.
The variation of mercury oxidation efficiency as a function of
reaction temperature is the results of thermodynamic and kinetic
effects. The temperature-dependent relationship between mercury
oxidation and heterogeneous reaction chemistry can be quantita-
tively described by a dimensionless temperature coefficient (ψ )
[224,337]. The temperature coefficient denotes the total contribu-
tion of the sensitive elementary reactions to mercury oxidation.
The sensitive reactions are divided into two groups: promotional
reactions (mechanism M1) and inhibitory reactions (mechanism
M2). The temperature coefficient can also represent the contribu-
tion of mechanism M1 and mechanism M2 to mercury oxidation.
Based on the temperature coefficient definition, the temperature
dependence of mercury oxidation by HBr on Fe2 O3 surface can be
well explained, as shown in Fig. 11(b). At the lower temperatures
(100–150 °C), ψ ≥ 0, the promotional effect of mechanism M1 is
much stronger than the inhibitory effect of mechanism M2, mer-
cury oxidation efficiency increases with increasing reaction tem-
perature. At the higher temperatures (20 0–50 0 °C), ψ < 0, the
promotional effect of mechanism M1 is much weaker than the in-
hibitory effect of mechanism M2, the increase in reaction temper-
ature inhibits mercury oxidation.
5.3.2. Mechanism of mercury oxidation over CuO
CuO within fly ash shows catalytic oxidation activity for mer-
cury oxidation in coal-fired flue gas [279,289,316,317,338,339]. In
the presence of HCl, CuO significantly catalyzes Hg0 oxidation
[279,316]. The understanding of heterogeneous reaction mecha-
 Y. Yang, J. Liu and Z. Wang / Progress in Energy and Combustion Science 79 (2020) 100844
Fig. 11. (a) Sensitivity analysis results for mercury oxidation by HBr on Fe2 O3 surface (Reprinted from [224] with permission of Elsevier). (b) Temperature coefficient and
mercury conversion at different reaction temperatures (Reprinted from [224] with permission of Elsevier).
nism controlling mercury oxidation over CuO is mainly based on
the density functional theory calculations [340–342].
Hg0 adsorption on different CuO surfaces (including CuO(110)
and CuO(111)) is controlled by different mechanisms. CuO(110)
is a low-index surface of CuO particle. Different terminations
of CuO(110) surface show different reactivity for Hg0 adsorp-
tion. Cu-terminated CuO(110) surface is much more favorable for
Hg0 adsorption than O-terminated CuO(110) surface [340]. Hg0 is
strongly and chemically adsorbed on Cu-terminated CuO(110) sur-
face, yielding an adsorption energy of −116.76 kJ/mol. The stronger
interaction between Hg0 and CuO(110) surface is closely associ-
ated with the significant overlap between Hg d-orbital and Cu s-
orbital. Cu atoms are the active sites of Hg0 adsorption on CuO sur-
face. Doping the lower electropositive element can significantly en-
hance the Hg0 adsorption capacity of O-terminated CuO(110) sur-
face [342].
CuO(111) is a thermodynamically stable surface. The adsorption
energy of Hg0 on CuO(111) surface is about −27.40 kJ/mol, which
is much lower than that of Hg0 adsorption on CuO(110) surface.
The physisorption mechanism is responsible for Hg0 adsorption
on CuO(111) surface [341]. However, Hg0 adsorption on CuO(110)
surface is controlled by the chemisorption mechanism [340]. HCl
and Cl2 are chemically adsorbed on CuO(111) surface. The energy
barriers of Hg0 oxidation by HCl and Cl2 on CuO(111) surface are
2.57 kJ/mol and 14.44 kJ/mol, respectively.
6. Mechanism of Hg oxidation over SCR catalysts
Selective catalytic reduction (SCR) of nitrogen oxides (NOx ) with
ammonia is widely used in coal-fired power plants for the con-
trol of NOx emissions. A co-benefit of SCR system is that SCR cat-
alysts can promote the oxidation of Hg0 to Hg2+ [343]. Accord-
ingly, catalytic oxidation of Hg0 to Hg2+ , followed by the removal
of Hg2+ in wet flue gas desulfurization (WFGD) units, is iden-
tified as the most convenient and economical method for mer-
cury abatement [20]. Up to now, studies on Hg0 oxidation over
SCR catalysts mainly focus on V2 O5 -based [344–347], MnOx -based
[348–350], and CeO2 -based [351–353] materials. Several mecha-
nisms, including the Deacon process, the Eley-Rideal (E-R) mecha-
nism, the Langmuir-Hinshelwood (L-H) mechanism, and the Mars-
Maessen (M-M) mechanism, have been proposed for Hg0 oxidation
over SCR catalysts [20]. However, none of the above mechanisms is
definitive for Hg0 catalytic oxidation, and the reaction mechanism
depends on the types of catalysts [20]. A brief update on the ox-
idation mechanism of Hg0 over SCR catalysts is included here to
outline the main results.
19
6.1. V2 O5 -based catalysts
6.1.1. Experimental studies
The commercial SCR catalysts (V2 O5 –WO3 /TiO2 or
V2 O5 −MoO3 /TiO2 ) show catalytic activity for Hg0 oxidation during
the bench-scale [255,343,344,354–360], pilot-scale [254,361–363],
and full-scale [346,364–368] experiments. The overall reaction of
Hg0 oxidation by HCl over SCR catalysts is normally defined as the
equation Hg0 + 2HCl + 1/2O2 = HgCl2 + H2 O [369]. Nevertheless,
the exact reaction mechanism of Hg0 oxidation over V2 O5 -based
SCR catalysts still remains controversial.
The Deacon process, where HCl is firstly oxidized by SCR cat-
alysts to produce Cl2 and then Cl2 oxidizes Hg0 to HgCl2 via ho-
mogeneous reaction, has been suggested to be responsible for Hg0
oxidation [370]. However, negligible Hg0 can be oxidized to Hg2+
when Hg0 is added into the HCl + O2 gas stream at the down-
stream of SCR catalysts [357]. In addition, the oxidation of HCl to
Cl2 is kinetically limited [109], the equilibrium concentration of Cl2
is only about 1% of the HCl concentration. Furthermore, the gas-
phase reaction between Hg0 and Cl2 plays an insignificant role in
mercury oxidation process [161,201]. Therefore, the Deacon process
is not responsible for Hg0 oxidation over SCR catalysts [357].
Langmuir-Hinshelwood and Eley-Rideal mechanisms are widely
used to interpret the heterogeneous Hg0 oxidation by HCl over SCR
catalysts. In the case of Langmuir-Hinshelwood mechanism, two
reactants (Hg0 and HCl) are adsorbed on catalyst surface and re-
act to form HgCl2 [355,357,371]. There are two types of Eley-Rideal
mechanism for Hg0 oxidation: (1) HCl is firstly dissociated on the
catalyst surface to form active chlorine complexes, and then reacts
with gaseous (or weakly adsorbed) Hg0 [344,345,354,372]. (2) Hg0
is firstly adsorbed on the catalyst surface to form the adsorbed Hg0
and then reacts with gaseous HCl [346]. The oxidation mechanism
is closely related to the adsorption characteristics of Hg0 and HCl
on SCR catalyst surface.
The Langmuir-Hinshelwood mechanism may be responsible for
Hg0 oxidation over V2 O5 -based SCR catalysts [355,357]. Hg0 ox-
idation efficiency of HCl-pretreated V2 O5 –WO3 /TiO2 catalyst de-
creases with increasing reaction temperature from 150 to 350 °C
[371], because the higher reaction temperature is not beneficial
for Hg0 adsorption. This indicates that gaseous Hg0 is firstly ad-
sorbed on catalyst surface and then takes part in Hg0 oxidation
reaction. However, it should be noted that the extent of adsorbed
Hg0 on V2 O5 -based SCR catalysts is very low and the presence of
HCl can further inhibit Hg0 adsorption [354,372]. In addition, the
adsorption of HCl on V2 O5 -based catalysts is much more intensive
20 Y. Yang, J. Liu and Z. Wang / Progress in Energy and Combustion Science 79 (2020) 100844
than that of Hg0 [357]. The X-ray photoelectron spectroscopy (XPS)
[355,364,371] and Fourier transform infrared spectroscopy (FTIR)
[357] data provide substantial evidence for the formation of ac-
tive chlorine species on SCR catalyst surface. The active chlorine
species then react with gaseous Hg0 , which is consistent with the
Eley-Rideal mechanism.
The Mars-Maessen mechanism is responsible for Hg0 oxida-
tion over V2 O5 -based SCR catalysts in the absence of acid gases
[360,364,373]. The adsorbed Hg0 reacts with lattice oxygen of
catalysts to form oxidized mercury. Oxygen vacancy is produced
during oxidized mercury desorption, and then replenished by
gaseous oxygen molecules. The Mars-Maessen mechanism can
be confirmed by the observation of Hg0 oxidation without the
aid of acid gases and the surface analysis of the used cata-
lysts. For example, adsorbed Hg0 can be oxidized to HgO over
V2 O5 /TiO2 and V2 O5 −MoO3 /TiO2 catalysts in N2 or O2 /N2 atmo-
sphere [360,364,374]. Meanwhile, HgO species adsorbed on the
used catalysts can be found by XPS and temperature-programmed
desorption (TPD) analyses. Mo6+ addition in V2 O5 /TiO2 catalyst can
promote the reoxidation of V3+ to V5+ and further increase the
number of active oxygen for Hg0 oxidation [364,374]. In the typical
SCR atmosphere, however, the first step of Mars-Maessen mech-
anism (i.e., Hg0 adsorption) may be markedly inhibited by NH3
and HCl, thereby hindering the Hg0 oxidation through the Mars-
Maessen mechanism.
6.1.2. Quantum chemistry calculations
Elucidating the heterogeneous reaction mechanism of Hg0 ad-
sorption and oxidation is crucial to the design of catalysts with
good catalytic properties. It is difficult to understand the mech-
anistic nature of mercury oxidation on catalyst surface by exper-
iments. Quantum chemistry calculations based on density func-
tional theory (DFT) can build an entire atomic-scale mechanistic
picture [313,375,376]. Recent progress in DFT makes it a power-
ful tool to accurately describe heterogeneous reactions on cata-
lyst surface and to comprehend the difference in catalytic activity
from one catalyst to another. The reaction states which maybe not
accessible to experimental methods, e.g., the electronic structure
of transitory reaction intermediates and activated complexes, can
be identified using DFT calculations [377]. DFT method has been
widely used to investigate the mechanisms of mercury adsorption
and oxidation on various sorbent/catalyst surfaces, such as acti-
vated carbon [19,270–272,274,275,295,378,379], metals [380–384],
metal oxides [340,385–402], and metal sulfides [403–407]. In this
section, we describe a series of theoretical studies involved in the
reaction mechanism of Hg0 oxidation over V2 O5 -based catalysts.
There is still controversy on the mechanism of Hg0 oxidation
over V2 O5 -based catalysts, as discussed in Section 6.1.1. The key
problem lies in the accurate understanding of Hg0 adsorption and
oxidation over V2 O5 -based catalysts. DFT method combined with
the periodic slab model can provide an atomic-level understanding
of Hg0 adsorption and oxidation. It is critical to construct a suitable
catalyst model for investigating the catalytic reaction process. V2 O5
is the active component of commercial SCR catalysts, and is gener-
ally supported on TiO2 . The strong interaction between active com-
ponent and support plays an important role in catalytic reaction
[312]. V2 O5 /TiO2 (001) model developed by Wilcox and cowork-
ers [398,408] can well represent the molecular structure of V2 O5 -
based catalysts. The adsorption energy of Hg0 on V2 O5 /TiO2 (001)
surface is much lower than that of Hg0 on V2 O5 (001) surface. The
surface composition and coverage show significant effects on the
reactivity of catalysts toward Hg0 oxidation. The ternary system
(V2 O5 –WO3 –TiO2 ) is more reactive for Hg0 oxidation than the bi-
nary systems (i.e., V2 O5 –TiO2 or WO3 –TiO2 ) [397], because the ad-
dition of tungsten oxide (WO3 ) can improve the local reactivity of
the O(1)−V active sites surrounding W atoms. Moreover, the activ-
ity of catalyst increases with increasing the active phase loading.
The observed increase in the activity is not related to the increase
of available active sites, but is caused by the change in the struc-
ture and coordination of active sites.
Identifying the intermediates (IMs), transition states (TSs), rate-
limiting steps and activation energy barriers of elementary reac-
tion steps is very important for understanding the catalytic reac-
tion mechanism of Hg0 oxidation over SCR catalysts. There have
been efforts to get these important information for Hg0 oxidation
by HCl and HBr on V2 O5 /TiO2 (001) surface [393,396]. HCl disso-
ciation over V2 O5 -based catalysts produces active chlorine species
(Cl–V5+ ) for Hg0 oxidation [357]. HCl dissociation needs to over-
come an energy barrier of 101.53 kJ/mol [396] (see Fig. 12). Hg0
oxidation by HCl on V2 O5 /TiO2 (001) surface follows the Eley-Rideal
mechanism and goes through three steps: (1) Hg0 + HCl → HgCl,
(2) HgCl + HCl → HgCl2 , and (3) HgCl2 desorption. The second
step presents the highest energy barrier (91.53 kJ/mol), and is
the rate-limiting step of Hg0 oxidation. Hg0 oxidation by HBr on
V2 O5 /TiO2 (001) surface is similar to that by HCl. The dissociation
energy barrier of HBr (85.59 kJ/mol) is lower than that of HCl, and
the energy barrier of the rate-limiting step for Hg0 oxidation by
HBr (66.97 kJ/mol) is also lower than that of Hg0 oxidation by HCl.
These can provide a molecular-level explanation for the experi-
mental observations [254,255,343] that HBr is much more effective
than HCl in promoting Hg0 oxidation.
The modification of V2 O5 -based catalysts by transition metals
can broaden the temperature window of Hg0 oxidation [394,399].
The higher temperature is beneficial for Hg0 oxidation over the
undoped V2 O5 /TiO2 catalyst due to the higher energy barrier and
positive reaction energy, while the lower temperature is benefi-
cial for Hg0 oxidation over the Fe-doped catalyst due to the lower
energy barrier and negative reaction energy. Meanwhile, Fe dop-
ing can also enhance the oxidation ability of catalyst towards Hg0
oxidation, because the substitution of V with Fe leads to the for-
mation of oxygen ions (O– ) with strong oxidizability. However, it
should be noted that the main function of SCR catalyst is NOx re-
duction. Accordingly, the modification of SCR catalyst to enhance
Hg0 oxidation should not obstruct NOx reduction.
6.1.3. Numerical simulation
In the monolith honeycomb reactor or plate reactor, mercury
oxidation by HCl is affected by many factors (such as temperature,
space velocity, catalyst configuration, NH3 /NO ratio, and HCl con-
centration). The mathematical models that have been developed
to describe the apparent mercury oxidation process in SCR hon-
eycomb reactors include the gas-solid mass transfer, intraporous
diffusion, and global reaction scheme. A lumped approach is usu-
ally used to describe mass transfer process. Different mathemat-
ical models have been developed to describe mercury oxidation
in monolith honeycomb reactor [344,346,409–412] or packed-bed
reactor [372,374,413–415]. As the flue gas stream moves through
the honeycomb channel of SCR reactor, Hg0 concentration change
caused by the gas-solid mass transfer can be expressed as [409–
412]:
dHg  bulk 
= −4ShHg Hg − Hg
wall
(1)
dz∗
where  Hg is the dimensionless Hg0 concentration, given by
 Hg =CHg /Cin . Cin is the inlet Hg0 concentration. z∗ is the Graetz
Hg Hg
coordinate, given by z∗ =z/DH Re•Sc. z is the axial distance. DH is the
hydraulic diameter. Re is the Reynolds number. Sc is the Schmidt
number. ShHg is the Sherwood number. Hg bulk is the dimensionless
concentration of Hg0 in the gas stream bulk phase. Hg
wall is the di-
mensionless concentration of Hg0 at the gas-solid interface.
The active sites on internal surface of catalyst also play an im-
portant role in mercury oxidation. Hg0 can approach to the active
 Y. Yang, J. Liu and Z. Wang / Progress in Energy and Combustion Science 79 (2020) 100844 21

Fig. 12. Potential energy surface of HCl adsorption and activation on V2 O5 /TiO2 (001) surface. The red, pink, gray, white, and green balls represent O, V, Ti, H, and Cl atoms,
respectively (Reprinted from [396] with permission of Elsevier).

sites through the intraporous diffusion. Given the inhibitory effects with increasing HCl concentration. Moreover, the effects of reaction
of NH3 on mercury oxidation, the intraporous concentration field temperature on mercury oxidation depend on HCl concentration.
of Hg0 can be determined by the solid-phase mass balance equa- In the packed-bed reactor, the effects of mass transfer on mer-
tion [410,411]: cury oxidation are usually neglected due to the larger gas hourly
space velocity (GHSV). Only the global reaction scheme is consid-
d2 Hg Hg (x )
= φHg
2
(2) ered in the mathematical model. The reaction rate of mercury ox-
dx∗2 1 + K ∗NH3 Hg Hg (x ) idation in a packed-bed reactor can be expressed as a function of
with the differential mass of catalyst [372,414]:
 dη
kHg in
rHg = −FHg (5)
φHg = s (3) dW
Deff,Hg
where η is the Hg0 oxidation efficiency. Fin 0
Hg is the inlet Hg molar
where x is the transverse intraporous coordinate. φ Hg is the Thiele
feed rate. W is the catalyst mass.
modulus. s is the catalyst wall half-thickness. kHg is the reaction
Moreover, the reaction rate of Hg0 oxidation is dependent upon
rate constant of Hg0 oxidation. Deff,Hg is the effective diffusion co-
the reaction temperature and reactant concentration. It is well-
efficient of Hg0 in the internal pores. K∗NH3Hg is the dimensionless
known that O2 concentration is much higher than Hg0 concen-
NH3 inhibition constant. tration in flue gas. Therefore, Hg0 oxidation is zeroth-order with
The global reaction rate used in the mathematical model respect to O2 concentration, whereas Hg0 oxidation is first-order
can be determined according to the mercury oxidation mecha- with respect to Hg0 concentration [372,374,414]. Hg0 oxidation rate
nism. Experiments [344,345,354,355,414] and theoretical studies can be expressed as a power-law form:
[389,393,396–398,401] have demonstrated that Hg0 oxidation over
V2 O5 -based catalysts follows the Eley-Rideal mechanism. There-
in
rHg = −kHgCHg (1 − η ) (6)
fore, the Eley-Rideal reaction rate [344,346,409–411] of Hg0 oxi-
Eq. (6) can be substituted into Eq. (5), and thus Eq. (5) can be
dation is given by
written as:

rHg =
kHgCHg dη
1 + KNH3 HgCNH3
(4) in
kHgCHg (1 − η ) = FHg
in
(7)
dW
where rHg is the global reaction rate per unit catalyst volume. Integrating Eq. (7), the relationship between mercury oxidation
KNH3Hg is the NH3 inhibition constant in Hg0 oxidation. CHg and efficiency and reaction rate constant can be obtained:
CNH3 are the Hg0 and NH3 concentrations, respectively. in
kHgCHg W
An example of numerical simulation for mercury oxidation in − ln (1 − η ) = in
(8)
the monolith honeycomb reactor is shown in Fig. 13(a) [412]. At FHg
the low temperatures below 300°C, Hg0 oxidation is insensitive
Under the given conditions (Fin and Cin ), there is a linear re-
to HCl concentration variations. Mercury oxidation efficiency in- Hg Hg

creases slightly with increasing HCl concentration from 2.5 ppmv
to 50 ppmv. HCl adsorption on catalyst surface reaches a satura-
tion state, and all vanadium active sites that participate in mer-
cury oxidation reaction are chlorinated. Therefore, Hg0 oxidation is
kinetically limited at the lower temperatures. At the high temper-
atures above 300 °C, Hg0 oxidation is sensitive to HCl concentra-
tion variations. Mercury oxidation efficiency increases significantly
lationship between –ln(1−η) and W/Fin Hg
. The rate constants of Hg0
oxidation at different reaction temperatures can be obtained from
the slopes of the plots of –ln(1−η) vs W/Fin Hg
. As an example taken
from Ref. [372], Fig. 13(b) shows the relationship between catalyst
mass and mercury oxidation efficiency at different reaction tem-
peratures. Mercury oxidation efficiency increases with increasing
catalyst mass. The reaction rate constant of Hg0 oxidation increases
22 Y. Yang, J. Liu and Z. Wang / Progress in Energy and Combustion Science 79 (2020) 100844
Fig. 13. Numerical simulations for mercury oxidation in different catalytic reactors: (a) monolith honeycomb reactor (Reprinted from [412] with permission of Elsevier), and
(b) packed-bed reactor (Reprinted from [372] with permission of Elsevier). The symbols denote experimental measurements, the lines denote simulations.
with increasing reaction temperature. Reaction temperature shows
a promotional effect on mercury oxidation over the range of 250–
350 °C.
6.2. MnO2 -based catalysts
V2 O5 -based commercial SCR catalysts are active within a nar-
row temperature window of 30 0–40 0 °C. This means that SCR unit
must be installed upstream of ESP/FF and WFGD where the cat-
alyst is exposed to high concentration of dust and SO2 , resulting
in a decreased service life. Thus, it is essential to develop novel
SCR catalysts with high activity at low temperatures (100–250 °C).
The SCR unit with the novel catalyst can be located downstream
of ESP/FF, where the flue gas is relatively clean and then cata-
lyst deactivation is weakened. To date, many SCR catalysts contain-
ing transition metals (Mn, Ce, Fe, Cr, Cu, and Co) have been re-
ported to have good activity in the low-temperature SCR of NOx
[416–419]. Among them, MnOx -based catalysts have exhibited ex-
cellent low-temperature SCR activity. Meanwhile, the high catalytic
activity, easy manufacturing and low cost of MnOx -based catalysts
make it to be one of the best candidates for Hg0 oxidation.
6.2.1. Experimental studies
There are various MnOx -based catalysts to catalyze Hg0 oxida-
tion [348,349,420–437]. These catalysts can be divided into three
types: unsupported Mn-based oxides (X-MnOx ), supported single
manganese oxides (MnOx /support) and supported composite man-
ganese oxides (MnOx −MOy /support). The reaction mechanism, ox-
idation efficiency and reaction condition of Hg0 oxidation over
MnOx -based catalysts are summarized in Table 7.
6.2.1.1. Unsupported Mn-based oxides. Unsupported Mn-based ox-
ides used for Hg0 oxidation include single MnOx (α -, β - and
γ -MnO2 ), Mn-based perovskite oxides (LaMnO3 , La1−x Srx MnO3 ,
La0.8 Ce0.2 MnO3 ), and Mn-based spinel oxides (LiMn2 O4 , Fe-Ti-Mn
and CuMn2 O4 spinel). Mn can exist in multiple valence states.
Generally, a higher valence of Mn causes a higher catalytic activ-
ity. MnO2 has higher intrinsic activity than other MnOx (Mn5 O8 ,
Mn2 O3 , Mn3 O4 , and MnO) [438]. The crystallinity is an important
factor affecting the catalytic activity of MnO2 , because the differ-
ences in the crystal structures lead to the differences in the mor-
phologies and specific surface areas [420].
Perovskites have excellent catalytic activity, high thermal stabil-
ity and unique redox behavior. The general formula of perovskites
is ABO3 , in which A is a typical rare-earth or alkaline-earth metal
ions and B is the transition metal ions. The rational substitution of
A or B cations with other elements can enhance the oxidation state
of B-site cation and/or form oxygen vacancy [422,423], and hence
greatly improve the catalytic activity of perovskites [440,441]. For
example, La substitution by Ce can improve the catalytic perfor-
mance of LaMnO3 [403], as shown in Fig. 14. La0.8 Ce0.2 MnO3 shows
>85% Hg0 oxidation and NO reduction efficiency in a temperature
window of 200–250 °C. Spinel-type manganese oxides also show
excellent catalytic activity for Hg0 removal [425,439,442,443]. A
notable one is CuMn2 O4 , which exhibits excellent Hg0 removal per-
formance in a wide temperature window of 50–350 °C. Meanwhile,
CuMn2 O4 shows good resistance to SO2 and H2 O poisoning during
Hg0 removal [223].
6.2.1.2. Supported single manganese oxides. The support plays an
important role in catalytic reaction [312]. Appropriate support can
not only supply a large surface area to disperse active component,
prevent sintering and improve mechanical strength, but also pro-
vide the room where catalytic reactions occur. MnOx has been
dispersed on different supports (including TiO2 [427,428], Al2 O3
[349], graphene [429], montmorillonite [430], Ce–Zr solid solutions
[431]) to develop MnOx /support catalysts for Hg0 oxidation.
Al2 O3 and TiO2 are the good catalyst supports due to their
high specific surface area, good temperature resistance and me-
chanical property. Al2 O3 includes inert alumina (α -Al2 O3 ) and ac-
tive alumina (γ -Al2 O3 ). MnOx can be highly dispersed on the
porous surface of γ -Al2 O3 , but MnOx tends to form a dense shell
over α -Al2 O3 particles. Thus, MnOx /γ -Al2 O3 is more effective than
MnOx /α -Al2 O3 in Hg0 removal [349]. However, the poor sulfur re-
sistance of Al2 O3 limits its practical application in coal-fired flue
gas [444]. The sulfur resistance of supports is associated with the
surface acidity [430]. Compared with Al2 O3 , TiO2 shows a good
sulfur resistance due to the sulfate species decomposition on its
surface [444].
Carbon-based materials, such as graphene, carbon sphere (CS),
carbon nanotube (CNT), and activated carbon (AC), have large
specific surface area and excellent electrical conductivity. These
carbon-based materials are often used as catalyst supports, be-
cause they can prevent MnOx particle aggregation and enhance the
electrical conductivity which is beneficial for Hg0 catalytic oxida-
tion [429]. Moreover, the porous structure of carbon-based materi-
als makes the formation of surface sulfate species difficult. For ex-
ample, MnO2 /CS catalyst exhibits superior performance and good
sulfur resistance for Hg0 removal [445]. Nevertheless, the mechan-
ical strength of carbon-based materials needs to be improved to
meet the requirement of practical application.
 Y. Yang, J. Liu and Z. Wang / Progress in Energy and Combustion Science 79 (2020) 100844 23

Table 7
Summary of the research results about Hg0 oxidation mechanism over MnOx -based catalysts in literatures.

Reaction Oxidation Reaction

Catalysts Reaction condition temperature (◦ C) efficiency (%) mechanism Refs.

Nano-MnO2 N2 , 4% O2 , 480,000 h−1 100−300 92 M-M [420]

OMS-2 N2 , 4% O2 , 10 ppmv HCl, 8% H2 O, 500 ppmv NO, 500 ppmv SO2 , 50–250 93 M-M [421]
1350,000 h−1
LaMnO3 N2 , 4% O2 , 478,000 h−1 100–300 ∼85 – [422]
La1−x Srx MnO3 N2 , 6% O2 , 10 ppmv HCl, 140,000 h−1 80–250 95 L-H [423]
La0.8 Ce0.2 MnO3 N2 , 4% O2 , 20 ppmv HCl, 30,000 h−1 200 99.5 L-H [424]
LiMn2 O4 N2 , 8% O2 100–300 95 M-M [425]
Fe-Ti-Mn spinel N2 , 5% O2 , 10 ppmv HCl, 8% H2 O, 50 ppmv NO, 500 ppmv SO2 , 250–400 ∼97 E-R [426]
600,000 h−1
CuMn2 O4 4% O2 , 12% CO2 , N2 as the balance gas 50–350 >90 M-M [439]
MnOx /TiO2 N2 , 5000 h−1 175−200 ∼90 M-M [427]
MnOx /TiO2 N2 , 4% O2 , 12% CO2 , 10 ppmv HCl, 400 ppmv SO2 , 400 ppmv NO, 200−280 ∼100 L-H and M-M [428]
400 ppmv NH3 , 4% H2 O, 50,000 h−1
MnOx /Al2 O3 N2 , 20 ppmv HCl, 500 ppmv SO2 , 400 ppmv NO, 2% CO2 , 5% H2 O, 100–350 92 L-H and M-M [349]
31,250 h−1
MnOx /Graphene N2 , 4% O2 100–300 92 M-M [429]
MnOx /MK10 N2 , 5% O2 , 478,000 h−1 100–400 ∼100 M-M [430]
MnOx /Ce0.75 Zr0.25 O2 N2 , 3% O2 , 10 ppmv HCl 150 83 L-H and M-M [431]
CuO-MnOx /TiO2 N2 , 4% O2 , 10 ppmv HCl, 600,000 h−1 150 ∼100 L-H [432]
MnOx -CoOy /TiO2 N2 , 6% O2 , 12% CO2 , 100,000 h−1 50–250 98 M-M [433]
Fe-MnOx /TiO2 N2 , 50,000 h−1 150–300 85 M-M [434]
Mo-Mn/α -Al2 O3 N2 , 500 ppmv O2 , 0–50 ppmv HCl, 44,000 h−1 100–250 95 Deacon process [348]
MnOx -CeO2 /γ -Al2 O3 N2 , 5% O2 , 10% CO2 , 10 ppmv HCl, 400 ppmv SO2 , 8% H2 O, 12,800 h−1 100–400 ∼100 L-H [435]
Mn-Mo/CNT N2 , 6% O2 , 0–100 ppmv HCl, 220,000 h−1 50–300 97 L-H and M-M [436]
CuO-MnOx /AC-H N2 , 5% O2 , 500 ppmv NO, 500 ppmv NH3 , 9300 h−1 80–200 92 M-M and L-H [437]

Langmuir-Hinshelwood (L-H) or Eley-Rideal (E-R) mechanism is deduced in the presence of HCl.

Mars-Maessen (M-M) mechanism is deduced in the absence of HCl.

Fig. 14. (a) Hg0 oxidation and NO reduction of different catalysts (Reprinted from [403] with permission of ACS); (b) Hg0 oxidation and NO reduction of La0.8 Ce0.2 MnO3 at
different temperatures (Reprinted from [403] with permission of ACS).

6.2.1.3. Supported composite manganese oxides. The introduction of ements doping can also improve the SO2 and H2 O resistance of
other metal cations as dopants can modify some catalytic proper- MnOx /support catalysts [348,433,435]. This can be explained by
ties of MnOx /support catalysts, such as catalytic activity, SO2 and the inhibitory effects of dopants on the sulfation of catalyst sur-
H2 O resistance, operation temperature window. To date, Hg0 ox- face [348].
idation activity of many supported composite manganese oxides
catalysts (such as CuO-MnOx /TiO2 [432], MnOx -CoOy /TiO2 [433],
6.2.1.4. Hg0 oxidation mechanism. Hg0 oxidation over MnOx -based
MnOx -CeO2 /γ -Al2 O3 [435], and Mn-Ce/SAPO-34 [446]) have been
catalysts mainly follows the Langmuir-Hinshelwood or Mars-
intensively studied and the effect of the doping metal cations has
Maessen mechanism, as shown in Table 7. The specific mechanism
been clarified as well.
is determined by the flue gas components, i.e., with or without
The doping of lanthanides (such as Ce) [435,447–449] and tran-
HCl. The methods of mechanism acquirement mainly include HCl-
sition metals (such as Cu, Fe, Co and Mo) [348,432–434] can im-
pretreatment experiments [424] and XPS characterization analysis
prove the catalytic properties of MnOx /support catalysts. The in-
[423].
creased catalytic activity may be attributed to the synergetic ef-
HCl is the most reactive species in terms of heterogeneous
fects between Mn and dopants [448], because the presence of
Hg0 oxidation. In the presence of HCl, Langmuir-Hinshelwood
dopants can enhance the proportion of Mn4+ [432] or increase
mechanism is generally used to interpret Hg0 catalytic oxidation
the oxygen storage capacity and redox activity [433]. Moreover, el-
over MnOx -based catalysts [349,423,428,431,432,435–437]. The ad-
24 Y. Yang, J. Liu and Z. Wang / Progress in Energy and Combustion Science 79 (2020) 100844
Fig. 15. Potential energy surfaces of Hg0 oxidation by HCl on MnO2 (110) surface via (a) IM1 and (b) IM1 (Reprinted from [386] with permission of Elsevier).
sorbed Hg0 reacts with the adsorbed active chlorine species
to form HgCl2 . MnOx -based catalysts also show superior Hg0
oxidation activity even under the adverse conditions such as
low-rank coal-fired flue gas with low content of HCl or with-
out HCl. In the absence of HCl, Hg0 oxidation over MnOx -
based catalysts generally occurs through Mars-Maessen mecha-
nism [420,421,425,429,433,434]. Hg0 is oxidized by chemisorbed
oxygen or lattice oxygen into HgO species. The participation of
chemisorbed oxygen and lattice oxygen can be confirmed by
XPS analysis results [425,427,429,431,433]. However, HgO desorp-
tion from MnOx -based catalysts is difficult at low temperatures
(T < 250 °C), which leads to HgO deposition on the catalyst sur-
face after a long-term reaction process.
6.2.2. Quantum chemistry calculations
The molecular-level reaction mechanism of Hg0 oxidation over
MnOx -based catalysts/sorbents is well understood by DFT calcu-
lations [386–388,391,392,395,450–453]. MnO2 is the most active
one among different manganese oxides [438]. Moreover, MnO2 is
the major active component of supported manganese oxides cat-
alysts [454]. Therefore, most of the theoretical studies are per-
formed based on MnO2 surface [386–388,450]. MnO2 (110) is the
most thermodynamically stable and catalytically active surface, and
is widely used to investigate the adsorption and oxidation behav-
iors of Hg0 on MnO2 surface [386,450].
The interaction between gaseous species (reactants and prod-
ucts) and catalyst surface plays an important role in Hg0 oxida-
tion over MnO2 -based catalysts. The adsorption process of different
mercury species on MnO2 (110) surface is controlled by chemisorp-
tion [388,450]. The strong interaction between Hg0 and MnO2 (110)
surface is closely associated with the orbital hybridization be-
tween Hg and Obr atoms. In the presence of HCl, HCl decomposes
on MnO2 surface to form active chlorine species for Hg0 oxida-
tion [386]. Hg0 oxidation on MnO2 surface may be controlled by
two reaction pathways (Hg0 → HgCl2 and Hg0 → HgCl → HgCl2 ), as
shown in Fig. 15. Since the two-step reaction pathway presents
a relatively lower energy barrier, Hg0 oxidation by HCl on MnO2
surface tends to Hg0 → HgCl → HgCl2 rather than Hg0 → HgCl2 . The
rate-limiting step of Hg0 oxidation via the two-step reaction path-
way is the HgCl → HgCl2 process.
In the absence of HCl, Hg0 can be catalytically oxidized by oxy-
gen species (gas-phase O2 , chemisorbed oxygen, and lattice oxy-
gen) over MnO2 -based catalysts. Gas-phase O2 is chemisorbed on
MnO2 surface in parallel and perpendicular manners. The adsorbed
O2 molecule can be dissociated into atomic oxygen for Hg0 ox-
idation. Different oxygen species show different reaction activity
for Hg0 oxidation. The perpendicularly adsorbed O2 molecule is
the most active oxygen for Hg0 oxidation due to the lower en-
ergy barrier [388]. Hg0 oxidation by O2 includes three steps: (1)
Hg0 → Hg(ads), (2) Hg(ads) → HgO(ads) and (3) HgO(ads) → HgO.
HgO desorption is the rate-limiting step of Hg0 oxidation. Com-
pared with the mercury-oxygen reaction, the mercury-chlorine re-
action is much more favorable for Hg0 oxidation.
6.2.3. Numerical simulation
The global reaction kinetics can be used to identify the mer-
cury oxidation mechanism (Eley-Rideal or Langmuir-Hinshelwood)
on catalyst surface through comparing their contributions to
Hg0 consumption. It is assumed that both Eley-Rideal and
Langmuir-Hinshelwood mechanisms are responsible for Hg0 oxida-
tion (rHg = rE-R + rL-H ). The reaction rate of Hg0 oxidation through
the Eley-Rideal mechanism can be expressed as:
α
rE−R = kE−RCHg θCl (9)
where rE-R is the Eley-Rideal reaction rate. kE-R is the Eley-Rideal
rate constant. θ Cl is the surface coverage of Cl atoms. α is the re-
action order of Eley-Rideal reaction with respect to Cl atoms.
The reaction rate of Hg0 oxidation through the Langmuir-
Hinshelwood mechanism is given by
β
rL−H = kL−H θHg θCl (10)
where rL-H is the Langmuir-Hinshelwood reaction rate. kL-H is the
Langmuir–Hinshelwood rate constant. θ Hg is the surface coverage
of adsorbed Hg0 . β is the reaction order of Langmuir–Hinshelwood
reaction with respect to Cl atoms.
The global reaction rate of Hg0 catalytic oxidation can be given
by
α +k β
rHg = kE−RCHg θCl L−H θHg θCl (11)
HCl concentration is typically 3–4 orders of magnitude higher
than Hg0 concentration in flue gas. The surface coverage variations
of Cl atoms caused by Hg0 oxidation can be neglected. Thus, the
surface coverage of Cl atoms is regarded as a constant at the steady
state. Moreover, the surface coverage of adsorbed Hg0 is also con-
sidered as a constant when the catalytic reaction system reaches
 Y. Yang, J. Liu and Z. Wang / Progress in Energy and Combustion Science 79 (2020) 100844 25

Table 8
Summary of the research results about Hg0 oxidation mechanism over CeO2 -based catalysts in literatures.

Reaction Oxidation Reaction

Catalysts Reaction condition temperature (◦ C) efficiency (%) mechanism Refs.

CePO4 N2 , 5% O2 , 600,000 h−1 150−400 ∼95 M-M [459]

CeO2 −MnOx N2 , 3% O2 , 5% CO2 ,10 ppmv HCl 150–300 89.6 L-H [461]
CeO2 /TiO2 N2 , 4% O2 , 12% CO2 , 10 ppmv HCl, 8% H2 O, 300 ppmv NO, 400 ppmv 120–400 ∼90 L-H [351]
SO2 , 60,000 h−1
MnOx -CeO2 /TiO2 N2 , 4% O2 , 12% CO2 , 10 ppmv HCl, 8% H2 O, 30 0 ppmv NO, 400 ppmv 120–400 ∼90 L-H [353]
SO2 , 60,000 h−1
CuO-CeO2 /TiO2 N2 , 4% O2 , 1000 ppmv NO and NH3 , 54,000 h−1 150–250 ∼100 L-H [467]
CeO2 -WO3 /TiO2 N2 , 4% O2 , 12% CO2 , 30 ppmv HCl, 300 ppmv NO, 400 ppmv SO2 , 150–350 95 E-R [352]
50,000 h−1
V2 O5 -CeO2 /TiO2 N2 , 5% O2 , 500 ppmv NO and NH3 , 65,000 h−1 150–400 81.55 M-M [468]
CeO2 /TiO2 -PILCs N2 , 5% O2 , 25 ppmv HCl 100–350 ∼90 Deacon process [465]
CoOx -CeO2 /BAC N2 , 6% O2 , 600 ppmv NO and NH3 , 100,000 h−1 80–320 96.8 M-M [469]
MnOx -CeO2 /AC N2 , 6% O2 , 5000 h−1 100–250 95 M-M [471]
V2 O5 -WO3 /TiO2 -CeO2 N2 , 5% O2 , 12% CO2 , 1000 ppmv NO, 500 ppmv SO2 , 100,000 h−1 80–350 94 M-M [373]
V2 O5 -WO3 -CeO2 /TiO2 CO2 , 5% O2 , 300 ppmv NO, 350 ppmv NH3 , 10–30 ppmv HCl, 200–400 93.05 Deacon process [472]
75,000 h−1
Langmuir-Hinshelwood (L-H) or Eley-Rideal (E-R) mechanism is deduced in the presence of HCl.
Mars-Maessen (M-M) mechanism is deduced in the absence of HCl.

the steady state. Therefore, there is a linear relationship between
the global reaction rate and Hg0 concentration. The Eley–Rideal
and Langmuir–Hinshelwood rate constants can be obtained from
the slops and intercepts of the plots of rHg vs CHg , respectively.
For example, the rate constants of Hg0 oxidation over Fe–Ti–Mn
spinel catalyst are obtained by fitting to experimental data [426].
The Eley–Rideal rate constant is much higher than the Langmuir–
Hinshelwood rate constant, which indicates that Hg0 oxidation
over Fe–Ti–Mn spinel catalyst follows the Eley–Rideal mechanism.
6.3. CeO2 -based catalysts
Besides the higher and narrow operation temperature window
(30 0–40 0 °C), V2 O5 -based commercial SCR catalysts have some
other drawbacks, such as high toxicity of V2 O5 , poor N2 selectivity
at high temperature, low Hg0 oxidation activity under low HCl con-
centration condition, and high conversion of SO2 to SO3 [254,455].
It is therefore desirable to develop environmentally friendly V2 O5 -
free catalyst with excellent catalytic properties for Hg0 oxidation
and NO reduction. CeO2 -based catalysts have attracted consider-
able attention due to their nontoxicity, low cost, and high cat-
alytic activities for low-temperature Hg0 oxidation and NO reduc-
tion even under the flue gas conditions of low chlorine content
[351,456–458].
6.3.1. Experimental studies
A variety of CeO2 -based catalysts, including unsupported
Ce-based oxides (such as CePO4 , CeO2 −MoO3 , CeO2 −MnOx )
[459–463], supported single cerium oxides (such as CeO2 /TiO2 ,
CeO2 /MWCNTs) [351,464–466], and supported composite cerium
oxides (such as CeO2 –WO3 /TiO2 , MnOx –CeO2 /TiO2 , CuO–
CeO2 /TiO2 ) [352,353,373,467–474], show good catalytic activity
for Hg0 oxidation at low temperatures. Table 8 lists the related
condition, efficiency and reaction mechanism of Hg0 oxidation
over CeO2 -based catalysts.
Hg0 oxidation mechanism over unsupported Ce-based oxides is
closely associated with HCl. It is widely accepted that HCl plays
a key role in Hg0 oxidation. However, the existence of HCl also
inhibits Hg0 removal due to the competitive adsorption between
Hg0 and HCl [459,468]. Moreover, HCl might inhibit NO reduction
by forming metal chlorides over SCR catalyst [475,476]. The effect
of HCl on Hg0 oxidation and NO reduction is related to the acid-
base properties of catalyst surface. For example, compared with
VMo/Ti catalyst, CeMoOx catalyst with medium-strength basic sites
shows good resistance to HCl and NH3 poisoning during NO reduc-
tion and Hg0 oxidation [460], as shown in Fig. 16(a) and (b). The
acid sites are responsible for Hg0 adsorption. Obviously, SCR cat-
alyst can be divided into two distinct zones: SCR zone and Hg0oxi
zone (see Fig. 16(c)).
TiO2 as support can provide large surface area, high thermal
stability and strong mechanical strength. TiO2 is the most com-
monly used support for dispersing CeO2 or Ce-based composite ox-
ides [351,352,467,468]. Mercury oxidation over TiO2 supported sin-
gle and composite cerium oxides is controlled by different mech-
anisms. The difference in mercury oxidation mechanism is caused
by the elements doping. For example, Hg0 oxidation by HCl over
CeO2 /TiO2 catalysts is controlled by the Langmuir–Hinshelwood
mechanism [351,464], whereas the Eley-Rideal mechanism is re-
sponsible for mercury oxidation over CeO2 –WO3 /TiO2 catalysts
[352]. CeO2 /TiO2 catalysts are easily deactivated by SO2 due to
the formation of high thermally stable Ce(SO4 )2 and Ce2 (SO4 )3
[477]. Elements doping can also improve the catalytic properties
(including reactivity, SO2 and H2 O resistance, long-term stability)
of CeO2 /TiO2 catalysts.
6.3.2. Quantum chemistry calculations
Although the aforementioned overall reaction mechanisms
(Langmuir-Hinshelwood and Eley-Rideal) are speculated on the ba-
sis of experimental observations, the elementary reaction pathways
and kinetic parameters of Hg0 oxidation over CeO2 -based catalysts
cannot be obtained from experiments. In order to provide insights
into the molecular-level reaction mechanism, DFT calculations have
been performed to examine the transition states and energy pro-
files of Hg0 oxidation over CeO2 -based catalysts [478–483].
In the presence of HCl, the chlorinated CeO2 surface can stably
exist in coal-fired flue gas [478]. Hg0 adsorption on CeO2 (111) sur-
face is controlled by the physisorption mechanism. The chemisorp-
tion mechanism is responsible for HCl adsorption on CeO2 (111)
surface. The weak interaction between Hg0 and CeO2 catalyst sur-
face can be confirmed by XPS analysis [484]. Obviously, Hg0 oxida-
tion by HCl over CeO2 catalyst follows the Eley-Rideal mechanism
[478]. This is consistent with experimental results [352]. The dom-
inant reaction pathway of Hg0 oxidation by HCl over CeO2 catalyst
is a two-step process (Hg0 → HgCl → HgCl2 ), as shown in Fig. 17.
The HgCl → HgCl2 process is the rate-limiting step of Hg0 oxida-
tion due to its relatively higher energy barrier. In the absence of
HCl, surface oxygen species play an important role in Hg0 oxidation
over Ce-based catalysts. The Mars-Maessen mechanism is respon-
sible for Hg0 oxidation by oxygen on CeO2 (111) surface [480]. Al-
26 Y. Yang, J. Liu and Z. Wang / Progress in Energy and Combustion Science 79 (2020) 100844

Fig. 16. (a) Effects of HCl and H2 O on the SCR performance of CeMoOx and VMo/Ti catalysts at 200°C (Reprinted from [460] with permission of ACS). (b) Effect of NH3 on
Hg0 oxidation over CeMoOx catalyst (Reprinted from [460] with permission of ACS). (c) Role of basic and acidic sites in the SCR and Hg0oxi zones for the simultaneous NO
reduction and Hg0 oxidation (Reprinted from [460] with permission of ACS).

Fig. 17. Potential energy surface of Hg0 oxidation by HCl on CeO2 (111) surface (Reprinted from [352] with permission of Elsevier).

though the energy barrier of HgO formation (20.70 kJ/mol) is lower
than that of HgCl2 formation (50.11 kJ/mol), the adsorption energy
(−163.81 kJ/mol) of HgO is much higher than that (−46.55 kJ/mol)
of HgCl2 . As a result, HgO desorption from CeO2 surface is very dif-
ficult. The tight binding of products may block the catalyst surface
and thus slow the overall catalytic reaction [485,486].
6.3.3. Numerical simulation
The mathematical model of Hg0 oxidation in the packed-bed
reactor has been discussed in the Section 6.1.3. Nevertheless, the
effect of mass transfer on Hg0 oxidation is neglected in the math-
ematical model. In order to further investigate the effect of mass
transfer on Hg0 oxidation in the packed-bed reactor, the gas-solid
external mass transfer has been incorporated into the mathemat-
ical model and used to investigate the apparent reaction kinetics
of Hg0 oxidation by HCl over CeO2 -TiO2 catalyst [487]. The global
reaction rate only involves the role of HCl in mercury oxidation,
and omits the competitive adsorption among other flue gas species
(such as NH3 , SO2 ). Finally, the relationship between Hg0 oxidation
 Y. Yang, J. Liu and Z. Wang / Progress in Energy and Combustion Science 79 (2020) 100844 27

Table 9
Summary of the research results about Hg0 adsorption and oxidation mechanisms over noble metal catalysts in literatures.

Catalyst surface model Level of theory Hg0 adsorption energy (kJ/mol) HCl/Cl adsorption energy (kJ/mol) Reaction mechanism Refs.

Au(111) GGA-PW91 −40.55 ∼ −52.67 −66.57 ∼ −95.52 L-H [496,497]

Au(001) GGA-PBE −33.77 ∼ −58.86 − Chemisorption [380]
Pdn (n = 1−6) cluster B3LYP/LANL2DZ −23.16 ∼ −222.69 − Amalgam [498,499]
Pd13 cluster GGA-PW91 −85.87 ∼ −146.66 − Chemisorption [500]
Pd(100) GGA-PBE −55.92 ∼ −97.45 −36.66 ∼ −77.18 L-H [384]
Pd(111) GGA-PW91 −81.05 − Chemisorption [501]
Pdn /g-C3 N4 GGA-PBE −53.07 ∼ −142.80 − Chemisorption [502]
Pdn /PNG GGA-PBE −47.28 ∼ −98.42 − Chemisorption [503]
Pd13 /graphene GGA-PW91 −90.70 ∼ −162.10 − Chemisorption [500]
S/Pd(111) GGA-PBE −106.13 ∼ −326.12 − Chemisorption [504]
Pd/γ -Al2 O3 (110) GGA-PBE −79.12 ∼ −146.66 − Chemisorption [505]
PdCu/γ -Al2 O3 (110) GGA-PBE −59.82 ∼ −166.92 − Chemisorption [506]
Pt(111) GGA-PBE −64.65 ∼ −72.36 − Chemisorption [380]
Pt(001) GGA-PBE −55.96 ∼ −105.17 − Chemisorption [380]
RuO2 (110) GGA-PW91 −16.19 ∼ −57.47 −49.17 ∼ −238.00 L-H [400]
RuO2 /TiO2 (110) GGA-PW91 −36.15 ∼ −54.99 −57.33 ∼ −80.54 L-H [507]
Ag(111) GGA-PBE −29.91 ∼ −35.70 − Physisorption [380]
Ag(001) GGA-PBE −28.95 ∼ −49.21 − Physisorption [380]
Ag13 cluster GGA-PW91 −41.49 ∼ −92.63 − Chemisorption [500]
Ag13 /graphene GGA-PW91 −45.35 ∼ −64.65 − Chemisorption [500]
Ag/Fe3 O4 (111) GGA-PBE −86.82 − Chemisorption [508]
Ag/TiO2 (110) GGA-PW91 −36.66 ∼ −66.57 − Amalgam [509,510]

Langmuir-Hinshelwood (L-H) mechanism is deduced in the presence of HCl.

Amalgamation, chemisorption and physisorption mechanisms are deduced in the absence of HCl.

efficiency and HCl concentration is given by
 
1 1 1 1 1 Cl atoms can be produced from the dissociation of Cl2 or HCl on
− = × + + (12)
ln (1 − η ) kHg KHCl t CHCl kHg t Dm St
where KHCl is the adsorption equilibrium constant. CHCl is the HCl
concentration. Dm is the external mass transfer constant. S is the
catalyst surface area.
The mathematical model can be used to fit the experimental
data. kHg and KHCl can be obtained from the intercept and slope
of the plots of −1/ln(1−η) vs 1/CHCl , respectively. The overall re-
action rate of Hg0 oxidation by HCl over CeO2 –TiO2 catalyst in-
creases with increasing CeO2 /TiO2 ratio [487]. However, the overall
reaction rate decreases when 400 ppmv SO2 is added to flue gas.
This phenomenon is attributed to the competitive adsorption be-
tween Hg0 and SO2 on CeO2 –TiO2 catalyst surface [351]. However,
this mathematical model cannot explain the competitive adsorp-
tion between Hg0 and SO2 on CeO2 –TiO2 catalyst surface.
7. Mechanism of Hg oxidation over noble metal catalysts
Noble metals (such as Au, Pd and Ru) are highly active to-
wards Hg0 oxidation, and usually show good SO2 and H2 O resis-
tance [488–492]. Noble metal catalysts are generally placed down-
stream of ESP/FF [20,488,493–495], where the temperature of flue
gas is low. The high cost of noble metals may not inhibit their ap-
plication in Hg0 oxidation due to their low mass loading, high ox-
idation activity, durable and regenerable properties [20]. This sec-
tion focuses on Hg0 oxidation over the widely used noble metal
catalysts (Au, Pd, Pt, Ru and Ag). The catalytic performance and re-
action mechanism of these catalysts are discussed below. The ad-
sorption energy and reaction mechanism of Hg0 over noble metal
catalysts are given in Table 9.
7.1. Au-based catalysts
7.1.1. Experimental studies
Au is regarded as a potential catalyst for Hg0 oxidation because
of its ability to adsorb Hg0 and its reluctance to adsorb other flue
gas compositions (such as NO, H2 O, and SO2 ), and widely tested by
laboratory-, pilot- and full-scale experiments [488–490,493–495].
Chlorine species (Cl2 and HCl) are the most important reactants
for the oxidation of adsorbed Hg0 over Au-based catalysts. Active
Au surface [511], and react with the adsorbed Hg0 . Clearly, Hg0
oxidation by chlorine species over Au-based catalysts follows the
Langmuir-Hinshelwood mechanism [489,493].
In order to further evaluate the catalytic activity and long-term
stability of Au catalysts, the pilot- and full-scale tests are impor-
tant for its practical application. For example, Hg0 oxidation effi-
ciency of the Au catalysts equipped at Fayette Power Project Unit 3
decreases from 80% to 77% after 6 months of operation and fur-
ther declines to 57% after 17 months [495]. The loss of activity
is attributed to the build-up of fly ash in the measured catalysts
rather than the SO2 poisoning. During Hg0 oxidation, Au catalysts
can preclude any inhibitory effects of NO, H2 O and SO2 .
7.1.2. Quantum chemistry calculations
Au has a strong ability to bind gas-phase Hg0 [489,512]. This
inherent property is closely associated with the mechanism of the
interaction between gaseous Hg0 and Au surface. The atomic or-
bital hybridization between Hg d-state and Au d-state is respon-
sible for the strong Hg0 adsorption ability of Au catalyst [496].
Hg0 adsorption on Au surface is affected by some factors, includ-
ing vacancy, impurity atoms, and Au cluster charge. For example,
the adsorption strength of Hg0 on Au(111) surface increases with
increasing the number of vacancies from 0 to 3, but decreases
with further increasing the vacancies [496]. The increased adsorp-
tion strength of Hg0 on the defective Au(111) surface with 3 va-
cancies is attributed to the upward shift of the d-band center to
Fermi level. The presence of S or O impurity atom weakens the in-
teraction between Hg0 and Au surface [496], because the impurity
atoms induce Au surface reconstruction to produce more under-
coordinated Au sites [513]. Compared with the neutral and anionic
Aun clusters, the cationic Aun clusters are more favorable for Hg0
adsorption [514].
The reaction pathways and activation energy barriers are im-
portant for understanding the reaction mechanism of Hg0 oxida-
tion over Au catalyst. Hg0 oxidation by chlorine species on Au(111)
surfaces prefers the two-step process (Hg0 → HgCl → HgCl2 ), rather
than the one-step process (Hg0 → HgCl2 ) [497]. HgCl2 formation is
28 Y. Yang, J. Liu and Z. Wang / Progress in Energy and Combustion Science 79 (2020) 100844
the rate-limiting step of the whole Hg0 oxidation reaction. Since
the adsorption strength of reaction intermediates on defective Au
surface is much stronger than that on perfect Au surface, the de-
fective Au surface is unfavorable for Hg0 oxidation. Moreover, the
presence of H atoms derived from HCl dissociation facilities Hg0
oxidation on Au surface, because it can weaken the interaction be-
tween reaction intermediates and Au surface.
7.2. Pd-based catalysts
7.2.1. Experimental studies
As with Au, Pd also has a strong ability for Hg0 adsorption even
at temperatures as high as 388 °C [515]. The adsorbed Hg0 can be
effectively oxidized over Pd-based catalysts in the presence of HCl
or Cl2 . This phenomenon has been demonstrated by bench-scale
[488,492], pilot-scale [490], and full-scale [494,495] experiments.
Hg0 oxidation depends on the presence of chlorine species. For ex-
ample, the reaction rate of Hg0 oxidation over Pd catalyst increases
with increasing HCl concentration from 50 ppmv to 100 ppmv
[488]. Hg0 oxidation continues when HCl is cut off, but the oxi-
dation rate declines. The continued oxidation is attributed to the
adsorbed chlorine species.
Pd catalyst has an excellent regeneration performance during
its practical application. This property can significantly reduce the
production cost of catalyst. However, the thermal regeneration pro-
cess should be conducted in the inert atmosphere (such as N2 and
CO2 ) to avoid the detrimental oxidation of Pd catalyst [494], be-
cause palladium oxides show little catalytic activity for Hg0 oxida-
tion. Nevertheless, N2 and CO2 can be easily separated from air for
the regeneration of the used Pd catalyst. Therefore, Pd is a promis-
ing catalyst for Hg0 oxidation due to its high catalytic activity and
excellent regeneration performance.
7.2.2. Quantum chemistry calculations
The strong interaction between Hg0 and Pd catalyst is closely
related to the electronic structure (such as atomic orbital, charge
transfer, and d-band center) of Pd cluster. During Hg0 adsorp-
tion, the charges are transferred from Hg s-orbital to Pd d-orbital
[498,499]. The adsorption energy of Hg0 on Pd cluster is directly
proportional to charge transfer. The adsorption energy of Hg0 on
cationic Pd cluster is much higher than that of Hg0 on neutral and
anionic clusters. Hg0 adsorption on cationic Pd cluster highly de-
pends on the energy of the lowest unoccupied molecular orbitals
of Pd cluster [498]. Moreover, the size of Pd cluster shows a signif-
icant effect on Hg0 adsorption [500,502,503]. The size-related ef-
fect is closely associated with the energy level of the d-band cen-
ter (ε d ) [501,503]. The stronger interaction between Hg0 and Pd
cluster can be observed if the ε d is close to the Fermi level.
The size of catalyst particle is much larger than the size of clus-
ter. Obviously, Pd cluster cannot accurately represent the Pd cat-
alyst surface. The periodic slab models, including Pd(111) [504–
506,516] and Pd(100) [384], can be used to well understand the
adsorption and oxidation mechanisms of Hg0 on Pd catalyst sur-
face. Pd(111) and Pd(100) surfaces show similar reactivity for
Hg0 adsorption, because the adsorption energy (−81.05 kJ/mol)
[501,505] of Hg0 on Pd(111) surface is comparable to that (−55.96
to −97.45 kJ/mol) [384] of Hg0 on Pd(100) surface. The signifi-
cant orbital overlap between Pd and Hg atoms is responsible for
the stronger interaction between Hg0 and Pd surface [384,501].
HCl readily dissociates into active Cl atoms for Hg0 oxidation.
Hg0 oxidation by HCl on Pd(100) surface follows the Langmuir-
Hinshelwood mechanism in which the adsorbed Hg0 reacts with
the active Cl atoms to form HgCl2 molecule [384]. Hg0 is directly
oxidized by the active Cl atoms into HgCl2 . Hg0 oxidation is ac-
tivated and exothermic by 67.13 kJ/mol and 92.06 kJ/mol, respec-
tively. HgCl2 is very difficult to desorb from Pd(100) surface due
to the higher energy barrier. HgCl2 desorption is the rate-limiting
step of Hg0 oxidation on Pd(100) surface.
7.3. Pt-based catalysts
Platinum (Pt) receives considerable attention in the catalysis
field due to its excellent catalytic properties [517]. Pt can also cat-
alyze Hg0 oxidation in coal-fired flue gas [488]. Therefore, exper-
imental studies [24,120,121,518–521] and theoretical calculations
[380,381] have focused on Hg0 adsorption and oxidation over Pt-
based catalysts.
7.3.1. Experimental studies
Hg0 oxidation over Pt-based catalyst highly depends on the
simultaneous presence of HCl and O2 [488]. No mercury ox-
idation is observed at 150 ºC in the reaction atmosphere of
Hg/CO2 /HCl/SO2 /N2 . However, O2 addition to the gas mixture leads
to significant Hg0 oxidation. Hg0 catalytic oxidation continues at a
reduced reaction rate and finally stops when HCl concentration de-
creases to 0 ppmv. There is residual surface-bound chlorine species
to sustain Hg0 oxidation. The observed oxidized mercury species
is HgCl2 rather than HgO, because no Hg0 catalytic oxidation oc-
curs when catalyst is exposed to the gas mixture of Hg/CO2 /O2 /N2 .
Hg0 reaction with HCl on Pt catalyst surface follows the Langmuir-
Hinshelwood mechanism [488].
Hg0 can also be adsorbed on Pt surface to form intermetallic
compounds (such as PtHg4 , PtHg2 , and PtHg) [518–521]. The pres-
ence of these intermetallic compounds leads to the great surface
instability, which is attributed to the atomic size factor of mercury
and platinum [520]. These intermetallic compounds have different
thermal stabilities [521]. In the temperature range of 184–271 ºC,
PtHg4 dissociates into PtHg2 . PtHg2 decomposes to form PtHg in
the temperature range of 271–340 ºC. PtHg eutectoid reaction oc-
curs on the solid surface at the temperature of 340 ºC. As the
temperature further increases, mercury is removed from the Hg-Pt
solid solution.
The deposition chemistry of mercury on platinum surface is
different from the catalytic reaction chemistry, because mercury
deposition on platinum surface is not dependent upon the pres-
ence of HCl. As an example taken from Ref. [24], Fig. 18 shows
the mercury deposition on the platinum clad probe surface. In
the sulfur-containing flue gas system, mercury can efficiently de-
posit as mercuric sulfate (HgSO4 ), whereas in the sulfur-free flue
gas system, mercuric oxide is formed on the platinum clad probe
surface at 250 ºC. Compared with HgO, HgSO4 is more thermally
stable and forms at the slightly higher temperatures. These mer-
cury species readily react with HCl to form gas-phase HgCl2 on Pt
surface if chlorine exists in flue gas [120,121]. The conversion pro-
cesses of mercury chemi-deposition appear to be mainly driven by
thermodynamic stabilities, and controlled by Pt surface and chlo-
rine species availability. Based on the mercury deposition chem-
istry, the split counter-rotating air pre-heater can be retrofitted for
mercury emission control [257]. This method has been tested in a
pilot-scale coal-fired boiler at Western Research Institute. Mercury
conversion efficiency of 50-65% can be obtained in two separate
weeks of tests.
7.3.2. Quantum chemistry calculations
Hg0 oxidation or deposition on Pt surface is heavily dependent
upon the availability and structure of active sites. Compared with
top and bridge sites, Hg0 prefers to adsorb on hollow site [380].
Hg0 adsorption on Pt surface leads to a dramatic decrease in the
work function. Hg0 is strongly adsorbed on Pt surface, yielding ad-
sorption energy up to −105.17 kJ/mol. Different Pt surfaces show
different reactivity for Hg0 adsorption. Pt(001) surface is much
 Y. Yang, J. Liu and Z. Wang / Progress in Energy and Combustion Science 79 (2020) 100844
Fig. 18. Deposition rates of HgSO4 and HgO as a function of temperature of plat-
inum clad probe. Inset: laminar flat flame fuel-lean C3 H8 /air burner (Adapted from
Schofield et al. [24,120] with permission of Elsevier).
more favorable for Hg0 adsorption than Pt(111) surface. The forma-
tion enthalpy of Hg-Pt amalgam can be used to evaluate the high-
temperature Hg0 adsorption performance of Pt. The formation en-
thalpies of PtHg and PtHg2 are 10.3 kJ/(mol-Hg) and −7.7 kJ/(mol-
Hg), respectively [381]. Pt can be used as a high-temperature sor-
bent for Hg0 capture from flue gas.
7.4. Ru-based catalysts
Cl2 produced from HCl conversion is an oxidant for Hg0 oxi-
dation in coal-fired flue gas [130]. RuO2 /TiO2 catalyst shows out-
standing performance (such as high catalytic activity, long-term
thermal stability, and lower reaction temperature) for Cl2 pro-
duction from HCl oxidation under the harsh industrial conditions
[522–524]. Thus, RuO2 -based catalysts also show good activity for
Hg0 oxidation [370,421,444,491,525,526]. The reaction mechanism
of Hg0 oxidation over RuO2 -based catalysts has been understood
by experimental observations [370,444,491] and theoretical stud-
ies [400,507].
7.4.1. Experimental studies
Although RuO2 /TiO2 catalyst shows good catalytic activity for
Hg0 oxidation, the catalytic activity of RuO2 /TiO2 catalyst depends
on the presence of HCl. RuO2 /TiO2 catalyst only shows about 23%
Hg0 oxidation efficiency in the absence of HCl [491]. RuO2 is also
used as promoter of catalyst to enhance the catalytic activity and
the resistance to SO2 poisoning. For example, the Hg0 oxidation ca-
pability of commercial SCR catalyst is enhanced by RuO2 modifica-
tion [370]. The increased reactivity is attributed to the synergetic
effects of RuO2 and WO3 or V2 O5 . The gas-phase Hg0 is first ad-
sorbed on cus-Ru sites and then oxidized by the adsorbed Cl atoms
to form HgCl2 . Moreover, RuO2 addition enhances the SO2 resis-
tance of Mn/TiO2 catalyst [525,526], and improves the resistance
to SeO2 poisoning of CeO2 -based catalysts [527]. The existence of
RuO2 weakens the interaction between active components and poi-
sonous species.
29
The X-ray absorption near edge spectroscopy (XANES) coupled
with in-situ Fourier transform infrared spectroscopy (FTIR) is an
advanced experimental method for the understanding of Hg0 ox-
idation mechanism over RuO2 /TiO2 catalyst. The active chlorine
species and HgCl2 on catalyst surface are detected by the in-situ
FTIR [491] and XANES [528] analyses, respectively. The formation
of Ru-H bond is an indicator of the active chlorine species, be-
cause H atom is produced from HCl dissociation. HCl is dissocia-
tively adsorbed on RuO2 /TiO2 catalyst surface to form active chlo-
rine species. Subsequently, the gas-phase Hg0 reacts with the ac-
tive chlorine species produced from HCl dissociation to form HgCl2 .
Hg0 oxidation by HCl over RuO2 /TiO2 catalyst follows the Eley-
Rideal mechanism [491,528]. Gas-phase Hg0 is first oxidized by ac-
tive chlorine species into HgCl, which is subsequently oxidized into
HgCl2 .
7.4.2. Quantum chemistry calculations
The catalytic process of Hg0 oxidation over RuO2 -based cata-
lysts is controlled by the microcosmic reaction mechanism, which
depends on the understanding of active sites, adsorption en-
ergy, reaction pathway, and activation energy barrier. Hg0 prefers
to adsorb on cus-Ru sites, yielding an adsorption energy of
−57.47 kJ/mol [400]. HCl activation is an O-assisted surface reac-
tion process in which HCl is oxidized into active Cl atom for Hg0
oxidation [507]. Hg0 oxidation by HCl over RuO2 -based catalysts
prefers to proceed through a four-step process in the sequence
of Hg0 adsorption, Hg → HgCl, HgCl → HgCl2 and HgCl2 desorption.
Based on the DFT-derived energetics, the complete catalytic cycle
proposed by Ref. [507] produces the correct stoichiometry, and is
used to well understand the reaction mechanism of Hg0 oxidation
over RuO2 -based catalysts. The catalytic cycle consists of HCl acti-
vation, mercury oxidation and surface reoxidation. Mercury oxida-
tion is the rate-limiting step of the complete catalytic cycle.
The presence of oxygen vacancy shows a significant effect on
Hg0 oxidation over RuO2 -based catalyst, because it changes the
energetics of reaction pathways. For example, the energy barri-
ers of rate-limiting steps of Hg0 oxidation on perfect and oxygen-
defective RuO2 (110) surfaces are 90.94 kJ/mol and 194.22 kJ/mol,
respectively [400]. The presence of oxygen vacancy is unfavorable
for Hg0 oxidation on RuO2 (110) surface. The strong interaction be-
tween active component and support plays an important role in
catalytic reaction process [312]. Hg0 oxidation over RuO2 /TiO2 cat-
alyst differs from that over unsupported RuO2 catalyst. The activa-
tion energy barrier (∼150 kJ/mol) of the rate-limiting step of Hg0
oxidation on RuO2 /TiO2 (110) surface [507] is much higher than
that (90.94 kJ/mol) of Hg0 oxidation on RuO2 (110) surface [400].
7.5. Ag-based catalysts
Silver shows a high affinity toward mercury atom [529].
Thus, silver is an active component to accomplish Hg0 re-
moval (including catalytic oxidation [530–535] and adsorption
[404,529,536–546]) from coal-fired flue gas. Silver is usually dis-
persed on different supports, such as SCR catalysts [531–533],
porous materials [404,536,538,540,541,544,545], carbon materials
[539,542,543,546], and metal oxides [508,530,534,537,547].
7.5.1. Experimental studies
Silver can improve the mercury catalytic oxidation performance
of SCR catalysts, such as V2 O5 /TiO2 [532], V2 O5 −MoO3 –TiO2 [531],
and CeO2 /TiO2 [533]. Moreover, the addition of silver can also
broaden the reaction temperature window. At the lower temper-
atures, Hg0 is first adsorbed on Ag particles to form Hg–Ag amal-
gam [532]. The amalgamated mercury reacts with the active chlo-
rine species to form HgCl2 . Mercury catalytic oxidation at the
30 Y. Yang, J. Liu and Z. Wang / Progress in Energy and Combustion Science 79 (2020) 100844
lower temperatures follows the Langmuir–Hinshelwood mecha-
nism [533]. At the higher temperatures, the Hg–Ag amalgam de-
composes to generate gas-phase Hg0 , thereby weakening the amal-
gamation effect of Hg–Ag [531]. The gas-phase Hg0 directly re-
acts with active chlorine species. Mercury catalytic oxidation at the
higher temperatures is dominated by the Eley-Rideal mechanism
[533].
Silver is also a sorbent material due to its high affinity to-
ward mercury. In order to decrease the cost of sorbent pro-
duction, silver particle is usually dispersed on different supports
[404,508,509,530,536–547]. Although these Ag-based sorbents con-
sist of different support materials, these sorbents show similar
capture mechanism for Hg0 removal. Hg0 capture by Ag-based
sorbents is mainly dominated by the formation of Ag-Hg amal-
gam (amalgamation mechanism). It may be noted that the silver-
activated oxygen oxidation mechanism is responsible for Hg0 cap-
ture at higher temperatures [404].
7.5.2. Quantum chemistry calculations
Hg–Ag amalgam formation plays an important role in Hg0 oxi-
dation over Ag-based catalysts, because it determines the types of
overall mechanism (Langmuir–Hinshelwood and Eley–Rideal). The
stability of Hg-Ag amalgam is closely associated with the active
sites, binding energy and microcosmic structure of Hg0 adsorp-
tion on Ag surface [380,500,508–510,548]. Different Ag surfaces
show different adsorption characteristics for mercury. For example,
Ag(001) surface is more favorable for Hg0 adsorption than Ag(111)
surface, because the adsorption energy of Hg0 on Ag(001) surface
is higher than that of Hg0 on Ag(111) surface [380]. On the Ag(001)
surface, Hg0 prefers to adsorb on the fourfold hollow sites, whereas
on the Ag(111) surface, the threefold hollow sites are the dominant
active sites.
Ag nanoparticles are mainly dispersed on different supports
during catalyst/sorbent production. The single Ag surface with-
out consideration of support cannot well represent the Ag-
based catalyst surface. The supported Ag surface model (such
as Ag/Fe3 O4 (111) [508], Ag/TiO2 (110) [509,510], and Ag/graphene
[500]) can be used to well investigate the reaction mechanism
of Hg0 oxidation. Hg0 adsorption on Ag-based catalyst surface is
an electron-transfer process. During Hg0 adsorption, electrons are
transferred from gas-phase Hg0 to Ag nanoparticles deposited on
supports. Silver exists in the forms of Ag0 and Ag+ . Ag+ cations
serve as the active sites for Hg0 adsorption. Hg0 is first adsorbed
on Ag+ cation, and subsequently reacts with Ag0 to form Hg-Ag
amalgam. Obviously, the formation process of Hg-Ag amalgam can
be explained by the electron-transfer mechanism.
8. Challenges and future prospects
The current review mainly focuses on the reaction mechanisms
and chemical kinetics of mercury transformation over a wide tem-
perature range during coal combustion. Despite remarkable ad-
vances in the fundamental chemistry that underlies mercury trans-
formation during combustion, there remain some challenges and
opportunities to pursue the deeper mechanistic insights into the
reaction mechanisms and to improve the performance of chemical
kinetic models. More attention needs to be paid to solve the prob-
lems/challenges in the chemistry of mercury transformation. Some
recommendations are summarized below:
(1) Elementary reaction rate measurements. The homogeneous reac-
tion mechanism of mercury transformation should be hierar-
chically investigated through well-characterized kinetic exper-
iments. While there are many room-/low-temperature kinetic
measurements of the specified initiation reactions, kinetic mea-
surements at medium temperatures (400–950 K) are less well
documented. Moreover, the subsequent chain branching reac-
tions of mercury transformation are rarely investigated through
kinetic experiments. The accuracies of reaction rate constants
used in the chemical kinetic models are in question, since the
temperature-dependent rate constants are usually determined
by extrapolation from the low-temperature measurements or
by theoretical studies which are not validated by medium-
temperature kinetic measurements. Experimental measurement
of the rate constant of the subsequent chain branching reac-
tion still remains a challenge at medium temperatures due to
the toxicity, high volatility, and chemical inertness of mercury.
A combination of in-situ non-intrusive optical diagnostic tech-
niques (such as LIF) and high-level theoretical studies is greatly
needed to obtain an accurate rate constant for elementary re-
actions. Meanwhile, advanced experimental techniques (such as
tunable synchrotron photoionization) and analysis methods are
required for accurate measurements for different mercury spe-
ciation in flue gas.
(2) Heterogeneous reaction kinetics. Compared with homogeneous
reaction mechanism, heterogeneous reaction mechanism is
much more complex owing to the difficulty of determining the
reaction rate. The primary challenge that lies ahead is the de-
termination of the kinetic and thermodynamic parameters of
heterogeneous reactions. Although DFT calculations performed
at 0 K have been extensively used to investigate the possi-
ble process of mercury oxidation over different solid surfaces,
the heterogeneous reaction mechanism of mercury oxidation
is not well understood by DFT at the specified temperature.
The temperature-dependent DFT calculation is presently an im-
portant unanswered question in heterogeneous mercury chem-
istry research. Furthermore, the rate constants of heterogeneous
reactions of mercury transformation are still rarely calculated
from the current DFT calculations. The advanced first-principles
quantum-mechanical calculation method [549] and the har-
monic transition state theory [550] will doubtless play an im-
portant role in solving these problems. For the temperature-
dependent DFT calculations, the thermochemical properties of
the surface species need to be calculated using the advanced
quantum-mechanical method [549]. For the rate constants, the
harmonic transition state theory [550] is urgently needed to
understand the kinetics of heterogeneous elementary reactions.
(3) Comprehensive chemical kinetic model. Advances are needed in
chemical kinetic model development to improve the quantita-
tive predictability of kinetic model. The existing kinetic mod-
els cannot well predict mercury speciation distribution in coal-
fired power plants equipped with SCR devices. There is a lack
of rate coefficients of heterogeneous elementary reactions over
SCR catalysts. Moreover, Hgp formation is still not well quanti-
tatively predicted by the existing kinetic models. The key chal-
lenge is to understand the reaction chemistry of Hg(NO3 )2 and
HgSO4 formation in the channels of the honeycomb SCR cat-
alysts and to reveal the important physical processes (such as
collision-coalescence) of mercury species over fly ash. Hg(NO3 )2
and HgSO4 can be formed over SCR catalysts [366,551], and sta-
bly exist in SCR processes. The reaction mechanism of Hg(NO3 )2
and HgSO4 formation should be investigated using in-situ opti-
cal diagnostic techniques and the quantum chemistry calcula-
tion method. Molecular dynamics simulations can be performed
to further understand the coagulation mechanism that controls
Hgp formation. More efforts are required to quantitatively pre-
dict Hg(NO3 )2 and HgSO4 formation in a practical combustion
system.
(4) Kinetic uncertainty quantification and propagation. Kinetic model
development is usually subjected to various uncertainties from
experimental measurements and theoretical calculations (i.e.,
fundamental theory assumptions) [552–555]. Kinetic uncer-
 Y. Yang, J. Liu and Z. Wang / Progress in Energy and Combustion Science 79 (2020) 100844
tainty quantification of mercury reaction chemistry is still not
performed in a rigorous and systematic manner. Kinetic uncer-
tainty propagation is not entirely clear in the field of mercury
reaction chemistry. One of the major challenges is the identi-
fication of the uncertainty sources (including model input un-
certainty, model form error, and numerical uncertainty). For-
ward uncertainty quantification and propagation should be per-
formed using intrusive or non-intrusive methods to estimate
the model confidence when the developed kinetic model is
used to make predictions outside thermodynamic regimes. Ki-
netic uncertainty minimization is needed to develop a reliable
kinetic model in the community of mercury reaction chemistry.
A new direction of efforts should focus on the quantification
and propagation of various uncertainties from experimental ki-
netics measurements and theoretical kinetics approximations.
(5) Hetero-/homogeneous elementary reaction chemistry and transport
coupling. The combustion chemistry community has recognized
the importance of transport properties in the chemical kinetic
modeling of hydrocarbon fuels combustion [134,556]. Mercury
transformation in coal-fired flue gas is a chemically reacting-
flow problem, and includes mass transfer process and intrin-
sic reaction process. Mass transfer plays an important role to
balance the chemical production and destruction of mercury
transformation. The transport properties of different mercury
species are not included in the existing kinetic models of mer-
cury speciation prediction. The role of mass transfer in mercury
transformation (particularly for heterogeneous gas-solid reac-
tions) is not well understood. An important challenge in ki-
netic modeling is how to handle the coupling of fluid dynamics
and elementary reaction chemistry. Transport parameters (such
as viscosity, diffusion, thermal conductivity, and thermal dif-
fusion) should be investigated using the TRANLIB, MKC, DRFM
or EGLIB methods. The complex interplay between mass trans-
fer and reaction chemistry needs to be clarified using direct
numerical simulations and non-intrusive laser diagnostic tech-
niques. Meanwhile, transport properties should be incorporated
into the kinetic model to provide accurate prediction of mer-
cury transformation during coal combustion.
(6) Kinetic model validation. While the Hg/Cl and Hg/Br sub-
mechanisms are widely evaluated with experimental data,
other sub-mechanisms (such as Hg/I, Hg/O, Hg/S, and Hg/N) are
still not tested by the available experimental data. The applica-
bility of the existing kinetic models is still rarely evaluated in
other industrial combustion fields (such as waste incineration,
cement production, ferrous and nonferrous metal production).
Understanding and identifying new reaction pathways that con-
trol mercury transformation during other combustion processes
remain a challenge. Experimental efforts are further needed to
accurately measure the mercury speciation distribution in other
combustion atmospheres using advanced measurement tech-
niques. Each sub-mechanism should be individually validated
with a sufficient amount of experimental data to improve the
accuracy and predictability of the kinetic model.
9. Conclusions
Significant advances in mercury reaction mechanisms and
chemical kinetics have been made for the fundamental under-
standing of mercury transformation behavior during coal combus-
tion. Literatures over the last two decades are surveyed to provide
a comprehensive and systematical review for mercury transforma-
tion chemistry in coal-fired flue gas. Thermodynamics and reac-
tion kinetics of mercury transformation in the chemically complex
post-combustion environment are discussed based on experimen-
tal measurements, equilibrium calculations, high-level theoretical
calculations, and kinetic modeling.
31
Recent progress in thermodynamic calculations is discussed
to understand the compositional properties of mercury-containing
system at equilibrium state in various reaction atmospheres. Mer-
cury speciation distribution in coal-fired flue gas is affected by
many factors such as chlorine content of coal, combustion environ-
ment (air- and oxy-fuel combustion), fly ash compositions, and op-
erating conditions. Chlorine is the most important species for mer-
cury transformation in the post-combustion gases. Oxidized mer-
cury mainly exists in the form of HgCl2 . Oxy-fuel combustion en-
vironment modifies the behavior and fate of mercury because of
the CO2 -rich flue gas re-circulation to the boiler. Some inorganic
components present in fly ash affect mercury speciation distribu-
tion due to their catalytic activity and adsorption capability.
Experimental techniques and high-level theoretical methods
used to achieve elementary reaction rates are summarized from
measurements and theoretical calculations. The PLP-PLIF technique
has provided a powerful tool for directly measuring elementary
reaction rates of mercury oxidation. The combination of exper-
imental measurements and theoretical studies is most welcome
for rate constants determination and is a signpost for the future.
The state-of-the-art, non-optimized chemical kinetic models for
mercury transformation chemistry during coal combustion are re-
viewed and evaluated against experimental data. Both homoge-
neous reactions and heterogeneous interactions with fly ash parti-
cles are simultaneously involved in the existing kinetic model. The
predictive capability of each kinetic model is evaluated by compar-
ison to the updated experimental data.
Hg0 oxidation mechanism over different catalysts (such as SCR
catalyst and noble metal catalyst) is critically reviewed to describe
mercury catalytic oxidation process. Several mechanisms, including
Eley-Rideal mechanism, Langmuir-Hinshelwood mechanism, Mars-
Maessen mechanism, and Deacon process have been proposed for
mercury oxidation over catalysts. None of the above mechanisms
are definitive for mercury catalytic oxidation, and the reaction
mechanism depends on the type of catalysts and the reaction con-
ditions.
These findings and advances in mercury reaction mechanisms
and chemical kinetics create some new opportunities and chal-
lenges for the future research. There remain large knowledge gaps
in the combustion-related mercury transformation chemistry. For
example, experimental data of kinetic measurements at medium
temperatures is scarce for the subsequent chain branching reac-
tions of homogeneous mercury oxidation. There is a lack of ki-
netic measurements or theoretical calculations of rate constants
of heterogeneous elementary reactions. Kinetic modeling involving
fluid dynamics and reaction chemistry coupling remains challeng-
ing. The quantification and propagation of kinetic uncertainty has
yet to be undertaken to improve the accuracy of kinetic model. The
existing kinetic models have not been extensively tested in other
industrial combustion conditions. In order to address these chal-
lenges, future efforts on experimental measurements, high-level
theoretical calculations, and kinetic modeling are needed.
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared to
influence the work reported in this paper.
Acknowledgments
This work was supported by National Key R&D Program of
China (2016YFB0600604), National Natural Science Foundation of
China (51376072), National Postdoctoral Program for Innovative
Talents (BX20180108), Fundamental Research Funds for the Central
32 Y. Yang, J. Liu and Z. Wang / Progress in Energy and Combustion Science 79 (2020) 100844
Universities (2019kfyRCPY021), and Program for HUST Academic
Frontier Youth Team (2018QYTD05).
Supplementary materials
Supplementary material associated with this article can be
found, in the online version, at doi:10.1016/j.pecs.2020.100844.
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 Y. Yang, J. Liu and Z. Wang / Progress in Energy and Combustion Science 79 (2020) 100844
Yingju Yang obtained his PhD in Thermal Engineering from Huazhong University of
Science and Technology in June 2018. He is currently a postdoctoral fellow in State
Key Laboratory of Coal Combustion at HUST. His research focuses on the homoge-
neous and heterogeneous reaction kinetics of mercury transformation in coal-fired
flue gas. He develops reaction paths and kinetic parameters for complex reaction
systems at a detailed level and applies the reactions in models to understand the
complex mercury transformation process in coal-fired flue gas. He was granted for
Innovative Talent by China Postdoctoral System in 2018.
Prof. Jing Liu received her PhD in Thermal Engineering in 2007 from Huazhong
University of Science and Technology (HUST). She was a visiting scholar in Centre
National de la Recherche Scientifique (CNRS) of France in 2004. She is currently
a Distinguished Professor of the State Key Laboratory of Coal Combustion at HUST.
She is a recognized author in development of heavy metals reaction mechanism and
using quantum chemistry calculations to develop detailed chemical kinetics. Her
research interests include: reaction mechanisms and chemical kinetics, emissions
41
and control of heavy metals, solid waste treatment, CO2 capture and utilization. She
has published more than 100 SCI-indexed papers including 7 highly cited papers,
and 2 books. She was granted for New Century Excellent Talent by the Education
Ministry (2010), Distinguished Young Scholar of Hubei Province (2015), and won the
first prize of natural science of Ministry of Education (2008). She was supported by
about 40 projects, including 7 National Natural Science Foundation of China, and 2
National Key Research and Development Programs.
Mr. Zhen Wang is currently a PhD student in the group of Prof. Jing Liu at
Huazhong University of Science and Technology. His research interests include the
development of sorbents and catalysts for mercury removal during coal combus-
tion and gasification processes. He combines experimental and theoretical methods
to investigate the reaction mechanisms of mercury adsorption and oxidation over
catalysts and sorbents.