Progress in Energy and Combustion Science 73 (2019) 26–64

Contents lists available at ScienceDirect

Progress in Energy and Combustion Science

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

A review on mercury in coal combustion process: Content and

occurrence forms in coal, transformation, sampling methods, emission
and control technologies
Shilin Zhao a,b, Deepak Pudasainee b, Yufeng Duan a,∗, Rajender Gupta b, Meng Liu a,
Jianhong Lu a
a
Key Laboratory of Energy Thermal Conversion and Control of Ministry of Education, School of Energy and Environment, Southeast University, Nanjing
210096, China
b
Department of Chemical and Materials Engineering, University of Alberta, Edmonton T6G 1H9, Canada

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

Article history: Mercury, as a global pollutant, has raised worldwide concern due to its high toxicity, long-distance trans-
Received 11 August 2018 port, persistence, and bioaccumulation in the environment. Coal-fired power plants (CFPPs) are consid-
Accepted 19 February 2019
ered as the major anthropogenic mercury emission source to the atmosphere, especially for China, India,
and the US. Studies on mercury in coal combustion process have been carried out for decades, which in-
Keywords: clude content and occurrence forms of mercury in coal, mercury transformation during coal combustion,
Mercury sampling, co-removal and emission of mercury in CFPPs, mercury removal technologies for CFPPs. This
Coal current review summarizes the knowledge and research developments concerning these mercury-related
Content and forms issues, and hopes to provide a comprehensive understanding of mercury in coal combustion process and
Transformation
guidance for future mercury research directions.
Coal-fired power plants
The average mercury content in the coal from China, the US, and South Africa is 0.20, 0.17, and
Emission and removal
0.20 mg/kg, respectively, which is higher than the world’s coal average value of 0.1 mg/kg. In general,
mercury in coal is in the forms of sulfide-bound mercury (mainly pyritic mercury, dominant), clay-bound
mercury, and organic matter-bound mercury, which are influenced by diagenetic, coalification, and post-
diagenetic conditions, etc. Mercury transformation in coal combustion includes homogeneous (without
fly ash) and heterogeneous (with fly ash) reaction. The transformation is affected by the coal types, flue
gas components, flue gas temperature, combustion atmosphere, coal ash properties, etc. The effects of
chlorine, NOx, SO2 , H2 O, O2 NH3 on elemental mercury (Hg0 ) homogeneous oxidation and the influence
of physical structure properties, unburned carbon, and metal oxides in fly ash as well as flue gas compo-
nents on Hg0 heterogeneous transformation are systematically reviewed in detail. For the mercury trans-
formation in oxy-coal combustion, O2 promotes Hg0 oxidation with Cl2 while NO and CO2 inhibit or do
not favor that reaction. CO2 increases Hg0 oxidation in the atmosphere of NO and N2 . SO2 will limit Hg0
oxidation, while HCl has a higher oxidation effect on Hg0 than that in air-coal combustion atmosphere.
Fly ash plays an important role in Hg0 oxidation. SO3 inhibits mercury retention by fly ash while H2 O
promotes the oxidation.
The sampling or analysis principle, sampling requirements, and advantages and disadvantages of the
commonly used on-site mercury sampling methods, namely, Ontarion Hydro Method (OHM), US EPA
Method 30B, and Hg-CEMS, are compared. The air pollution control devices (APCDs) in CFPPs also have
the mercury co-removal ability besides the conventional pollutants, such as NOx , particulate matter (PM),
SO2 , and fine PM. Selective catalytic reduction (SCR) equipment, electrostatic precipitator (ESP) or fab-
ric filter (FF), and wet flue gas desulfurization (WFGD) device are good at Hg0 oxidation, particulate
mercury (Hgp ) removal, and oxidized mercury (Hg2+ ) capture, respectively. The Hg0 oxidation rate for
SCR equipment, and the total mercury (Hgt , Hgt = Hg0 + Hg2+ + Hgp ) removal rate for ESP, FF, and WFGD

∗
Corresponding author at: Key Laboratory of Energy Thermal Conversion and
Control of Ministry of Education, School of Energy and Environment, Southeast Uni-
versity, Nanjing 210096, China.
E-mail addresses: 230149314@seu.edu.cn (S. Zhao), yfduan@seu.edu.cn (Y. Duan).

https://doi.org/10.1016/j.pecs.2019.02.001
0360-1285/© 2019 Elsevier Ltd. All rights reserved.
 S. Zhao, D. Pudasainee and Y. Duan et al. / Progress in Energy and Combustion Science 73 (2019) 26–64 27

device is 6.5–79.9%, 11.5–90.4%, 28.5–90%, and 3.9–72%, respectively. Wet electrostatic precipitator (WESP)
can capture Hg0 , Hg2+ , and Hgp simultaneously. The mercury transformation process in SCR, ESP, FF,
WFGD, and WESP is also discussed. Hgt removal in ESP+WFGD, SCR+ESP+WFGD, SCR+ESP+FF+WFGD,
and SCR+ESP+WFGD+WESP is 35.5–84%, 43.8–94.9%, 58.78–73.32%, and 56.59–89.07%, respectively. The
mercury emission concentration in the reviewed CFPPs of China, South Korea, Poland, the Netherlands,
and the US is 0.29–16.3 μg/m3 . Mercury in some fly ash and gypsum, and in most WFGD and WESP
wastewater, is higher than the relevant limits, which needs to be paid attention to during their process-
ing.
Mercury removal technologies for CFPPs can be divided into pre-combustion (including coal wash-
ing technology and mild pyrolysis method), in-combustion (including low-NOx combustion technology,
circulating fluidized bed combustion technology, and halogens addition into coal), and post-combustion
(including existing commercial SCR catalyst improvement, inhibiting Hg0 re-emission in WFGD, mercury
oxidizing catalysts, injecting oxidizing chemicals, carbon-based adsorbents, fly ash, calcium-based adsor-
bents, and mineral adsorbents) based on the mercury removal position. The mercury removal effects,
mercury removal mechanism, and/or influencing factors are summarized in detail. One of the regenera-
ble mercury removal adsorbents, the magnetic adsorbent modified by metal oxides or the metal halides,
is the most promising sorbent for mercury removal from CFPPs. It has advantages of high mercury re-
moval efficiency, low investment, easy separation from fly ash, and mercury recovery, etc. Lastly, further
works about mercury transformation in coal combustion atmosphere, mercury co-removal by APCDs, the
emission in CFPPs, and mercury removal technologies for CFPPs are noted.
© 2019 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
1.1. Mercury migration in the environment and its hazards . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
1.2. Mercury emission sources . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
1.3. Mercury emission regulation and the international initiatives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
2. Coal consumption and utilization across the world. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
2.1. Coal consumption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
2.2. Coal utilization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
3. Mercury content and forms in coal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
3.1. Determination methods for mercury content in coal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
3.2. Mercury content in coal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
3.3. Mercury forms in coal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
3.3.1. Correlational analysis method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
3.3.2. Float-sink test and sequential chemical extraction procedure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
3.3.3. Thermal treatment method and methods combined . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
4. Mercury transformation in coal combustion process. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
4.1. General transformation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
4.2. Homogeneous reaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
4.2.1. Effect of chlorine . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
4.2.2. Effect of NOx . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
4.2.3. Effect of SO2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
4.2.4. Effect of H2 O. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
4.2.5. Effect of O2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
4.2.6. Effect of NH3 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
4.3. Heterogeneous reaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
4.3.1. Physical structure properties of fly ash . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
4.3.2. Unburned carbon in fly ash . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
4.3.3. Metal oxides in fly ash . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
4.3.4. Flue gas components . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
4.4. Oxy-coal combustion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
4.4.1. Definition and characteristics of oxy-coal combustion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
4.4.2. Mercury emission from oxy-coal combustion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
4.4.3. Mercury transformation under oxy-coal combustion. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
5. Sampling, co-removal, and emission of mercury in coal-fired power plants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
5.1. On-site mercury sampling methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
5.1.1. Ontario Hydro Method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
5.1.2. US EPA Method 30B . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
5.1.3. Mercury-continuous emission monitoring system . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
5.1.4. Comparison of OHM, US EPA Method 30B, and Hg-CEMS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
5.2. Co-removal efficiencies across air pollution control devices. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
5.2.1. Selective catalytic reduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
5.2.2. Electrostatic precipitator and fabric filter . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44
5.2.3. Wet flue gas desulfurization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44
28 S. Zhao, D. Pudasainee and Y. Duan et al. / Progress in Energy and Combustion Science 73 (2019) 26–64

5.2.4. Wet electrostatic precipitator . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45

5.2.5. Combination of each air pollution control device . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
5.3. Emission concentration and emission factor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
5.4. Mercury content in combustion by-products. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
6. Mercury removal technologies for coal-fired power plants. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46
6.1. Pre-combustion mercury removal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46
6.1.1. Coal washing technology. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46
6.1.2. Mild pyrolysis method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
6.2. In-combustion mercury removal. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
6.3. Post-combustion mercury capture . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48
6.3.1. Existing commercial selective catalytic reduction catalyst improvement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48
6.3.2. Inhibiting Hg0 re-emission in wet flue gas desulfurization. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48
6.3.3. Mercury oxidizing catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
6.3.4. Injecting oxidizing chemicals. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
6.3.5. Carbon-based adsorbents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
6.3.6. Fly ash . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53
6.3.7. Calcium-based adsorbents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54
6.3.8. Mineral adsorbents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54
6.4. Novel mercury control approaches . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55
6.4.1. Non-separable regenerable mercury removal adsorbent . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55
6.4.2. Separable regenerable mercury removal adsorbent . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55
6.4.3. Multipollutant control . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
7. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
8. Further works . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58
Notes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58
Supplementary material . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58

1. Introduction
1.1. Mercury migration in the environment and its hazards
Mercury has caused widespread concern around the world due
to its great toxicity, which can damage human health and the en-
vironment [1,2]. The schematic diagram of the overall mercury cy-
cle in the atmosphere, modified from Travnikov [3], is shown in
Fig. 1. Mercury emitted from natural and anthropogenic sources, or
re-emitted from natural surfaces, includes gaseous elemental mer-
cury (Hg0 ), gaseous oxidized mercury (Hg2+ ), and particulate mer-
cury (Hgp ). The Hg0 will undergo a series of chemical reactions in
both gaseous and aqueous phases to transform into Hg2+ or Hgp .
Due to the high volatility of Hg0 , it can stay in the atmosphere for
6–18 months. However, the residence time for the gaseous Hg2+
and Hgp in the atmosphere is estimated in hours and days [4].
Then, Hg2+ and Hgp will be deposited in soil, plants, or water,
which can combine with organic molecules to form methyl mer-
cury (MeHg; CH3 Hg+ ). Thus, there are four common forms of mer-
cury in the environment, namely, Hg0 , Hg2+ , Hgp , and MeHg.
The various forms of mercury determine its toxicity level. Mer-
cury and its compounds can enter human body via the diges-
tive tract, respiratory tract, and skin absorption. In general, the
toxicity of mercury follows the decreasing order of organic mer-
cury > inorganic mercury > Hg0 . Hg0 can harm the human central
nervous system through the respiratory tract, while inorganic mer-
cury (such as water-soluble Hg2+ ) will affect the kidneys via gas-
trointestinal absorption. Organic mercury (such as MeHg) can be
accumulated in fish and plants and then become enriched in hu-
man bodies. It is the most toxic, as it can damage the cerebral

Fig. 1. Schematic diagram of the overall mercury cycle in the atmosphere, modified from Travnikov [3].
 S. Zhao, D. Pudasainee and Y. Duan et al. / Progress in Energy and Combustion Science 73 (2019) 26–64
Fig. 2. Proportion of global anthropogenic emissions of mercury to air in 2005 from
various sectors [10].
cortex, cerebellum, and peripheral nerves [5,6]. The world-famous
Minamata Disease, which occurred in Japan in the 1950s, was be-
cause the residents ate the fish contaminated by MeHg. Mercury
emitted into atmosphere can be transported all over the globe de-
pending upon the meteorological conditions. Thus, mercury is a
global pollutant, which has the properties of long-distance trans-
port, high toxicity, persistence, and bioaccumulation in the envi-
ronment [7].
1.2. Mercury emission sources
Mercury emission sources can be divided into two parts: natu-
ral and anthropogenic sources. The primary natural sources of mer-
cury include volcano eruptions, weathering of rocks, forest fires,
and soil erosion, whereas the secondary natural release occurs
from soils, sediments, bodies of water, landfills, etc. The anthro-
pogenic sources are fossil fuel combustion, metal production, ce-
ment production, etc. [2,8]. The contribution of mercury emissions
from natural sources is estimated at 45–66% of the total mercury
emissions [4]. In 2005, the global anthropogenic mercury emission
amount was estimated to be 1930 tonnes [9]. For the same year,
the proportion of global anthropogenic emissions of mercury to air
from various sections is shown in Fig. 2 [10]. It shows that the
fossil fuel (primarily coal) combustion for power and heating was
the largest single anthropogenic mercury emission source, occupy-
ing 45% of the total anthropogenic emission amount [11]. The ten
largest mercury emitting countries based on their emissions to air
in 2005 from various anthropogenic sectors are shown in Fig. 3
[10], the top three anthropogenic mercury emitting countries are
China, India, and the US. In addition, the fossil fuel combustion for
power and heating, mainly coal-fired power plants (CFPPs), are the
major anthropogenic source of mercury emissions [11].
1.3. Mercury emission regulation and the international initiatives
To solve the problem of mercury pollution, many countries have
taken relevant measures and formulated relevant regulations. In
29
Fig. 3. Emissions of mercury to air in 2005 from various anthropogenic sectors in
the ten largest emitting countries [10].
Table 1
Mercury emission concentration limits for the new and
existing CFPPs in China and the US (μg/m3 ) [7].
China The US
30 New: 1 (bituminous, gangue), 5 (lignite)
Existing: 2 (bituminous, gangue), 6 (lignite)
the 1990 Clean Air Act Amendments of the US, mercury and its
compounds were classified as hazardous air pollutants. In 2005,
the US Environmental Protection Agency (US EPA) issued the Clean
Air Mercury Rule (CAMR), which restricted the mercury emission
amount from new CFPPs [12]. In 2008, the US Court of Appeals
ruled to abolish CAMR and required the US EPA to develop more
stringent mercury emission regulations. In December 2011, the US
EPA’s Mercury and Air Toxics Standards (MATS) ruled the final
standards for limiting mercury emissions from CFPPs [13]. In Jan-
uary 2005, the European Commission also adopted a strategy to
reduce mercury emission levels in the environment [14].
The Ministry of Environmental Protection in China initiated a
pilot mercury emission control project based on 16 CFPPs in 2010
[7]. The concentration limit (30 μg/m3 ) for mercury and its com-
pounds emitted from CFPPs of China was firstly given in 2011,
which has been executed since January 1, 2015 [15]. In October
2013, more than 120 countries signed the Minamata Convention,
which focused on anthropogenic mercury emissions and aimed to
reduce global mercury pollution in the coming decades [2,4]. In or-
der to meet the Minamata Convention, mercury emission concen-
tration from CFPPs should be restricted under a value of 5 μg/m3
and 3 μg/m3 in 2020 and 2030, respectively, recommended by An-
cora et al. [16]. The mercury emission concentrations limits for the
new and existing CFPPs in China and the US are shown in Table 1
[7]. The emission standard of China is far higher than that of the
US, which means China should take strong measures to signifi-
cantly decrease the mercury emissions from CFPPs.
From the issues raised above, it is clear that mercury is a global
pollutant that has been prioritized worldwide and there is an ur-
gent need to act on controlling mercury emission into the envi-
ronment. Among the various anthropogenic sources, CFPPs are the
major source of mercury emissions into the atmosphere. Thus, this
30 S. Zhao, D. Pudasainee and Y. Duan et al. / Progress in Energy and Combustion Science 73 (2019) 26–64

paper focuses on content, occurrence forms, transformation, emis-

sion, and removal of mercury during coal combustion, which aims
to give a detail and comprehensive summary and propose future
research directions. This paper also aims to provide a reference for
choosing the most suitable mercury control technology. The con-
tents of this paper are as follows:

- Introduction, including mercury migration in the environment

and its hazards, mercury emission sources, and mercury emis-
sion regulation and the international initiatives;
- Coal consumption and utilization across the world;
- Mercury content and forms in coal, including determining
methods for mercury content in coal, mercury content in coal,
and mercury forms in coal;
- Mercury transformation in coal combustion process, including
general transformation, homogeneous reaction, heterogeneous
reaction, and oxy-coal combustion;
- Sampling, co-removal, and emission of mercury in CFPPs, in-
cluding on-site mercury sampling methods, co-removal efficien-
cies across air pollution control devices (APCDs), emission con-
centration and emission factor, and mercury content in com-
bustion by-products (CBPs);
- Mercury removal technologies for CFPPs, including pre-
combustion mercury removal, in-combustion mercury removal,
post-combustion mercury capture, and novel mercury control
approaches;
- Conclusions and further works.
2. Coal consumption and utilization across the world
2.1. Coal consumption
The global primary energy consumption from 1992 to 2017 and
the shares of global primary energy consumption from 1965 to
2017 are shown in Figs. 4 and 5, respectively, according to the BP
Statistical Review of World Energy (2018) [17]. It can be seen that
the coal consumption amount shows an increasing trend, which
has risen from about 2191 to 3731 Mt oil equivalent since 1992.
Although the share of coal in the global primary energy consump-
tion has been fluctuating since 1965, coal has always been the ma-
jor primary energy source with its share at nearly 30%, second only
to the share of oil.
Based on the reported regional consumption of fuel in 2017
[17], the top four regions of coal consumption are Asia Pacific,
Africa, Commonwealth of Independent States (CIS), and Europe in
Fig. 4. Global primary energy consumption from 1992 to 2017 (Mt oil equivalent)
[17] (data source comes from BP Statistical Review of World Energy 2018).
Fig. 5. Shares of global primary energy consumption from 1965 to 2017 (%)
[17] (data source comes from BP Statistical Review of World Energy 2018).
decreasing order. China is the largest coal consumer in the world,
which accounts for 50.7% of the total coal consumption amount
in 2016. The following top ten countries behind China are In-
dia (11.0%), the US (8.9%), Japan (3.2%), Russian Federation (2.5%),
South Korea (2.2%), South Africa (2.2%), Germany (1.9%), Indone-
sia (1.5%), and Poland (1.3%). In addition, coal makes a significant
contribution to each country’s own primary energy consumption
in some cases, such as for China (60.43%), India (56.26%), Japan
(26.40%), and the US (14.86%). For China, the total coal consump-
tion kept growing in the period of the 13th Five-year Plan (2016–
2020) [18]. Thus, the trend of coal as a primary energy source
around the world, especially for China, will not change in the com-
ing decades [19].
2.2. Coal utilization
Coal can be used in many industries, including the steel, ce-
ment, building, coal power, coke, coal chemistry, and paper and
textile industries, etc. [18,20]. Most of these industries need the
heat from coal combustion. Based on the International Energy
Agency (IEA) statistics, the world’s consumption of coal used for
power production accounted for 62.7% of total coal production in
2011, which had an average annual increase of 0.4% from 1990 to
2011. In the case of China, about 50% of coal production is con-
sumed to generate electricity. However, the ratio of coal consump-
tion for power production in most developed countries is signif-
icantly higher and mostly above 80%, such as 91% in the US and
76.2% in the EU in 2011 [21]. In 2015, 65.5% of the coal consump-
tion in the world was used in electricity and commercial heat,
while 82.7% of the consumption took place for this purpose in
Organization for Economic Cooperation and Development (OECD)
member countries [22]. In China, power production will be a key
industry for coal utilization, although the government has made
efforts to further enhance the constraints on the coal consumption
cap to comply with the requirements of its pollution control policy
in the long term (2020–2050) [23].
Mercury in coal is known to be of concern to public health
[11,23] and the environment. Facing the huge amount of coal con-
sumption every year worldwide, knowing the content and occur-
rence forms of mercury in coal is very important and necessary for
obtaining the mercury emission assessment and optimum mercury
removal technology during coal utilization, especially coal combus-
tion for power generation [24–27].
 S. Zhao, D. Pudasainee and Y. Duan et al. / Progress in Energy and Combustion Science 73 (2019) 26–64 31

Table 2
Content of mercury in coal around the world.

Countries Mercury content (mg/kg) Number of samples Data sources

Range Mean value

China 0.003–10.5 0.16a 990 Zhang et al. [32]

China 0.003–10.5 0.20a 1413 Ren et al. [33]
China 0.01–0.5 0.1a 1458 Tang et al. [34]
China 0–45.0 0.19a 1699 Zheng et al. [35]
China 0–45.0 0.20a 1793 Yang et al. [36]
India 0.11–0.80 – – Mukherjee et al. [37]
Russia 0.02–0.9 – – Mukherjee et al. [37]
US 0–10.0 0.17a 7649 Finkelman et al. [38]
South African 0.14–0.30 0.20a 17 Lusilao-Makiese et al. [39]
Indonesia 0.02–0.19 0.10a 8 Belkin et al. [40]
Poland 0.02b –0.07c 0.05d 312 Wierzchowski et al. [41]
Australia 0.01–0.14 0.06a – Swaine and Goodarzi [42]
World 0.02–1.0 0.1e – Yudovich and Ketris [43]

Note:
a
Arithmetic.
b
Lower quartiles value in histogram.
c
upper quartiles value in histogram.
d
Mean value in histogram.
e
Clarke value.

3. Mercury content and forms in coal
3.1. Determination methods for mercury content in coal
The major standard mercury determination methods in coal in-
clude ASTM D6414-14: Acid extraction or wet oxidation/cold va-
por atomic absorption [28], ASTM D6722-01: Direct combustion
analysis [29], EPA Methods 7471B: Mercury in solid or semisolid
waste (manual cold-vapor technique) [30], and ISO 15237: 2016:
Solid mineral fuels -Determination of total mercury content of coal
[31]. The main difference between these methods is the pretreat-
ment techniques of coal samples, which are chemical digestion and
thermal decomposition. Cold vapor atomic absorption spectrom-
etry and cold vapor atomic fluorescence spectroscopy are usually
used for the detection of mercury after pretreatment. With a long
history and high recognition, the analytical method with chemi-
cal digestion has been widely adopted. However, the pretreatment
process involves many steps and requires mercury to be dissolved
in solution, which leads to an increased chance of sample contam-
ination in the digestion process [25]. In addition, the experimen-
tal personnel need to be well trained. Due to the advantages of
quickness, convenience, and high efficiency, the thermal decompo-
sition analytical method has become more favorable. The commer-
cial mercury analysis instruments include Hydra AA Hg Analyzer
(Teledyne Leeman Labs), DMA-80 Direct Hg Analyzer (Milestone),
the AMA 254 Hg Analyzer (Leco), the Hydra-C Hg Analyzer (Tele-
dyne Leeman Labs), and the RA-915M Hg Analyzer equipped with
the pyrolyzer PYRO-915, etc.
3.2. Mercury content in coal
Many researchers have determined the mercury content in coal
around the world [32–43]. Due to the combined effects of var-
ious geological factors in the depositional environment, mercury
content in coal varies greatly in different regions, different coal-
forming periods, and different degrees of deterioration. For China,
Zhang et al. [32] measured 990 coal samples, finding that the av-
erage mercury content in the studied Chinese coal was 0.16 mg/kg
with a range of 0.003–10.5 mg/kg. Ren et al. [33], Tang and Huang
[34], Zheng et al. [35], and Yang et al. [36] also reported the aver-
age concentration of mercury in Chinese coal with values of 0.20,
0.1, 0.19, and 0.20 mg/kg based on the sample numbers of 1413,
1458, 1699, and 1793, respectively. Mukherjee et al. [37] collected
the information on mercury concentration in coal from India and
Russia, presenting the range of 0.11–0.80 and 0.02–0.9 mg/kg, re-
spectively. Finkelman [38] reported the average mercury value of
0.17 mg/kg in the US coal with changing scope of 0–10.0 mg/kg ac-
cording to 7649 coal samples. The mean mercury concentration in
the coal of South Africa, Indonesia, Poland, and Australia is 0.20,
0.10, 0.05, and 0.06 mg/kg, respectively [39–42]. Compared with
the mean value of 0.1 mg/kg in the world’s coal given by Yudovich
and Ketris [43], it can found that mercury content in the coal of
China, the US, and South Africa is higher, which needs to be given
more attention. The content of mercury in coal around the world
is summarized in Table 2.
3.3. Mercury forms in coal
In general, the occurrence forms of mercury in coal can be de-
termined by using the following methods [37,44–46]:
(1) Correlational analysis method is used to explore the occur-
rence forms of mercury in coal based on the content corre-
lation of mercury with ash or sulfur (including total sulfur,
organic sulfur, pyrite sulfur, sulfate sulfur) in coal.
(2) The float-sink test uses several organic solvents to divide
the coal into sub-coal samples with different densities [47].
Then, the correlation between the main component and
mercury content in the sub-coal samples is studied [48].
(3) Sequential chemical extraction procedure (SCEP) adopts spe-
cific chemical solvents to extract the different mercury forms
in coal samples step by step based on their different solubil-
ity. In general, the chemical forms of mercury in coal can be
divided into six chemical species, namely, water-leachable,
ion-exchangeable, organic-bound, carbonate-bound, silicate-
bound, and sulfide-bound [49,50].
(4) Thermal treatment method is used to obtain the occurrence
mode of mercury based on the specified release temper-
atures of the specified mercury compounds, as shown in
Table 3 [47,51–55].
(5) Direct test analysis technology uses advanced equipment
(such as X-ray absorption spectroscopy (XAS) and X-ray pho-
toelectron spectroscopy (XPS)) to determine the speciation
and binding of mercury on coal directly. However, it is very
difficult to implement due to the low mercury concentra-
tion in the actual application. The silicon in the coal inter-
feres with the XPS detection results [56]. Thus, this method
is generally applied for the mercury sorbents, which have
high mercury content [57–59].
32 S. Zhao, D. Pudasainee and Y. Duan et al. / Progress in Energy and Combustion Science 73 (2019) 26–64

Table 3 selenide-bound mercury. Zheng et al. [50] adopted the SCEP to in-
The decomposition temperatures of specific mercury compounds.
vestigate the mercury occurrence mode in Permian Huaibei coal
Hg compound Peak range [°C] Peak max [°C] Source from China. Based on the 34 coal samples, they reported that
Hg0 30–160 120 [51] sulfide-bound mercury, organic-bound mercury, and silicate-bound
Hg2 Cl2 30–370 138, 228 [54] mercury were the main species. Bool and Helble [68] and Palmer
120–300 148, 240 [55] et al. [69] also presented that organic-bound mercury and sulfide-
HgCl2 60–400 200 [51] bound mercury were the main mercury forms in the coal based
125–225 180 [47]
on the SCEP for the mercury form analysis of the Pittsburgh No.8
140–500 200; 320 [52]
Humic acid-bound 190–340 270 [51] coal and the Antelope mine in the Powder River basin, Wyoming,
100–240 170 [47] respectively.
HgS 230–350 310 [51]
225–500 340 [47]
3.3.3. Thermal treatment method and methods combined
150–350 300 [53]
225–500 340 [53] Mashyanov et al. [24] used a gradual heating method to de-
240–410 350 [52] termine the thermal characteristics of mercury in coal of differ-
Hg(NO3 )2 270–540 470 [52] ent types from deposits in Russia, Ukraine, and South Africa, re-
HgO 190–530 410 [52] vealing the existence of various mercury thermospecies, includ-
Hg2 SO4 240–640 359, 560 [54]
120–265 145, 225 [55]
ing in part the absorbed elemental mercury and mercury bound
HgSO4 220–450 330; 390 [52] to pyrites. Zheng et al. [49] concluded that sulfide-bound mer-
Pyrite-bound Hg 40 0–60 0 About 500 [51] cury and organic-bound mercury were the main mercury forms
in low-sulfur coals (sulfur content <1.0%), by adopting the corre-
lational analysis method and sequential extraction procedure, and
In some cases, two or three of these methods are combined to
they concluded that the correlation between mercury and dif-
discover the forms of mercury in coal.
ferent forms of sulfur in the study was in the order of pyrite
sulfur > total sulfur > organic sulfur > sulfate sulfur. Guo et al.
3.3.1. Correlational analysis method [70] used temperature-programmed decomposition (TPD) coupled
Liu et al. [60] conducted a correlation analysis between mer- with online atomic fluorescence spectroscopy and acid leaching
cury concentration and the content of ash and total sulfur in the to study the characterization of mercury in six Chinese coals
coal, which found that mercury in the coal of Indonesia and Rus- with different ranks. They found that mercury in the coals had
sia was mainly in the sulfide-bound form while that in Australian organic-bound mercury (16−36%) releasing at 220−600 °C, silicate-
coal was mainly bound to aluminosilicate. Feng et al. [61] found bound mercury (10−26%) releasing at >600 °C, pyrite-bound mer-
that mercury in the 32 coal samples had a relationship with to- cury (5−44%) releasing at 250−630 °C, and HCl-soluble mercury
tal sulfur and Fe. With the strong correlation between total sul- (10−34%) releasing at 150−600 °C. Lusilao-Makiese et al. [39] com-
fur and Fe as well as a large amount of pyrite observed by micro- bined the SCEP and correlation analysis to investigate the mercury
scope, it might be inferred that mercury mainly exists in pyrite. occurrence forms in South African coals, concluding that a large
Kostova [62] confirmed that mercury had strong connection with portion of the mercury in the studied coals was associated with
organic matter, especially the organic sulphur compounds for the organic constituents and pyrite. Feng and Hong [71] used the SCEP
lignite from the Karlovo basin, while the organic-bound mercury and density separation method to study the mercury species in
and partially silicate-bound mercury were the main mercury forms coals from Guizhou, China, concluding that mercury in the coals
based on the high positive correlation of mercury with ash yield mainly existed in pyrite. Strezov et al. [72] investigated the form of
and organic sulphur for the Beli Breg lignite. However, Ohki et al. mercury in three coals by using the SCEP, physical separation, and
[63] found that mercury content in coal had no correlation with thermal treatment methods, which confirmed a strong relationship
sulfur (or pyrite sulfur) content but had a certain correlation with between mercury and the pyritic sulfur in coal.
ash content for the bituminous coals used for Japanese power In summary, there are three main mercury forms in coal, in
plants and industries. Dziok et al. [64] used the correlation analysis which sulfide-bound mercury (mainly pyritic mercury) is domi-
to explore the mercury form in Polish hard coals, which found that nant, followed by clay-bound mercury and organic matter-bound
mercury in the studied coals was both in the organic and inorganic mercury. The occurrence mode of mercury in coal has a strong cor-
matter. For the organic matter, there was a significant correlation relation with sulfur content in coal for most coals, in which pyritic
between mercury and the total sulfur and organic sulfur. For the mercury is the typically dominant species; organic-bound mercury
inorganic matter, an obvious correlation could be found between and sulfide-bound mercury (mainly pyritic mercury) are the main
mercury and pyritic sulfur. forms in low-sulfur coals. However, many factors, namely, diage-
netic, coalification, and post-diagenetic conditions, including phe-
3.3.2. Float-sink test and sequential chemical extraction procedure nomena such as mineralization that post-dates coal formation and
Wagner and Tlotleng [48] found that mercury was in both magmatic intrusion, etc., can affect the occurrence form of mer-
the float and sink fractions during the float-sink test, indicat- cury in coal [64], which results in the large changes in ratio range
ing the existence of organic- and inorganic-bound mercury in the of various mercury forms. Thus, the general results and the meth-
coals. Finkelman [65] concluded that mercury mainly existed in ods above can provide a suitable way to explore the mercury oc-
inorganic minerals, such as sulfide (sphalerite) or selenide in the currence forms for each specific coal, based on their different pur-
coals by studying the occurrence of trace elements in Illinois (US) poses, such as mercury removal by coal washing or mild pyrolysis,
coals through the float-sink test. Pan et al. [66] adopted the SCEP or release in coal combustion or gasification, etc.
to study the mercury occurrence mode in the coals from four
different coal preparation plants in China, and found that mer- 4. Mercury transformation in coal combustion process
cury was mainly distributed in sulfide (mainly pyrite). Riley et al.
[67] adopted the SCEP to explore the occurrence mode of mercury 4.1. General transformation
in six Australian coals, finding that mercury was predominantly as-
sociated with pyrite, while it might also be in some other forms, In coal combustion process, coal particles firstly begin pyroly-
such as organically bound and elemental mercury, sulphides, and sis and ignition. With the volatile releasing, the char starts to burn
 S. Zhao, D. Pudasainee and Y. Duan et al. / Progress in Energy and Combustion Science 73 (2019) 26–64
Fig. 6. General mercury transformation process during coal combustion, modified after [83]. Reprinted with permission from Elsevier, 2012.
and break into smaller particles [73]. At the high combustion flame
temperature, almost all the mercury in coal decomposes into Hg0
based on the mercury forms, mentioned above, in coal [74,75]. As
the flue gas cools, Hg0 can react with flue gas components, such as
halogens (Cl2 , Br2 ), acid gas (HCl, HBr, NO2 ), and O2 , etc. to trans-
form into Hg2+ through homogeneous reactions [75–77]. Part of
the Hg0 will be catalytically oxidized to Hg2+ or absorbed on fly
ash acting as Hgp through heterogeneous oxidation with the help
of fly ash and flue gas components [74,78–80]. In addition, some
Hg2+ can also be absorbed on the fly ash surface as Hgp while
some Hg0 keeps its form without transformation in the cooling
process. Finally, the mercury emitted into the atmosphere can ex-
ist in three forms: Hg0 , Hg2+ , and Hgp [81,82]. The general mer-
cury transformation process, modified after [83], is shown in Fig. 6.
For CFPP, Hg2+ is easily removed by wet flue gas desulfurization
(WFGD) devices because of its high water solubility. The Hgp can
be captured with the use of particulate matter (PM) control de-
vices, such as an electrostatic precipitator (ESP) or fabric filter (FF).
Due to its high volatility and water insolubility, it is very difficult
for APCDs in power plants to capture Hg0 [74–86]. Thus, under-
standing the transformation mechanism of mercury in coal com-
bustion is very important for the selection or development of its
removal method. Many factors can influence mercury transforma-
tion, such as coal types, flue gas components, flue gas temperature,
combustion atmosphere, coal ash properties, etc. Based on partici-
pation of fly ash or not, the mercury reaction can be divided into
homogeneous (without fly ash) and heterogeneous (with fly ash)
reaction, which are discussed in Sections 4.2 and 4.3.
4.2. Homogeneous reaction
4.2.1. Effect of chlorine
Chlorine is considered as the key element for Hg0 oxidation
[87–89]. During coal combustion, chlorine in coal will be released
in the main form of atomic Cl, which transforms into HCl or Cl2
with flue gas cooling. The relevant transformation process can be
described by the reactions (1)–(4) [90,91]. Ghorishi [92] examined
the effects of HCl concentration and temperature on Hg0 oxidation
at the gas mixture of 40 μg/m3 Hg0 , 5% CO2 , 2% O2 , and the balance
N2 , finding that the increasing concentration of HCl resulted in an
increase in Hg0 oxidation. The Hg0 oxidation rate ranged from 9.1%
33
to 27.2%, corresponding to the 50 to 200 ppmv of HCl. Agarwal
et al. [93] summarized that HCl oxidized Hg0 more effectively at
temperatures higher than 600 °C, while Cl2 led to a stronger mer-
cury oxidation effect at temperatures below 500 °C. It has been
shown that the Hg0 reaction with HCl was favorable at higher tem-
peratures [94,95] while it reacted favorably with Cl2 at lower tem-
peratures [96–98]. Laudal et al. [97] performed bench-scale exper-
iments to investigate the effects of various flue gas components on
Hg0 oxidation using the Ontario Hydro Method (OHM) and found
that 10-ppmv Cl2 could realize 84.8% Hg0 oxidation at 175 °C with
flue gas components of N2 , O2 , CO2 , and H2 O. The experiments
of Agarwal et al. [99] demonstrated that Hg0 oxidation reached
above 95% as Cl2 concentration exceeded 50 ppmv. Based on the
electronic structure, Cl2 is much stronger than HCl as an oxidizing
agent.
Cl + H ↔ HCl (1)
2Cl ↔ Cl2 (2)
4Cl + 2H2 O ↔ 4HCl + O2 (3)
4HCl + O2 ↔ 2Cl2 + 2H2 O (4)
Thermodynamic equilibrium calculations show that all the mer-
cury in the flue gas exists as Hg0 at temperatures above 627 °C
while it will be in the form of HgCl2 entirely at temperatures
below 452 °C for typical coals [100]. However, the measurement
of mercury in the flue gas with a temperature of about 127 °C
in the full-scale combustion system does not support the equilib-
rium calculations results, the reported data of which is 30−95% of
Hg2+ [89]. The experimental data of Fry et al. [101] showed that
quench rate had obvious effects on homogeneous mercury oxida-
tion, in which a change from −210 to −440 K/s led to the mer-
cury oxidation from 34% to 86% at 300 ppmv chlorine. It indicates
mercury oxidation with flue gas is kinetically controlled. Many re-
searchers have developed the reaction kinetic mechanisms to ex-
plore the Hg0 oxidation process in the presence of Cl2 or HCl.
Widmer and West [102] firstly gave the rate constants in the Hg0
oxidation mechanism with chlorine, which was the eight reaction
paths. Due to few experiments about the rate constants, assump-
tions and analogies were used by Widmer and West [102] that re-
sulted in the inaccurate kinetic parameters. Then, theoretical rate
34 S. Zhao, D. Pudasainee and Y. Duan et al. / Progress in Energy and Combustion Science 73 (2019) 26–64

Table 4
Rate constants in Hg0 oxidation mechanism with chlorine.

No. Reactions A cm3 /mol·s β Ea kal/mol References

R1 Hg + Cl + M = HgCl + M 4.25E7 0.0 17.1 Wilcox et al. [105]

R2 Hg + Cl2 = HgCl + Cl 6.15E13 0.0 43.3 Wilcox [104]
R3 HgCl + Cl2 = HgCl2 + Cl 5.18E4 2.4 −3.4 Krishnakumar and Helble [110]
R4 HgCl + Cl + M = HgCl2 + M 7.43E11 0.0 73.2 Wilcox and Blowers [107]
R5 Hg + HOCl = HgCl + OH 3.06E13 0.0 36.6 Wilcox [104]
R6 Hg + HCl = HgCl + H 1.93E13 0.0 93.3 Wilcox [104]
R7 HgCl + HCl = HgCl2 + H 2.49E13 0.0 25.0 Krishnakumar and Helble [110]
R8 HgCl + HOCl = HgCl2 + OH 3.28E5 2.4 0.3 Krishnakumar and Helble [110]

constants for some of the eight Hg-Cl reactions were determined
by quantum chemistry and transition state theory (TST), such as
in the works of Sliger et al. [94], Li et al. [103], Wilcox et al. [104–
108], Khalizov et al. [109], Krishnakumar and Helble [110], Liu et al.
[111], and Zheng et al. [112], which helped to improve the accuracy
of the reaction kinetic parameters, shown in Table 4. Wilcox et al.
[113] summarized that the radical combination reactions concern-
ing HgCl and Cl intermediate species could be the main pathways
with the existence of chlorine radical chemistry based on theoret-
ical calculations. In addition, Cl2 and HOCl seemed to play a ma-
jor role in mercury oxidation over HCl, while atomic Cl might be
in the dominant oxidation pathway, indicated by both the kinetic
and thermodynamic predications [104]. Krishnakumar and Helble
[110] adopted high-level quantum chemistry calculations to get the
TST rate constants for the eight-step homogeneous Hg-Cl reactions.
It was found that the rate constants of Hg/HgCl reactions with
HOCl were faster or comparable to those with Cl2 , while reactions
between Hg/HgCl and HCl were the lowest. The conversion of Hg+
to Hg2+ was faster than that of Hg0 to Hg+ , which indicated that
HgCl was a reactive intermediate. Hou et al. [114] used the chem-
ical dynamics software Chemkin to investigate the level of effect
of each reaction on Hg0 oxidation, finding that R1, R7, and R5 had
great impact. It can be inferred that Cl, HOCl, and HCl are the im-
portant Cl species for Hg0 oxidation. The gaseous mercury oxida-
tion behavior in homogeneous reaction with Cl compounds done
by Naruse et al. [115] showed that Hg0 firstly reacted with Cl rad-
icals to produce HgCl. Then, the HgCl reacted with Cl2 to form
HgCl2 . The Cl radical played a significant role in the relevant re-
action chains. Qiao and Xu [116] also concluded that Cl2 was more
effective than HCl for Hg0 oxidation in the Hg/O/H/Cl system. In
addition, the reaction between Hg and Cl is faster than that be-
tween Hg/HgCl and Cl2 [117]. Thus, it can be summarized that the
degree of effect of Cl forms on Hg0 oxidation is the Cl radical, Cl2 ,
and HCl in decreasing order.
Thermodynamic equilibrium calculations show that Cl2 domi-
nates HCl at temperatures below 475 °C while HCl dominates over
Cl2 above that temperature for typical O2 and H2 O concentrations
[99]. The Cl is predicted to be HCl at flame temperatures while
half of it is thought to be Cl2 at the temperature of APCDs inlet by
equilibrium calculations. However, the kinetic calculations indicate
that less than 1% of the Cl is converted to Cl2 at that temperature
[89]. The field test on halides emission at a 200 MW pulverized
coal combustion boiler showed that HCl was the main Cl form in
flue gas while Cl2 concentration was extremely low [118].
Based on the studies above, it can be summarized that Hg0 ox-
idation by Cl is affected by the flue gas temperature, Cl forms, and
their concentration, etc., which is summarized in Fig. 7.
to a mercury oxidation rate of 11% at 340 °C [119], which indicated
NO2 promoted Hg0 oxidation in the Hg0 + NO2 system. Rumayor
et al. [120] demonstrated that adding 200 and 400 ppmv of NO
could result in 5.0% and 7.5% of Hg2+ in the atmosphere of NO
balanced with N2 at a flue gas temperature of 150 °C, shown in
reaction (5). With the addition of CO2 and O2 in the gas mixture,
the ratio of Hg2+ increased up to 14%. This might be NO reacting
with O2 to form NO2 and radical oxygen atoms (reaction (6)),
which had strong oxidative properties (reactions (7) and (8)).
Then, NO and NO2 could react with Hg0 to generate Hg(NO2 )2
(reaction (9)) and Hg(NO3 )2 with the presence of oxygen.
2Hg0 (g ) + 2NO(g ) → 2HgO(g ) + N2 (g ) (5)
NO(g ) + O2 (g ) ↔ NO2 (g ) + O · (6)
Hg0 (g ) + O · (g ) → HgO(g, s ) (7)
Hg0 (g ) + NO2 (g ) → HgO(g ) + NO(g ) (8)
Hg0 (g ) + NO2 (g ) → Hg(NO2 )2 (g ) + NO(g ) (9)
In addition, the effect of NO on Hg0 oxidation by chlorine has
also been investigated by some researchers. Work done by Laudal
et al. [97] showed that the addition of NO could result in a de-
crease in the presence of oxidized mercury in the gas mixture of
N2 , O2 , CO2 , and SO2 , which might be due to a reaction between
NO and Cl2 (reaction (10)). This reaction consumed Cl2 , which was
thermodynamically favorable at temperatures near the end of a
typical power plant. Niksa et al. [121] predicted that lower NO
concentration (<20 ppmv) benefited Hg0 oxidation while higher
NO concentration inhibited the Hg0 conversion in the presence of
HCl. Auzmendi-Murua and Bozzelli [122] indicated that NO sig-
nificantly decreased mercury oxidation with the addition of chlo-
rine (Cl = 500 ppmv). Preciado et al. [123] studied the effects of
halogens on mercury oxidation under air- and oxygen-fired condi-
tions in a bench-scale, methane-fired, 300 W, quartz-lined reactor,
which found that the addition of NO (<300 ppmv) had little or
no effect on mercury oxidation by chlorine. Another explanation
for the influence of NO on mercury oxidation with the presence of
chlorine is that NO can react with OH, which takes away OH that
would react with H. Thus, more free H can react with Cl to produce
HCl, which results in little available chlorine reacting with mercury
[122]. The relevant reactions are shown in reactions (11)–(13).
2NO(g ) + Cl2 (g ) → 2NOCl(g ) (10)

4.2.2. Effect of NOx NO + OH → HONO (11)

NOx produced during the coal combustion process mainly
consists of NO with little amount of NO2 . As the temperature
H + OH → H2 O (12)
increases, the NO2 will start to decompose into NO at 150 °C
and finish at 600 °C. The experiment on Hg0 oxidation with NO2
showed that the initial NO2 concentration of 10 0 0 μL/L could lead Cl + H → HCl (13)
 S. Zhao, D. Pudasainee and Y. Duan et al. / Progress in Energy and Combustion Science 73 (2019) 26–64
Fig. 7. Effect of chlorine on Hg0 oxidation. Note: temp.=temperature; conc.=concentration
4.2.3. Effect of SO2
It has been reported that the SO2 alone does not lead to Hg0
oxidation [119]. Smith et al. [124] showed that injecting SO2 into
the CH4 combustion flue gas resulted in Hg0 oxidation, in which
20% oxidation was obtained with an SO2 concentration of 100–
900 ppmv. Rumayor et al. [120] found that adding 5% of O2 to
the atmosphere of SO2 , N2 , and CO2 increased the ratio of Hg2+
to 5.5%. These findings indicate that the presence of O2 enhances
Hg0 oxidation by SO2 , which can be explained by reaction (14).
2Hg0 (g ) + 2SO2 (g ) + O2 (g ) → 2HgO(g ) + 2SO3 (g )
In addition, it is reported that SO2 has an inhibitory effect on
Hg oxidation by HCl or Cl2 [93,125]. SO2 inhibits Hg0 oxidation
with the presence of HCl in the gas mixture of O2 , CO2 , and bal-
anced N2 at a temperature of 754 °C, in which an SO2 concen-
tration of 500 ppmv decreases the percentage of Hg2+ from 27%
to 20% at an HCl concentration of 200 ppmv [95]. Agarwal et al.
[99] indicated that adding 370 ppmv SO2 led to Hg0 oxidation de-
creasing from 77% to 52% with the presence of N2 , O2 , CO2 , and
Cl2 . Meanwhile, the addition of the same concentration of SO2 de-
creased the Hg0 oxidation from 90% to 57% in the gas mixture of
N2 , O2 , CO2 , H2 O, and Cl2 . The reason for the inhibitory influence
of SO2 on Hg0 oxidized by Cl2 may be similar to NO, which irre-
versibly reacts with Cl2 , as shown in reaction (15). However, mer-
cury oxidation is promoted with the existence of SO2 as HCl con-
centration is 200 ppmv and inhibited as HCl concentration reaches
555 ppmv [124]. It seems that the promotion or inhibition of SO2
on mercury oxidation by HCl depends on the concentration of SO2
and HCl. Studies in full-scale utilities indicate that SO2 had a pos-
itive correlation with Hg0 oxidation, and the interactions are af-
fected by the operating conditions, chlorine content in coal, and
temperature [126].
SO2 ( g ) + Cl2 ( g ) → SO2 Cl2 ( g )
4.2.4. Effect of H2 O
The H2 O is thought to inhibit Hg0 oxidation by chlorine (Cl2 ), as
concluded by some researchers [93,99]. Zhao et al. [127] conducted
mercury homogeneous oxidation experiments, the results of which
showed that adding 8% H2 O resulted in a decrease in Hg0 oxida-
tion rate from 38% to 4% in the presence of 200-ppmv SO2 and
13-ppmv Cl2 . Agarwal et al. [99] also thought that the existence of
H2 O intensified the inhibitory effect of SO2 and NO on mercury ox-
idation by Cl2 . Auzmendi-Murua and Bozzelli [122] predicted that
the presence of H2 O inhibited Hg0 oxidation for 10 and 30 ppmv
of NO with 500 ppmv of Cl. The main reason was that the H2 O re-
acted with Cl to form OH and HCl (reaction (16)), which removed
Cl from HCl, and slowed the mercury conversion by chlorine. Niksa
35
et al. [121] concluded that H2 O was a strong inhibitor for Hg0 ox-
idation. In summary, the H2 O is negative for Hg0 oxidation, which
further inhibits oxidation in the presence of SO2 or NO, or both of
them.
H2 O + Cl → OH + HCl (16)
4.2.5. Effect of O2
Hall et al. [128] investigated the Hg0 homogeneous oxidation
by O2 in the temperature range of 20–700 °C, in which no mer-
(14) cury oxidation was observed. However, Niksa et al. [121] argued
that O2 could weakly promote homogeneous Hg oxidation by the
kinetic model. Xu et al. [129,130] adopted detailed chemical kinet-
ics to study homogeneous mercury oxidation and also found that
O2 benefited Hg0 oxidation, especially at the low Cl2 concentra-
tion; 1.5−6.0% of mercury was predicted to be present as HgO in
all cases. Based on the studies mentioned above, it can be inferred
that O2 may promote Hg0 oxidation, but the enhancement effect is
slight.
4.2.6. Effect of NH3
In addition to the conventional flue gas components described
above, NH3 is also a non-negligible flue gas component after se-
lective catalytic reduction (SCR) device in coal-fired power plants.
In the findings of Hall et al. [119], it is found that there is no re-
action between Hg0 and NH3 for the reaction temperature ranges
of 20–600 °C. However, the works about influence of NH3 on Hg0
homogeneous reaction with other flue gas components are little
reported, which need more studies.
4.3. Heterogeneous reaction
Though some homogenous mercury oxidation mechanisms have
been proposed to predict mercury oxidation in simulated flue gas,
(15)
these mechanisms are unable to accurately predict mercury oxida-
tion in actual coal-fired flue gas [79]. One reason is that the kinetic
parameters of the homogeneous reaction are not accurate enough
and incomplete. Another reason is the existence of heterogeneous
reaction between fly ash and Hg0 in the presence of flue gas com-
ponents, which also plays an important role in mercury oxidation
or adsorption. Many factors can affect the heterogeneous reaction
of fly ash on Hg0 , which include physical structure properties (sur-
face area, particle sizes, etc.) of fly ash, unburned carbon, metal
oxides (Fe2 O3 , Al2 O3 , etc.) in fly ash, and flue gas components, as
elaborated below.
4.3.1. Physical structure properties of fly ash
Zhou et al. [131] conducted mercury adsorption by coal-fired
fly ash with particle sizes of 25–50 μm, 50–74 μm, and 74–100 μm
36 S. Zhao, D. Pudasainee and Y. Duan et al. / Progress in Energy and Combustion Science 73 (2019) 26–64
Fig. 8. Relationship between BET surface area and the mercury concentration of fly
ashes [138]. Reprinted with permission from American Chemical Society, 2007.
Fig. 9. Mercury concentration in the sized fractions from the four ashes [138].
Reprinted with permission from American Chemical Society, 2007.
in a fixed bed and found that fly ash with 50–74 μm showed the
best mercury adsorption performance. Though the smaller fly ash
had a larger specific surface area, it would be with a low sur-
face area utilization rate for mercury adsorption because of low
unburned carbon content (UBC) [132,133]. He et al. [134] inves-
tigated mercury retention by fly ash with five size fractions of
>106 μm, 75–106 μm, 58–75 μm, 48–58 μm, and 23–48 μm from a
CFPP. The results showed that the fly ash with the largest size
had the highest mercury retention capacity, which might be due
to its high UBC. Wu et al. [135] indicated that fly ash with a
particle size larger than 100 μm had the highest mercury adsorp-
tion efficiency of 67.83%, while fly ash with a particle size smaller
than 25 μm possessed the lowest mercury adsorption efficiency of
13.67%. Bhardwaj et al. [136] conducted mercury uptake tests by
four fly ashes from different CFPPs and found that both the sur-
face area and particle size had positive effects on mercury oxida-
tion and adsorption. Kostova et al. [137] suggested that the cap-
tured mercury increased as the Brunauer-Emmett-Teller (BET) sur-
face area and micropore surface area increased based on the rela-
tion of mercury content with BET and the micropore surface area
of fly ashes from the Republika power plant in Bulgaria. Suarez-
Ruiz and Parra [138] gave the relationship between the BET sur-
face area and mercury concentration of the fly ashes, and mercury
concentration in the sized fractions from four fly ashes, as shown
in Figs. 8 and 9, respectively. It was revealed that there was a poor
relationship between the surface areas and mercury retention for
these fly ashes, while the finest particle size fraction had the low-
est mercury concentration. Gao et al. [139] concluded that there
was little correlation between the fly ash particle size and the mer-
cury captured, which indicated that particle size was not the main
factor for mercury capture. Hower et al. [140] reviewed the mer-
cury capture by native fly ash carbons in CFPPs and concluded that
mercury capture by fly ash is more related to unburned carbon
amount and surface chemistry.
It can be further generalized that the fly ash with larger parti-
cle sizes or surface area generally benefited mercury adsorption. In
fact, the changes of particle size and surface area are a reflection of
the content and type of unburned carbon in fly ash to some extent
[135,138], which have great influence on mercury oxidation and/or
adsorption.
4.3.2. Unburned carbon in fly ash
In general, the UBC in coal fly ash is in the range of 2−12%.
With the installation of low-NOx burners, which require low-
oxygen and/or low-temperature combustion conditions, the UBC
can reach up to 20% in some cases [141]. The close relationship
of UBC in fly ash with mercury capture has been reported; the
capture increases with the increase in UBC content in fly ash
[140,142–144]. Wilcox et al. [113] reported that UBC correlated
with coal rank, in which low-rank coal-(such as lignite) derived fly
ash had the highest mercury capture efficiency compared to that
from high-rank coals (such as anthracite and bituminous). Hower
et al. [140,144,145] summarized that mercury capture by coal com-
bustion fly ash is also affected by the accessibility and type of
fly ash carbon. Kostova et al. [137] indicated that fly ash carbon
from subbituminous coal was more efficient in capturing mercury
than ashes with much higher carbon from bituminous coal. Zhao
et al. [146] argued that UBC was not the only factor that con-
trolled mercury captured by fly ash, and there were obvious dif-
ferences in mercury retention capacities for various carbon forms.
The anisotropic carbon particles with porous network structure
had a good mercury capture effect. Based on the study of influence
of fly ash carbon type on mercury adsorption, Lopez-Anton et al.
[147] showed that the capture of different mercury species by fly
ashes was dependent on their nature and the type of anisotropic
particles. In addition, the oxygen functional groups formed on the
carbon surface are indicated to be responsible for mercury reten-
tion [148,149] while other researchers conclude there is no obvi-
ous relationship between them [150]. Jew et al. [151] found that
mercury was bound to the carboxylic acid functional groups in the
fly ash. By investigating the chemical forms of the fluorine, chlo-
rine, oxygen, and carbon in coal fly ash and their correlations with
mercury retention, Deng et al. [152] revealed that carbon-oxygen
complexes, such as C=O, OH/C–O, and (O–C=O)–O, on the surface
were significant for mercury capture on fly ash.
Mercury adsorption on unburned carbon can be explained by
the physical and chemical reactions between the carbon surface
and mercury. The unburned carbon surface may contain some ad-
sorption centers, called major active sites, which can adsorb some
molecules to act as a secondary canter for the adsorption of more
molecules [141]. The existence of halogens, such as Cl or Br, can
promote mercury oxidation/adsorption on the unburned carbon
surface. The heterogeneous Hg/Cl mechanism on unburned carbon
is proposed as reactions (17)–(24) [153].
StSA(s ) + HCl → StCl(s ) + H (17)
StCl(s ) + Cl → Cl2 + StSA(s ) (18)
StCl(s )Hg0 → StHgCl(s ) (19)
StCl(s ) + Hg0 → StSA(s ) + HgCl (20)
StCl(s ) + HgCl → StSA(s ) + HgCl2 (21)
StHgCl(s ) + HCl → StSA(s ) + HgCl2 + H (22)
 S. Zhao, D. Pudasainee and Y. Duan et al. / Progress in Energy and Combustion Science 73 (2019) 26–64
Fig. 10. Factors affecting Hg0 heterogeneous reaction on fly ash surface involving
unburned carbon.
StCl(s ) + HgCl2 → StHgCl(s ) + Cl2 (23)
StCl(s ) + H2 O → HCl + OH + StSA(s ) (24)
Where, StSA(s), StCl(s), and StHgCl(s) represent the unoccupied,
chlorinated, and Hgp site on the unburned carbon surface, respec-
tively. It can be found that the existence of HCl can form Cl active
site StCl(s) on the unburned carbon surface (17). On one hand, the
StCl(s) can react with Hg0 and HgCl2 to form Hgp . On the other
hand, it can react with Hg0 , HgCl, and H2 O to release the Cl ac-
tive site. Niksa et al. [154] also proposed the heterogeneous Hg/Br
reaction paths on unburned carbon surface, which were similar
to Hg/Cl on unburned carbon surface. The minor differences were
that Hg0 adsorption was faster on brominated sites, and higher
Br in flue gas accelerated the recombination reactions which kept
very low surface coverage of Hg/Br species.
In summary, the mercury heterogeneous reaction on fly ash in-
volving unburned carbon includes physical adsorption and chem-
ical reactions. The gaseous Hg0 and Hg2+ physically absorbed on
the surface can form Hg0 (ads) and Hg2+ (ads), which are the Hgp .
The surface structure characteristics, including particle size, surface
area, etc., affect the physical adsorption, which have a positive re-
lationship with UBC. On the other hand, the Hg0 (g) can react with
the active sites on the surface to generate Hg2+ (ads) and Hg2+ (g),
the active sites for which may be some certain unburned carbon
forms (anisotropic carbon particles), oxygen function groups (C=O,
OH/C–O, (O–C=O)–O), and halogens, etc. The factors affecting the
Hg0 heterogeneous reaction on the fly ash surface concerning un-
burned carbon are illustrated in Fig. 10.
4.3.3. Metal oxides in fly ash
In addition to unburned carbon, some metal oxides, such as
Fe2 O3 , CuO, Al2 O3 , and TiO2 , etc., in fly ash are reported to ben-
efit Hg0 oxidation or adsorption [136,155–157]. Due to the ad-
vantages of easy accessibility, easy separation, nonsecondary pol-
lution, and a lower price than other sorbents, the iron oxides
in fly ash have gained significant attention. The normal range of
Fe2 O3 content in fly ash produced from different coal types is
10–40% (bituminous), 4–10% (subbituminous), and 4–15% (lignite),
respectively [141]. The amount of magnetospheres (mainly con-
sisting of magnetite (Fe3 O4 ), hematite (α -Fe2 O3 ), maghemite (γ -
Fe2 O3 ), Fe2+ -silicate, Fe3+ -silicate, FeSi, and others) presented in
fly ash from ESP of seven pulverized CFPPs of China is 1.5–11.5%
[158]. Bench-scale experiments showed that the α -Fe2 O3 and γ -
Fe2 O3 promoted Hg0 to Hg2+ and/or Hgp in the presence of HCl
and/or NOx in simulated coal combustion flue gas [159]. The inves-
tigation of NOx , α -Fe2 O3 , γ -Fe2 O3 , and HCl into actual coal-fired
flue gas on mercury transformation indicated that injection of NO2
and α -Fe2 O3 into Absaloka and Falkirt coal combustion flue gases
37
did not affect mercury speciation significantly, while γ -Fe2 O3 cat-
alyzed Hg2+ formation [159]. Zhang et al. [160] found that the two
crystalline forms of Fe2 O3 were beneficial for mercury capture, and
γ -Fe2 O3 was better than α -Fe2 O3 in Hg0 removal performance. In
addition, the mercury oxidation activity and capacity of α -Fe2 O3
and γ -Fe2 O3 increased after water treatment, which might be due
to the formation of Fe-OH groups. Li et al. [161] conducted ex-
periments to see the influence of magnetic grains separated from
fly ash, α -Fe2 O3 , and γ -Fe2 O3 on mercury distribution in flue gas.
They found that magnetic grains in fly ash could oxidize the mer-
cury, and the influence of γ -Fe2 O3 on mercury distribution was
higher than α -Fe2 O3 . Yang et al. [162] performed the Hg0 removal
capacities of magnetospheres from fly ash at a temperature range
of 10 0–40 0 °C, which revealed that the optimal Hg0 removal capac-
ity for magnetospheres was 250 °C with the main Hg0 adsorption
process occurring at a low reaction temperature (100 and 150 °C)
and the dominant Hg0 oxidation process happening at a high tem-
perature (20 0–40 0 °C). Based on these findings, it can be concluded
that iron oxides in fly ash can promote the oxidation and adsorp-
tion of Hg0 , which is affected by iron oxides types and reaction
temperature.
The Hg0 heterogeneous reaction mechanism on the Fe2 O3
surface in the presence of HCl has been investigated by some
researchers. Yang et al. [153] developed a detailed chemical
model containing the Hg0 homogeneous and heterogeneous mech-
anism to predict mercury oxidation in coal-fired flue gas, in
which the Hg0 heterogeneous model included the catalytic ef-
fects of Fe2 O3 within fly ash. The sensitivity analysis showed that
Hg0 → FeHgCl(s) → HgCl2 was the main channel of mercury hetero-
geneous oxidation by HCl on the Fe2 O3 surface. Moreover, Yang
et al. [163] used the experimental method to confirm that Hg0 het-
erogeneous oxidation by HCl over the Fe2 O3 surface occurred by
the gas-solid reaction between gaseous Hg0 and active adsorbed
Cl species produced from HCl dissociation. The mercury oxidation
over Fe2 O3 in the presence of HCl was described by Yang et al.
[163] through the eight-step heterogeneous reaction kinetic model,
shown in reactions (25)–(32). Jung et al. [164] used density func-
tional theory (DFT) to theoretically investigate the interaction be-
tween mercury and α -Fe2 O3 , results of which showed Cl played a
vital role in mercury adsorption onto α -Fe2 O3 . It was consistent
with experimental results, finding the relationship of Hg-Fe-Cl ex-
isted in fly ash. Liu et al. [57] adopted the DFT and experimen-
tal methods to study the Hg0 adsorption mechanism on α -Fe2 O3
(001) surface in the existence of HCl, which found that the reac-
tion followed the Eley−Rideal mechanism with HCl pre-adsorption,
showing good agreement with that of Yang et al. [163]. Further-
more, Liu et al. [165] also used the bench-scale fixed bed reactor
to investigate Hg0 oxidation over α -Fe2 O3 and γ -Fe2 O3 samples
in the presence of HCl, which considered the wide reaction tem-
perature range of 80–680 °C. It was reported that the Hg0 removal
mechanism with HCl and Fe2 O3 could be divided into three stages
based on the reaction temperature. At low temperatures (80–
280 °C), the most probable Hg0 oxidation path was the Eley-Rideal
mechanism with HCl pre-adsorption, shown in Fig. 11(a). For tem-
peratures of 280–580 °C, Hg0 removal efficiency by α -Fe2 O3 and
γ -Fe2 O3 was different with the suitable Langmuir–Hinshelwood
mechanism, which was the reaction of adsorbed HCl and Hg0 on
the Fe2 O3 surface to generate most probable HgCl2 (s, g), shown
in Fig. 11(b). For temperatures higher than 680 °C, both the ho-
mogenous reaction of Hg0 and HCl and the Langmuir–Hinshelwood
mechanism were responsible for Hg0 transformation.
Fe(s ) + HCl → FeCl(s ) + H (25)
FeCl(s ) → Fe(s ) + Cl (26)
FeCl(s ) + Cl → Cl2 + Fe(s ) (27)
38 S. Zhao, D. Pudasainee and Y. Duan et al. / Progress in Energy and Combustion Science 73 (2019) 26–64
Fig. 11. Hg0 oxidation mechanism with HCl on Fe2 O3 surface [165]. Reprinted with permission from Elsevier, 2016.
FeCl(s ) + Hg0 → FeHgCl(s )
FeCl(s ) + Hg0 → Fe(s ) + HgCl
FeCl(s ) + HgCl → Fe(s ) + HgCl2
FeHgCl(s ) + HCl → Fe(s ) + HgCl2 + H
FeCl(s ) + HgCl2 → FeHgCl(s ) + Cl2
4.3.4. Flue gas components
Flue gas components can also affect the Hg0 heterogeneous
reaction with fly ash [78,139]. Based on the stepwise regres-
sion analysis [117], it is reported that chlorine promotes mercury
chemisorption onto fly ash while sulfur inhibits adsorption of oxi-
dized mercury onto fly ash. At a typical flue gas temperature, SO2
inhibits fly ash-induced Hg0 removal slightly while NO has a posi-
tive effect with the help of Br2 in the simulated flue gas [166]. For
actual flue gas conditions, injection of HBr will enhance mercury
capture by Powder River Basin (PRB) fly ash in a low temperature
range [167]. The overall influence of NO2 on mercury oxidation
with the presence of fly ash is greater than that of Cl generating
from HCl by the Deacon reaction [126]. The results from mercury
retention by fly ash or fractions of fly ash enriched in unburned
carbon particles conducted in a fixed bed with a reaction tem-
perature of 120 °C indicated that SO2 might block the active sites
on the fly ash surface for a reduction in mercury retention while
HCl bound to the fly ash surface favored the retention of mercury
[168]. The mercury oxidation by fly ash in N2 , air, and HCl, respec-
tively, showed that fly ash catalyzed Hg0 oxidation and the more
stable mercury compounds bound to fly ash occurred in the HCl at-
mosphere [169]. The high H2 O concentration in flue gas has the in-
hibitive influence on mercury oxidation by fly ash [153]. Moreover,
the active sites on fly ash for the Hg0 heterogeneous reaction were
proposed by Zhao et al. [169], which were low-binding-energy cat-
alytic oxidation active sites, catalytic oxidation active sites, adsorp-
tion active sites, and high-binding-energy adsorption active sites,
respectively.
Compared to the mercury homogenous reaction, the heteroge-
neous reaction mechanism among fly ash, flue gas components,
and mercury is complicated. Based on published studies, the works
for the mercury heterogeneous reaction mainly focus on the phys-
ical structure properties of fly ash, unburned carbon, and Fe2 O3 ,
while the influence of flue gas components (including NH3 , etc.)
and wide reaction temperature ranges for the fly ash on mercury
oxidation or adsorption has rarely been investigated. Mercury het-
erogeneous reaction needs further study.
(28)
(29)
(30)
(31)
(32)
Fig. 12. System diagram of the oxy-coal combustion technology (cited from Zhuang
et al. [176]). Reprinted with permission from American Chemical Society, 2012.
4.4. Oxy-coal combustion
4.4.1. Definition and characteristics of oxy-coal combustion
Greenhouse gas emissions are now known to be a serious en-
vironmental problem, in which CO2 has caused widespread con-
cern. The amount of CO2 emissions from electricity production all
over the world is mainly from CFPPs [170]. There are three main
ways to capture CO2 from coal combustion: pre-combustion cap-
ture, oxy-coal combustion, and post-combustion capture [171,172].
The oxy-coal combustion technology, considered to be a promis-
ing technology for CO2 capture, uses pure O2 (about 95–98%) and
recycled flue gas for coal burning. The main flue gas components
for the oxy-coal combustion are CO2 and H2 O, which can realize
the separation and storage of CO2 [170,173]. The recycled flue gas
can be extracted from an outlet of the ESP or WFGD, and the non-
recycled flue gas is cleaned by the APCDs, which will be purified
for CO2 storage. This technology has the advantages of easy CO2
capture, being easily established in the existing CFPPs, and low in-
vestment, etc. [173–175]. The system diagram of the oxy-coal com-
bustion technology is shown in Fig. 12 [176].
The gas components between air-coal and oxy-coal combustion
are shown in Table 5 [177]. It shows that the concentration of CO2
and H2 O in the outlet flue gas for oxy-coal combustion is higher
than that for air-coal combustion. Compared to air-coal combus-
tion, content of CO and SO2 is also higher while that of NOx is
lower under oxy-coal combustion [170,178,179]. Due to the low flue
gas volume and flue gas circulation, the fly ash concentration in
oxy-coal combustion flue gas is about 1.5-times greater than that
in air-coal combustion flue gas [177]. Moreover, the Cl content and
 S. Zhao, D. Pudasainee and Y. Duan et al. / Progress in Energy and Combustion Science 73 (2019) 26–64
Table 5
Gas components between air-coal and oxy-coal combustion [177].
Item Gaseous species
Inlet - wind box O2
N2
CO2
H2 O
Others
Outlet - Flue Gas O2
N2
CO2
H2 O
Total sulfur concentration (SO2 , H2 S, COS)
Total nitrogen concentration (NO, NO2 ,
NH3 , HCN, etc.)
Fig. 13. Mercury emission from coal combustion under different atmosphere on the
10 kWth bubbling fluidized bed [186]. Reprinted with permission from American
Chemical Society, 2014.
UBC in fly ash under oxy-coal combustion conditions are higher
than those under the air-coal combustion atmosphere. The inlet
SO2 concentration and NO can significantly affect SO3 formation,
while SOx will be adsorbed by some metal oxides of fly ash in oxy-
coal combustion [180–182]. These characteristics result in different
fly ash properties between the air-coal and oxy-coal combustion.
Mercury emitted from oxy-coal combustion not only causes envi-
ronmental pollution but can also be retained at the inner of CO2
compressor [183]. In addition, mercury can damage aluminum heat
exchangers, which is dangerous for CO2 separation and capture.
Thus, knowing the emission and transformation of mercury during
oxy-coal combustion is a vital step for its removal from oxy-coal
combustion flue gas.
4.4.2. Mercury emission from oxy-coal combustion
The studies on mercury emission from oxy-coal combustion has
been conducted by several researchers in different reactors, which
include drop tube furnace, bubbling fluidized bed, circulating flu-
idized bed (CFB), and pulverized coal furnace with input heat from
6 kWth to 35 MWth [176,183–191]. Wang et al. [184] conducted the
air-coal and oxy-coal combustion of two kinds of coal on a 6 kWth
CFB, the results of which showed that Hg2+ concentration under
oxy-coal combustion was lower than that under air-coal combus-
tion. The higher percentage of Hg2+ under oxy-coal combustion
was found in the experiments on a 50 kWth CFB [185]. The mer-
cury emission from coal combustion under a different atmosphere
on the 10 kWth bubbling fluidized bed is shown in Fig. 13 [186].
Total gaseous mercury (Hgg , total Hgg = Hg2+ + Hg0 ) concentration
under oxy-coal combustion (26 μg/Nm3 ) was higher than that un-
der air-coal combustion (20 μg/Nm3 ). In addition, there was a lager
39
Air-coal combustion (wet basis) Oxy-coal combustion (wet basis)
21 vol% 21–30 vol%
79 vol% (0)−10 vol%
0 vol% 40–50 vol%
Small 10–20 vol%
NOx , SOx ,
3–vol% 3–4 vol%
70–75 vol% (0)–10 vol%
12–14 vol% 60–70 vol%
10–15 vol% 20–25 vol%
10 0–20 0 0 ppmv 60 0–180 0 ppmv (black coal)
30 0–90 0 ppmv (brown coal)
100–1000 ppmv 30 0–70 0 ppmv (black coal) 10 0–20 0 ppmv
(brown coal)
Hg0 percentage (73%) under oxy-coal combustion compared to that
(69%) under air-coal combustion, which was different from the re-
sults of Wang et al. [185]. The investigation of air-coal and oxy-coal
combustion in a 20 kWth drop-tube furnace indicated that the ra-
tio of Hg2+ to total Hgg and total Hgg concentration were higher
under oxy-coal combustion [187,188]. Zhuang and Pavlish [176] and
Yang et al. [191] found that mercury concentration at the ESP inlet
in oxy-coal combustion was about two times of that under air-coal
combustion conditions based on the experiments in a 173.5 kWth
and 35 MWth pulverized coal furnace, which might be due to the
accumulative effect of flue gas recycling and the reduction in gas
volume in the oxy-coal combustion process. The transformation
from Hgg to Hgp and Hg0 to Hg2+ is promoted under the oxy-coal
combustion, which is ascribed to continuous reactions of mercury
with enriched HCl, unburned carbon, and other flue gas compo-
nents [176]. Mitsui et al. [183], using data from the 1.5 MWth Com-
bustion & Air Quality Control System (AQCS) test facility, indicated
that mercury concentration at the SCR inlet in oxy-coal combustion
was more than that in air-coal combustion. Experiments on the
Callide Oxy-fuel Project (20 MWth oxy-PCC demonstration plant)
showed that Hg2+ was the main form in the flue gas after the cy-
clone (68%) or the stack (99% or 89%) [189,190].
Based on these results, it can be found that total Hgg concentra-
tion is higher for oxy-coal combustion than that for air-coal com-
bustion. However, there is still a disagreement in the proportion of
Hg2+ to total Hgg . In addition, mercury emission data from oxy-
coal combustion is sparse, especially the concentration and distri-
bution of various mercury species, mercury removal efficiencies by
each APCD, etc.
4.4.3. Mercury transformation under oxy-coal combustion
Mercury transformation concerning homogeneous (without fly
ash) and heterogeneous (with fly ash) reaction under oxy-coal
combustion has been investigated by various studies. For the mer-
cury homogeneous reaction, O2 in the oxy-coal simulated flue gas
is found to promote the reaction between Hg and Cl2 , while NO
limits that reaction by consuming O and ClO radicals at a simu-
lated flue gas temperature of 200 °C [178]. About 15% of total mer-
cury is oxidized when Hg0 is in an atmosphere of NO and N2 . The
co-existence of CO2 and O2 can lead to an increase in mercury ox-
idation, which has no relation with CO2 concentration [179]. The
existence of H2 O in oxy-coal combustion benefits mercury oxida-
tion (25–45%) compared to the dry atmosphere (9%) of 10 0 0 ppmv
SO2 , 10 0 0 ppmv NO, 100 ppmv NO2 , 25 ppmv HCl, 4% O2 , 56–70%
CO2 , and N2 at a temperature of 150 °C [179]. Wu et al. [192] con-
ducted experimental tests on Hg0 homogenous oxidation by Cl2 ,
HCl, NO, and SO2 under simulated O2 /N2 and O2 /CO2 atmospheres
at temperatures of 20 0–10 0 0 °C. It was confirmed that high CO2
concentration did not benefit Hg0 oxidation by Cl2 compared to N2
atmosphere. Moreover, the oxidation of SO2 on Hg0 under O2 /CO2
40 S. Zhao, D. Pudasainee and Y. Duan et al. / Progress in Energy and Combustion Science 73 (2019) 26–64
atmosphere was lower than that under O2 /N2 atmosphere, which
was because that conversion of SO2 to SO3 could eliminate O and
OH radicals (very important reactants for producing the main Hg0
oxidant, such as Cl and HOCl). The high H2 O concentration in oxy-
coal combustion inhibited Hg0 oxidation in the atmosphere of 6%
O2 , 15-, 30-, 60-, and 120-ppmv HCl; 0%, 5%, 10%, 20%, 30%, and
40% H2 O; and equilibrium gas CO2 at 900 °C, which might be due
to reaction (33) [193]. The addition of SO2 in the simulated oxy-
coal combustion flue gas also reduced Hg0 oxidation by reaction
(34). For the homogeneous mercury oxidation under air-coal and
oxy-coal (27% O2 in CO2 ) firing conditions conducted in a lam-
inar, methane-fired, bench-scale, quartz-lined reactor, Hg0 oxida-
tion by HCl under oxy-firing conditions was higher than that un-
der air combustion. The addition of NO (less than 300 ppmv) and
SO2 (less than 400 ppmv) had little or no influence on the Hg0 ox-
idation by chlorine under both firing conditions [123]. Wang et al.
[194] showed that an increase in H2 O concentration would inhibit
Hg0 oxidation by chlorine. More mercury oxidation in the atmo-
sphere of NO, CO2 , and O2 could be found compared to that with-
out CO2 , which was due to the high proportion of NO2 production
with the presence of CO2 . Meanwhile, the existence of 500-ppmv
SO2 could cause mercury oxidation owing to a dramatic decrease
in the atmosphere of 27% O2 /CO2 by the consumption of O or OH
radicals shown in reactions (35)–(37).
2H2 O + Cl2 → 4HCl + O2
Cl2 + SO2 + H2 O → 2HCl + SO3
SO2 + O + M → SO3 + M
SO2 + OH → SO3 + H
HgO(g ) + SO2 + 1/2O2 → HgSO4
Based on these works, the following summary for the mercury
homogenous transformation under the oxy-coal combustion can be
drawn: (1) O2 promotes Hg0 oxidation with Cl2 while NO and CO2
inhibit or do not favor that reaction; (2) CO2 increases the Hg0 ox-
idation in NO and N2 atmospheres; (3) SO2 limits Hg0 oxidation
while HCl has a higher oxidation effect on Hg0 than that under
air-coal combustion conditions; and (4) the effect of H2 O on Hg0
oxidation has not come to an agreement yet, which may be re-
lated to the flue gas temperature or flue gas components. In ad-
dition, most explanations for the effects of flue gas components
on mercury transformation in the oxy-coal combustion atmosphere
are only speculation without credible evidence. The mercury ho-
mogeneous transformation models under oxy-coal combustion are
sparse, which is important for the prediction of mercury species.
For the mercury heterogeneous transformation, fly ash is con-
sidered to be a main pathway for Hg0 oxidation under oxy-coal
combustion conditions. The work on a fixed-bed experimental rig
showed that SO3 reduced mercury adsorption on fly ash, while
mercury capture by fly ash decreased as temperature increased
[195]. In the simulated oxy-coal combustion flue gas (30% H2 O,
6% O2 , 60-ppmv HCl, and 700 °C), the Hg0 oxidation rate increased
from 37% (without fly ash) to 80% (with fly ash), which indicated
that fly ash had a significant promotional role on Hg0 oxidation.
This may be due to many active sites on unburned carbon surface
in fly ash, which not only benefit the conversion of HCl to oxida-
tive Cl but also provide possible favorable sites for Hg0 oxidation
[193]. Izquierdo et al. [196] found that the increase of O2 under ac-
tual oxy-coal combustion conditions had little effect on the relative
partition between Hgp and Hgg , from the results in a 3 kWth bub-
bling fluidized bed combustor. Combining the mercury adsorption
and desorption experiments under a simulated oxy-coal combus-
tion flue gas atmosphere, organic mercury, and HgS were the main
mercury species in fly ash. In addition, mercury TPD analysis indi-
cated mercury retention by fly ash was mainly by the carbon [197].
Release behavior of mercury in a 10 kWth fluidized bed combustor
under a different atmosphere showed that mercury retained in fly
ash decreased by 44% as the O2 concentration increased from 15%
to 30%, which might be ascribed to O2 -promoted Hg0 evaporation
[198]. This differs from the findings of Izquierdo et al. [196]. How-
ever, the addition of H2 O favored mercury adsorption by fly ash,
which was caused by the generation of some active sites via reac-
tion between H2 O and carbon-oxygen complexes or changes of the
surface conditions [198].
Based on the literature review, mercury heterogeneous trans-
formation in the oxy-coal combustion atmosphere can be summa-
rized: (1) fly ash plays an important role for Hg0 oxidation; (2) SO3
inhibits mercury retention by fly ash while H2 O promotes this phe-
nomenon; and (3) there is no agreement in distribution between
Hgp and Hgg affected by O2 . In fact, little work has been conducted
on the mercury heterogeneous transformation with fly ash under
oxy-coal combustion conditions. Further works should include the
following: (1) difference in characteristics of fly ash between the
air-coal and oxy-coal combustion atmosphere, such as physical sur-
face structure, chemical composition, and mercury compounds in
fly ash; (2) effects of typical flue gas components on mercury re-
action by fly ash in a wide temperature range; and (3) establish-
ment of models of mercury heterogeneous transformation, which
(33)
helps in the development of mercury prediction in actual oxy-coal
combustion flue gas.
(34)
(35) 5. Sampling, co-removal, and emission of mercury in coal-fired
power plants
(36)
5.1. On-site mercury sampling methods
(37)
There are three main methods to sample mercury in flue gas
in CFPPs, namely, the wet-chemistry method based on the OHM,
the sorbent-trap method based on the US Environmental Protec-
tion Agency (US EPA) Method 30B, and the mercury-continuous
emission monitoring system (Hg-CEMS) [199], all of which are de-
scribed in detail as follows.
5.1.1. Ontario Hydro Method
The Ontario Hydro Method (OHM), the internationally recog-
nized method for flue gas mercury sampling in CFPPs, uses chem-
ical solutions to selectively adsorb Hgg . It can also separate Hgp
from Hgg and determine specific Hgg species (namely Hg0 and
Hg2+ ) [200,201]. The schematic diagram of the OHM mercury sam-
pling device is shown in Fig. 14 [86]. It mainly consists of a
Fig. 14. Schematic diagram of the OHM mercury sampling device [86]. Reprinted
with permission from Elsevier, 2017.
 S. Zhao, D. Pudasainee and Y. Duan et al. / Progress in Energy and Combustion Science 73 (2019) 26–64
sampling probe, glass filter, impinger box, vacuum line, pump, and
a metering console. During sampling, mercury in flue gas is with-
drawn isokinetically via the probe and the filter with the tem-
perature maintained at 120 °C, followed by a series of impingers
in an ice bath. The Hgp is collected at the filter in the form of
particle. The first three impingers containing 1.0 mol/L KCl solu-
tion are used to adsorb Hg2+ , while the fourth impinge with 5%
(V/V) HNO3 ·10% (V/V) H2 O2 solution and last three impingers with
4% (w/V) KMnO4 ·10% (V/V) H2 SO4 solution are used for Hg0 cap-
ture. The mercury in fly ash and absorbing solution can be de-
termined by the relevant mercury analyzer, and the concentra-
tion of each mercury species in flue gas can be calculated by the
data of mercury analysis value, fly ash mass, flue gas volume, and
the volume related with absorbing solution. To ensure accuracy of
the test data, OHM requires that relative standard deviation (RSD)
should be less than 34% when mercury concentration is lower than
3 μg/m3 . Otherwise, the RSD should be less than 11% if mercury
concentration is higher than 3 μg/m3 [46].
5.1.2. US EPA Method 30B
The US EPA Method 30B uses solid mercury adsorbent to cap-
ture mercury in flue gas, which can adsorb the total Hgg or spe-
cific mercury species (Hg0 and Hg2+ ) based on the adsorbent type.
The schematic diagrams of US EPA Method 30B for Hgg and spe-
cific mercury species are shown in Fig. 15(a) [202] and Fig. 15(b)
[203], respectively. In general, the activated carbon (AC) modified
by halogens acts as the adsorbent to adsorb total gaseous mercury,
while the oxidized mercury is adsorbed by a special adsorbent.
From Fig. 15(a) and (b), it can be seen that there are two identi-
cal adsorbents in the trap for mercury adsorption, where the front
part is called mercury collection and the latter is called mercury
breakthrough. To ensure the accuracy of mercury data sampled by
this method, the breakthrough rate (BR) and relative deviation (RD)
are selected as the main parameters for quality control based on
quality assurance and quality control (QA/QC) criteria [204,205],
which requires that BR and RD should be no more than 10% if
total Hgg concentration is higher than 1 μg/m3 while the values
should be no more than 20% when the total Hgg concentration is
lower than 1 μg/m3 . The expressions of BR and RD are shown as
Eqs. (1a)–(5a) [202,203].
m2
BRHg(g) = × 100%
m1
m4
BRHg(2+) = × 100%
m3
m6
BRHg(0 ) = × 100%
m5
|COHM − C30B |
RD30B−OHM = × 100%
COHM
|C30B1 − C30B2 |
RD30B = × 100%
C30B1 + C30B2
where, BRHg(g) , BRHg(2+) , and BRHg(0) present the breakthrough rate
of Hgg , Hg2+ , and Hg0 , respectively, in %. m2 , m4 , and m6 rep-
resent the mercury mass in the second section of corresponding
adsorbents for Hgg , Hg2+ , and Hg0 , respectively, in μg; and m1 ,
m3 , and m5 represent the mercury mass in the first section, in
μg. RD30B-OHM represents the relative deviation between the total
Hgg concentrations determined by US EPA Method 30B and OHM,
in %. COHM and C30B represent the total Hgg concentration deter-
mined by OHM and US EPA 30B, respectively, in μg/m3 . RD30B rep-
resents the relative deviation between total Hgg concentrations de-
termined by the paired sorbent traps applied in the same sampling
situation, in %. C30B1 and C30B2 represent the total Hgg concentra-
tion determined by the paired sorbent traps, respectively, in μg/m3 .
41
5.1.3. Mercury-continuous emission monitoring system
The mercury continuous emission monitoring system (Hg-
CEMS) can monitor the real-time concentration of different Hgg ,
including Hgg , Hg2+ , and total Hgg . It is mainly composed of pre-
treatment/conversion unit and analysis unit, the schematic dia-
gram of which is shown in Fig. 16. At present, the mercury an-
alyzer can only determine the Hg0 concentration. Thus, Hg2+ in
flue gas should be firstly transformed into Hg0 , and then be deter-
mined. There are two ways to transform Hg2+ into Hg0 , which are
(1) wet chemical reduction method using SnCl2 solution, and (2)
high-temperature catalyst or high-temperature heating conversion
method.
5.1.4. Comparison of OHM, US EPA Method 30B, and Hg-CEMS
The OHM, which has been accepted as a standard mercury sam-
pling method worldwide, can determine Hgp , Hg0 , and Hg2+ in the
flue gas. The data from this method is usually used to check the ac-
curacy of data from US EPA Method 30B and Hg-CEMS. However, it
needs a long mercury sampling time (about 2–3 h) and larger flue
gas volume (about 1–2.5 m3 , dry flue gas) for each time of mercury
sampling. OHM can not give the real-time mercury concentration.
In addition, the mercury sampling operation is complicated and
needs a significant number of chemical solutions and skilled oper-
ators. It is reported that Cl2 in flue gas can form hypochlorite ion
in KCl solution, which can oxidize a certain amount of Hg0 to Hg2+
in the solution [206]. The experiments of Linak et al. [207] showed
that the low concentration of 1-ppm Cl2 in a simulated flue gas
mixture resulted in a bias of 10–20% of Hg0 misreported as Hg2+
for the OHM. The existence of SO2 in flue gas or the addition of
Na2 S2 O3 can inhibit the oxidation in the solution [208,209]. In fact,
the existence of SO2 in actual coal combustion flue gas eliminates
this bias of mercury speciation measurements, but it might be a
problem for the few combustor or research works where Cl2 is
present with little SO2 [207]. The obtained mercury concentration
in flue gas is affected by the sampling operation, purity of chemi-
cal solutions, error in recovery, and digestion of the absorption so-
lution, etc.
Compared to the OHM, the sampling operation of US EPA
Method 30B, which uses mercury adsorbent traps instead of the
absorption solution in OHM, is simpler. It saves the time and cost
for preparation, recovery, and digestion of the absorption solution.
(1a)
For US EPA Method 30B, the mercury sampling needs about 1–3 h
with a flue gas volume of 20–100 L; it cannot monitor the online
(2a) mercury concentration. Generally, it cannot determine Hgp in flue
gas without collection of fly ash. Moreover, the flue gas compo-
nent, such as high SO2 or NOx concentration, will affect the accu-
(3a) racy of the data. Thus, the method is usually applied at the outlet
of FGD. The types of mercury adsorbent and adsorption efficiency
are other factors that influence the accuracy of the data.
(4a)
With implementation of the increasingly strict emission stan-
dards for mercury from coal-fired flue gas, Hg-CEMS is encour-
(5a) aged to be installed in CFPPs. Different from OHM and US EPA
Method 30B, the Hg-CEMS can give the real-time mercury emis-
sion concentration, which is very important for providing immedi-
ate feedback for boiler operation and applied removal technology
concerning mercury concentration. However, it can not determine
Hgp concentration. In addition, Hg-CEMS involves high purchase
and maintenance costs, as well as periodic calibration tests. The
comparison of OHM, US EPA Method 30B, and Hg-CEMS is shown
in Table 6.
5.2. Co-removal efficiencies across air pollution control devices
With more stringent emission limits on air pollutants from coal
combustion, the install share of APCDs, such as SCR equipment,
ESP or FF, WFGD device, even wet electrostatic precipitator (WESP),
42 S. Zhao, D. Pudasainee and Y. Duan et al. / Progress in Energy and Combustion Science 73 (2019) 26–64

Fig. 15. (a) Schematic diagram of US EPA Method 30B for total gas mercury [202]. Reprinted with permission from Elsevier, 2017. (b) Schematic diagram of US EPA Method
30B for specific mercury species [203]. Reprinted with permission from Elsevier, 2018.

used for removal of NOx, PM, SO2 , and fine PM has increased in
CFPPs. Taking China as an example, almost 90% of CFPPs have been
equipped with ESP, while the rest have ESP+FF [2]. By the end of
2007, the installed capacity of SO2 removal devices in total thermal
power unit capacity was more than 50% with little share of SCR
[210]. However, the installed capacity of SO2 control devices and
SCR equipments has accounted for 93.0% of total coal-fired gener-
ating unit capacity and 85.8% of the total thermal power unit ca-
pacity, respectively, by the end of 2016 [211]. It has been confirmed
that these APCDs have a co-removal effect on mercury emission
 S. Zhao, D. Pudasainee and Y. Duan et al. / Progress in Energy and Combustion Science 73 (2019) 26–64 43

Table 6
Comparison of OHM, US EPA Method 30B, and Hg-CEMS.

On-site Hg sampling method Advantages Disadvantages

OHM (1) Standard method; (1) No real-time monitoring;

(2) Good accuracy; (2) Complicated sampling operation;
(3) Determine HgP , Hg2+ , Hg0 ; (3) Lots of chemical solutions;
(4) Adapt to various environments. (4) Need skilled operators.
US EPA Method 30B (1) Method is simple; (1) No real-time monitoring;
(2) Save time and cost; (2) No Hgp ;
(3) Determine Hgg or Hg2+ , Hg0 . (3) Affected by flue gas components and adsorbent quality.
Hg-CEMS (1) Real-time monitoring. (1) High purchase and maintenance costs;
(2) Periodic calibration tests;
(3) No Hgp .

Hgp out,ESP , Hg2+ out,WFGD , and Hgt out,APCDs represent the concentra-
tion of Hg0 , Hgp , Hg2+ , and Hgt in flue gas at the outlet of SCR,
ESP, WFGD, and APCDs, respectively, in μg/m3 ; Hgt represents the
total mercury, Hgt = Hg0 + Hg2+ + Hgp . APCDs represent the ESP,
ESP+WFGD, SCR+ESP+WFGD, SCR+(ESP+FF)+WFGD, etc.
The transformation process of mercury in flue gas across the
APCDs in CFPPs is shown in Fig. 17.

5.2.1. Selective catalytic reduction

SCR equipment is used for NOx removal from coal combustion
in CFPPs, which uses NH3 as a reducing agent. The SCR catalysts
are mainly composed of V2 O5 , WO3 , TiO2 with a working temper-
ature of 30 0–40 0 °C [240]. Field tests on mercury concentration in
flue gas at the inlet and outlet of SCR have shown that the SCR
device also has a co-effect on Hg0 oxidation [241]. It is confirmed
that active Cl is the oxidizer for Hg0 oxidation on the SCR cata-
lyst surface. Hg-Cl and NO–NH3 redox reactions occur on the active
sites of SCR catalysts simultaneously [240]. Some mechanisms have
Fig. 16. Schematic diagram of the Hg-CEMS.
been proposed to elaborate the Hg0 oxidation process across SCR
catalysts. These mechanisms include: (1) HCl is firstly absorbed on
the catalysts to produce active sites and then react with gaseous
control. Though some papers [7,212] have summarized mercury co- or weakly bound Hg0 [242]; (2) the Eley-Rideal reaction, which in-
removal efficiencies by various APCDs in CFPPs, the data is mainly volves Cl compounds as intermediates [243,244]; and (3) hetero-
from China. It should be updated in light of the large installa- geneous reactions, which obey the Langmuir-Hinshelwood mecha-
tion share and many new APCDs combination types at present. In nism [245]. The detailed Hg0 oxidation mechanism across SCR cat-
this section, the field-test data of mercury co-removal efficiencies alysts needs further study, and it can be studied by a combination
across APCDs, mercury emission concentration in flue gas to the of experiments and theoretical calculation.
atmosphere, and mercury content in coal CBPs in CFPPs is collected Under the actual operation conditions in CFPPs, Hg0 oxidation
from almost all the papers published from 20 0 0 to 2018 around by SCR device can be affected by flue gas components, boiler load,
the world, as shown in Tables S1 and S2 in Supplementary ma- SCR space velocity, SCR catalyst structure, and service time of the
terial [85,86,199,213–239]. The Hg0 oxidation rate across SCR and catalysts.
mercury removal rate across the APCDs in Tables S1 and S2 are (1) Flue gas components: Increasing HCl content in flue gas pro-
defined as Eqs. (6a)–(9a). motes Hg0 oxidation, while increasing the NH3 /NO ratio at
H g0in,SCR − H g0out,SCR SCR inlet reduces Hg0 oxidation [243]. In addition, the in-
ηHg(0),oxi = × 100% (6a) teractions of O2 , CO, SOx , NH3 , H2 O, etc. may play a role on
Hg0in,SCR
Hg0 oxidation.
p
H gin,ESP p
− H gout,ESP (2) Boiler load: Decreasing boiler load increases Hg0 oxidation
ηHg( p),ESP = p × 100% (7a) [246]. In fact, the boiler load has a relationship with the flue
Hgin,ESP gas temperature, and decreasing flue gas temperature ben-
efits Hg0 oxidation. Studies observed that the mercury oxi-
H g2+ − H g2+
ηHg(2+),W F GD = in,W F GD out,W F GD
× 100% (8a) dation rate increased from 50% at 410 °C to 78% at 290 °C in
Hg2+
in,W F GD a flue gas atmosphere with 10-ppmv HCl while it increased
from 8% at 320 °C to 43% at 260 °C in a flue gas of 0.3-ppmv
H gtin,APCD − H gtout,APCD HCl, 70-ppmv SO2 , 400-pmv NO, and 300-ppmv NH3 [113].
ηHg(t ),APCDs = × 100% (9a)
(3) SCR space velocity: Increasing space velocity decreases Hg0
Hgtin,APCD
oxidation by SCR [247].
Where, ηHg(0),oxi represents the Hg0 oxidation rate across SCR, (4) SCR catalyst structure: The different structures of SCR cat-
in %; ηHg(p),ESP , ηHg(2+), WFGD , and ηHg(t),APCDs represent the removal alysts have various specific surface areas. The honey-comb
rate of Hgp , Hg2+ , Hgt across ESP, WFGD and APCDs, respectively, structure generally has higher Hg0 oxidation efficiency than
in %; Hg0 in,SCR , Hgp in,ESP , Hg2+ in,WFGD , and Hgt in,APCDs represent the the plate type [248].
concentration of Hg0 , Hgp , Hg2+ and Hgt in flue gas at the inlet (5) Service time of the catalysts: A long service time of the cat-
of SCR, ESP, WFGD and APCDs, respectively, in μg/m3 ; Hg0 out,SCR , alysts decreases Hg0 oxidation ability [246].
44 S. Zhao, D. Pudasainee and Y. Duan et al. / Progress in Energy and Combustion Science 73 (2019) 26–64
Fig. 17. Transformation process of mercury in flue gas across the APCDs in CFPPs, modified on Ref. [220]. Reprinted with permission from American Chemical Society, 2017.
To evaluate the effects of SCR device on Hg0 oxidation, the Hg0
oxidation rate is adopted. Based on the data in Table S1, the Hg0
oxidation rate across SCR device in CFPPs is in the range of 6.5–
79.9%.
5.2.2. Electrostatic precipitator and fabric filter
The ESP and FF are good at capturing Hgp in flue gas, benefit-
ing from the higher PM removal efficiency (>99%). With flue gas
cooling, some parts of Hg0 and Hg2+ will be adsorbed on fly ash
to generate Hgp , and Hg0 will react with fly ash to produce Hg2+
or Hgp . Compared to ESP, FF has a higher PM removal ability, espe-
cially for fine PM. Thus, the mercury removal rate for FF is higher
than that for ESP, which can be found in Zhang et al. [225] (ESP-
11.5%, FF-52.3%), Cui et al. [199] (ESP-68.3%, FF-70.0–71.6%), and
Tian et al. [237] (ESP-33.17%, FF-67.92%) in Table S1.
The mercury removal rate across ESP or FF is influenced by
flue gas temperature, mercury species in flue gas, fly ash compo-
nents (unburned carbon and metal oxides), capture ability of ESP
or FF for PM, etc. [221]. According to the data in Table S1, the Hgt
removal rate for ESP and FF is 11.5–90.4% and 28.5–90%, respec-
tively. Wang et al. [249] summarized that average Hgt removal rate
for ESP in China, the US, South Korea, and Japan was 22%, 36%,
59%, and 52%, respectively. In addition, Sung et al. [233] found
that more Hg2+ was generated when flue gas passed through FF,
compared to ESP, which benefited its removal by WFGD. Under
the same conditions, installing FF between ESP and WFGD made
mercury removal efficiency across the whole APCDs increase from
62.44% to 86.73%.
5.2.3. Wet flue gas desulfurization
The WFGD device is installed to removal SO2 in flue gas in CF-
PPs, which usually uses the limestone-gypsum method. In addi-
tion, fine PM can also be captured by the WFGD device. Due to
high water-solubility of Hg2+ in flue gas, WFGD device has high
co-capture ability. Based on the data in Table S1, the Hg2+ removal
rate across WFGD device is in the range of 83.45–94.53%. How-
ever, in some cases the Hg0 re-emission occurs during the Hg2+
removal process in the WFGD device, which is thought to be ex-
plained by two reasons [229,86]: (1) Hg2+ and Hg0 in flue gas can
generate Hg2 2+ on the water layer on the external surface of desul-
furizer. Then, Hg2 2+ reacts with OH− in seriflux to generate Hg0
and HgO. SO2 in flue gas can reduce HgO to form Hg0 . This is de-
scribed by reactions (38)–(40); (2) Hg2+ dissolved in scrubber so-
lution can react with sulfite and sulfate to form HgSO3 and HgSO4 ,
in which sulfite and sulfate are from SO2 dissolving in scrubber
solution. A portion of HgSO3 and HgSO4 may further participate in
some reactions to release Hg0 . This is described as reactions (41)–
(42). Moreover, the Hg0 re-emission is affected by the operating
temperature, pH, O2 concentration in flue gas, transitional metal
ions concentration, etc. It is found that high availability of excess
oxygen in the flue gas contacting with the desulfurization solution
leads to the lower reduction of Hg2+ to Hg0 while decreasing the
slurry pH or increasing the operating temperature enhances Hg0
re-emission significantly [250,251]. However, Wu et al. [252] found
the opposite results by doing the Hg0 re-emission experiments in
a lab-scale simulated scrubber, which indicated that the increase
of the slurry pH resulted in the increase in Hg0 re-emission con-
centration.
In the summary of Table S1, the Hgt removal rate of WFGD de-
vice is 3.9–72%.
Hg2+ + Hg0 ↔ Hg2+ (38)
2
−
Hg2+
2 + 2OH ↔ H2 O + HgO + Hg
0
(39)
HgO + SO2 ↔ Hg0 + SO3 (40)
Hg2+ + SO23− → HgSO3 → Hg0 (41)
Hg2+ + SO24− → HgSO4 → Hg0 (42)
 S. Zhao, D. Pudasainee and Y. Duan et al. / Progress in Energy and Combustion Science 73 (2019) 26–64
5.2.4. Wet electrostatic precipitator
To meet strict emission limits, WESP is installed widely in
the ultra-low emission (ULE) power plants and has an impor-
tant role in collecting ultrafine particles and aerosols. Zhang et al.
[229] found WESP also has the co-effect for Hgt capture with a re-
moval rate of 34.52–47.42%. When the flue gas went through the
WESP, concentration of both Hg2+ and Hg0 decreased. Studies by
the US Department of Energy [253] indicated that the average re-
moval rate of Hg0 , Hg2+ , and Hgp in flue gas by WESP was 32–40%,
72–82%, and 33–100%, respectively. It is known that Hg2+ and Hgp
can be collected by WESP, while there should be transformation of
Hg0 to Hg2+ or Hgp for Hg0 removal. It is inferred that electrode
of WESP can produce an electronic corona, which results in gener-
ation of free radicals, such as O, OH, O3 , Cl, and Cl2 from O2 , H2 O,
and HCl by gas discharge. Thus, the Hg0 in flue gas will be oxidized
into Hg2+ by free radicals and then form Hgp . The transformation
process of Hg0 to Hg2+ can be interpreted by reactions (43)–(54)
[254–258].
O2 + 2e− → 2O + 2e−
O2 + O → O3
O + H2 O → OH + OH
HCl + e− → H + Cl + e−
Hg0 + O → HgO
Hg0 + O3 → HgO + O2
Hg0 OH → HgOH
Hg0 + Cl → HgCl
HgCl + Cl → HgCl2
Hg0 + Cl2 → HgCl + Cl
HgCl + Cl2 → HgCl2 + Cl
Hg0 + Cl2 → HgCl2
5.2.5. Combination of each air pollution control device
Based on the above discussion, it can be found that each APCD,
such as SCR, ESP, FF, WFGD, and WESP, has a positive effect on
flue gas mercury removal. Pudasainee et al. [221] reported the re-
lationship between the flue gas mercury oxidation rate of SCR or
removal rate of ESP, and WFGD with the total removal rate across
SCR+ESP+WFGD, which is shown in Fig. 18(a)–(c). The Hgt re-
moval rate by SCR+ESP+WFGD has a strong relationship with mer-
cury removed by ESP, which is followed by WFGD and SCR device.
Because many factors, like coal type, flue gas components, mer-
cury species in flue gas, fly ash composition, and operation condi-
tions, can affect the mercury removal rate by the APCD, it should
be given specific treatment to evaluate the contribution of each
APCD for the Hgt removal rate. According to summarized data in
Table S1, the Hgt removal rate for ESP+WFGD, SCR+ESP+WFGD,
SCR+ESP+FF+WFGD, and SCR+ESP+WFGD+WESP is 35.5–84%,
43.8–94.9%, 58.78–73.32%, and 56.59–89.07%, respectively.
45
5.3. Emission concentration and emission factor
Hgt emission concentration in flue gas from the stack of CFPPs
to the atmosphere has raised widespread concern. Some countries,
such as China and the US, have issued relevant limits for mer-
cury in flue gas emitted from CFPPs, which are 30 μg/m3 (China)
[15], 7 μg/m3 (bituminous, the US), 20–35 μg/m3 (subbituminous,
the US), 60 μg/m3 (lignite, the US), and 6 μg/m3 (coal gangue, the
US) [259], respectively. Based on the data in Table S2, mercury
emission concentration for China and South Korea is in the range
of 0.29–9.16 μg/m3 and 0.48–16.3 μg/m3 , respectively, while that for
Poland, the Netherlands, and the US is within the range of 2.0–
15.1 μg/m3 .
To compare the mercury emission situations from different CF-
PPs, the mercury emission factor (MEF) is adopted in the work. The
MEF can be described as the ratio of the ultimate mercury emit-
ted to the atmosphere to the heat value coming from the feed-
ing coal [118]. From Table S2, the MEF for the CFPPs in China
ranges from 0.052–12.06 g/1012 J. The MEF for 80 CFPPs in the US
(43) with burning bituminous, subbituminous, and lignite coal is 0.046–
12.50 (average 1.63), 0.198–4.565 (average 2.08), and 1.723–24.04
(44) (average 6.79) g/1012 J, respectively, while that for Poland is 0.71–
6.09 g/1012 J.
(45)
5.4. Mercury content in combustion by-products
(46) Though there are no specific mercury emission standards on the
CBPs from CFPPs, the mercury content in the CBPs needs to be
given attention, which can provide guidance for their subsequent
(47) use and processing. Mercury content in bottom ash is extremely
low, with a range of 1.0 × 10−4 –<0.3 mg/kg, which is mainly due
(48) to the high formation temperature. With flue gas cooling, part of
the mercury in flue gas can be transformed into Hgp through ab-
sorption or heterogeneous reaction between mercury and fly ash.
(49) The mercury concentration in the fly ash, summarized in Table
S2, ranges from 0.009 to 1.89 mg/kg, which is obviously higher
(50) than the range of mercury concentration in bottom ash. With mer-
cury removal by WFGD and WESP, the concentration of mercury
in gypsum, WFGD wastewater, and WESP wastewater is 0.006–
(51) 6.16 mg/kg, 1.0 × 10−5 –10 mg/L, and 9 × 10−4 –0.867 mg/L, respec-
tively. Comparing to the relevant standards for soil and ground
(52) water that are proposed by the State Technical Supervision Bureau
and National Environmental Protection Agency in China, which are
0.50 mg/kg for soil focused on agricultural production and human
(53) health, and 0.001 mg/L for water applied in drinking and agricul-
tural irrigation, respectively [260,261], mercury in some fly ash and
(54) gypsum as well as most WFGD and WESP wastewater is higher
than the limits, which needs to be dealt with care during their
processing.
In summary, the APCDs in CFPPs have a positive effect on flue
gas mercury removal, in which SCR, ESP or FF, and WFGD are good
at Hg0 oxidation, Hgp capture, and Hg2+ removal, respectively.
WESP also has the flue gas mercury removal ability. Due to the
diversity and complexity in coal properties, flue gas components,
mercury forms in flue gas, fly ash composition, operation condi-
tions, etc., the Hg0 oxidation by SCR equipment, mercury removal
efficiency across APCDs, flue gas emission concentration, and
mercury content in CBPs vary widely. For mercury co-removal
and emission in CFPPs, the following studies need to be done:
(1) detail mercury transformation or the removal mechanism
across each APCD; (2) determine the way to improve the Hg0
oxidation rate in SCR equipment, or removal efficiency by APCDs;
(3) obtain more mercury content data in CBPs, and give relevant
emission limits; and (4) define the chemical species of mercury
in fly ash and gypsum, which is important for their utilization or
disposal.
46 S. Zhao, D. Pudasainee and Y. Duan et al. / Progress in Energy and Combustion Science 73 (2019) 26–64
Fig. 18. Flue gas mercury oxidation rate of SCR or removal rate of ESP, and WFGD vs. Total removal rate across SCR+ESP+WFGD [221]. Reprinted with permission from
Elsevier, 2017.
6. Mercury removal technologies for coal-fired power plants
Based on the mercury removal position in the CFPPs, mer-
cury removal technologies can be divided into pre-combustion, in-
combustion, and post-combustion mercury removal technologies.
The pre-combustion technology introduced is to remove mercury
from coal before coal burning, which mainly includes coal wash-
ing and mild pyrolysis methods. The in-combustion technology
includes low-NOx combustion technology, CFB combustion tech-
nology, coal blending, and the use of oxidizing chemicals in the
coal or furnace. The post-combustion technology mainly includes
the existing APCDs, mercury oxidizing catalysts, injecting oxidizing
chemicals into the flue gas, and mercury sorbents injection. Both
the in-combustion and post-combustion mercury removal tech-
nologies are to transform more Hg0 into easily capturable Hg2+
and Hgp and then remove them by the existing APCDs. Accord-
ing to the composition of adsorbents, mercury removal adsorbents
can be classified into carbon-based adsorbents (AC, biochar, and
petroleum coke), fly ash, calcium-based adsorbents, and mineral
adsorbents. Recently, some novel mercury control approaches have
been developed to improve the mercury removal efficiency and re-
duce the mercury removal cost further, which include regenerable
mercury removal adsorbent and multipollutant control technology.
The technologies for in-combustion and post-combustion mercury
removal in CFPPs are shown in Fig. 19 [81].
6.1. Pre-combustion mercury removal
6.1.1. Coal washing technology
The coal washing technologies can be divided into physical
and non-physical. The physical washing technology for mercury re-
moval is based on the density and surface physical-chemical prop-
erties of the components in the coal. Generally, mercury is mainly
associated with pyrite and clay in coal. The washed coal is hy-
drophobic while the most impurity components are hydrophilic. In
the physical coal washing process, the mercury will accumulate in
flotation residue and then be removed. Physical coal washing tech-
nologies include conventional and advanced physical separation
 S. Zhao, D. Pudasainee and Y. Duan et al. / Progress in Energy and Combustion Science 73 (2019) 26–64
Fig. 19. In-combustion and post-combustion mercury removal technologies in CFPPs [81]. Reprinted with permission from American Chemical Society, 2013.
methods, such as dense media separation, froth flotation, and en-
hanced gravity concentration, etc. [262]. Smit et al. [263] adopted
column flotation and selective agglomeration to study the mercury
concentration changes in coal before and after coal washing based
on five types of coal. Results showed that conventional washing
and column flotation reduced mercury concentration in raw coal in
the range of 40–>57% with average value of 55%. Selective agglom-
eration reduced the mercury content in coal by 8–38% with an av-
erage of 16%. Ferris and Bencho [264] used a heavy-media cyclone
(conventional cleaning method) followed by a water-only cyclone
and a column flotation system to clean three types of coal. Results
showed that mercury concentration reduction was 42–45% in the
raw coals by heavy-media cyclone and 21–23% in the cleaned coals
by water-only cyclone and column flotation system. A combination
of these methods reduced mercury concentration in the coals by
63–65%. Neme [265] found that physical washing removed 0–26%
of mercury for the US midwestern bituminous coals. Brown et al.
[266] observed that the average mercury reduction rate for vari-
ous commercial operations by conventional washing methods was
21–37%. For the US, the coal washing rate for bituminous coal and
western coal is reported as approximately 77% and 10–15%, respec-
tively [75]. For China, the coal washing rate is relatively low, which
is 11.2%, 31.7%, and 10.9% for Inner Mongolia, Shanxi, and Shaanxi
(main raw coal production regions), respectively [267]. The differ-
ent physical coal washing methods and coal types affect the mer-
cury removal rate from coal significantly, which has wide range
from 0% to 65% as mentioned above. The coal washing rate needs
improvement, especially for China. Thus, it is hard to meet mer-
cury removal requirements only by coal washing. In addition, phys-
ical coal washing technology may cause water or soil pollution by
mercury and an increase in capital investment, which also needs
attention.
Non-physical coal washing technologies have been explored by
the US Department of Energy: magnetic separation to capture mer-
cury in the form of pyrite (dry coal cleaning), mild chemical treat-
ments, and naturally occurring microbes [266]. Though the in-
creased liberation of the pyrite caused by the particle size reduc-
tion in the pulverizer might reduce the mercury removal cost for
dry coal cleaning, the removal rate significantly depends on the
content of pyrite-bound mercury. In addition, the chemical coal
cleaning method is considered as a high-cost control technology.
6.1.2. Mild pyrolysis method
The US Western Research Institute developed the pre-
combustion mild pyrolysis concept for mercury removal from coal,
which is shown in Fig. 20 [268]. There are two zones in this con-
cept: one is to remove moisture in coal with a temperature of
approximately 149 °C, and the other is a hazardous air pollutants
(HAPs) zone, which aims to remove the mercury with a tempera-
ture of about 288 °C. The volatilized mercury will be collected and
47
Fig. 20. The mild pyrolysis concept for mercury removal from coal [268]. Reprinted
with permission from Elsevier, 2004.
processed while the processed coal can be used for stockpile or
direct combustion.
Keener et al. [51,269] studied the thermal release characteris-
tics of mercury in several bituminous coals, finding that maximum
mercury removal of approximately 80% was achieved at a tempera-
ture of 400 °C. Guffey and Bland [268] studied the effects of pyrol-
ysis parameters on mercury removal from low-rank PRB coal and
lignite, which indicated that the mercury removal rate was positive
to residence time and the sweep gas flow rate. A residence time of
4 min led to the maximum mercury removal efficiency, while in-
creasing the sweep gas flow rate from 10 to 125 cm3 /min increased
the removal rate from 40% to 74%. Chmielniak et al. [270] used
the mild pyrolysis method to remove mercury from lignite and an-
thracite coal, finding that mercury removal efficiency for lignite at
a temperature of 300 °C was about 93%, while that for hard coal at
a temperature of 350 °C was only approximately 24%. Minami et al.
[271] showed that the thermal treatment temperature of 200 °C
could remove about 30% of mercury from Alberta subbituminous
coals. The mild pyrolysis method can remove mercury from coal to
a certain extent. However, the mercury removal rate has a wide
range, which is affected by the thermal treatment temperature,
residence time, sweep gas flow rate, and, especially, the mercury
forms in coal.
6.2. In-combustion mercury removal
The low-NOx combustion technology is beneficial for mercury
removal, which may be due to the increased oxidized mercury con-
tent caused by the low operating temperature and high UBC in
fly ash. The CFB combustion technology can enhance the chance
of mercury adsorption by fly ash by extending the residence time
of flue gas in the furnace. Coal blending is used to mix the coal
with different types of coal or biomass with the main purpose of
48 S. Zhao, D. Pudasainee and Y. Duan et al. / Progress in Energy and Combustion Science 73 (2019) 26–64
increasing Cl content, which favors the transformation of Hg0 to
Hg2+ or Hgp . Compared to these methods, putting chemicals into
coal to remove mercury is widely studied, in which halogens are
the most popular oxidant. This method has the advantages of sim-
ple operation, high mercury removal efficiency, and low cost.
Berry [272] conducted a field test at Plant Miller to study
the effect of CaBr2 on mercury oxidation, the results of which
showed that mercury oxidation efficiency increased from 60% to
90% under the addition of 5 mg/kg bromine to coal. Zhuang et al.
[273] found that adding 20 0–80 0 mg/kg (coal basis) of chlorine (in
the form of CaCl2 ) into a 650 MW subbituminous CFPP equipped
with SCR + FF + WFGD could achieve an overall mercury removal
of 75–96%, which was only 18–32% without the addition. A series
of spot tests conducted by the US Government Accountability Of-
fice at 14 different power plants showed that the addition of 25–
300 mg/kg CaBr2 to coal resulted in more than 90% of Hg0 being
oxidized in flue gas [274]. Pan et al. [275] used numerical simula-
tion and experimental method to study the effect of NH4 Cl injec-
tion into the furnace on mercury transformation, which found that
the proportion of Hg0 and Hg2+ to the total mercury decreased
while that of Hgp increased as the addition amount of NH4 Cl in-
creased. Shi [276] used US EPA Method 30B, OHM, and Hg-CEMS to
determine the mercury removal from a 300 MW power plant in-
stalled with SCR, ESP, and WFGD by putting CaBr2 into the coal,
which indicated that the addition amount of 20, 50, 100, and
200 mg/kg could reduce the gas mercury emission ratio by about
20%, 30%, 60%, and 30%, respectively. Zhou et al. [277] and Zhao
et al. [278] indicated that the gaseous Hg0 concentration showed
a decreasing trend with increasing the addition amount of CaCl2 ,
NH4 Cl, and NH4 Br, respectively. However, all the above studies fo-
cus on mercury removal rate, which neglect the detailed mercury
removal mechanism.
6.3. Post-combustion mercury capture
6.3.1. Existing commercial selective catalytic reduction catalyst
improvement
SCR system has been installed widely in CFPPs, due to its ad-
vantages of high DeNOx efficiency, selectivity, and economic feasi-
bility. The vanadia phase V2 O5 in typical commercial SCR catalysts
can not only catalyze the reduction of NOx but also catalyze the
Hg0 oxidation. Stolle et al. [279] found that the Hg0 oxidation abil-
ity increased with increasing the concentration of V2 O5 in the SCR
catalyst. This finding was similar to the results of Kamata et al.
[280], which reported that the Hg0 oxidation rate showed almost
linear increasing trend with addition amount of VOx until 10 wt%.
Negreira and Wilcox [281] used two models, which represented
TiO2 -supported systems with low and high loading of V2 O5 and
WO3 , to study the influence of the surface composition and sur-
face coverage on the reactivity of a commercial SCR catalyst (V2 O5 -
WO3 -TiO2 ) on mercury oxidation. They found the increasing load-
ing of both V2 O5 and WO3 enhanced reactivity of the SCR catalyst,
and 75% V2 O5 -25% WO3 -TiO2 was suggested as the optimal V-W-
Ti composition for mercury oxidation. Though the SCR catalyst is
effective for NOx reduction and Hg0 oxidation, it has some draw-
backs, such as a narrower temperature window and the potential
effect of V loss on the environment and humans during the cat-
alyst preparation and operation [282]. In addition, a low Hg0 oxi-
dation rate is obtained in the flue gas with low HCl concentration.
NH3 and SO2 are reported to inhibit Hg0 oxidation over the con-
ventional SCR catalysts [283].
To overcome these disadvantages, various studies have been
done to improve the SCR catalyst. RuO2 , which can catalytically
oxidize Hg0 by itself, is confirmed to work well with the SCR cat-
alyst for Hg0 oxidation [284]. Moreover, Hg0 oxidation or removal
effects by the commercial SCR catalysts impregnated with various
metal oxides, such as Cr2 O3 , ZnO, CuO, NiO, and MnO, have been
investigated [285], the results of which show that the impregnated
commercial SCR catalysts have a higher Hg0 oxidation ability than
their original catalysts. Zhao et al. [286] used Ce-Mn oxides to
modify the spent TiO2 -based SCR catalysts for Hg0 removal, which
found that the modified SCR catalysts (Ce1.00Mn/SCR1) performed
the best catalytic activities with about a 92.80% Hg0 oxidation rate
at a temperature of 150 °C. Zhao et al. [287] studied the promo-
tional effect of the CeO2 -modified V2 O5 -WO3 /TiO2 catalyst for Hg0
oxidation in a simulated coal-fired flue gas, the results of which in-
dicated that the introduction of CeO2 benefited Hg0 oxidation and
improved the H2 O-resistance ability. Huang et al. [288] used Fe2 O3
to modify the SCR catalyst, concluding that Fe2 O3 /SCR (1wt% Fe)
was the optimal catalyst, as it increased the mercury oxidation rate
from about 30% (without Fe2 O3 addition) to higher than 90% at
350 °C in a simulated flue gas. Besides metal oxides, a study of the
effect on Hg0 oxidation by a commercial SCR catalyst added with
CaCl2 was conducted by Zhang et al. [289]. The addition of CaCl2
was found to significantly enhance the Hg0 oxidation activity over
the catalyst, which increased the Hg0 oxidation rate from 7.7% to
78.8% with the addition amount of 1.0 wt% CaCl2 .
6.3.2. Inhibiting Hg0 re-emission in wet flue gas desulfurization
As described in Section 5.2.3, Hg0 re-emission, namely Hg2+ re-
duction, will occur in WFGD, which reduces mercury removal effi-
ciency. To suppress this phenomenon, oxidants or special chemical
reagents are introduced in the desulfurization solution. Krzyżyńska
et al. [290] found that the extent of scrubbed mercury increased
from 40% to 70% with the amount of NaClO2 added in the
slurry increasing from 0.81 to 1.62 mol/L. The lab-scale experi-
ments to achieve mercury reduction by adding aluminum sulfate
in the aqueous solutions and gypsum slurries were performed by
González et al. [291], the results of which showed that the alu-
minum sulfate decreased the slurry pH to a level where the sulfite
ions, responsible for mercury reduction, ceased to form. The ef-
fects of thiocyanate ions (SCN− ) or sulfide ions (S2− and HS− ) on
Hg0 re-emission from simulated WFGD solutions were conducted
by Wang et al. [292], who concluded that both thiocyanate and
sulfide ions inhibited reduction of aqueous Hg2+ to Hg0 . For the
thiocyanate ions addition, inhibition of mercury reduction was be-
cause of the formation of a sulfite-thiocyanate- mercury complex
(HgSO3 SCN− ) and thiocyanate-mercury complex [Hg(SCN)x−(x-2)
(x = 2–4)]. The formation of HgS could be the main reason for
inhibition of mercury reduction with sulfide ions addition. Wu
et al. [252] reported that Hg0 re-emission suppression rates could
reach 80.82% and 70.42% when adding 0.00125% (w/w) Na2 S4 and
0.0 0 05% (V/V) trisodium salt nonahydrate (TMT15) in the simu-
lated scrubber, respectively. Omine et al. [250] demonstrated the
influence of sulfide-based additives on Hg0 re-emission in a sim-
ulated batch scrubber, which showed that the suppression effec-
tiveness of sodium hydrogen sulfide, sodium sulfide (Na2 S), TMT15,
and the Nalco-8034 reagent was 99%, 97%, 93%, and 99%, respec-
tively. These additives benefited the precipitation of ionic mer-
cury as mercury sulfide. In addition, Na2 S, 2,4,6-trimercaptotiazine,
TMT, and sodium dithiocarbamate (DTCR) were confirmed to be ef-
fective enough to suppress Hg0 re-emission from simulated FGD
liquors by Tang et al. [293], who found that the addition of these
agents could make more than 90% of ionic mercury into a precipi-
tate and decreased Hg2+ reduction efficiency from 54% to less than
3%. Sun et al. [294] concluded that DTCR had a better inhibitive
performance than TMT for the stabilization of mercury in flue gas
desulfurization gypsum. In summary, the methods to inhibit Hg0
re-emission in WFGD mainly involve adjusting the pH, or sulfite
ions concentration, or forming a precipitate of mercury. However,
all the current available data are from simulated lab-scale WFGD
 S. Zhao, D. Pudasainee and Y. Duan et al. / Progress in Energy and Combustion Science 73 (2019) 26–64
Fig. 21. Reaction pathway of mercury oxidation on perfect Au(111)-p(4 × 4) surfaces
[299]. Reprinted with permission from American Chemical Society, 2013.
experiments. To obtain the technical and economic additives, pilot-
and full-scale tests are needed in the following studies.
6.3.3. Mercury oxidizing catalysts
According to the components, mercury oxidizing catalysts can
be divided into noble metal-based catalysts and non-noble metal-
based catalysts.
For the noble metal-based catalysts, a noble metal, such as Au,
Pd, Pt, and Rh, is used as the active ingredient with potential Hg0
oxidation ability, regeneration potential, and good stability at high
temperature [283]. Aboud et al. [295] used DFT calculation to in-
vestigate the binding mechanism of mercury on the binary alloys
PdAu(111), PdAg(111), and PdCu(111), finding that small addition
amount of Au, Ag, and Cu alloyed with Pd increased the over-
all mercury binding energy. Sasmaz et al. [296] concluded that
Pd had the highest mercury binding energy compared to Au, Ag,
and Cu, and the location of Au, Ag, and Cu atoms in both sur-
face and the subsurface layers affected the reactivity of the sur-
face. To obtain the maximum specific surface areas of the catalysts,
the noble metals are loaded on various porous materials, includ-
ing alumina (Al2 O3 ), silica (SiO2 ), zirconia (ZrO2 ), titania (TiO2 ),
carbons, and zeolite, etc. Hou et al. [297] found that the Al2 O3
loaded with 8 wt% Pd could remove 90% of mercury at operation
temperatures of up to 270 °C. Hrdlicka et al. [298] reported that
Au/TiO2 and Pd/Al2 O3 had an effect on mercury oxidation with
rate of 40–60% and 50–80%, respectively, in a simulated flue gas.
Li and Wilcox [299] adopted the DFT to study the reaction mecha-
nism of mercury oxidation on Au (111), and found that mercury ox-
idation obeyed the Langmuir-Hinshelwood mechanism where each
Hg0 and Cl2 (or HCl) species was adsorbed on the gold surface sep-
arately then the bimolecular reaction occurred by the formation of
bound HgCl and HgCl2 . The reaction pathway of mercury oxidation
on perfect Au(111)-p(4 × 4) surfaces is shown in Fig. 21 [299].
To reduce the cost of noble metal-based catalysts, the non-
noble metal catalysts, which include transition metal catalysts,
have been investigated. Recently, many studies on Hg0 oxidation
involving transition metal oxide catalysts (such as V2 O5 , MnO2 ,
Co3 O4 , CuO, CeO2 , and TiO2 ) loaded on various materials (alumina,
silica, titania, carbons, zeolite, etc.) have been extensively con-
ducted. The lower-cost transition metal catalysts can exhibit high
catalytic oxidation activity by comparison with the noble metal
catalysts. Li et al. [300] combined the copper oxides and cerium
oxides with TiO2 into a CuO–CeO2 /TiO2 (CuCeTi) catalyst, the re-
sults of which showed that the Hg0 oxidation rate of 99.0% was
obtained on the CuCeTi catalyst at 200 °C, even under the ex-
tremely high gas hourly space velocity. Zhou et al. [301] found
that the CeO2 -ZrO2 sorbents loaded with an optimal amount of 6
wt% CuCl2 exhibited superior and stable Hg0 removal performances
49
(89.6–97.1%) within a wide temperature range of 10 0–30 0 °C with-
out the presence of HCl. Li et al. [302] indicated that CeO2 -TiO2
(CeTi) catalysts with a CeO2 /TiO2 weight ratio of 1–2 possessed
a high Hg0 oxidation ability from 150 to 250 °C, in which the
high content of surface cerium and oxygen was the reason for
their superior performance. The CuO/TiO2 catalyst is confirmed to
concurrently increase higher than the 80% NO reduction and 90%
Hg0 oxidation rate by the experiments at 250 °C in a simulated
NH3 SCR atmosphere [303]. The Hg0 capture by the activated coke
modified with V2 O5 (V2 O5 /AC) catalyst was conducted by Wang
et al. [304], the results of which indicated that Hg0 capture of
V2 O5 /AC was much higher than that of AC. Zhang et al. [305] found
that Hg0 oxidation on MnOx /TiO2 followed the Mars-Maessen and
Langmuir-Hinshelwood mechanisms. Yang et al. [306] concluded
that the presence of HCl significantly enhanced mercury oxida-
tion over CeO2 -WO3 /TiO2 (CeW/Ti) catalysts with a mass ratio of
0.5:0.5:1 and resulted in more than 95% of the mercury oxidized.
In addition, the main reaction pathway of mercury oxidation was
a two-step process (Hg0 →HgCl→HgCl2 ) with the rate-limiting step
of the second step (HgCl→HgCl2 ).
6.3.4. Injecting oxidizing chemicals
Cao et al. [167] conducted experiments on mercury capture
by adding HBr or both the HBr and selected fly ash in real
flue gas in a slipstream reactor. Results showed that HBr injec-
tion had an effective ability for Hg0 capture at a low tempera-
ture of 155 °C, which could obtain Hg0 oxidation rate of higher
than 90% at the HBr addition concentration of 4 ppmv. Compared
to only the addition of HBr, the simultaneous injection of HBr
(4 ppmv) and bituminous coal-derived fly ash (minimum amount
of 4.80 × 105 μg/m3 ) could increase the mercury removal rate by
30%. The enhancement of hydrogen halogens (HF, HCl, HBr, and
HI) injection on Hg0 oxidation was also investigated in the PRB
coal combustion flue gas in the slipstream reaction with and with-
out SCR catalyst by Cao et al. [307], which indicated that the im-
pact level of the hydrogen halogens on Hg0 oxidation was HBr,
HI, and HCl or HF, in decreasing order. An injection of approx-
imately 3-ppmv HBr or 5-ppmv HI could achieve 80% and 40%
of the Hg0 oxidation rate for the empty bed. However, the ad-
dition concentration of HCl should increase to 300 ppmv to get
a 40% Hg0 oxidation rate. Stolle et al. [308] carried out lab ex-
periments on Hg oxidation and reduction through the commer-
cial V2 O5 /WO3 (MoO3 )/TiO2 honeycomb and plate-type DeNOx cat-
alysts, the results of which demonstrated that the addition of HBr
was ten times more effective than HCl in enhancing the Hg0 ox-
idation under the same conditions based on the mass concentra-
tion. Wen et al. [309] used quantum chemistry, kinetic simulation,
and experimental methods to study the mechanism and kinetics of
the Hg0 oxidation by injecting ozone in the flue gas. They found
that the Hg0 oxidation ability of oxidizing radicals obeyed the de-
creasing order of NO3 > O3 > NO2 , which were generated during
ozone injection. The Hg0 oxidation rate had a positive linear rela-
tionship with the mole ratio of O3 /NO or the reaction temperature,
in which Hg0 oxidation rate of about 32% and 39% could be ob-
tained for the O3 /NO mole ratio of 2.0 at 150 °C and a reaction
temperature of 250 °C with the O3 /NO mole ratio of 1.6. With the
key reaction of Hg+NO3 = NO2 +HgO for Hg0 oxidation, the con-
centration of NO3 was the vital factor for influencing Hg0 oxida-
tion. Martinez and Deshpande [310] added H2 O2 as a source of OH
radicals to promote Hg0 to Hg2+ , concluding that the best tem-
perature range for Hg0 oxidation was 480–490 °C. With addition of
260-ppmv H2 O2 , the greatest Hg0 oxidation rate of 68% could be
observed at 491 °C. The sensitivity analysis of the reaction mech-
anism indicated that the supplementing of OH radicals promoted
the atomic Cl formation, which enhanced the oxidation process by
accelerating the generation of HgCl2 .
50 S. Zhao, D. Pudasainee and Y. Duan et al. / Progress in Energy and Combustion Science 73 (2019) 26–64
In summary, the main mercury control thought of injecting oxi-
dizing chemicals into flue gas to remove mercury is similar to that
of putting oxidizing chemicals into coal or furnace. The studied in-
jected oxidizing chemicals mainly include hydrogen halogens (HF,
HCl, HBr, and HI), ozone, and H2 O2 . The literature data shows that
HBr has the more effective ability of Hg0 oxidation based on the
equal addition amount of oxidizing additives.
6.3.5. Carbon-based adsorbents
6.3.5.1. Activated carbon. Injecting activated carbon (AC) upstream
of the particle control device, such as ESP or FF, has been con-
sidered to be a mature and promising mercury removal technol-
ogy, the mercury removal effects of which have been evaluated
in bench, pilot, and field-scale tests [311–315]. The pilot and field
tests have shown that the mercury removal rate by AC sorbents
ranges from 25% to 95% with the mass ratio of carbon/mercury in-
creasing from 20 0 0 to 15,0 0 0 [75]. Lots of factors can affect the
mercury capture ability of the AC sorbents, including the surface
area, particle sizes, and pore volume of AC; mercury concentra-
tion in flue gas; flue gas temperature; flue gas components; and
surface chemical properties; etc. [316,317]. Min et al. [318] found
that mercury adsorption efficiency showed a linear increase with
the BET surface area increasing in the baseline gas condition. The
increase in particle size would decrease the mercury adsorptive ca-
pacity significantly while high initial mercury concentration led to
the increase in mercury uptake [319]. Ochiai et al. [320] investi-
gated the effects of HCl and SO2 on mercury removal by AC sor-
bents in simulated coal combustion flue gas, the results of which
indicated that increasing HCl concentration benefited Hg0 removal
by the AC sorbents while the presence of SO2 inhibited Hg0 cap-
ture with the presence of HCl. Miller et al. [321] indicated that
adding one of HCl, NO, or NOx at a time to the baseline gas (mix-
ture of O2 , CO2 , N2 , and H2 O) could improve the mercury capture
rate to 90–100% from 10–20% (baseline gas conditions) by lignite-
based AC at 107 °C. With increasing the CO2 concentration from 0%
to 12% at 150 °C, the mercury adsorption efficiency of Calgon F400
AC decreased from about 60% to 25% [322]. Li et al. [149] used
heat treatment (927 °C) in N2 , air oxidation (420 °C), and nitric acid
(6 N HNO3 ) treatment to vary the surface oxygen functional groups
on two ACs and found that lactone and carbonyl groups might
be beneficial for Hg0 capture while phenol groups inhibited Hg0
adsorption. Moreover, Liu et al. [323] confirmed that lactone, car-
bonyl, and semiquinone were the active sites for Hg0 adsorption
and phenol and carboxyl functional groups indicated a physisorp-
tion of mercury, which reduced mercury capture through DFT cal-
culation.
The high cost is an important reason for limiting the wide ap-
plication of AC injection mercury removal technology; it is es-
timated that the cost for 82% mercury removal by using AC is
between $110,0 0 0 and $150,0 0 0 per kg of mercury [317]. Thus,
many methods are used to modify the AC to improve its mer-
cury removal efficiency, including halogen (Br, Cl, I) impregnation
or vapour deposition [324–328], sulfur impregnation [329–331],
metal oxide or metal chloride modification [82,332–336], and non-
thermal plasma (NTP) treatment [337–339]. Jang et al. [324] found
that the AC impregnated with 1% of KI and HCl solutions im-
proved the mercury adsorption efficiency to 80–100% and almost
100% within 1.5 h, respectively, whereas the mercury adsorption
efficiency was 60–80% for the raw AC. Zhou et al. [340] reported
that NH4 Br modified AC (NH4 Br-AC) had a significantly larger mer-
cury adsorption capability compared to the raw AC, and the mer-
cury removal efficiency of both the ACs increased with an in-
crease in inlet Hg0 concentration. O2 and NO in flue gas benefited
mercury adsorption on NH4 Br-AC while SO2 had negative effects.
In general, mercury removal effects obey the increasing order of
AC < Cl-impregnated AC < Br-impregnated AC < I-impregnated
AC [341]. The DFT calculation of Padak et al. [342] on mercury
adsorption by halide-impregnated AC showed that the sequence
of mercury binding strength on halogenated AC was F-AC > Cl-
AC > Br-AC > I-AC. This result differs from the above experimen-
tal results of Zhou et al. [340], which indicates the adsorption en-
ergy of mercury halide species on AC is not the only factor for
mercury adsorption on halogenated AC. Rungnim et al. [343] used
the DFT method to investigate the reaction mechanisms of mer-
cury adsorption and oxidation on halogenated AC completely, by
adopting two different halogenated AC modes (namely, X-AC and
X-AC-X, X = Cl, Br, I). They showed that halide types did not influ-
ence the mercury adsorption energy but affected the activation en-
ergy barrier of HgX formation significantly, which increased in the
order of HgI < HgBr < HgCl. This trend agreed with experimen-
tal results that mercury removal efficiency by halogen-impregnated
AC decreased as I-AC > Br-AC > Cl-AC. The oxidation mechanism of
the mercury at (a) atop and (b) bridge sites of X-AC and X-AC-
X modes is shown in Fig. 22(a) and (b), respectively. Some tests
indicated that obtaining 90% mercury capture needed injection
rates of 8.01 × 104 μg brominate AC (Br-AC) per cubic meter of
stack gas while the injection rate for raw AC was 16.03 × 104 –
32.06 × 104 μg/m3 [317]. Zhong et al. [327] compared the mer-
cury removal efficiency by the AC modified with different halo-
gens (shown in Fig. 23) and concluded that AC modified by iodine
steam vapour deposition had a much better mercury removal abil-
ity than that modified by bromide deposition, as well as by NH4 Br
and NaBr impregnation, under the same experimental conditions.
Generally, sulfur impregnation decreases the surface area while
increases the maximum Hg0 adsorption capacity compared to the
raw AC fiber [311]. Sano et al. [344] found that the sulfur impreg-
nated AC contributed to a mercury adsorption 50- times greater
than that of raw AC. Qiu et al. [345] showed that the mer-
cury removal capacity of composite sulfurized activated carbon
(CSAC), which was impregnated wth aqueous-phase Na2 S and fol-
lowed with vapour phase elemental sulfur, was 1.5 times higher
than the AC impregnated with single elemental sulfur. Yan et al.
[329] concluded that mercury adsorption by sulphur-impregnated
carbon involved both physical and chemical processes. Lee and
Park [346] stated that the pore characteristics of raw AC and types
of sulfur are the main factors affecting mercury capture perfor-
mance on sulfur-impregnated AC, rather than the amount of im-
pregnated sulfur. Hsi et al. [347] indicated that elemental sulfur,
organic sulfur, and sulfate were formed on the sorbents (including
AC, pistachio shell char and pistachio AC, and zeolite) in the sulfur
impregnation process, in which elemental and organic sulfur were
vital active sites for Hg0 and HgCl2 adsorption. In addition, Hsi
and Chen [330] investigated the effects of acidic/oxidizing gases
on Hg0 adsorption behavior on sulfur-impregnated AC, the results
of which showed that mercury-capture ability was promoted as
one acidic/oxidizing component added in the baseline components
(CO2 , H2 O, and N2 ) with a declining order of NO, HCl, O2 , followed
by SO2 .
Du et al. [332] studied the catalytic oxidation and adsorption of
Hg0 on neutral Al2 O3 , artificial zeolite, and AC impregnated with
CuCl2 . They showed that CuCl2 -impreganted AC had the best mer-
cury removal ability, and the value was over 90% for AC impreg-
nated with 5% CuCl2 in the presence of 20-ppmv HCl at 140 °C in
a 5 min test. Wang et al. [333] found that FeCl3 impregnated AC
showed a significant performance for Hg0 capture, in which the
conversion of Hg0 to Hg2+ was promoted by the chlorine in metal
chlorides. Tao et al. [82] demonstrated that CeCl3 enhanced Hg0
removal by the AC, and the best CeCl3 loading amount and reac-
tion temperature was approximately 6% and 170 °C. The presence
of NO and SO2 benefited Hg0 oxidation with the presence of O2
while SO2 inhibited the Hg0 capture without O2 in the flue gas.
The X-ray diffraction (XRD) and XPS analyses results indicated that
 S. Zhao, D. Pudasainee and Y. Duan et al. / Progress in Energy and Combustion Science 73 (2019) 26–64 51

Fig. 22. (a) The oxidation mechanism of the Hg at (a) atop and (b) bridge sites of X-AC (X = Cl, Br and I) models. The optimized structures along reaction steps of I-AC are
presented as an example of reaction mechanism [343]. Reprinted with permission from Elsevier, 2016. (b). The oxidation mechanism of the Hg at (a) atop and (b) bridge
sites of X-AC-X (X = Cl, Br and I) models. The optimized structures along reaction steps of I-AC-I are presented as an example of the reaction mechanism [343]. Reprinted
with permission from Elsevier, 2016.
52 S. Zhao, D. Pudasainee and Y. Duan et al. / Progress in Energy and Combustion Science 73 (2019) 26–64
Fig. 23. Mercury removal efficiencies by raw AC and AC modified by differ-
ent halides (test conditions: C0 = 50 μg/m3 , m = 0.1 g, V = 7 L/min, T = 50 °C) [327].
Reprinted with permission from Elsevier, 2017.
Fig. 24. Hg0 removal efficiency by AC and AC treated with oxygen NTP [337].
Reprinted with permission from Elsevier, 2016.
Cex Oy and C–Cl were formed on the CeCl3 -impregnated AC sur-
face, which were beneficial active elements for Hg0 removal. Shen
et al. [348] studied the effects of several loaded metal chlorides
and metal oxides on mercury adsorption of AC, finding that metal
chlorides showed better Hgg removal performance than metal ox-
ides loaded on AC. They concluded that metal chlorides loaded on
AC had both the catalytic effect of valance-variable metal and chlo-
rine oxidation for mercury capture.
Recently, NTP treatment has been adopted to modify the AC,
which has the advantages of no chemical solution and time-saving
compared to the impregnation method. Zhang et al. [337] used the
oxygen NTP to modify AC for Hg0 capture, the results of which
indicated that AC treated with oxygen NTP had a better Hg0 re-
moval performance than that of raw AC, as shown in Fig. 24. The
average Hg0 removal rate by the oxygen-NTP-treated AC was al-
most 2-3-times higher than that of raw AC. It was suggested that
oxygen NTP treatment increased the ester groups (C–O), carbonyl
groups (C=O), and adsorption activate sites on the AC surface, all
of which were vital for Hg0 adsorption. Hu et al. [338] compared
the modification effects of AC treated with NTP in different atmo-
spheres (N2 , O2 , air, and HCl) on Hg0 removal. It is shown that
the NTP treatment with air, O2 , and HCl promoted mercury re-
Fig. 25. Instantaneous mercury removal efficiency curves of raw AC, AC-T60
(treated by NTP in N2 without Cl2 for 60 s), AC–C15 (placed in 1500 ppmv Cl2 for
60 s without NTP treatment), and AC–C15T60 (treated with NTP with 1500 ppmv
Cl2 for 60 s) at 30 °C [339]. Reprinted with permission from American Chemical So-
ciety, 2016.
moval efficiency compared to raw AC and AC–N2 , which was due
to the large increase of oxygen-containing functional groups (C=O
and C(O)−O−C) present on the AC surface. In addition, AC modified
in HCl could generate C–Cl groups, which benefited the improve-
ment of Hg0 oxidizing ability. Zhang et al. [339] used NTP to add
Cl active sites on AC in the Cl2 atmosphere, finding that AC treated
with NTP in the Cl2 atmosphere (AC–C15T60) possessed the best
mercury removal efficiency among the four samples, with a stable
removal rate of higher than 96% in one hour (shown in Fig. 25).
Scanning electron microscopy (SEM) and XPS analysis illustrated
that C–Cl groups were formed during the Cl2 NTP treatment, which
were the active sites for conversion of Hg0 to HgCl2 , as well as for
mercury adsorption.
6.3.5.2. Biochar. To economize the cost of mercury removal by
using AC or modified AC, biochar as the adsorbent carrier has
been developed by some researchers. The mainstream modification
method is halogen impregnation [349–356]. Zhu et al. [350] com-
pared the mercury removal performance of the rice husk char
modified with HBr, NH4 Br, CaBr2 , (NH4 )2 SO4 and NH4 OH based
on same amount of bromine or ammonia, confirming that halogen
played an important role in mercury capture. Li et al. [352] used a
low-cost biochar pyrolyzed from municipal solid waste to capture
Hg0 , which found that the biochar pyrolyzed at 600 °C had better
mercury removal effects than that at 400 °C. Both microwave acti-
vation and NH4 Cl modification promoted Hg0 capture by the sor-
bents, which decreased from 67% to 55% within the initial 100 min.
XPS results indicated that the Hg0 removal mechanism was mainly
the conversion of Hg0 to HgCl2 with the help of C–Cl groups. Shen
et al. [353] illustrated that the biochar (derived from medicinal-
residue pyrolysis) impregnated with NH4 Cl showed much better
mercury adsorption performance than the biochar impregnated
with ZnCl2 and HCl. The chemisorption governed the overall Hg0
capture process for the chloride-impregnated biochars. For the
biochar (derived from waste tea) modified with NH4 Cl, the ultra-
sound impregnation process enhanced its Hg0 removal efficiency
by 20–30%, which was because of uniform distribution and the
larger specific surface area. In addition, NO and SO2 promoted mer-
cury removal while H2 O inhibited mercury capture by the biochar
[354]. Yang et al. [355] concluded that O2 and NO had positive ef-
fects on mercury removal by the NH4 Br modified sargassum chars,
while the effects of SO2 and H2 O were related to their concentra-
tion. The C-Br and C=O covalent groups were the main chemisorp-
tion sites for Hg0 removal. Li et al. [351,356] used the cotton
 S. Zhao, D. Pudasainee and Y. Duan et al. / Progress in Energy and Combustion Science 73 (2019) 26–64
Fig. 26. Mercury adsorption efficiency of the two modified fly ashes [365]. Reprinted with permission from Elsevier, 2014.
straw biochars modified with NH4 Br, NH4 Cl, and NH4 I to remove
mercury in a N2 atmosphere, the results of which indicated that
the modification effect of ammonium halides on mercury adsorp-
tion performance followed the order of NH4 I (7643.1 μg/g) > NH4 Br
(842.0 μg/g) > NH4 Cl (365.3 μg/g). Based on the contrast testing and
XPS analysis, the C-X (X: I, Br, Cl) covalent groups acted as the
mercury adsorption sites and played a major role in mercury re-
moval capacity for the modified biochars.
In summary, halogen modification can enhance the mercury re-
moval efficiency of the biochar, in which C-X (X: I, Br, Cl) and C=O
may act as the major chemisorption sites for Hg0 adsorption. NO
and O2 are beneficial for mercury removal while the effects of SO2
and H2 O have a relationship with their concentration.
6.3.5.3. Petroleum coke. Petroleum coke is a low-priced carbon ob-
tained as a byproduct from the upgrading of bitumen or petroleum
refinement [357,358]. It has a high-sulphur content, and the
petroleum coke is usually dumped off as waste. Thus, some stud-
ies propose to use it as a potential mercury sorbent after ac-
tivation with different chemicals. Lee et al. [357] applied high-
temperature pyrolysis to petroleum coke so as to bring sulfur
to its surface, which was believed to capture gas-phase mercury.
Their result showed that the specific surface area of petroleum
coke increased by nearly 10 times and mercury capture was sig-
nificantly increased after pyrolysis. The pyrolyzed petroleum coke
was claimed to have high potential as a sorbent for mercury cap-
ture. Hong et al. [359] evaluated the mercury adsorption effects of
petroleum coke, modified by NH4 Br solution, the results of which
showed that 1% NH4 Br-impregnated petroleum coke could remove
almost all the mercury in a fixed bed within 120 min, and the mer-
cury removal rate was more than 90% in the entrained flow reac-
tor system with a temperature of 120 °C, residence time of 2 s, and
C/Hg ratio of 90,0 0 0. Their results highly supported that the mod-
ified high sulfur petroleum coke could be used as highly effective
mercury capture adsorbent for CFPPs. Cai and Jia [360] modified
petroleum coke with a KOH-SO2 activation method and used it to
remove mercury from the aqueous phase.
The activation processes mentioned above are energy intensive,
costly, and produce harmful pollutants. In order to overcome these
issues, Xiao et al. [361,362] adopted a chemical-mechanical bromi-
nation method to modify the petroleum coke for Hg0 capture from
flue gas. Their study showed that the mercury removal efficiency
of petroleum coke was improved by 60–70% after bromination, and
bromine and sulfur in petroleum coke enhanced mercury capture.
The chemical-mechanical bromination process created more active
53
mercury adsorption sites on the brominated petroleum cokes. The
inherent thiophene and organic sulfide in petroleum coke played a
major role in mercury removal. In addition, the leaching test re-
vealed that the brominated petroleum coke showed a negligible
leachability of bromine and mercury from the spent sorbent, which
was safe for disposal after its use.
Common features of carbon-based adsorbents modification are
to obtain more mercury adsorption or oxidation active sites on
their surface, and to ensure a certain degree of surface physical
structure. In addition, the flue gas components, such as O2 , NO,
and SO2 , have a significant effect on the mercury removed by the
adsorbent.
6.3.6. Fly ash
Fly ash produced from CFPPs is considered to be a promising
sorbent for mercury capture [363]. The mercury removal efficien-
cies of fly ash are affected by its physical and chemical proper-
ties, including fly ash particle size [135], surface area and average
pore size [137,364], UBC, and metal oxides in fly ash [137,157,168].
To improve the mercury capture rate, fly ash is usually modi-
fied by halogens or metal oxides. Zhang et al. [365] compared
the mercury removal effects of two fly ashes impregnated with
CaCl2 , CaBr2 , and HBr in an air-entrained-flow reactor, the results
of which showed that the HBr modified fly ashes had the great-
est mercury adsorption ability among the three modifiers. Both
the two fly ashes modified with HBr increased their mercury re-
moval efficiency from 8.1% and 3.4% to 98.4% and 59.8%, respec-
tively, as shown in Fig. 26. In addition, Zhang et al. [366] con-
firmed that HgCl2 , HgS, and HgO were the main mercury species
on the unmodified fly ash while HgBr2 and HgO were the major
mercury forms in the HBr modified fly ash after Hg0 adsorption in
the entrained-flow reactor through the determination of mercury
compounds by using the TPD method. HBr was thought to be the
major factor for Hg0 oxidation. Zhou et al. [367] studied the influ-
ence of flue gas components and ash composition on Hg0 oxidation
or adsorption by NH4 Br modified fly ash (NH4 Br-FA), the results of
which indicated that NH4 Br modification of the fly ash enhanced
Hg0 oxidation and adsorption, improving the Hg0 removal rate of
0–10% to 50% in 120 min. HgBr2 was the major adsorption specie
on the NH4 Br-FA surface because of the formation of Br-containing
functional groups in the modification. O2 could not promote Hg0
oxidation or adsorption, while NO enhanced Hg0 adsorption signif-
icantly. SO2 had negative effects on Hg0 adsorption on the NH4 Br-
FA surface, which had little influence on Hg0 oxidation. The main
metal oxides (Fe2 O3 , TiO2 , CaO, and Al2 O3 ) in the NH4 Br-FA had
54 S. Zhao, D. Pudasainee and Y. Duan et al. / Progress in Energy and Combustion Science 73 (2019) 26–64
poor mercury removal ability, but the NH4 Br-Fe2 O3 and the NH4 Br-
TiO2 showed excellent Hg0 oxidation performance with poor Hg0
adsorption. Wang et al. [368] used halogen-modified fly ash to
control mercury emission in a 300 MW CFPP in China. The re-
sults indicated that the modified fly ash could reduce 40–50% of
Hg0 with no obvious change in oxidized mercury. With the com-
bination of SCR, ESP, and WFGD as well as modified fly ash injec-
tion, the total mercury removal rate could reach 75–90%. Xu et al.
[369] indicated that fly ash modified with CaBr2 , CuCl2 , and FeCl3
possessed great mercury removal performance compared with the
raw sample, in which both the chlorine and Cu2+ and Fe3+ pro-
moted Hg0 oxidation. Xu et al. [370] adopted a wet-impregnation
method to load cobalt on fly ash for Hg0 removal and found that
the well-dispersed Co3 O4 on the fly ash surface benefited Hg0 oxi-
dation. The optimal Co loading of 9 wt% increased the Hg0 removal
efficiency to 76% in a laboratory fixed-bed reactor with O2 at low
temperatures.
It can be summarized that the modified fly ash can be used for
mercury removal, especially with halogen modification. However,
the mercury capture effects will be changed in a wide range due to
the complexity of the physical and chemical structure of the fly ash
surface from different power plants. In addition, the mixture of the
modified fly ash and original fly ash from CFPPs should be tested
for stability and leaching of mercury and halogens before using it,
for example, in cement kilns, when producing brick or tiles, and
when disposing off in landfills, etc. [371,372].
6.3.7. Calcium-based adsorbents
Ghorishi and Gullett [373] reported the effects of bed temper-
ature, mercury concentration, acid gases (HCl and SO2 ), and wa-
ter vapour on the uptake of Hg0 and HgCl2 by the Ca-based sor-
bents, namely, Ca(OH)2 and mixtures of Ca(OH)2 and fly ash, in a
laboratory-scale, fixed-bed reactor. They showed that many HgCl2
adsorption sites existed in Ca-based sorbents. The gas-phase HgCl2
concentration had a very strong influence on its adsorption, which
increased with an increase in HgCl2 concentration. Increasing bed
temperature decreased the HgCl2 adsorption by the sorbents, but
the influence was weak. HgCl2 removed by Ca(OH)2 would obvi-
ously be decreased in the presence of acid gases (10 0 0-ppmv SO2
and 50-ppmv HCl), and the inhibition effect of SO2 was stronger
than that of HCl. The main reason was thought to be that the
acid gases could compete with HgCl2 for available alkaline sites.
Pilot-scale tests indicated that injection of hydrated lime into fur-
nace could get high system HgCl2 removal, with rate of 55–85% at
Ca/Hg weight ratio of 50 0 0 and 10,0 0 0, respectively. However, the
corresponding Hg0 capture efficiency was from 10% to 20%, even
with the Ca/Hg weight ratio as high as 30 0,0 0 0 [374].
Li et al. [203] used the chemical impregnation method to de-
velop a novel calcium-based sorbent synthesized from calcium ac-
etate and mesoporous silica, the results of which indicated that the
sorbent could adsorb the Hg2+ completely under N2 and a sim-
ulated flue gas atmosphere, but with almost no capture of Hg0 .
Wang and Duan [375] adopted different concentration of KMnO4
solution to modify Ca(OH)2 to form the Mnx+ /Ca(OH)2 mercury
adsorbent. It was shown that the initial Hg0 removal rate for
Ca(OH)2 , and Ca(OH)2 impregnated with 1% and 5% KMnO4 was
about 20%, 30%, and 37%, respectively. As the adsorbing time in-
creased, the Hg0 capture rate decreased. The ultimate Hg0 ad-
sorption amount for the three Ca-based adsorbents was 0.74, 1.05,
and 1.30 mg/kg, respectively. The mercury adsorption ability of
Mnx+ /Ca(OH)2 was slightly higher than that of Ca(OH)2 .
In general, Ca-based sorbent is less effective in mercury cap-
ture even after activation, which is more beneficial for Hg2+ cap-
ture than Hg0 adsorption. The presence of SO2 has a negative effect
on mercury removal of the adsorbent.
6.3.8. Mineral adsorbents
Cai et al. [376] used KI and KBr to modify clays (named KI-
clays and KBr-clays) to remove Hg0 in simulated flue gas atmo-
spheres, the results of which indicated that KBr and KI modifi-
cation significantly enhanced Hg0 removal by the clays. Increas-
ing KI or KBr loading and adsorption temperature had positive ef-
fects on Hg0 removal. This was especially the case with the clay
loaded with 3 wt% KI as it had the highest Hg0 removal efficiency
of 78–89% in N2 +O2 atmosphere during the 3 h of adsorption,
whereas the unmodified clay almost captured no Hg0 . The pres-
ence of O2 and SO2 benefited Hg0 removal while the occurrence of
H2 O inhibited the Hg0 capture by the modified clays. Both the ex-
perimental results and pseudo-second-order model demonstrated
that KI-clays were more active than KBr-clays concerning Hg0
removal.
Shen et al. [377] developed a new kind of titanium-pillared clay
(Ti-PILC) impregnated by KI to capture Hg0 in the simulated flue
gas. With a larger BET surface area and more mesopores of 2–
10 nm, the KI-impregnated Ti-PILC had a greater Hg0 removal abil-
ity than the original clay or the KI-impregnated clay. For the Ti-
PILC loaded with 3 wt% KI, the Hg0 removal efficiency was almost
100% to 65% with an initial 300 min in 6% O2 +N2 atmosphere at
80 °C. NO and SO2 promoted while H2 O inhibited Hg0 removal.
Chemisorption was considered to occur between the iodine and
Hg0 on the sorbent surface within temperatures of 80–180 °C in
the adsorption process, the major product of which might be HgI2 .
The experiments and kinetic models analysis demonstrated that
chemisorption was the main Hg0 adsorption process.
Chiu et al. [378] investigated the effects of CuCl2 -impregnated
zeolite MCM-41 (CuCl2 −MCM) on Hg0 removal. They showed that
all the studied CuCl2 -impregnated amounts (2, 4, 8, and 16 wt%)
could obtain the average Hg0 removal rate of 74.3–83.4% and 34.5–
73.4% at an adsorption temperature of 150 °C, in N2 and flue gas at-
mosphere (14% CO2 + 10% H2 O + 6% O2 + 50-ppmv HCl + 200-ppmv
SO2 + 200-ppmv NO + balanced N2 ), respectively.
Shao et al. [379] compared the Hg0 removal efficiency of the
KI-modified bentonite supported by starch sorbent (B-S-I) and tra-
ditional KI-modified bentonite sorbent (B-I). They found that B-S-I
possessed a better Hg0 removal ability than B-I due to the iodine
uptake capacity between iodine and the starch on B-S-I. O2 had
positive effects while H2 O showed a negative influence on Hg0 re-
moval by both the B-S-I and B-I. SO2 could promote or inhibit the
Hg0 capture, which mainly depended on SO2 concentration. The
starch-iodine complex was thought to be able to provide I2 for Hg0
adsorption, the product of which was mainly HgI2 on the B-I-S sur-
face.
Liu et al. [380] evaluated the Hg0 removal capacity of paly-
gorskite (Pal) impregnated with the active substances CuCl2 , CuBr2 ,
NaBr, sulfur, MnO2 , and Co3 O4 in a bench-scale fixed-bed reac-
tor in simulated flue gas. The results showed that the active sub-
stances modification improved the mercury removal capability of
Pal significantly, and the removal rate of CuCl2 and CuBr2 impreg-
nated Pal (namely, CuCl2 -Pal and CuBr2 -Pal) reached 90.9% and
95.2%, respectively, with that of other modified adsorbents being
higher than 80%. For the CuCl2 -Pal and CuBr2 -Pal, O2 and HCl had
positive effects while SO2 and NO showed negative effects on mer-
cury removed by them. In the preparation process of the CuCl2 -
Pal and CuBr2 -Pal adsorbents, the Pal underwent complexation
and adsorption by cupric halide molecules existing on its polarity
and hydroxyl group. During heating, the cupric halide of hydrate
could change into cupric oxide while some HX (X: Br, Cl) might be
formed. The halogen atom from cupric halide was enough to cap-
ture gaseous Hg0 and then promote the transformation of it into
Hg2+ via attaching to the active sites of Pal. The preparation and
mercury removal mechanism of CuCl2 -Pal and CuBr2 -Pal is illus-
trated in Fig. 27 [380].
 S. Zhao, D. Pudasainee and Y. Duan et al. / Progress in Energy and Combustion Science 73 (2019) 26–64
Fig. 27. Preparation and mercury removal mechanism of CuCl2 -Pal and CuBr2 -Pal
[380]. Reprinted with permission from Elsevier, 2017.
In brief, using the mineral as the mercury removal adsorbent
is mainly modified by the halogens. The chemisorption played an
important role in mercury adsorption by the modified adsorbent.
In addition, the mercury removal efficiency is affected by the flue
gas components, such as O2 , HCl, SO2 , NO, and H2 O.
6.4. Novel mercury control approaches
6.4.1. Non-separable regenerable mercury removal adsorbent
Liu et al. [381] synthesized the natural chabazite-based silver
nanocomposite (AgMC) to remove mercury from coal-fired flue gas,
finding that the mercury could be captured by the AgMC com-
pletely when the reaction temperature reached up to 250 °C. The
nano-silver particles were confirmed to be the main active com-
ponent for mercury removal via the amalgamation mechanism. In
addition, the removed mercury in the spent AgMC could be eas-
ily released for safe disposal and the sorbent could be regener-
ated by heating at 400 °C. Rodríguez-Pérez et al. [382] developed
a regenerable sorbent by dispersing gold nano-particles on an AC
to remove the mercury in flue gas after desulfurization units in
CFPPs. It showed that the regenerable sorbent prepared by using
5% doped gold to disperse gold nanoparticles on a carbon material
could capture mercury effectively, and the mercury removal effi-
ciency could be 100% over several cycles of generation. The sorbent
could be regenerated by thermal treatment at about 240 °C, and
Hg0 could be recovered and collected. The main mercury capture
mechanism was the mercury amalgamation with gold and oxidized
mercury retained by the AC.
Yao et al. [383] tried to investigate the mercury adsorption
and cyclic mercury retention on the MnOx /γ -Al2 O3 sorbent. They
found that the mercury removal ability over regenerated sorbents
could not be restored through thermal desorption at high temper-
atures, which was due to the irreversible reduction of MnO2 to
Mn2 O3 . Qu et al. [384] demonstrated that Ce0.5 Mn0.5 Oy had the
best mercury adsorption performance at 100 °C (about 5.6 mg Hg
/g adsorbent). The removed mercury could be released from the
adsorbent in the form of Hg0 by heating to 350 °C. In addition, the
sorbent could be generated and reused, the mercury removal abil-
ity of which did not show an obvious decrease after five runs of
adsorption and desorption.
6.4.2. Separable regenerable mercury removal adsorbent
The separable regenerable mercury removal sorbent is based on
magnetic material to achieve separation of the adsorbent from the
55
Fig. 28. Schematic diagram of applying regenerated FeMnOx for mercury removal
in CFPPs [385]. Reprinted with permission from Elsevier, 2017.
fly ash. Zeng et al. [385] found that the FeMnOx sorbents treated
with NTP showed higher mercury removal ability than raw sor-
bents. The content of the high-valence manganese oxides and lat-
tice oxygen were increased greatly by the NTP, which was signifi-
cant for mercury removal. During mercury removal, high-valence
manganese oxides and lattice oxygen were consumed. However,
the NTP treatment could supplement it, which increased the mer-
cury removal regeneration performance compared to that with-
out NTP treatment. The mercury removal efficiency for FM-1 for
the first (without NTP treatment), third (with NTP treatment), and
fifth (with NTP treatment) was about 90%, 82%, and 75%, respec-
tively. O2 and HCl benefited mercury capture by the sorbent while
NO, SO2 , and H2 O had negative effects. It is worth noting that the
sorbents can be separated from fly ash with magnetic separation.
Thus, a combination of magnetic separation, thermal regeneration,
and plasma treatment can make FeMnOx an excellent recyclable
sorbent for mercury emission control, the schematic diagram of
which is shown in Fig. 28 [385].
Yang et al. [386] developed a new regenerable magnetic cata-
lyst by loading cobalt oxide on magnetospheres (Co-MF) from fly
ash and found that the catalyst could obtain about 95% Hg0 re-
moval efficiency at 150 °C in a simulated flue gas atmosphere with
the optimal loading of 5.8% cobalt species. The repeated oxidation-
regeneration cycles illustrated that the spent Co-MF catalyst could
be regenerated effectively by thermal treatment at 400 °C for 2 h.
Moreover, the catalyst characterization and performance evalua-
tion, involving reaction mechanism, regeneration performance in
realistic flue gas atmosphere, and the performance of sorbent
injection in an entrained flow reactor system of the recyclable
CuCl2 modified magnetospheres from fly ash, were also studied
by Yang et al. [387–390], the results of which demonstrated that
the magnetic catalyst loaded with 6% CuCl2 obtained the high-
est Hg0 removal efficiency of 90.6% at 150 °C. The interaction be-
tween Hg0 and CuCl2 was a cycle with the presence of O2 and
HCl in the reaction system. The mercury removal capacity did not
vary significantly compared to a fresh catalyst after multiple re-
generations through the four cycle tests of mercury adsorption-
catalyst regeneration. With the residence time of 1.61 s and sor-
bent concentration of 1.09 g/m3 , the Hg0 removal rate could reach
80.6%.
The magnetic adsorbent modified by metal oxides or the metal
halide will be the most promising sorbent for mercury removal
from a coal-fired flue gas, which has the advantages of high mer-
cury removal efficiency, low investment, easy separation from fly
ash, mercury recovery, etc. However, the field tests of applying
these adsorbents in CFPPs are sparse and the method needs fur-
ther study.
56 S. Zhao, D. Pudasainee and Y. Duan et al. / Progress in Energy and Combustion Science 73 (2019) 26–64
6.4.3. Multipollutant control
Flue gas cleaning technologies used today are mostly effective
in removing single pollutants: either NOx or SO2 , or PMs or met-
als. CFPPs need to install pollutant specific control devices, which
require a high cost. In order to cope with this situation, there
have been some studies done on multi-pollutant control technolo-
gies, which generally employ post-combustion flue gas treatment
technologies to simultaneously remove NOx , SO2 , and mercury.
Krzyżyńska et al. [290] introduced an oxidizing additive-sodium
chlorite (NaClO2 ) in a limestone-based WFGD scrubber. The re-
sults showed that the extent of the scrubbed mercury amount
increased with an increase in the chlorite addition in the slurry,
which ranged from 40% (at 0.81 M NaClO2 ) to approximately 70%
(at 1.62 M NaClO2 ). However, the selected NaClO2 only resulted in
the NO removal rate in the range of 15–30%. Ping et al. [391] used
urea and KMnO4 to remove Hg0 , SO2 , and NO simultaneously by
wet scrubbing. They found that the NO and Hg0 removal rate
was mainly affected by the KMnO4 concentration. The highest re-
moval efficiencies of SO2 , NO, and Hg0 could reach 98.78%, 53.05%,
and 99.21%, respectively, under the optimal conditions. Chiu et al.
[378] indicated that the average Hg0 oxidation rate over the MCM-
16% (zeolite MCM-41(MCM) impregnated with CuCl2 content of 16
wt%) was 53.7%. After CuCl2 impregnation, the SO2 removal rate
by the modified MCM decreased from 42.3% to about 38% while
the NO removal rate increased from 62.8% to 73%. In addition,
Chiu et al. [392,393] adopted transition metal oxide to modified
SCR catalyst and metal oxide/mesoporous SiO2 composites, respec-
tively, to investigate their multipollutant control effects of Hg0 ,
SO2 , and NO. They demonstrated that Hg0 oxidation, SO2 removal,
and NO reduction of the SCR catalyst was greatly improved after
the metal oxide impregnation, which was 81.6–96.4%, 10.4–20.8%,
and 89.0–91.8%, respectively, under simulated coal-combustion flue
gas condition. The CuOx /SiO2 had 42.6% of the Hg0 removal rate
while the metal oxide/SiO2 composites could remove 62% NO with
NH3 injection at 350 °C. Yuan et al. [394] synthesized novel TiO2 -
aluminum silicate fiber nanocomposite for the removal of multiple
pollutants with the help of UV irradiation. Results indicated that
the removal rates for SO2 , NO, and Hg0 at 120 °C and with UV in-
tensity of 3 mWcm−2 could reach 33%, 31%, and 80%, respectively,
in the simulated flue gas (4% O2 , 12% CO2 , 2% H2 O, 400-ppmv SO2 ,
50-ppmv NO).
The development of a novel, efficient, multi-pollutant sorbent
is extremely important, as it will reduce the cost of installing ex-
pensive equipment and minimize the environmental impact. How-
ever, it is very difficult for the present multipollutant control tech-
nologies to realize the highest removal rate for the NO, SO2 , and
Hg0 simultaneously. In addition, the effect of some additives on
the equipment and the catalyst production costs should be com-
prehensively taken into consideration.
Finally, in order to provide more information about the mercury
in coal combustion process to new readers, most of the important
organizations/institutes/groups in this field especially focusing on
mercury emission control have been listed in Table S3.
7. Conclusions
Mercury is a global pollutant with high toxicity, long-distance
transport, persistence, and bioaccumulation in the environment.
Coal has always been the major primary energy source in the
world, and it has been mainly utilized to generate electricity. CFPP
is the major anthropogenic mercury emission source to the atmo-
sphere, especially for China, India, and the US. Many countries have
issued stringent mercury emission limits for CFPPs.
With advantages of quickness, convenience, and high efficiency,
the thermal decomposition analytical method to determine mer-
cury content in coal has become more favorable than the chemi-
cal digestion analytical method. The mean mercury concentration
in the coal of China (0.20 mg/kg), the US (0.17 mg/kg), and South
Africa (0.20 mg/kg) is higher than that of the world (0.1 mg/kg),
which needs more attention. Mercury forms in coal are sulfide-
bound mercury (mainly pyritic mercury, dominant), clay-bound
mercury, and organic matter-bound mercury in general. Mercury
in coal is strongly correlated with sulfur content for most coals,
in which pyritic mercury is the typically dominant form while
organic- and sulfide-bound mercury (mainly pyritic mercury) are
the major species in low-sulfur coals. In addition, the existing
forms of mercury in coal are affected by many factors, including
diagenetic, coalification, and post-diagenetic conditions.
Mercury transformation during coal combustion can be divided
into homogeneous (without fly ash) and heterogeneous (with fly
ash) reaction, which are influenced by the coal types, flue gas
components, flue gas temperature, combustion atmosphere, coal
ash properties, etc. For the mercury homogeneous reaction, chlo-
rine benefits Hg0 oxidation and the oxidation degree are affected
by the chlorine forms (Cl radical > Cl2 > HCl), flue gas tempera-
ture (HCl is favorable at high temperature while Cl2 is favorable
at low temperature), and chlorine concentration (Hg0 oxidation
rate increases as their concentration increases), etc. NO or NO2
are positive for Hg0 oxidation. With the addition of chlorine, the
effects of NO on Hg0 oxidation have not reached into a consis-
tent conclusion, which include negative, little, or sometimes pos-
itive influence. SO2 alone can not lead to Hg0 oxidation, while
the existence of O2 promotes Hg0 oxidized by SO2 . The enhance-
ment or inhibition of SO2 on Hg0 oxidation by HCl is affected by
the concentration of SO2 and HCl. H2 O can inhibit Hg0 oxidation
mainly through consuming Cl. O2 may benefit Hg0 oxidation with
slight enhancement. For the Hg0 heterogeneous reaction, fly ash
with larger particle size is generally beneficial for mercury adsorp-
tion, which has a relationship with the UBC and carbon types.
The mercury heterogeneous reaction on fly ash concerning UBC
contains the physical adsorption and chemical reaction, in which
the physical adsorption is influenced by the particle size, surface
area, etc. that are positive with UBC. In addition, the active sites,
including some certain unburned carbon forms (anisotropic car-
bon particles), oxygen function groups (C=O, OH/C–O, (O–C=O)–
O), and halogens, etc., can transform Hg0 (g) into adsorbed and
gaseous Hg2+ . The iron oxides in fly ash promote Hg0 oxidation
and adsorption, which are influenced by the iron oxides type and
reaction temperature. The Hg0 → FeHgCl(s) → HgCl2 is thought to
be the main route for Hg0 oxidation by HCl on the Fe2 O3 sur-
face. For different reaction temperatures, the Hg0 removal mecha-
nism with HCl and Fe2 O3 includes the Eley-Rideal mechanism with
HCl pre-adsorption (80–280 °C), the Langmuir-Hinshelwood mech-
anism (280–580 °C), and both the homogenous reaction of Hg0
and HCl and the Langmuir-Hinshelwood mechanism (higher than
680 °C). Chlorine and bromine in flue gas promote the Hg0 hetero-
geneous reaction with fly ash while SO2 and H2 O have inhibitory
effects.
The Hgg concentration in oxy-coal combustion is higher than
that in air-coal combustion. There is no common agreement in the
ratio of Hg2+ to Hgg for all the studied oxy-coal combustion condi-
tions. For the mercury homogenous transformation under oxy-coal
combustion, O2 promotes Hg0 oxidation with Cl2 while NO and
CO2 inhibit or do not favor that reaction. CO2 increases Hg0 oxi-
dation in the atmosphere of NO and N2 . SO2 limits Hg0 oxidation
while HCl has a higher oxidation effect on Hg0 than that under
air-coal combustion conditions. The influence of H2 O on Hg0 oxida-
tion has not reached into an agreement yet, which may be related
to the flue gas temperature or flue gas components. For mercury
heterogeneous transformation under oxy-coal combustion, fly ash
plays an important role for Hg0 oxidation. SO3 inhibits mercury re-
tention by fly ash while H2 O promotes this phenomenon. There is
 S. Zhao, D. Pudasainee and Y. Duan et al. / Progress in Energy and Combustion Science 73 (2019) 26–64
no agreement in the distribution between Hgp and Hgg affected by
O2 .
The generally used on-site mercury sampling methods, namely,
OHM, US EPA Method 30B, and Hg-CEMS, are summarized, in-
cluding the sampling or analysis principle, sampling requirements,
and the comparsion of their advantages and disadvantages. With
more and more strict limits on pollutants emitted from CFPPs, the
installation share of APCDs, which include SCR, ESP, FF, WFGD,
and WSEP, increases. The APCDs have co-beneficial effects on mer-
cury besides the conventional pollutants, like NOx , PM, SO2 , and
fine PM. The SCR equipment is good at Hg0 oxidation with rate
of 6.5–79.9%, affected by flue gas components, boiler load, SCR
space velocity, SCR catalyst structure, and service time of the
catalysts. With high PM removal efficiency, the ESP and FF spe-
cialize in Hgp capture. The Hgt removal rate of ESP and FF is
11.5–90.4% and 28.5–90%, respectively, influenced by the flue gas
temperature, mercury species in flue gas, fly ash components,
and their PM capture performance, etc. FF exerts a higher mer-
cury removal rate than ESP, due to its higher PM capture abil-
ity. WFGD device has high co-removal performance for Hg2+ be-
cause of its high water-solubility. The Hg2+ removal rate by WFGD
is 83.45–94.53%, with the Hgt removal rate of 3.9–72%. However,
Hg0 re-emission may also occur in WFGD process, which is af-
fected by the operating temperature, pH, O2 concentration in flue
gas, transitional metal ions concentration, etc. WESP can remove
32–40%, 72–82%, and 33–100% of Hg0 , Hg2+ , and Hgp , respec-
tively. The mercury transformation across SCR, ESP, FF, WFGD, and
WESP is also reviewed. ESP seems to be a stronger contributor
for Hgt removal by SCR+ESP+WFGD, followed by WFGD and SCR
device. The Hgt removal rate for ESP+WFGD, SCR+ESP+WFGD,
SCR+ESP+FF+WFGD, and SCR+ESP+WFGD+WESP is 35.5–84%,
43.8–94.9%, 58.78–73.32%, and 56.59–89.07%, respectively. The
mercury emission concentration in the reviewed CFPPs of China,
South Korea, and Poland, the Netherlands and the US is 0.29–
16.3 μg/m3 . The MEF expressed as g/1012 J for the CFPPs is 0.052–
12.06 (China), 0.046–12.50 (average 1.63, the US, bituminous coal),
0.198–4.565 (average 2.08, the US, subbituminous coal), 1.723–
24.04 (average 6.79, the US, lignite coal), and 0.71–6.09 (Poland).
Mercury in some fly ash and gypsum, and in most WFGD and
WESP wastewater is higher than the relevant limits, and attention
needs to be given to whether they are processed further or dis-
posed off.
For the pre-combustion mercury removal, physical coal wash-
ing technologies can obtain 0–65% of the mercury removal rate,
which is mainly affected by coal types. However, it is difficult to
meet mercury removal requirements only by coal washing. The
mild pyrolysis method can remove mercury from coal to a cer-
tain extent, and the mercury removal performance has a wide
range, influenced by the thermal treatment temperature, residence
time, sweep gas flow rate, and especially the mercury forms in
coal. For in-combustion mercury removal, the low-NOx combustion
technology and CFB combustion technology enhance mercury re-
moval. Compared to these methods, putting halogens into coal to
transform Hg0 to Hg2+ or Hgp has been widely studied to remove
mercury, which is a method that is simple to operate, highly effi-
cient, and low in cost. It can achieve a 60–96% mercury removal
rate with little addition of halogens in field tests. Post-combustion
mercury removal can be divided into three aspects. One aspect is
the improvement of the existing APCDs, such as enhancing Hg0
oxidation by the SCR catalyst, which can be improved through
modifying the catalyst by metal oxides such as RuO2 , Ce-Mn ox-
ides, CeO2 , Fe2 O3 , and CaCl2 ; and suppressing Hg0 re-emission in
WFGD by adding oxidants or special chemical reagents, such as
NaClO2 , Al2 (SO4 )3 , SCN- or S2− and HS− , Na2 S4 , TMT15, Nalco-8034
reagent, DTCR, etc. The second aspect is to use mercury oxidiz-
ing catalysts and oxidizing chemicals to transform Hg0 into Hg2+
57
and/or Hgp , including noble metal-based catalysts and non-noble
metal-based catalysts, hydrogen halogens (HF, HCl, HBr, and HI),
ozone, and H2 O2 . For oxidizing chemicals, the HBr seems to be
more effective for Hg0 oxidation. The last aspect is to adopt mer-
cury removal adsorbents, including carbon-based adsorbents (AC,
biochar, and petroleum coke), fly ash, calcium-based adsorbents,
and mineral adsorbents. To enhance Hg0 removal efficiency by the
AC, halogens, sulfur, metal chlorides, and NTP treatment have been
adopted to modify the AC. Mercury removal performance by the
AC follows the decreasing order of AC < Cl-impregnated AC < Br-
impregnated AC < I-impregnated AC. Halogen modification can im-
prove mercury removal efficiency by the biochar, in which C-X and
C=O may be the major chemisorption sites for Hg0 adsorption. The
chemical-mechanical bromination process can generate more ac-
tive mercury adsorption sites on the brominated petroleum cokes,
which benefits Hg0 removal. The modified fly ash can be adopted
to capture Hg0 , especially by using the halogen modification. The
complexity of the physical and chemical structure of the fly ash
surface from different power plants results in a wide mercury re-
moval rate. Moreover, the subsequent utilization or disposal of the
fly ash adsorbents in light of the stability and leaching of mercury
and halogens should be considered. Ca-based sorbents have little
effect on mercury removal even after activation, which have more
Hg2+ adsorption ability than Hg0 . The mineral mercury removal
adsorbent is mainly modified by the halogens, in which chemisorp-
tion plays an important role in mercury adsorption.
For the regenerable mercury removal adsorbent, the magnetic
adsorbent modified by metal oxides or the metal halide is the most
promising sorbent for the removal of mercury in coal-fired flue
gas compared to the noble metal and conventional metal oxides,
which has advantages of high mercury removal efficiency, low in-
vestment, easy separation from fly ash, and mercury recovery, etc.
It is very difficult for the current multipollutant control technolo-
gies to realize a higher removal rate for NO, SO2 , and Hg0 simulta-
neously.
8. Further works
For mercury transformation in coal combustion process, the
heterogeneous reaction mechanism among fly ash, flue gas com-
ponents, and mercury is complicated compared to the mercury ho-
mogenous reaction. However, the present published studies mainly
focus on effects of fly ash physical structure properties, unburned
carbon, and Fe2 O3 on Hg0 oxidation. The influence of flue gas com-
ponents and the wide reaction temperature range on mercury ox-
idation or adsorption by fly ash is rarely studied systematically,
which needs further attention. The mercury emission data for oxy-
coal combustion is not enough, especially the concentration and
distribution of various mercury species, mercury removal efficien-
cies by APCDs, etc. Many explanations for the effects of flue gas
components on mercury transformation in oxy-coal combustion at-
mosphere are only prediction, which has no credible evidence. The
models for mercury homogeneous and heterogeneous transforma-
tion under oxy-coal combustion conditions should be developed.
For mercury co-removal and emission in CFPPs, the following
aspects need further study, including developing a detailed mer-
cury transformation or removal mechanism across each APCD, es-
pecially SCR equipment; exploring the way to improve the Hg0 ox-
idation rate in SCR equipment, or the removal efficiency of APCDs
and their combination; obtaining more mercury content data in
CBPs and giving relevant emission limits; and determining the
chemical species of mercury in fly ash and gypsum, which is im-
portant for their utilization or disposal.
For mercury removal technologies for CFPPs, further studies
include those investigating the inhibition of Hg0 re-emission in
WFGD device by oxidants or special chemical reagents on pilot-
58 S. Zhao, D. Pudasainee and Y. Duan et al. / Progress in Energy and Combustion Science 73 (2019) 26–64
and full-scale tests with technically and economically feasible addi-
tives; exploring the deep mercury removal mechanism by putting
halogens into the coal; studying the stability and leaching of mer-
cury and halogens of commonly used carbon-based adsorbents and
fly ash for their following disposal; and conducting more field tests
applying regenerable mercury removal adsorbent, especially mag-
netic adsorbent modified by metal oxides or the metal halides in
CFPPs which are foreseen to evaluate their applicability.
Acknowledgments
This work was financially supported by the National Key R&D
Program of China (2016YFB0600604), the National Natural Science
Foundation of China (51876039, 51576044, 51376046, 51076030),
the Scientific Research Foundation of Graduate School of Southeast
University (YBJJ1706), the Graduate Student Research and Innova-
tion Program of Jiangsu Province (KYCX17_0072), the Fundamen-
tal Research Funds for the Central Universities, and the financial
support from the China Scholarship Council (CSC). The mercury re-
search team members at the Southeast University are specially ac-
knowledged for which most of their work was based on this paper.
We would like to thank the editor and reviewers of this manuscript
for their valuable suggestions and comments.
Notes
The authors declare no competing financial interest.
Supplementary material
Supplementary material associated with this article can be
found, in the online version, at doi:10.1016/j.pecs.2019.02.001.
References
[1] Wang S, Zhang L, Zhao B, Meng Y, Hao J. Mitigation Potential of mercury
emissions from coal-fired power plants in China. Energ Fuel 2012;26:4635–42.
[2] Hu Y, Cheng H. Control of mercury emissions from stationary coal combus-
tion sources in China: current status and recommendations. Environ Pollut
2016;218:1209–21.
[3] Travnikov O. Atmospheric transport of mercury. In: Liu G, Cai Y, O’Driscoll N,
editors. Environmental chemistry and toxicology of mercury. New Jersey: Wiley;
2012. p. 331–65.
[4] Gworek B, Dmuchowski W, Baczewska AH, Bragoszewska ˛ P, Be-
mowska-Kałabun O, Wrzosek-Jakubowska J. Air contamination by mer-
cury, emissions and transformations-a review. Water Air Soil Pollut
2017;228(123):1–31.
[5] Beckersa F, Rinklebe J. Cycling of mercury in the environment: sources,
fate, and human health implications: a review. Crit Rev Env Sci
2017;47(9):693–794.
[6] Zhang X. The investigation of the stabilization of mercury in WFGD solution and
gypsum (Master thesis). Huazhong University of Science and Technology; 2015.
(in Chinese).
[7] Wang S, Zhang L, Wang L, Wu Q, Wang F, Hao J. A review of atmospheric
mercury emissions, pollution and control in China. Front Environ Sci Eng
2014;8(5):631–49.
[8] Pirrone N, Cinnirella S, Feng X, Finkelman RB, Friedli HR, Leaner J, Mason R,
Mukherjee AB, Stracher GB, Streets DG, Telmer K. Global mercury emissions
to the atmosphere from anthropogenic and natural sources. Atmos Chem Phys
2010;10:5951–64.
[9] Glodek A, Pacyna JM. Mercury emission from coal-fired power plants in
Poland. Atmos Environ 2009;43:5668–73.
[10] AMAP/UNEP. Technical background report to the global atmospheric, 2008.
http://wedocs.unep.org/bitstream/handle/20.500.11822/13770/Technical_
background_report.pdf?sequence=1&isAllowed=y
[11] Pacyna EG, Pacyna JM, Sundseth K, Munthe J, Kindbom K, Wilson S, Steen-
huisen F, Maxson P. Global emission of mercury to the atmosphere from
anthropogenic sources in 2005 and projections to 2020. Atmos Environ
2010;44:2487–99.
[12] Milford JB, Pienciak A. After the clean air mercury rule: prospects for re-
ducing mercury emissions from coal-fired power plants. Environ Sci Technol
2009;43:2669–73.
[13] United States Environmental Protection Agency National emission standards
for hazardous air pollutants from coal- and oil-fired electric utility steam
generating units and standards of performance for fossil-fuel-fired elec-
tric utility, industrial-commercial-institutional, and small industrial-commer-
cial-institutional steam generating units; Proposed Rule, United States Envi-
ronmental Protection Agency. Federal Register 2011;76(85).
[14] Dίaz-Somoano M, Unterberger S, Hein KRG. Mercury emission control
in coal-fired plants: the role of wet scrubbers. Fuel Process Technol
2007;88:259–63.
[15] MEP, Ministry of Environmental Protection of China. Emission standard of air
pollutants for thermal power plants, GB 13223–2011, 2011 (in Chinese).
[16] Ancora MP, Zhang L, Wang S, Schreifels JJ, Hao J. Meeting minamata: cost-ef-
fective compliance options for atmospheric mercury control in Chinese coal–
fired power plants. Energy Policy 2016;88:485–94.
[17] BP statistical review of World Energy 2017. https://www.bp.com/
content/dam/bp/en/corporate/pdf/energy-economics/statistical-review-2017/
bp-statistical-review-of-world-energy-2017-full-report.pdf.
[18] Shang Y, Hei P, Lu S, Shang L, Li X, Wei Y, Jia D, Jiang D, Ye Y, Gong J, Lei X,
Hao M, Qiu Y, Liu J, Wang H. China’s energy-water nexus: assessing water
conservation synergies of the total coal consumption cap strategy until 2050.
Appl Energy 2018;210:643–60.
[19] Zhang D, Wang J, Lin Y, Si Y, Huang C, Yang J, Huang B, Li W. Present situa-
tion and future prospect of renewable energy in China. Renew Sust Energ Rev
2017;76:865–71.
[20] Mishra S, Pradha N, Panda S, Akcil A. Biodegradation of dibenzothiophene
and its application in the production of clean coal. Fuel Process Technol
2016;152:325–42.
[21] Bai X, Ding H, Lian J, Ma D, Yang X, Sun N, Xue W, Chang Y. Coal
production in China: past, present, and future projections. Int Geol Rev
2018;60(5–6):535–47.
[22] International Energy Agency. Coal information: overview (2017 edi-
tion). http://www.iea.org/publications/freepublications/publication/
CoalInformation2017Overview.pdf.
[23] Vejahati F, Xu Z, Gupta R. Trace elements in coal: associations with coal
and minerals and their behaviour during coal utilization-a review. Fuel
2010;89:904–11.
[24] Mashyanov NR, Pogarev SE, Panova EG, Panichev N, Ryzhov V. Determination
of mercury thermospecies in coal. Fuel 2017;203:973–80.
[25] Xu P, Zhang B, Zeng X, Xu Y, Luo G, Yao H. Influence of Hg occurrence in coal
on accuracy of Hg direct measurement based on thermal decomposition. Int
J Coal Geol 2017;170:14–18.
[26] Jongwana LT, Crouch AM. Mercury speciation in South African coal. Fuel
2012;94:234–9.
[27] Zhang L, Wang S, Meng Y, Hao J. Influence of mercury and chlorine content
of coal on mercury emissions from coal-fired power plants in China. Environ
Sci Technol 2012;46:6385–92.
[28] ASTM: D6414-14. Standard test methods for total mercury in coal and coal com-
bustion residues by acid extraction or wet oxidation/cold vapour atomic absorp-
tion https://compass.astm.org/download/D6414.16009.pdf.
[29] ASTM D6722-01. Standard test method for total mercury in coal and coal
combustion residues by direct combustion analysis https://www.scribd.com/
document/300616906/D6722- Standard- Testing- Method- for- Total- Mercury-
in- Coal- and- Coal- Combustion- Residues- by-Direct-Combustion-Analysis.
[30] EPA Method 7471B (SW-846): Mercury in solid or semisolid wastes (manual
cold-vapour technique). Revision 2. Washington, DC: U.S. EPA. https://www.
epa.gov/sites/production/files/2015-12/documents/7471b.pdf.2007.
[31] ISO 15237:2016. Solid mineral fuels -Determination of total mercury content
of coal. https://www.iso.org/obp/ui/#iso:std:70207:en. 2016-11.
[32] Zhang J, Ren D, Xu D, Zhao H. Mercury in coal and its effect on environment.
Adv Environ Sci 1997;7(3):100–4.
[33] Ren D, Zhao F, Dai S, Zhang J, Luo K. Geochemistry of trace elements in coals.
Beijing: the Science Press; 2006. p. 268–79. (in Chinese).
[34] Tang X, Huang W. Trace elements in chinese coals. Beijing: The Commercial
Press; 2004. p. 8–9. (in Chinese).
[35] Zheng L, Liu G, Qi C, Chen Y, Zhang Y. Study on environmental geochemistry
of mercury in Chinese coals. J Uni Sci Technol China 2007;37(8):953–63 (in
Chinese).
[36] Yang A, Yan Z, Hui R, Shen Z, Zhuang K. The abundance, distribu-
tion, and modes of occurrence of Hg in Chinese coals. Sci Technol Eng
2015;15(32):1671–815 (in Chinese).
[37] Mukherjee AB, Zevenhoven R, Bhattacharya P, Sajwan KS, Kikuchi R. Mercury
flow via coal and coal utilization by-products: a global perspective. Resour
Conserv Recy 2008;52:571–91.
[38] Finkelman RB. Trace and minor elements in coal. In: Engel MH, Macko SA,
editors. Organic geochemistry. New York: Plenum; 1993. p. 10–12.
[39] Lusilao-Makiese J, Tessier E, Amouroux D, Tutu H, Chimuka L, Cukrowska EM.
Speciation of mercury in South African coals. Toxicol Environ Chem
2012;94(9):1688–706.
[40] Belkin HE, Tewalt SJ, Hower JC, Stucker JD, O’Keefe JMK. Geochemistry and
petrology of selected coal samples from Sumatra, Kalimantan, Sulawesi, and
Papua. Indonesia. Int J Coal Geol 2009;77:260–8.
[41] Wierzchowski K, Checko J, Pyka I. Variability of mercury content in coal
matter from coal seams of the Upper Silesia Coal Basin. Arch Min Sci
2017;62(4):843–56.
[42] Swaine DJ, Goodarzi F. Environmental aspects of trace elements in coal.
Netherlands: Kluwer Academic Publishers; 1995. p. 23–8.
 S. Zhao, D. Pudasainee and Y. Duan et al. / Progress in Energy and Combustion Science 73 (2019) 26–64
[43] Yudovich YE, Ketris MP. Mercury in coal: a review. Part 1. Geochemistry. Int J
Coal Geol 2005;62:107–34.
[44] Song D, Li C, Song B, Yang Ci, Li Y. Geochemistry of mercury in the Permian
tectonically deformed coals from Peigou mine, Xinmi coalfield, China. Acta
Geol Sin-Engl 2017;91(6):2243–54.
[45] Zhai J, Guo S, Wei XX, Cao Y, Gao L. Characterization of the modes of oc-
currence of mercury and their thermal stability in coal gangues. Energ Fuel
2015;29:8239–45.
[46] López-Antón MA, Díaz-Somoano M, Ochoa-González R, Martínez-Tara-
zona MR. Analytical methods for mercury analysis in coal and coal combus-
tion by-products. Int J Coal Geol 2012;94:44–53.
[47] Luo G, Yao H, Xu M, Gupta R, Xu Z. Identifying modes of occurrence
of mercury in coal by temperature programmed pyrolysis. P Combust Inst
2011;33:2763–9.
[48] Wagner NJ, Tlotleng MT. Distribution of selected trace elements in den-
sity fractionated Waterberg coals from South Africa. Int J Coal Geol
2012;94:225–37.
[49] Zheng L, Liu G, Chou CL. Abundance and modes of occurrence of mercury in
some low-sulfur coals from China. Int J Coal Geol 2008;73:19–26.
[50] Zheng L, Liu G, Qi C, Zhang Y, Wong M. The use of sequential extraction to
determine the distribution and modes of occurrence of mercury in Permian
Huaibei coal, Anhui Province, China. Int J Coal Geol 2008;73:139–55.
[51] Merdes AC, Keener TC, Khang SJ, Jenkins R G. Investigation into the fate of
mercury in bituminous coal during mild pyrolysis. Fuel 1998;77(15):1783–92.
[52] Uruski L, Gorecki J, Macherzynski M, Dziok T, Golas J. The ability of Polish
coals to release mercury in the process of thermal treatment. Fuel Process
Technol 2015;140:12–20.
[53] Reis AT, Coelho JP, Rodrigues SM, Rocha R, Davidson CM, Duarte AC, Pereira E.
Development and validation of a simple thermo-desorption technique for
mercury speciation in soils and sediments. Talanta 2012;99:363–8.
[54] Sui Z, Zhang Y, Li W, Orndorff W, Cao Y, Pan WP. Partitioning effect of mer-
cury content and speciation in gypsum slurry as a function of time. J Therm
Anal Calorim 2015;119:1611–18.
[55] Liu X, Wang S, Zhang L, Wu Y, Duan L, Hao J. Speciation of mercury in FGD
gypsum and mercury emission during the wallboard production in China.
Fuel 2013;111:621–7.
[56] Laumb JD, Benson SA, Olson EA. X-ray photoelectron spectroscopy analysis of
mercury sorbent surface chemistry. Fuel Process Technol 2004;85:577–85.
[57] Liu T, Xue L, Guo X, Huang Y, Zheng C. DFT and experimental study on
the mechanism of elemental mercury capture in the presence of HCl on
α -Fe2 O3 (001). Environ Sci Technol 2016;50:4863–8.
[58] Li H, Zhu L, Wang J, Li L, Lee PH, Feng Y, Shih K. Effect of nitrogen oxides on
elemental mercury removal by nanosized mineral sulfide. Environ Sci Technol
2017;51:8530–6.
[59] Li H, Wu S, Wu CY, Wang J, Li L, Shih K. SCR atmosphere induced reduc-
tion of oxidized mercury over CuO−CeO2 /TiO2 catalyst. Environ Sci Technol
2015;49:7373–9.
[60] Liu S, Li C, Zhu X, Zhou H. Distribution characteristics of total mercury in im-
ported coals at Shanghai port. Rock Miner Anal 2014;33(5):730–6 (in Chinese).
[61] Feng X, Hong Y, Ni J, Zhou B, Wang Y. Distribution, occurrence of mer-
cury in Guizhou coal and its impact on environment. Coal Geol Explor
1998;26(2):12–14 (in Chinese).
[62] Kostova I. Abundance, distribution and mode of occurrence of mercury
in Bulgarian low to medium-sulphur coals. Compt Rend Acad Bulg Sci
2017;70(9):1279–88.
[63] Ohki A, Taira M, Hirakawa S, Haraguchi K, Kanechika F, Nakajima T,
Takanashi H. Determination of mercury in various coals from different coun-
tries by heat-vapourization atomic absorption spectrometry: influence of par-
ticle size distribution of coal. Microchem J 2014;114:119–24.
[64] Dziok T, Strugała A, Rozwadowski A, Macherzynski M. Studies of the correla-
tion between mercury content and the content of various forms of sulfur in
Polish hard coals. Fuel 2015;159:206–13.
[65] Finkelman RB. Mode of occurrence of trace elements in coal. US Geol Surv
Open-file Report 1981;312:81–99.
[66] Pan JH, Zhou CC, Cong LF, Zhang NN, Liu C, Peng CB, Ouyang CH. Mercury
in Chinese coals: modes of occurrence and its removal statistical laws during
coal separation. Energ Fuel 2017;31:986–95.
[67] Riley KW, French DH, Farrell OP, Wood RA, Huggins FE. Modes of occur-
rence of trace and minor elements in some Australian coals. Int J Coal Geol
2012;94:214–24.
[68] Bool LE, Helble JJ. A laboratory study of the partitioning of trace-elements
during pulverized coal combustion. Energ Fuel 1995;9(5):880–7.
[69] Palmer CA, Mroczkowski SJ, Kolker A. Chemical analyses and modes of
occurrence of selected trace elements in a Powder River Basin coal and
its corresponding simulated cleaned coal. US Geol Surv Open-File Report
20 0 0;52:0 0 0–323.
[70] Guo S, Yang J, Liu Z. Characterization of Hg in coals by temperature-pro-
grammed decomposition-atomic fluorescence spectroscopy and acid-leaching
techniques. Energ Fuel 2012;26:3388–92.
[71] Feng X, Hong Y. Modes of occurrence of mercury in coals from Guizhou, Peo-
ple’s Republic of China. Fuel 1999;78:1181–8.
[72] Strezov V, Evans TJ, Ziolkowski A, Nelson PF. Mode of occurrence and thermal
stability of mercury in coal. Energ Fuel 2010;24:53–7.
[73] Zhao S, Duan Y, Wang C, Liu M, Lu J, Tan H, Wang X, Wu L. Migration be-
haviour of trace elements at a coal-fired power plant with different boiler
loads. Energ Fuel 2017;31:747–54.
59
[74] Galbreath KC, Zygarlicke CJ. Mercury transformations in coal combustion flue
gas. Fuel Process Technol 20 0 0;65-66:289–310.
[75] Pavlish JH, Sondreal EA, Mann MD, Olson ES, Galbreath KC, Laudal DL, Ben-
son SA. Status review of mercury control options for coal-fired power plants.
Fuel Process Technol 2003;82:89–165.
[76] Hall B, Schager P, Lindqvist O. Chemical reaction of mercury in combustion
flue gases. Water Air Soil Poll 1991;56(1):3–14.
[77] Niksa S, Naik CV, Berry MS, Monroe L. Interpreting enhanced Hg oxidation
with Br addition at Plant Miller. Fuel Process Technol 2009;90:1372–7.
[78] Nortona GA, Yang H, Brown RC, Laudal DL, Dunham GE, Erjavec J. Hetero-
geneous oxidation of mercury in simulated post combustion conditions. Fuel
2003;82:107–16.
[79] Yang Y, Liu J, Wang Z, Zhang Z. Homogeneous and heterogeneous reaction
mechanisms and kinetics of mercury oxidation in coal-fired flue gas with
bromine addition. P Combust Inst 2017;36:4039–49.
[80] Czaplicka M, Pyta H. Transformations of mercury in processes of solid fuel
combustion - review. Arch Environ Prot 2017;43(4):82–93.
[81] Gao Y, Zhang Z, Wu J, Duan L, Umar A, Sun L, Guo Z, Wang Q. A critical
review on the heterogeneous catalytic oxidation of elemental mercury in flue
gases. Environ Sci Technol 2013;47:10813–23.
[82] Tao S, Li C, Fan X, Zeng G, Lu P, Zhang X, Wen Q, Zhao W, Luo D, Fan C.
Activated coke impregnated with cerium chloride used for elemental mercury
removal from simulated flue gas. Chem Eng J 2012;210:547–56.
[83] Zheng Y, Jensen AD, Windelin C, Jensen F. Review of technologies for mercury
removal from flue gas from cement production processes. Prog Energ Combust
Sci 2012;38:599–629.
[84] Wang Y, Liu Y, Wu Z, Mo J, Cheng B. Experimental study on the absorption
behaviours of gas phase bivalent mercury in Ca-based wet flue gas desulfur-
ization slurry system. J Hazard Mater 2010;183:902–7.
[85] Park KS, Seo YC, Lee SJ, Lee JH. Emission and speciation of mercury from
various combustion sources. Powder Technol 2008;180:151–6.
[86] Zhao S, Duan Y, Yao T, Liu M, Lu J, Tan H, Wang X, Wu L. Study on the mer-
cury emission and transformation in an ultra-low emission coal-fired power
plant. Fuel 2017;199:653–61.
[87] Edwards JR, Srivastava Ravi K, Kilgroe James D. A study of gas-phase mer-
cury speciation using detailed chemical kinetics. J Air Waste Manage Assoc
2001;51:869–77.
[88] Sable SP, Jong W, Spliethoff H. Combined homo- and heterogeneous model
for mercury speciation in pulverized fuel combustion flue gases. Energ Fuel
2008;22:321–30.
[89] Senior CL, Sarofim AF, Zeng T, Helble JJ, Mamani-Paco R. Gas-phase trans-
formations of mercury in coal-fired power plants. Fuel Process Technol
20 0 0;63:197–213.
[90] Cao Y, Li L, Duan Y, Pan G, Li S, Xu W, Liu K, Riley JT, Pan W, Chu P, Mehta A.
Impact of coal chlorine on mercury emission and its speciation profiles and
metal corrosion from a 100 MW utility PC boiler with cold ESP and low-NOx
burner. In: Proceedings of the 28th international technical conference on coal
utilization and fuel systems, 11, Clearwater, FL; 2003 March.
[91] Shao D, Hutchinson EJ, Cao H, Pan W. Behaviour of chlorine during coal py-
rolysis. Energ Fuel 1994;8(2):399–401.
[92] Ghorishi SB. Fundamentals of mercury speciation and control in coal-fired boil-
ers, report EPA-600/R-98-014, U.S. Washington, DC: Environmental Protection
Agency; February 1998.
[93] Agarwal H, Romero CE, Stenger HG. Comparing and interpreting labora-
tory results of Hg oxidation by a chlorine species. Fuel Process Technol
2007;88:723–30.
[94] Sliger RN, Kramlich JC, Marinov NM. Towards the development of a chemical
kinetic model for the homogenous oxidation of mercury by chlorine species.
Fuel Process Technol 20 0 0;65–66:423–38.
[95] Kilgroe JD, Sedman CB, Srivastava RK, Ryan JV, Lee CW, Thorneloe SA. Interim
Report, No. EPA-600/R-01-109. Washington, DC: US Environmental Protection
Agency; December 2001.
[96] Mamani-Paco RM, Helble JJ. Bench-scale examination of mercury oxidation
under non-isothermal conditions. In: Proceedings of the A&WMA Annual
Conference, Salt Lake City; June 20 0 0.
[97] Laudal DL, Brown TD, Nott BR. Effects of flue gas constituents on mercury
speciation. Fuel Process Technol 20 0 0;65-66:157–65.
[98] Hall B, Schager P, Lindqvist O. Chemical reactions of mercury in combustion
flue gases. Water Air Soil Poll 1991;56:3–14.
[99] Agarwal H, Stenger HG, Wu S, Fan Z. Effects of H2 O, SO2 , and NO on homo-
geneous Hg oxidation by Cl2 . Energ Fuel 2006;20:1068–75.
[100] Wang J, Clements B, Zanganeh K. An interpretation of flue-gas mercury spe-
ciation data from a kinetic point of view. Fuel 20 03;82:10 09–11.
[101] Fry A, Cauch B, Silcox GD, Lighty JS, Senior CL. Experimental evaluation of
the effects of quench rate and quartz surface area on homogeneous mercury
oxidation. P Combust Inst 2007;31:2855–61.
[102] Widmer NC, West J. Annual meeting. 93rd. Salt Lake City, Utah: Air Waste
Manage Assoc; 20 0 0.
[103] Li L, Deng P, Tian A, Xu M, Zheng C, Wong N. A study on the reaction
mechanism and kinetic oxidation of mercury by chlorine species. J Mol Struct
2003;625:277–81.
[104] Wilcox J. A kinetic investigation of high-temperature mercury oxidation by
chlorine. J Phys Chem A 2009;113(24):6633–9.
[105] Wilcox J, Robles J, Marsden DCJ, Blowers P. Theoretically predicted rate con-
stants for mercury oxidation by hydrogen chloride in coal combustion flue
gases. Environ Sci Technol 2003;37(18):4199–204.
60 S. Zhao, D. Pudasainee and Y. Duan et al. / Progress in Energy and Combustion Science 73 (2019) 26–64
[106] Wilcox J, Marsden DCJ, Blowers P. Evaluation of basis sets and theoretical
methods for estimating rate constants of mercury oxidation reactions involv-
ing chlorine. Fuel Process Technol 2004;85(5):391–400.
[107] Wilcox J, Blowers P. Decomposition of mercuric chloride and application to
combustion flue gases. Environ Chem 2004;1:166–71.
[108] Wilcox J, Blowers P. Some comments on ‘A study on the reaction mecha-
nism and kinetic of mercury oxidation by chlorine species’. [J. Mol. Struct.
(Theochem) 625 (2003) 277]. J Mol Struct -Theochem 2004;674:275–8.
[109] Khalizov AF, Viswanathan B, Larregaray P, Ariya PA. A theoretical study on
the reactions of Hg with halogens: atmospheric implications. J Phys Chem A
2003;107:6360–5.
[110] Krishnakumar B, Helble JJ. Determination of transition state theory rate con-
stants to describe mercury oxidation in combustion systems mediated by Cl,
Cl2, HCl and HOCl. Fuel Process Technol 2012;94:1–9.
[111] Liu J, Qu W, Yuan J, Wang S, Qiu J, Zheng C. Theoretical studies of properties
and reactions involving mercury species present in combustion flue gases.
Energ Fuel 2010;24:117–22.
[112] Zheng C, Liu J, Liu Z, Xu M, Liu Y. Kinetic mechanism studies on reactions of
mercury and oxidizing species in coal combustion. Fuel 2005;84:1215–20.
[113] Wilcox J, Rupp E, Ying SC, Lim DH, Negreira AS, Kirchofer A, Feng F, Lee K.
Mercury adsorption and oxidation in coal combustion and gasification pro-
cesses. Int J Coal Geol 2012;90-91:4–20.
[114] Hou W, Zhang B, Zhou Q, Gu D, Zhong Z, Yang H. Numerical simulation of
homogeneous mercury oxidation by chemical kinetic coupled with computa-
tion fluid dynamics. P CSEE 2010;30(5):23–7 (in Chinese).
[115] Naruse I, Yoshiie R, Kameshima T, Takuwa T. Gaseous mercury oxidation be-
haviour in homogeneous reaction with chlorine compounds. J Mater Cycles
Waste Manag 2010;12:154–60.
[116] Qiao Y, Xu MH. The oxidation kinetics of mercury in Hg/O/H/Cl system. Dev
Chem Eng Mineral Process 2005;13(3/4):483–94.
[117] Kellie S, Cao Y, Duan Y, Li L, Chu P, Mehta A, Carty R, Riley JT, Pan WP. Factors
affecting mercury speciation in a 100-MW coal-fired boiler with low-NOx
burners. Energ Fuel 20 05;19:80 0–6.
[118] Wu H, Qiu JR, Tang SL, Liu H, Wang QH, Zeng HC. Mercury and halides emis-
sions from 200 MW pulverized coal combustion boiler. Asia-Pac J Chem Eng
2010;5:281–6.
[119] Hall B, Schager P, Lindqvist O. Chemical reactions of mercury in combustion
flue gas. Water Air Soil Pollut 1991;56:3–14.
[120] Rumayor M, Svoboda K, Svehla J, Pohorelý M, Syc M. Mitigation of gaseous
mercury emissions from waste-to-energy facilities: homogeneous and hetero-
geneous Hg-oxidation pathways in presence of fly ashes. J Environ Manage
2018;206:276–83.
[121] Niksa S, Helble JJ, Fujiwara N. Kinetic modeling of homogeneous mercury oxi-
dation: the importance of NO and H2 O in predicting oxidation in coal-derived
systems. Environ Sci Technol 2001;35:3701–6.
[122] Auzmendi-Murua I, Bozzelli JW. Gas phase mercury oxidation by halogens
(Cl, Br, I) in combustion effluents: influence of operating conditions. Energ
Fuel 2016;30:603–15.
[123] Preciado I, Young T, Silcox G. Mercury oxidation by halogens under air- and
oxygen-fired conditions. Energ Fuel 2014;28:1255–61.
[124] Smith CA, Krishnakumar B, Helble JJ. Homo- and heterogeneous mer-
cury oxidation in a bench-scale flame-based flow reactor. Energ Fuel
2011;25:4367–76.
[125] Qiu J, Sterling RO, Helble JJ. Development of an improved model for deter-
mining the effects of SO2 on homogeneous mercury oxidation. In: Proceed-
ings of the Clear Water Conference; 2003.
[126] Morris EA, Morita K, Jia CQ. Understanding the effects of sulfur on mercury
capture from coal-fired utility flue gases. J Sulfur Chem 2010;31(5):457–75.
[127] Zhao Y, Mann M D, Olson ES, Pavlish JH, Dunham GE. Effects of sulfur diox-
ide and nitric oxide on mercury oxidation and reduction under homogeneous
conditions. J Air Waste Manage Assoc 2006;56:628–35.
[128] Hall B, Schager P, Weesman J. The homogeneous gas phase reaction of mer-
cury with oxygen, and the corresponding heterogeneous reactions in the
presence of active carbon and fly ash. Chemosphere 1995;30(4):611–27.
[129] Xu M, Qiao Y, Zheng C, Li L, Liu J. Modeling of homogeneous mercury speci-
ation using detailed chemical kinetics. Combust Flame 2003;132:208–18.
[130] Xu M, Qiao Y, Liu J, Zheng C. Kinetic calculation and modeling of trace ele-
ment reactions during combustion. Powder Technol 2008;180:157–63.
[131] Zhou Q, Duan Y, Zhu C, Zhang J, She M, Wei H, Hong Y. Adsorption equilib-
rium, kinetics and mechanism studies of mercury on coal-fired fly ash. Korean
J Chem Eng 2015;32(7):1405–13.
[132] Lu Y, Rostam-Abadi M, Chang R, Richardson C, Paradis J. Characteristics of fly
ashes from full-scale coal-fired power plants and their relationship to mer-
cury adsorption. Energ Fuel 2007;21:2112–20.
[133] Külaots I, Hurt RH, Suuberg EM. Size distribution of unburned carbon in coal
fly ash and its implications. Fuel 2004;83(2):223–30.
[134] He P, Jiang X, Wu J, Pan W, Ren J. Characterization of fly ash from coal–
fired power plant and their properties of mercury retention. Surf Rev Lett
2015;22(1):1–11 1550018 (11 pages).
[135] Wu J, Wang P, He L, Pan W, Ren J, He P, Wu Q, Zhang J. Experimental study
of the effect of fly ash particle size on its mercury adsorption capability in
the flue gas. Adv Mater Res 2012;356–360:1664–7.
[136] Bhardwaj R, Chen X, Vidic RD. Impact of fly ash composition on mercury spe-
ciation in simulated flue gas. J Air Waste Manage Assoc 2009;59:1331–8.
[137] Kostova IJ, Hower JC, Mastalerz M, Vassilev SV. Mercury capture by selected
Bulgarian fly ashes: influence of coal rank and fly ash carbon pore structure
on capture efficiency. Appl Geochem 2011;26:18–27.
[138] Suárez-Ruiz I, Parra JB. Relationship between textural properties, fly ash car-
bons, and Hg capture in fly ashes derived from the combustion of anthracitic
pulverized feed blends. Energ Fuel 2007;21:1915–23.
[139] Gao Z, Ding Y, Han W, Hu H, Lv S. Species and thermal stability of mercury
captured by fly ashes. Environ Prog Sustain Energ 2017;36(2):460–7.
[140] Hower JC, Senior CL, Suuberg EM, Hurt RH, Wilcox JL, Olson ES. Mercury cap-
ture by native fly ash carbons in coal-fired power plants. Prog Energ Combust
Sci 2010;36:510–29.
[141] Ahmaruzzaman M. A review on the utilization of fly ash. Prog Energ Combust
Sci 2010;36:327–63.
[142] Gibb WH, Clarke F, Mehta AK. Fate of coal mercury during combustion. Fuel
Process Technol 20 0 0;65:365–77.
[143] Kolker A, Senior CL, Quick JC. Mercury in coal and impact of coal
quality on mercury emissions from combustion systems. Appl Geochem
2006;21:1821–36.
[144] Hower JC, Clack HL, Hood MM, Hopps SG, Thomas GH. Impact of coal source
changes on mercury content in fly ash: examples from a Kentucky power
plant. Int J Coal Geol 2017;170:2–6.
[145] Hower JC, Groppo JG, Graham UM, Ward CR, Kostova IJ, Maroto-Valer MM,
Dai S. Coal-derived unburned carbons in fly ash: a review. Int J Coal Geol
2017;179:11–27.
[146] Zhao Y, Zhang J, Liu J, Diaz-Somoano M, Abad-Valle P, Martinez-Tarazona MR,
Zheng C. Experimental study on fly ash capture mercury in flue gas. Sci China
Technol Sci 2010;53(4):976–83.
[147] López-Antón MA, Abad-Valle P, Díaz-Somoano M, Suárez-Ruiz I, Martínez–
Tarazona MR. The influence of carbon particle type in fly ashes on mercury
adsorption. Fuel 2009;88:1194–200.
[148] Maroto-Valer M, Zhang Y, Granite EJ, Tang Z, Pennline HW. Effect of porous
structure and surface functionality on the mercury capacity of a fly ash car-
bon and its activated sample. Fuel 2005;84:105–8.
[149] Li Y, Lee C, Gullett B. Importance of activated carbon’s oxygen surface func-
tional groups on elemental mercury adsorption. Fuel 2003;82:451–7.
[150] Kwon S, Borguet E, Vidic RD. Impact of surface heterogeneity on mercury up-
take by carbonaceous sorbents under UHV and atmospheric pressure. Environ
Sci Technol 2002;36:4162–9.
[151] Jew AD, Rupp EC, Geatches DL, Jung JE, Farfan G, Bahet L, Hower JC, Brown GE
Jr, Wilcox J. Mercury interaction with the fine fraction of coal-combus-
tion fly ash in a simulated coal power plant flue gas stream. Energ Fuel
2015;29:6025–38.
[152] Deng S, Shu Y, Li S, Tian G, Huang J, Zhang F. Chemical forms of the fluo-
rine, chlorine, oxygen and carbon in coal flyash and their correlations with
mercury retention. J Hazard Mater 2016;301:400–6.
[153] Yang Y, Liu J, Shen F, Zhao L, Wang Z, Long Y. Kinetic study of heterogeneous
mercury oxidation by HCl on fly ash surface in coal-fired flue gas. Combust
Flame 2016;168:1–9.
[154] Niksa S, Padak B, Krishnakumar B, Naik CV. Process chemistry of Br addition
to utility flue gas for Hg emissions control. Energ Fuel 2010;24:1020–9.
[155] Ghorishi SB, Lee CW, Jozewicz WS, Kilgroe JD. Effects of fly ash transition
metal content and flue gas HCl/SO2 ratio on mercury speciation in waste
combustion. Environ Eng Sci 2005;22:221–31.
[156] Zhuang Y, Thompson JS, Zygarlicke CJ, Pavlish JH. Development of a mer-
cury transformation model in coal combustion flue gas. Environ Sci Technol
2004;38:5803–8.
[157] Wang F, Wang S, Meng Y, Zhang L, Wu Q, Hao J. Mechanisms and roles of
fly ash compositions on the adsorption and oxidation of mercury in flue gas
from coal combustion. Fuel 2016;163:232–9.
[158] Yang J, Zhao Y, Zyryanov V, Zhang J, Zheng C. Physical-chemical character-
istics and elements enrichment of magnetospheres from coal fly ashes. Fuel
2014;135:15–26.
[159] Galbreath KC, Zygarlicke CJ, Tibbetts JE, Schulz RL, Dunham GE. Effects of NOx ,
α -Fe2 O3 , γ -Fe2 O3 , and HCl on mercury transformations in a 7-kW coal com-
bustion system. Fuel Process Technol 2004;86:429–48.
[160] Zhang H, Sun H, Zhao K, Han Y, Wu J, Jiao T, Liang P. Influences of water
vapour and fly ash on elemental mercury removal over cerium-oxide-modi-
fied semi-coke. Fuel 2018;217:211–17.
[161] Li C, Zhang J, Wu J, Zhang X, Chen X, Li C, Zhang J, Zhang L. Experimental
study of the fly ash iron morphology effect on flue gas mercury removal. Adv
Mater Res 2014;864–867:1513–18.
[162] Yang J, Zhao Y, Zhang S, Liu H, Chang L, Ma S, Zhang J, Zheng C. Mercury
removal from flue gas by magnetospheres present in fly ash: role of iron
species and modification by HF. Fuel Process Technol 2017;167:263–70.
[163] Yang Y, Liu J, Wang Z, Liu F. Heterogeneous reaction kinetics of mercury oxi-
dation by HCl over Fe2 O3 surface. Fuel Process Technol 2017;159:266–71.
[164] Jung JE, Geatches D, Lee K, Aboud S, Brown GE, Wilcox J. First-principles in-
vestigation of mercury adsorption on the α − F e2O3(11̄02 ). J Phys Chem C
2015;119:26512–18.
[165] Liu T, Man C, Guo X, Zheng C. Experimental study on the mechanism of mer-
cury removal with Fe2 O3 in the presence of halogens: role of HCl and HBr.
Fuel 2016;173:209–16.
[166] Liu S, Yan N, Liu Z, Qu Z, Wang HP, Chang SG, Miller C. Using bromine gas to
enhance mercury removal from flue gas of coal-fired power plants. Environ
Sci Technol 2007;41:1405–12.
[167] Cao Y, Wang Q, Li J, Cheng J, Chan C, Cohron M, Pan W. Enhancement of
mercury capture by the simultaneous addition of hydrogen bromide (HBr)
and fly ashes in a slipstream facility. Environ Sci Technol 2009;43:2812–17.
 S. Zhao, D. Pudasainee and Y. Duan et al. / Progress in Energy and Combustion Science 73 (2019) 26–64
[168] Abad-Valle P, Lopez-Anton MA, Diaz-Somoano M, Martinez-Tarazona MR. The
role of unburned carbon concentrates from fly ashes in the oxidation and
retention of mercury. Chem Eng J 2011;174:86–92.
[169] Zhao Y, Zhang J, Liu J, Mercedes D, Rosa MM, Zheng C. Study on mecha-
nism of mercury oxidation by fly ash from coal combustion. Chinese Sci Bull
2010;55(2):163–7.
[170] Wang C, Liu X, Li D, Wu W, Xu Y, Si J, Zhao B, Xu M. Effect of H2 O and SO2 on
the distribution characteristics of trace elements in particulate matter at high
temperature under oxy-fuel combustion. Int J Greenh Gas Con 2014;23:51–60.
[171] Oboirien BO, Thulari V, North BC. Enrichment of trace elements in bottom ash
from coal oxy-combustion: effect of coal types. Appl Energ 2016;177:81–6.
[172] Font O, Córdoba P, Leiva C, Romeo LM, Bolea I, Guedea I, Moreno N,
Querol X, Fernandez C, Díez LI. Fate and abatement of mercury and other
trace elements in a coal fluidised bed oxy combustion pilot plant. Fuel
2012;95:272–81.
[173] Hu C, Li W, Yu X, Zheng J, Gao F, Xu M, Li J. Research progress in homoge-
neous oxidation mechanism of element mercury in oxy-fuel combustion flue
gas. Therm Power Generat 2015;44(7):1–11 (in Chinese).
[174] Tan Y, Croiset E, Douglas MA, Thambimuthu KV. Combustion characteristics
of coal in a mixture of oxygen and recycled flue gas. Fuel 2006;85:507–12.
[175] Buhre BJP, Elliot LK, Sheng CD, Gupta RP, Wall TF. Oxy-fuel combus-
tion technology for coal-fired power generation. Prog Energy Combust Sci
2005;31:283–307.
[176] Zhuang Y, Pavlish JH. Fate of hazardous air pollutants in oxygen-fired
coal combustion with different flue gas recycling. Environ Sci Technol
2012;46:4657–65.
[177] Wang F, Shen B, Yang J, Singh S. Review of mercury formation and
capture from CO2 -enriched oxy-fuel combustion flue gas. Energ Fuel
2017;31(2):1053–64.
[178] Wang H, Wang S, Duan Y, Li Y, Ying Z. Experimental study of homogeneous
Hg oxidation in air and oxy-simulated flue gas. J Energy Inst 2018. doi:10.
1016/j.joei.2018.01.010.
[179] Fernańdez-Miranda N, Lopez-Anton MA, Díaz-Somoano M, Martínez-Tara-
zona MR. Effect of oxy-combustion flue gas on mercury oxidation. Environ
Sci Technol 2014;48:7164–70.
[180] Choudhury NN, Bihter Padak. A comprehensive experimental and modeling
study of sulfur trioxide formation in oxy-fuel combustion. Int J Greenh Gas
Con 2016;51:165–75.
[181] Galloway BD, Sasmaz E, Padak B. Binding of SO3 to fly ash components: CaO,
MgO, Na2 O and K2 O. Fuel 2015;145:79–83.
[182] Galloway BD, MacDonald RA, Padak B. Characterization of sulfur products
on CaO at high temperatures for air and oxy-combustion. Int J Coal Geol
2016;167:1–9.
[183] Mitsui Y, Imada N, Kikkawa H, Katagawa A. Study of Hg and SO3 be-
haviour in flue gas of oxy-fuel combustion system. Int J Greenh Gas Con
2011;5S:S143–50.
[184] Wang H, Duan Y, Xue Y, Li Y, Liu M, Wei H. Effects of different coals on mer-
cury distribution in a 6 kWth circulating fluidized bed under air and O2 /CO2
atmosphere via experiment and thermodynamic equilibrium calculation. J En-
ergy Inst 2017;90:229–38.
[185] Wang H, Duan Y, Li Y, Xue Y, Liu M. Investigation of mercury emission and its
speciation from an oxy-fuel circulating fluidized bed combustor with recycled
warm flue gas. Chem Eng J 2016;300:230–5.
[186] Roy B, Chen L, Bhattacharya S. Nitrogen oxides, sulfur trioxide, and mercury
emissions during oxyfuel fluidized bed combustion of Victorian brown coal.
Environ Sci Technol 2014;48:14844–50.
[187] Spörl R, Maier J, Belo L, Shah K, Stanger R, Wallb T, Scheffknecht G. Mercury
and SO3 emissions in oxy-fuel combustion. Energy Proc 2014;63:386–402.
[188] Spor̈l R, Belo L, Shah K, Stanger R, Giniyatullin R, Maier J, Wall T, Schef-
fknecht G. Mercury emissions and removal by ash in coal-fired oxy-fuel com-
bustion. Energ Fuel 2014;28:123–35.
[189] Córdoba P, Maroto-Valer M, Delgado MA, Diego R, Font O, Querol X. Speci-
ation, behaviour, and fate of mercury under oxy-fuel combustion conditions.
Environ Res 2016;145:154–61.
[190] Stanger R, Belo L, Ting T, Spero C, Wall T. Mercury and SO3 measurements on
the fabric filter at the Callide Oxy-fuel Project during air and oxy-fuel firing
transitions. Int J Greenh Gas Con 2016;47:221–32.
[191] Yang J, Ma S, Zhao Y, Zhang J, Liu Z, Zhang S, Zhang Y, Liu Y, Feng Y, Xu K,
Xiang J, Zheng C. Mercury emission and speciation in fly ash from a 35 MWth
large pilot boiler of oxyfuel combustion with different flue gas recycle. Fuel
2017;195:174–81.
[192] Wu H, Liu H, Wang Q, Luo G, Yao H, Qiu J. Experimental study of ho-
mogeneous mercury oxidation under O2 /CO2 atmosphere. Proc Combust Inst
2013;34:2847–54.
[193] Hu C, Hang D, Guo R, Guo Z, Yu X. Influence of H2 O on Hg0 oxida-
tion in the simulated flue gas in oxygen-enriched combustion. Energ Fuel
2017;31:7272–81.
[194] Wang F, Shen B, Yang J, Singh S. Review of mercury formation and
capture from CO2 -enriched oxy-fuel combustion flue gas. Energ Fuel
2017;31(2):1053–64.
[195] Belo LP, Elliott LK, Stanger RJ, Wall TF. Impacts of sulfur oxides on mercury
speciation and capture by fly ash during oxy-fuel pulverized coal combustion.
Energ Fuel 2016;30:8658–64.
[196] Izquierdo MT, Obras-Loscertales M, Diego LF, García-Labiano F, Mendiara T,
Abad A, Gayán P, Adánez J. Mercury emissions from coal combustion in flu-
idized beds under oxy-fuel and air conditions: influence of coal characteris-
tics and O2 concentration. Fuel Process Technol 2017;167:695–701.
61
[197] Fernańdez-Miranda N, Rumayor M, Lopez-Anton MA, Díaz-Somoano M,
Martínez-Tarazona MR. Mercury retention by fly ashes from oxy-fuel pro-
cesses. Energ Fuel 2015;29:2227–33.
[198] Roy B, Bhattacharya S. Release behaviour of Hg, Se, Cr and As during oxy-fuel
combustion using Loy Yang brown coal in a bench-scale fluidized bed unit.
Powder Technol 2016;302:328–32.
[199] Cui J, Duan L, Jiang Y, Zhao C, Anthony EJ. Migration and emission of mercury
from circulating fluidized bed boilers co-firing petroleum coke and coal. Fuel
2018;215:638–46.
[200] Wu J, Cao Y, Pan W, Pan W. Coal-fired-derived flue gas mercury measure-
ment. Coal fired flue gas mercury emission controls. Energy and environment
research in China. Berlin, Heidelberg: Springer; 2015.
[201] Cheng CM, Chen CW, Zhu J, Chen CW, Kuo YW, Lin TH, Wen SH, Zeng YS,
Liu JC, Pan WP. Measurement of vapour phase mercury emissions at coal–
fired power plants using regular and speciating sorbent traps with in-stack
and out-of-stack sampling methods. Enery Fuel 2009;23:4831–9.
[202] Tang H, Duan Y, Zhu C, Li C, She M, Zhou Q, Cai L. Characteristics of a
biomass-based sorbent trap and its application to coal-fired flue gas mercury
emission monitoring. Int J Coal Geol 2017;170:19–27.
[203] Chunfeng Li, Duan Y, Tang H, Zhu C, Zheng Y, Huang T. Mercury emissions
monitoring in a coal-fired power plant by using the EPA Method 30B based
on a calcium-based sorbent trap. Fuel 2018;221:171–8.
[204] Laudal DL. Conducting a RATA of continuous mercury monitors using EPA
Method 30B. Fuel Process Technol 2009;90:1343–7.
[205] US EPA. Determination of total vapour phase mercury emissions from Coal-fired
combustion sources using carbon sorbent traps, Washington D.C.: United States
Environmental Protection Agency; 2008. (EPA Method 30B).
[206] Cauch B, Silcox GD, Lighty JS, Wendt JOL, Fry A, Senior CL. Confounding ef-
fects of aqueous-phase impinger chemistry on apparent oxidation of mercury
in flue gases. Environ Sci Technol 2008;42:2594–9.
[207] Linak WP, Ryan JV, Ghorishi BS, Wendt JOL. Issues related to solu-
tion chemistry in mercury sampling impingers. J Air Waste Manage Assoc
2001;51:688–98.
[208] Fry A, Cauch B, Wendt JOL, Silcox GD, Lighty JS, Senior CL. Impact of NO and
SO2 on measurement of mercury speciation in a wet chemical conditioning
system. In: Proceedings pf the 23rd annual international pittsburgh coal con-
ference, PCC - coal-energy. Environment and Sustainable Development; 2006.
[209] Buitrago PA, Otten BV, Senior CL, Silcox GD. Impinger-based mercury speci-
ation methods and gas-phase mercury oxidation by bromine in combustion
systems. Energ Fuel 2013;27:6255–61.
[210] China Electric Power Yearbook Editorial Board. China electric power yearbook
2008, Beijing: China Electric Power Press; 2008. (in Chinese).
[211] China Electric Power Yearbook Editorial Board. China electric power yearbook
2017, Beijing: China Electric Power Press; 2017. (in Chinese).
[212] Zhao Y, Yang J, Ma S, Zhang S, Liu H, Gong B, Zhang J, Zheng C. Emission con-
trols of mercury and other trace elements during coal combustion in China:
a review. Int Geol Rev 2018;60(5-6):638–70.
[213] Tang S, Wang L, Feng X, Feng Z, Li R, Fan H, Li K. Actual mercury specia-
tion and mercury discharges from coal-fired power plants in Inner Mongolia,
Northern China. Fuel 2016;180:194–204.
[214] Goodarzi F, Huggins FE, Sanei H. Assessment of elements, speciation of As,
Cr, Ni and emitted Hg for a Canadian power plant burning bituminous coal.
Int J Coal Geol 2008;74:1–12.
[215] Chen B, Liu G, Sun R. Distribution and fate of mercury in pulverized bitu-
minous coal-fired power plants in coal energy-dominant Huainan city, China.
Arch Environ Contam Toxicol 2016;70:724–33.
[216] Pudasainee D, Lee SJ, Lee SH, Kim JH, Jang HN, Cho SJ, Seo YC. Effect of se-
lective catalytic reactor on oxidation and enhanced removal of mercury in
coal-fired power plants. Fuel 2010;89:804–9.
[217] Gao L, Wang Y, Huang Q, Guo S. Emission of mercury from six low calorific
value coal-fired power plants. Fuel 2017;210:611–16.
[218] Wu C, Cao Y, Dong Z, Cheng C, Li H, Pan W. Evaluation of mercury specia-
tion and removal through air pollution control devices of a 190 MW boiler. J
Environ Sci 2010;22(2):277–82.
[219] Burmistrz P, Kogut K, Marczak M, Zwoździak J. Lignites and subbituminous
coals combustion in Polish power plants as a source of anthropogenic mer-
cury emission. Fuel Process Technol 2016;152:250–8.
[220] Su S, Liu L, Wang L, Syed-Hassan SSA, Kong F, Hu S, Wang Y, Jiang L, Xu K,
Zhang A, Xiang J. Mass flow analysis of mercury transformation and effect of
seawater flue gas desulfurization on mercury removal in a full-scale coal-fired
power plant. Energ Fuel 2017;31:11109–16.
[221] Pudasainee D, Seo YC, Sung JH, Jang HN, Gupta R. Mercury co-beneficial cap-
ture in air pollution control devices of coal-fired power plants. Int J Coal Geol
2017;170:48–53.
[222] Wang SX, Zhang L, Li GH, Wu Y, Hao JM, Pirrone N, Sprovieri F, Ancora MP.
Mercury emission and speciation of coal-fired power plants in China. Atmos
Chem Phys 2010;10:1183–92.
[223] Wang X, Chen P, Jiang X, Wu Q, Liu Y, Yan J, Ma P. Mercury emission char-
acteristics of flue gases from two coal-fired power plants in Xinjiang, China.
Energ Source Part A 2017;39(2):240–5.
[224] Pudasainee D, Kim JH, Seo YC. Mercury emission trend influenced by strin-
gent air pollutants regulation for coal-fired power plants in Korea. Atmos En-
viron 2009;43:6254–9.
[225] Zhang L, Zhuo Y, Chen L, Xu X, Chen C. Mercury emissions from six coal-fired
power plants in China. Fuel Process Technol 2008;89:1033–40.
62 S. Zhao, D. Pudasainee and Y. Duan et al. / Progress in Energy and Combustion Science 73 (2019) 26–64
[226] Wang J, Wang W, Xu W, Wang X, Zhao S. Mercury removals by existing pol-
lutants control devices of four coal-fired power plants in China. J Environ Sci
2011;23(11):1839–44.
[227] Hsi HC, Lee HH, Hwang JF, Chen W. Mercury speciation and distribution in
a 660-Megawatt utility boiler in Taiwan firing bituminous coals. J Air Waste
Manage Assoc 2010;60:514–22.
[228] Tao Y, Zhuo Y, Zhang L, Chen C, Xu X. Mercury transformation across various
air pollution control devices in a 200 MW coal-fired boiler of China. Asia-Pac
J Chem Eng 2010;5:756–62.
[229] Zhang Y, Yang J, Yu X, Sun P, Zhao Y, Zhang J, Chen G, Yao H, Zheng C. Mi-
gration and emission characteristics of Hg in coal-fired power plant of China
with ultra low emission air pollution control devices. Fuel Process Technol
2017;158:272–80.
[230] Zhao S, Duan Y, Chen L, Li Y, Yao T, Liu S, Liu M, Lu J. Study on emission of
hazardous trace elements in a 350 MW coal-fired power plant. Part 1. Mer-
cury. Environ Pollut 2017;229:863–70.
[231] Pudasainee D, Kim JH, Yoon YS, Seo YC. Oxidation, reemission and mass dis-
tribution of mercury in bituminous coal-fired power plants with SCR, CS-ESP
and wet FGD. Fuel 2012;93:312–18.
[232] Zheng C, Wang L, Zhang Y, Zhang J, Zhao H, Zhou J, Gao X, Cen K. Parti-
tioning of hazardous trace elements among air pollution control devices in
ultra-low-emission coal-fired power plants. Energ Fuel 2017;31:6334–44.
[233] Sung JH, Back SK, Jung BM, Kang YS, Lee CG, Jang HN, Seo YC. Speciation and
capture performance of mercury by a hybrid filter in a coal-fired power plant.
Int J Coal Geol 2017;170:35–40.
[234] Lee SJ, Seo YC, Jang HN, Park KS, Baek JI, An HS, Song KC. Speciation and
mass distribution of mercury in a bituminous coal-fired power plant. Atmos
Environ 2006;40:2215–24.
[235] Kim JH, Pudasainee D, Yoon YS, Son SU, Seo YC. Studies on speciation changes
and mass distribution of mercury in a bituminous coal-fired power plant by
combining field data and chemical equilibrium calculation. Ind Eng Chem Res
2010;49:5197–203.
[236] Meij R, Vredenbregt LHJ, Winkel H. The fate and behaviour of mercury in
coal-fired power plants. J Air Waste Manage Assoc 2002;52:912–17.
[237] Tian HZ, Wang Y, Xue ZG, Cheng K, Qu YP, Chai FH, Hao JM. Trend and char-
acteristics of atmospheric emissions of Hg, As, and Se from coal combustion
in China, 1980–2007. Atmos Chem Phys 2010;10:11905–19.
[238] Meij R, Winkel H. Mercury emissions from coal-fired power stations: the cur-
rent state of the art in the Netherlands. Sci Total Environ 2006;368:393–6.
[239] Bilirgen H, Romero C. Mercury capture by boiler modifications with sub-bi-
tuminous coals. Fuel 2012;94:361–7.
[240] Zhang L, Wang S, Wu Q, Wang F, Lin CJ, Zhang L, Hui M, Yang M, Su H, Hao J.
Mercury transformation and speciation in flue gases from anthropogenic
emission sources: a critical review. Atmos Chem Phys 2016;16:2417–33.
[241] Xu YY, Xue JM, Wang HL, Li B, Guan YM, Liu J. Research on mercury collab-
orative control by conventional pollutants purification facilities of coal-fired
power plants. P CSEE 2014;34:3924–31 (in Chinese).
[242] Niksa S, Fujiwara N. A predictive mechanism for mercury oxidation on se-
lective catalytic reduction catalysts under coal-derived flue gas. J Air Waste
Manage Assoc 2005;55(12):1866–75.
[243] Senior CL. Oxidation of mercury across selective catalytic reduction catalysts
in coal-fired power plants. J Air Waste Manage Assoc 2006;56:23–31.
[244] Gao W, Liu Q, Wu CY, Li H, Li Y, Yang J, et al. Kinetics of mercury oxidation in
the presence of hydrochloric acid and oxygen over a commercial SCR catalyst.
Chem Eng J 2013;220:53–60.
[245] He S, Zhou J, Zhu Y, Luo Z, Ni M, Cen K. Mercury oxidation over a vanadi-
a-based selective catalytic reduction catalyst. Energ Fuel 2009;23(1):253–9.
[246] Zhou ZJ, Liu XW, Zhao B, Chen ZG, Shao HZ, Wang LL, Xu MH. Effects of
existing energy saving and air pollution control devices on mercury removal
in coal-fired power plants. Fuel Process Technol 2015;131:99–108.
[247] Pudasainee D, Kim JH, Yoon YS, Seo YC. Oxidation, reemission and mass dis-
tribution of mercury in bituminous coal fired power plants with SCR, CS-ESP
and wet FGD. Fuel 2012;93:312–18.
[248] Richardson C, Machalek T, Miller S, Dene C, Chang R. Effect of NOx control
processes on mercury speciation in utility flue gas. J Air Waste Manage Assoc
2002;52:941–7.
[249] Wang S, Zhang L, Wu Y, Ancora MP, Zhao Y, Hao J. Synergistic mercury re-
moval by conventional pollutant control strategies for coal-fired power plants
in China. J Air Waste Manage Assoc 2010;60:722–30.
[250] Omine N, Romero CE, Kikkawa H, Wu S, Eswaran S. Study of elemental mer-
cury re-emission in a simulated wet scrubber. Fuel 2012;91:93–101.
[251] Chang L, Zhao Y, Li H, Tian C, Zhang Y, Yu X, Zhang J. Effect of sulfite on
divalent mercury reduction and re-emission in a simulated desulfurization
aqueous solution. Fuel Process Technol 2017;165:138–44.
[252] Wu CL, Cao Y, He CC, Dong ZB, Pan WP. Study of elemental mercury re-emis-
sion through a lab-scale simulated scrubber. Fuel 2010;89:2072–80.
[253] Reynold J, Bayless DL, Caine J. Multi-pollutant control using membrane-based
up-flow wet electrostatic precipitation, DOE final report. Akron, Ohio: Ohio Uni-
versity; 2004.
[254] Ma S, Zhao Y, Yang J, Zhang S, Zhang J, Zheng C. Research progress of pol-
lutants removal from coal-fired flue gas using non-thermal plasma. Renew
Sustain Energy Rev 2017;67:791–810.
[255] Wang ZH, Jiang SD, Zhu YQ, Zhou JS, Zhou JH, Li ZS, Cen KF. Investigation on
elemental mercury oxidation mechanism by non-thermal plasma treatment.
Fuel Process Technol 2010;91:1395–400.
[256] Ko KB, Byun Y, Cho M, Namkung W, Shin DN, Koh DJ, Kim KT. Influence of
HCl on oxidation of gaseous elemental mercury by dielectric barrier discharge
process. Chemosphere 2008;71:1674–82.
[257] Chen Z, Mannava DP, Mathur VK. Mercury oxidization in dielectric barrier
discharge plasma system. Ind Eng Chem Res 2006;45:6050–5.
[258] An JT, Shang KF, Lu N, Jiang YZ, Wang TC, Li J, Wu Y. Oxidation of elemen-
tal mercury by active species generated froma surface dielectric barrier dis-
charge plasma reactor. Plasma Chem Plasma Process 2013;34:217–28.
[259] Wang K, Zhu L, Chen Q, Jiang Y, Bu F. Research of latest United States
mercury emission standards. Power Technol Environ Prot 2013;29(4):24–5 (in
Chinses).
[260] STSB & NEPA, State Technical Supervision Bureau and National Environmen-
tal Protection Agency of China. Environmental quality standard for soils, GB
15618-1995, 1995. (in Chinese).
[261] STSB & NEPA, State Technical Supervision Bureau and National Environmental
Protection Agency of China. Quality standard for ground water, GB/T 14848–9,
1993 (in Chinese).
[262] Luttrell GH, Kohmuench JN, Yoon RH. An evaluation of coal preparation
technologies for controlling trace element emissions. Fuel Process Technol
20 0 0;65-66:407–22.
[263] Smit FJ, Moro N, Shields GL, Jha MC, Feeley TJ. Reduction of toxic trace el-
ements in coal by advanced coal cleaning. In: Proceedings of the thirteenth
annual international pittsburgh coal conference, 2; 1996. p. 879–84.
[264] Ferris DD, Bencho JR. Engineering development of advanced physical fine coal
cleaning technologies - froth flotation. ICF Kaiser Engineers; 1992. final report
for DOE contract no. DE-AC22-88PC88881 December.
[265] Neme C. Electric utilities and long-range transport of mercury and other toxic
air pollutants, Washington, DC: Center for Clean Air Policy; 1991. November.
[266] Brown TD, Smith DN, Hargis RA, O’Dowd WJ. Mercury measurement and its
control: what we know, have learned, and need to further investigate. J. Air
Waste Manage Assoc 1999:1–97.
[267] Zhu C, Tian H, Cheng K, Liu K, Wang K, Hua S, Gao J, Zhou J. Potentials
of whole process control of heavy metals emissions from coal-fired power
plants in China. J Clean Prod 2016;114:343–51.
[268] Guffey FD, Bland AE. Thermal pretreatment of low-ranked coal for control of
mercury emissions. Fuel Process Technol 2003;85:521–31.
[269] Wang M, Keener TC, Khang SJ. The effects of coal volatility on mercury
removal from bituminous coal during mild pyrolysis. Fuel Process Technol
20 0 0;67:147–61.
[270] Chmielniak T, Słowik K, Sajdak M. Mercury removal by mild thermal treat-
ment of coal. Fuel 2017;195:290–8.
[271] Minami W, Xu Z, Kim H. Mercury removal characteristics during ther-
mal upgrading of fractionated Alberta subbituminous coal. Energ Fuel
2007;21:3607–11.
[272] Berry M. Air quality VI conference Arlington, Washington DC. Crystal Gateway
Marriott; 2007. September.
[273] Zhuang Y, Thompson JS, Zygarlicke CJ, Pavlish JH. Impact of calcium chlo-
ride addition on mercury transformations and control in coal flue gas. Fuel
2007;86:2351–9.
[274] Yang Y, Xu W, Wu Y, Xiong J, Zhu T, Zhou X, Tong L. Effect of HBr formation
on mercury oxidation via CaBr2 addition to coal during combustion. RSC Adv
2016;6:59009–15.
[275] Pan WG, Wu J, Wang WH, He P, Zhang YD, Leng XF, Shen MQ. Study on the
effect of NH4 Cl addition on Hg and NO produced by coal combustion. P CSEE
2009;29:41–6 (in Chinese).
[276] Shi X. Study on mercury removal from a 300 MW coal-fired power plant
with existing pollution control equipments. Chinese Coal 2014;40(Supple-
ment):146–9 (in Chinese).
[277] Zhou Q, Duan YF, Zhao SL, Du HF, Zhu C, She M, Wei HQ. Mercury transfor-
mation and NO emission of coal combustion with CaCl2 and NH4 Cl additives
in a 6 kW CFB combustor. Energ Fuel 2015;29:5267–73.
[278] Zhao S, Duan Y, Zhou Q, Zhu C, Liu M, Lu J. Effects of NH4 Br additive on mer-
cury transformation and removal during CFB coal combustion. J Chem Technol
Biotechnol 2017;92:391–8.
[279] Stolle R, Koeser H, Gutberlet H. Oxidation and reduction of mercury by SCR
DeNOx catalysts under flue gas conditions in coal fired power plants. Appl
Catal B: Environ 2014;144:486–97.
[280] Kamata H, Ueno SI, Naito T, Yamaguchi A, Ito S. Mercury oxidation by hy-
drochloric acid over a VOx /TiO2 catalyst. Catal Commun 2008;9:2441–4.
[281] Negreira AS, Wilcox J. Role of WO3 in the Hg oxidation across
the V2 O5 –WO3 –TiO2 SCR catalyst: a DFT study. J Phys Chem C
2013;117:24397–406.
[282] Gao X, Du XS, Cui LW, Fu YC, Luo ZY, Cen KF. A Ce–Cu–Ti oxide cata-
lyst for the selective catalytic reduction of NO with NH3 . Catal Commun
2010;12:255–8.
[283] Zhao L, Li C, Zhang X, Zeng G, Zhang J, Xie Y. A review on oxidation of el-
emental mercury from coal-fired flue gas with selective catalytic reduction
catalysts. Catal Sci Technol 2015;5:3459–72.
[284] Yan NQ, Chen WM, Chen J, Qu Z, Guo YF, Yang SJ, Jia JP. Significance of RuO2
modified SCR catalyst for elemental mercury oxidation in coal-fired flue gas.
Environ Sci Technol 2011;45:5725–30.
[285] Zeng KB, Stolle R, Köser H. Mercury oxidation on metal oxide doped SCR-De-
NOx catalysts. Chem Eng Technol 2009;81:1046 (in German).
[286] Zhao L, Li C, Zhang X, Zeng G, Zhang J, Xie Y. Oxidation of elemental mer-
cury by modified spent TiO2 -based SCR-DeNOx catalysts in simulated coal–
fired flue gas. Environ Sci Pollut Res 2016;23:1471–81.
 S. Zhao, D. Pudasainee and Y. Duan et al. / Progress in Energy and Combustion Science 73 (2019) 26–64
[287] Zhao L, Li C, Zhang J, Zhang X, Zhan F, Ma J, Xie Y, Zeng G. Promotional effect
of CeO2 modified support on V2 O5 -WO3 /TiO2 catalyst for elemental mercury
oxidation in simulated coal-fired flue gas. Fuel 2015;153:361–9.
[288] Huang WJ, Xu HM, Qu Z, Zhao SJ, Chen WM, Yan NQ. Significance of Fe2 O3
modified SCR catalyst for gas-phase elemental mercury oxidation in coal-fired
flue gas. Fuel Process Technol 2016;149:23–8.
[289] Zhang M, Wang P, Dong Y, Sui H, Xiao D. Study of elemental mercury ox-
idation over an SCR catalyst with calcium chloride addition. Chem Eng J
2014;253:243–50.
[290] Krzyżyńska R, Zhao Y, Hutson N. Absorption of NOx , SO2 , and mercury in
a simulated additive-enhanced wet flue gas desulphurization scrubber. Pol J
Environ Stud 2010;19(6):1255–62.
[291] González RO, Díaz-Somoano M, López Antón MA, Martínez-Tarazona MR. Ef-
fect of adding aluminum salts to wet FGD systems upon the stabilization of
mercury. Fuel 2012;96:568–71.
[292] Wang Q, Liu Y, Yang Z, Wang H, Weng X, Wang Y, Wu Z. Study of mercury
re-emission in a simulated WFGD solution containing thiocyanate and sulfide
ions. Fuel 2014;134:588–94.
[293] Tang T, Xu J, Lu R, Wo J, Xu X. Enhanced Hg2+ removal and Hg0 re-emis-
sion control from wet fuel gas desulfurization liquors with additives. Fuel
2010;89:3613–17.
[294] Sun M, Hou J, Tang T, Lu R, Cheng L, Xu X. Stabilization of mercury in flue gas
desulfurization gypsum from coal-fired electric power plants with additives.
Fuel Process Technol 2012;104:160–6.
[295] Aboud S, Sasmaz E, Wilcox J. Mercury adsorption on PdAu, PdAg and PdCu
alloys. Main Group Chem 2008;7(3):205–15.
[296] Sasmaz E, Aboud S, Wilcox J. Hg binding on Pd binary alloys and overlays. J
Phys Chem C 2009;113:7813–20.
[297] Hou WH, Zhou JS, Yu CJ, You SL, Gao X, Luo ZY. Pd/Al2 O3 sorbents for el-
emental mercury capture at high temperatures in syngas. Ind Eng Chem Res
2014;53:9909–14.
[298] Hrdlicka JA, Seames WS, Mann MD, Muggli DS, Horabik CA. Mercury oxida-
tion in flue gas using gold and palladium catalysts on fabric filters. Environ
Sci Technol 2008;42:6677–82.
[299] Lim DH, Wilcox J. Heterogeneous mercury oxidation on Au(111) from first
principles. Environ Sci Technol 2013;47:8515–22.
[300] Li H, Zhu L, Wu S, Liu Y, Shih K. Synergy of CuO and CeO2 combination for
mercury oxidation under low-temperature selective catalytic reduction atmo-
sphere. Int J Coal Geol 2017;170:69–76.
[301] Zhou Z, Liu X, Hu Y, Liao Z, Cheng S, Xu M. An efficient sorbent based on
CuCl2 loaded CeO2 -ZrO2 for elemental mercury removal from chlorine-free
flue gas. Fuel 2018;216:356–63.
[302] Li H, Wu CY, Li Y, Zhang J. CeO2 –TiO2 catalysts for catalytic oxidation of el-
emental mercury in low-rank coal combustion flue gas. Environ Sci Technol
2011;45:7394–400.
[303] Li H, Zhang W, Wang J, Yang Z, Li L, Shih K. Coexistence of enhanced Hg0
oxidation and induced Hg2+ reduction on CuO/TiO2 catalyst in the presence
of NO and NH3 . Chem Eng J 2017;330:1248–54.
[304] Wang J, Yang J, Liu Z. Gas-phase elemental mercury capture by a V2 O5 /AC
catalyst. Fuel Process Technol 2010;91:676–80.
[305] Zhang S, Zhao Y, Wang Z, Zhang J, Wang L, Zheng C. Integrated removal of
NO and mercury from coal combustion flue gas using manganese oxides sup-
ported on TiO2 . J Environ Sci 2017;53:141–50.
[306] Yang Y, Liu J, Zhang B, Zhao Y, Chen X, Shen F. Experimental and theoretical
studies of mercury oxidation over CeO2 - WO3 /TiO2 catalysts in coal-fired flue
gas. Chem Eng J 2017;317:758–65.
[307] Cao Y, Gao Z, Zhu J, Wang Q, Huang Y, Chiu C, Parker B, Chu P, Pan WP.
Impacts of halogen additions on mercury oxidation, in a slipstream selective
catalyst reduction (SCR), reactor when burning sub-bituminous coal. Environ
Sci Technol 2008;42:256–61.
[308] Stolle R, Koeser H, Gutberlet H. Oxidation and reduction of mercury by SCR
DeNOx catalysts underflue gas conditions in coal fired power plants. Appl
Catal B: Environ 2014;144:486–97.
[309] Wen Z, Wang Z, Li Y, Cen K. Mechanism and kinetic study on ele-
mental mercury oxidation in flue gas by ozone injection. Ozone-Sci Eng
2018;40(1):29–36.
[310] Martinez AI, Deshpande BK. Kinetic modeling of H2 O2 -enhanced oxidation of
flue gas elemental mercury. Fuel Process Technol 2007;88:982–7.
[311] Yang H, Xu Z, Fan M, Bland AE, Judkins RR. Adsorbents for capturing mercury
in coal-fired boiler flue gas. J Hazard Mater 2007;146:1–11.
[312] Sjostrom S, Durham M, Bustard CJ, Martin C. Activated carbon injection for
mercury control: overview. Fuel 2010;89:1320–2.
[313] Feeley TJ, O’Palko BA, Jones AP. Developing mercury control technology for
coal-fired power plants – from concept to commercial reality. Main Group
Chem 2008;7(3):169–79.
[314] Bustard J, Durham M, Starns T, Lindsey C, Martin C, Schlager R, Baldrey K.
Full-scale evaluation of sorbent injection for mercury control on coal-fired
power plants. Fuel Process Technol 2004;85:549–62.
[315] Yudovich YE, Ketris MP. Mercury in coal: a review. Part 2. Coal use and envi-
ronmental problems. Int J Coal Geol 2005;62:135–65.
[316] Zhou W, Eggenspieler G, Rokanuzzaman A, Lissianski V, Moyeda D. Prediction
of activated carbon injection performance for mercury capture in a full-scale
coal-fired boiler. Ind Eng Chem Res 2010;49:3603–10.
[317] Liu Y, Bisson TM, Yang H, Xu Z. Recent developments in novel sorbents for
flue gas clean up. Fuel Process Technol 2010;91:1175–97.
63
[318] Min H, Ahmad T, Lee SS. Mercury adsorption characteristics as dependent
upon the physical properties of activated carbon. Energ Fuel 2017;31:724–9.
[319] Skodras G, Diamantopoulou I, Pantoleontos G, Sakellaropoulos GP. Kinetic
studies of elemental mercury adsorption in activated carbon fixed bed re-
actor. J Hazard Mater 2008;158:1–13.
[320] Ochiai R, Uddin MA, Sasaoka E, Wu S. Effects of HCl and SO2 concentration
on mercury removal by activated carbon sorbents in coal-derived flue gas.
Energ Fuel 2009;23:4734–9.
[321] Miller SJ, Dunham GE, Olson ES, Brown TD. Flue gas effects on a carbon-based
mercury sorbent. Fuel Process Technol 20 0 0;65-66:343–63.
[322] Diamantopoulou I, Skodras G, Sakellaropoulos GP. Sorption of mercury by ac-
tivated carbon in the presence of flue gas components. Fuel Process Technol
2010;91:158–63.
[323] Liu J, Cheney MA, Wu F, Li M. Effects of chemical functional groups on
elemental mercury adsorption on carbonaceous surfaces. J Hazard Mater
2011;186:108–13.
[324] Jang HN, Back SK, Sung JH, Jeong BM, Kang YS, Lee CK, Jurng J, Seo YC.
Adsorption and kinetics of elemental mercury vapour on activated carbons
impregnated with potassium iodide, hydrogen chloride, and sulfur. Korean J
Chem Eng 2017;34(3):806–13.
[325] Yim YJ, Park SJ. Effect of halide impregnation on elemental mercury removal
of activated carbons. Bull Korean Chem Soc 2017;38:191–5.
[326] Zhou Q, Duan YF, Hong YG, Zhu C, She M, Zhang J, Wei HQ. Experimental and
kinetic studies of gas-phase mercury adsorption by raw and bromine modi-
fied activated carbon. Fuel Process Technol 2015;134:325–32.
[327] Zhong L, Li W, Zhang Y, Norris P, Cao Y, Pan WP. Kinetic studies of mercury
adsorption in activated carbon modified by iodine steam vapour deposition
method. Fuel 2017;188:343–51.
[328] Rupp EC, Wilcox J. Mercury chemistry of brominated activated carbons –
packed-bed breakthrough experiments. Fuel 2014;117:351–3.
[329] Yan R, Liang DT, Tsen L, Wong YP, Lee YK. Bench-scale experimental
evaluation of carbon performance on mercury vapour adsorption. Fuel
2004;83:2401–9.
[330] Hsi HC, Chen CT. Influences of acidic/oxidizing gases on elemental mercury
adsorption equilibrium and kinetics of sulfur-impregnated activated carbon.
Fuel 2012;98:229–35.
[331] Lee SS, Lee JY, Keener TC. The effect of methods of preparation on the perfor-
mance of cupric chloride-impregnated sorbents for the removal of mercury
from flue gases. Fuel 2009;88:2053–6.
[332] Du W, Yin L, Zhuo Y, Xu Q, Zhang L, Chen C. Catalytic oxidation and adsorp-
tion of elemental mercury over CuCl2 -impregnated sorbents. Ind Eng Chem
Res 2014;53:582–91.
[333] Wang XQ, Wang P, Ning P, Ma YX, Wang F, Guo XL, Lan Y. Adsorption of
gaseous elemental mercury with activated carbon impregnated with ferric
chloride. RSC Adv 2015;5:24899–907.
[334] Hu C, Zhou J, He S, Luo Z, Cen K. Effect of chemical activation of an acti-
vated carbon using zinc chloride on elemental mercury adsorption. Fuel Pro-
cess Technol 2009;90:812–17.
[335] Xie Y, Li C, Zhao L, Zhang J, Zeng G, Zhang X, Zhang W, Tao S. Experimen-
tal study on Hg0 removal from flue gas over columnar MnOx -CeO2 /activated
coke. Appl Surf Sci 2015;333:59–67.
[336] Hua X, Zhou J, Li Q, Luo Z, Cen K. Gas-phase elemental mercury removal by
CeO2 impregnated activated coke. Energ Fuel 2010;24:5426–31.
[337] Zhang J, Duan Y, Zhou Q, Zhu C, She M, Ding W. Adsorptive removal of
gas-phase mercury by oxygen non-thermal plasma modified activated carbon.
Chem Eng J 2016;294:281–9.
[338] Hu P, Duan Y, Ding W, Zhang J, Bai L, Li N, Wei H. Enhancement of mercury
removal efficiency by activated carbon treated with nonthermal plasma in
different atmospheres. Energ Fuel 2017;31:13852–8.
[339] Zhang B, Zeng X, Xu P, Chen J, Xu Y, Luo G, Xu M, Yao H. Using the novel
method of nonthermal plasma to add Cl active sites on activated carbon for
removal of mercury from flue gas. Environ Sci Technol 2016;50:11837–43.
[340] Zhou Q, Duan Y, Chen M, Liu M, Lu P. Studies on mercury adsorption species
and equilibrium on activated carbon surface. Energ Fuel 2017;31:14211–18.
[341] De M, Azargohar R, Dalai AK, Shewchuk SR. Mercury removal by bio-char
based modified activated carbons. Fuel 2013;103(1):570–8.
[342] Padak B, Brunetti M, Lewis A, Wilcox J. Mercury binding on activated carbon.
Environ Prog 2006;25(4):319–26.
[343] Rungnim C, Promarak V, Hannongbua S, Kungwan N, Namuangruk S. Com-
plete reaction mechanisms of mercury oxidation on halogenated activated
carbon. J Hazard Mater 2016;310:253–60.
[344] Sano A, Takaoka M, Shiota K. Vapour-phase elemental mercury adsorption
by activated carbon co-impregnated with sulfur and chlorine. Chem Eng J
2017;315:598–607.
[345] Qiu L, Zhai Y, Chen H, Liu X, Zhu L, Li C, Zeng G. Removal of elemental mer-
cury from simulated flue gas by a novel composite sulfurized activated car-
bon. Energ Source Part A 2018;40(4):381–7.
[346] Lee SH, Park YO. Gas-phase mercury removal by carbon-based sorbents. Fuel
Process Technol 2003;84:197–206.
[347] Hsi HC, Rood MJ, Rostam-Abadi M, Chen S, Chang R. Mercury adsorption
properties of sulfur-impregnated adsorbents. J Environ Eng 2002;128:1080–9.
[348] Shen Z, Ma J, Mei Z, Zhan J. Metal chlorides loaded on activated carbon to
capture elemental mercury. J Environ Sci 2010;22(11):1814–19.
[349] Liu Z, Yang W, Xu W, Liu Y. Removal of elemental mercury by bio-chars
derived from seaweed impregnated with potassium iodine. Chem Eng J
2018;339:468–78.
64 S. Zhao, D. Pudasainee and Y. Duan et al. / Progress in Energy and Combustion Science 73 (2019) 26–64
[350] Zhu C, Duan Y, Wu CY, Zhou Q, She M, Yao T, Zhang J. Mercury removal and
synergistic capture of SO2 /NO by ammonium halides modified rice husk char.
Fuel 2016;172:160–9.
[351] Li G, Wang S, Wu Q, Wang F, Shen B. Mercury sorption study of halides mod-
ified bio-chars derived from cotton straw. Chem Eng J 2016;302:305–13.
[352] Li G, Shen B, Li F, Tian L, Singh S, Wang F. Elemental mercury removal
using biochar pyrolyzed from municipal solid waste. Fuel Process Technol
2015;133:43–50.
[353] Shen B, Li G, Wang F, Wang Y, He C, Zhang M, Singh S. Elemental mer-
cury removal by the modified bio-char from medicinal residues. Chem Eng
J 2015;272:28–37.
[354] Shen B, Tian L, Li F, Zhang X, Xu H, Singh S. Elemental mercury removal by
the modified bio-char from waste tea. Fuel 2017;187:189–96.
[355] Yang W, Liu Z, Xu W, Liu Y. Removal of elemental mercury from flue gas
using sargassum chars modified by NH4 Br reagent. Fuel 2018;214:196–206.
[356] Li G, Wang S, Wu Q, Wang F, Ding D, Shen B. Mechanism identification of
temperature influence on mercury adsorption capacity of different halides
modified bio-chars. Chem Eng J 2017;315:251–61.
[357] Lee SH, Rhim YJ, Cho SP, Baek JI. Carbon-based novel sorbent for removing
gas-phase mercury. Fuel 2006;85:219–26.
[358] Morris EA, Jia CQ, Morita K. Effects of O2 on characteristics of sulfur
added to petroleum coke through reaction with SO2 . Ind Eng Chem Res
2010;49:12709–17.
[359] Hong Y, Duan Y, Zhu C, Zhou Q, She M, Wei H. Experimental study on mer-
cury removal of high-sulfur petroleum coke activated carbon impregnated
with bromine. P CSEE 2014;34(11):1762–8.
[360] Cai JH, Jia CQ. Mercury removal from aqueous solution using coke-derived
sulfur-impregnated activated carbons. Ind Eng Chem Res 2010;49:2716–21.
[361] Xiao Y, Pudasainee D, Gupta R, Xu Z, Diao Y. Bromination of petroleum coke
for elemental mercury capture. J Hazard Mater 2017;336:232–9.
[362] Xiao Y, Pudasainee D, Gupta R, Xu Z, Diao Y. Elemental mercury reaction
chemistry on brominated petroleum cokes. Carbon 2017;124:89–96.
[363] He P, Zhang X, Peng X, Wu J, Jiang X. Effect of fly ash composition on
the retention of mercury in coal-combustion flue gas. Fuel Process Technol
2016;142:6–12.
[364] Zhong L, Zhang Y, Liu Z, Sui Z, Cao Y, Pan WP. Study of mercury adsorption
by selected Chinese coal fly ashes. J Therm Anal Calorim 2014;116:1197–203.
[365] Zhang Y, Duan W, Liu Z, Cao Y. Effects of modified fly ash on mercury ad-
sorption ability in an entrained-flow reactor. Fuel 2014;128:274–80.
[366] Zhang Y, Zhao L, Guo R, Song N, Wang J, Cao Y, Orndorff W, Pan W. Mer-
cury adsorption characteristics of HBr-modified fly ash in an entrained-flow
reactor. J Environ Sci 2015;33:156–62.
[367] Zhou Q, Duan Y, Chen M, Liu M, Lu P, Zhao S. Effect of flue gas component
and ash composition on elemental mercury oxidation/adsorption by NH4 Br
modified fly ash. Chem Eng J 2018;345:578–85.
[368] Wang S, Zhang Y, Gu Y, Wang J, liu Z, Zhang Y, Cao Y, Romero CE, Pan W.
Using modified fly ash for mercury emissions control for coal-fired power
plant applications in China. Fuel 2016;181:1230–7.
[369] Xu W, Wang H, Zhu T, Kuang J, Jing P. Mercury removal from coal combustion
flue gas by modified fly ash. J Environ Sci 2013;25(2):393–8.
[370] Xu Y, Zhong Q, Xing L. Gas-phase elemental mercury removal from
flue gas by cobalt-modified fly ash at low temperatures. Environ Technol
2014;35(22):2870–7.
[371] Zhao S, Duan Y, Lu J, Liu S, Pudasainee D, Gupta R, Liu M, Lu J. Enrichment
characteristics, thermal stability and volatility of hazardous trace elements in
fly ash from a coal-fired power plant. Fuel 2018;225:490–8.
[372] Zhao S, Duan Y, Lu J, Gupta R, Pudasainee D, Liu S, Liu M, Lu J. Chemical
speciation and leaching characteristics of hazardous trace elements in coal
and fly ash from coal-fired power plants. Fuel 2018;232:463–9.
[373] Ghorishi B, Gullett BK. Sorption of mercury species by activated carbons and
calcium-based sorbents: effect of temperature, mercury concentration and
acid gases. Waste Manage Res 1998;16:582–93.
[374] Stouffer MR, Rosenhoover WA, Burke FP. Investigation of flue gas mercury
measurement and control for coal-fired sources. Presented at the 89th An-
nual Air & Waste Management Association Meeting Nashville, TN; 1996. June
23–2896-WP64B.06.
[375] Wang Y, Duan Y. Effect of manganese ions on the structure of Ca(OH)2 and
mercury adsorption performance of Mnx+ /Ca(OH)2 composites. Energ Fuel
2011;25:1553–8.
[376] Cai J, Shen B, Li Z, Chen J, He C. Removal of elemental mercury by clays im-
pregnated with KI and KBr. Chem Eng J 2014;241:19–27.
[377] Shen B, Chen J, Yue S. Removal of elemental mercury by titanium pil-
lared clay impregnated with potassium iodine. Micropor Mesopor Mater
2015;203:216–23.
[378] Chiu CH, Hsi HC, Lin CC. Control of mercury emissions from coal-combustion
flue gases using CuCl2 -modified zeolite and evaluating the cobenefit effects
on SO2 and NO removal. Fuel Process Technol 2014;126:138–44.
[379] Shao H, Liu X, Zhou Z, Zhao B, Chen Z, Xu M. Elemental mercury removal
using a novel KI modified bentonite supported by starch sorbent. Chem Eng J
2016;291:306–16.
[380] Liu H, Yang J, Tian C, Zhao Y, Zhang J. Mercury removal from coal combustion
flue gas by modified palygorskite adsorbents. Appl Clay Sci 2017;147:36–43.
[381] Liu Y, Kelly DJA, Yang H, Lin CCH, Kuznicki SM, Xu Z. Novel regenerable sor-
bent for mercury capture from flue gases of coal-fired power plant. Environ
Sci Technol 2008;42:6205–10.
[382] Rodríguez-Pérez J, López-Antón MA, Díaz-Somoano M, García R, Martínez–
Tarazona MR. Regenerable sorbents for mercury capture in simulated coal
combustion flue gas. J Hazard Mater 2013;260:869–77.
[383] Yao T, Duan Y, Zhu C, Zhou Q, Xu J, Liu M, Wei H. Investigation of mercury
adsorption and cyclic mercury retention over MnOx/γ -Al2 O3 sorbent. Chemo-
sphere 2018;202:358–65.
[384] Qu Z, Xie J, Xu H, Chen W, Yan N. Regenerable sorbent with a high capacity
for elemental mercury removal and recycling from the simulated flue gas at
a low temperature. Energ Fuel 2015;29:6187–96.
[385] Zeng X, Xu Y, Zhang B, Luo G, Sun P, Zou R, Yao H. Elemental mercury
adsorption and regeneration performance of sorbents FeMnOx enhanced via
non-thermal plasma. Chem Eng J 2017;309:503–12.
[386] Yang J, Zhao Y, Zhang J, Zheng C. Regenerable cobalt oxide loaded magneto-
sphere catalyst from fly ash for mercury removal in coal combustion flue gas.
Environ Sci Technol 2014;48:14837–43.
[387] Yang J, Zhao Y, Zhang J, Zheng C. Removal of elemental mercury from flue gas
by recyclable CuCl2 modified magnetospheres catalyst from fly ash. Part 1.
Catalyst characterization and performance evaluation. Fuel 2016;164:419–28.
[388] Yang J, Zhao Y, Zhang J, Zheng C. Removal of elemental mercury from flue
gas by recyclable CuCl2 modified magnetospheres catalyst from fly ash. Part
2. Identification of involved reaction mechanism. Fuel 2016;167:366–74.
[389] Yang J, Zhao Y, Zhang J, Zheng C. Removal of elemental mercury from flue
gas by recyclable CuCl2 modified magnetospheres catalyst from fly ash. Part
3. Regeneration performance in realistic flue gas atmosphere. Fuel 2016;173:
1–7.
[390] Yang J, Zhao Y, Guo X, Li H, Zhang J, Zheng C. Removal of elemental mercury
from flue gas by recyclable CuCl2 modified magnetospheres from fly ash. Part
4. Performance of sorbent injection in an entrained flow reactor system. Fuel
2018;220:403–11.
[391] Fang P, Cen C, Wang X, Tang Z, Tang Z, Chen D. Simultaneous removal of
SO2 , NO and Hg0 by wet scrubbing using urea + KMnO4 solution. Fuel Process
Technol 2013;106:645–53.
[392] Chiu CH, Hsi HC, Lin HP. Multipollutant control of Hg/SO2 /NO from coal–
combustion flue gasesusing transition metal oxide-impregnated SCR catalysts.
Catal Today 2015;245:2–9.
[393] Chiu CH, Kuo TH, Chang TC, Lin SF, Lin HP, His HC. Multipollutant removal
of Hg0 /SO2 /NO from simulated coal-combustion flue gases using metal ox-
ide/mesoporous SiO2 composites. Int J Coal Geol 2017;170:60–8.
[394] Yuan Y, Zhang J, Li H, Li Y, Zhao Y, Zheng C. Simultaneous removal of SO2 ,
NO and mercury using TiO2 -aluminum silicate fiber by photocatalysis. Chem
Eng J 2012;192:21–8.
Shilin Zhao: Male, born in April, 1992. Education: 2010.9–2014.6: Bachelor of En-
gineering, Thermal and Power Engineering, Nanjing Normal University, Nanjing,
China; 2014.9–present: Ph.D. candidate, Thermal Engineering, Southeast University,
Nanjing, China; 2017.10–2018.10: visiting PhD student, Department of Chemical and
Materials Engineering, University of Alberta, Edmonton, Canada. Publications: Has
published 27 journal papers including 13 SCI (first author) and 5 SCI (co-author)
papers with cites times of 140, and 7 international conference papers in energy, en-
vironment and chemical engineering areas. Current research areas: Transformation,
emission, and control of mercury and trace elements from coal combustion.
Yufeng Duan: Male, born in April, 1963. Education: 1980.9–1984.6: Bachelor of En-
gineering, Thermal Engineering, Beijing University of Science and Technology, Bei-
jing, China; 1984.9–1987.6: Master of Engineering, Thermal Engineering, Beijing
University of Science and Technology, Beijing, China; 1987.9–1991.9: Ph.D. Ther-
mal Engineering, Southeast University, Nanjing, China. Career: 1991.9–1993.12: Lec-
turer, Thermal Engineering Institute, Southeast University, Nanjing, China; 1993.12–
2002.4: Associate Professor, Thermal Engineering Institute, Southeast University,
Nanjing, China; 1995.8–1996.2: Senior visiting scholar, Korea Energy Research Insti-
tute (KIER), Korea; 20 01.9–20 03.8: Visiting Professor, Institute of Combustion Sci-
ence and Environmental Technology (ICSET), Western Kentucky University, USA;
2002.4–present: Professor, Thermal Engineering Institute, Southeast University, Nan-
jing, China; Publications: Has authored or co-authored (mostly as corresponding au-
thor) more than 300 journal papers including more than 150 SCI/EI papers with
cites times of 820 and more than 30 international conference papers in energy,
environment and chemical engineering areas. Has authorized more than 30 Chi-
nese patents. Co-authored and edited one book. Current research areas: Mercury
and trace elements removal technologies for coal combustion, solid waste recy-
cling, circulating fluidized bed combustion and gasification, numerical simulation
of combustion process, slurry transport and atomization, integrated removal of pol-
lutants from power station boilers, etc. Hosting research projects: 3 National Key
Research & Development Projects (2016); 5 National Natural Science Foundations
(2011, 2014, 2016, 2018); 2 National Science and Technology Support Projects (2006,
2012); 5 National “973” Third-Level Projects (1999, 20 03, 20 04, 20 06, 2010); 2 Na-
tional Science and Technology Research Project (1991, 1997); 1 Jiangsu Province In-
dustry, Education and Research Joint Innovation Fund (2013); 2 Jiangsu Environmen-
tal Protection Research Project (2011, 2016); 3 National Key Experiment Room Open
Fund (2010, 2010, 2011). He has undertaken more than 30 projects entrusted by
enterprises.