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燃煤过程中汞的综述
燃煤过程中汞的综述
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,
Available online 11 March 2019
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
1. Introduction and Hgp in the atmosphere is estimated in hours and days [4].
Then, Hg2+ and Hgp will be deposited in soil, plants, or water,
1.1. Mercury migration in the environment and its hazards which can combine with organic molecules to form methyl mer-
cury (MeHg; CH3 Hg+ ). Thus, there are four common forms of mer-
Mercury has caused widespread concern around the world due cury in the environment, namely, Hg0 , Hg2+ , Hgp , and MeHg.
to its great toxicity, which can damage human health and the en- The various forms of mercury determine its toxicity level. Mer-
vironment [1,2]. The schematic diagram of the overall mercury cy- cury and its compounds can enter human body via the diges-
cle in the atmosphere, modified from Travnikov [3], is shown in tive tract, respiratory tract, and skin absorption. In general, the
Fig. 1. Mercury emitted from natural and anthropogenic sources, or toxicity of mercury follows the decreasing order of organic mer-
re-emitted from natural surfaces, includes gaseous elemental mer- cury > inorganic mercury > Hg0 . Hg0 can harm the human central
cury (Hg0 ), gaseous oxidized mercury (Hg2+ ), and particulate mer- nervous system through the respiratory tract, while inorganic mer-
cury (Hgp ). The Hg0 will undergo a series of chemical reactions in cury (such as water-soluble Hg2+ ) will affect the kidneys via gas-
both gaseous and aqueous phases to transform into Hg2+ or Hgp . trointestinal absorption. Organic mercury (such as MeHg) can be
Due to the high volatility of Hg0 , it can stay in the atmosphere for accumulated in fish and plants and then become enriched in hu-
6–18 months. However, the residence time for the gaseous Hg2+ 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 29
Fig. 2. Proportion of global anthropogenic emissions of mercury to air in 2005 from Table 1
various sectors [10]. Mercury emission concentration limits for the new and
existing CFPPs in China and the US (μg/m3 ) [7].
China The US
cortex, cerebellum, and peripheral nerves [5,6]. The world-famous
Minamata Disease, which occurred in Japan in the 1950s, was be- 30 New: 1 (bituminous, gangue), 5 (lignite)
cause the residents ate the fish contaminated by MeHg. Mercury Existing: 2 (bituminous, gangue), 6 (lignite)
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- the 1990 Clean Air Act Amendments of the US, mercury and its
port, high toxicity, persistence, and bioaccumulation in the envi- compounds were classified as hazardous air pollutants. In 2005,
ronment [7]. the US Environmental Protection Agency (US EPA) issued the Clean
Air Mercury Rule (CAMR), which restricted the mercury emission
1.2. Mercury emission sources amount from new CFPPs [12]. In 2008, the US Court of Appeals
ruled to abolish CAMR and required the US EPA to develop more
Mercury emission sources can be divided into two parts: natu- stringent mercury emission regulations. In December 2011, the US
ral and anthropogenic sources. The primary natural sources of mer- EPA’s Mercury and Air Toxics Standards (MATS) ruled the final
cury include volcano eruptions, weathering of rocks, forest fires, standards for limiting mercury emissions from CFPPs [13]. In Jan-
and soil erosion, whereas the secondary natural release occurs uary 2005, the European Commission also adopted a strategy to
from soils, sediments, bodies of water, landfills, etc. The anthro- reduce mercury emission levels in the environment [14].
pogenic sources are fossil fuel combustion, metal production, ce- The Ministry of Environmental Protection in China initiated a
ment production, etc. [2,8]. The contribution of mercury emissions pilot mercury emission control project based on 16 CFPPs in 2010
from natural sources is estimated at 45–66% of the total mercury [7]. The concentration limit (30 μg/m3 ) for mercury and its com-
emissions [4]. In 2005, the global anthropogenic mercury emission pounds emitted from CFPPs of China was firstly given in 2011,
amount was estimated to be 1930 tonnes [9]. For the same year, which has been executed since January 1, 2015 [15]. In October
the proportion of global anthropogenic emissions of mercury to air 2013, more than 120 countries signed the Minamata Convention,
from various sections is shown in Fig. 2 [10]. It shows that the which focused on anthropogenic mercury emissions and aimed to
fossil fuel (primarily coal) combustion for power and heating was reduce global mercury pollution in the coming decades [2,4]. In or-
the largest single anthropogenic mercury emission source, occupy- der to meet the Minamata Convention, mercury emission concen-
ing 45% of the total anthropogenic emission amount [11]. The ten tration from CFPPs should be restricted under a value of 5 μg/m3
largest mercury emitting countries based on their emissions to air and 3 μg/m3 in 2020 and 2030, respectively, recommended by An-
in 2005 from various anthropogenic sectors are shown in Fig. 3 cora et al. [16]. The mercury emission concentrations limits for the
[10], the top three anthropogenic mercury emitting countries are new and existing CFPPs in China and the US are shown in Table 1
China, India, and the US. In addition, the fossil fuel combustion for [7]. The emission standard of China is far higher than that of the
power and heating, mainly coal-fired power plants (CFPPs), are the US, which means China should take strong measures to signifi-
major anthropogenic source of mercury emissions [11]. cantly decrease the mercury emissions from CFPPs.
From the issues raised above, it is clear that mercury is a global
1.3. Mercury emission regulation and the international initiatives pollutant that has been prioritized worldwide and there is an ur-
gent need to act on controlling mercury emission into the envi-
To solve the problem of mercury pollution, many countries have ronment. Among the various anthropogenic sources, CFPPs are the
taken relevant measures and formulated relevant regulations. In 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
Table 2
Content of mercury in coal around the world.
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 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
3.1. Determination methods for mercury content in coal 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 major standard mercury determination methods in coal in- the coal of South Africa, Indonesia, Poland, and Australia is 0.20,
clude ASTM D6414-14: Acid extraction or wet oxidation/cold va- 0.10, 0.05, and 0.06 mg/kg, respectively [39–42]. Compared with
por atomic absorption [28], ASTM D6722-01: Direct combustion the mean value of 0.1 mg/kg in the world’s coal given by Yudovich
analysis [29], EPA Methods 7471B: Mercury in solid or semisolid and Ketris [43], it can found that mercury content in the coal of
waste (manual cold-vapor technique) [30], and ISO 15237: 2016: China, the US, and South Africa is higher, which needs to be given
Solid mineral fuels -Determination of total mercury content of coal more attention. The content of mercury in coal around the world
[31]. The main difference between these methods is the pretreat- is summarized in Table 2.
ment techniques of coal samples, which are chemical digestion and
thermal decomposition. Cold vapor atomic absorption spectrom- 3.3. Mercury forms in coal
etry and cold vapor atomic fluorescence spectroscopy are usually
used for the detection of mercury after pretreatment. With a long In general, the occurrence forms of mercury in coal can be de-
history and high recognition, the analytical method with chemi- termined by using the following methods [37,44–46]:
cal digestion has been widely adopted. However, the pretreatment (1) Correlational analysis method is used to explore the occur-
process involves many steps and requires mercury to be dissolved rence forms of mercury in coal based on the content corre-
in solution, which leads to an increased chance of sample contam- lation of mercury with ash or sulfur (including total sulfur,
ination in the digestion process [25]. In addition, the experimen- organic sulfur, pyrite sulfur, sulfate sulfur) in coal.
tal personnel need to be well trained. Due to the advantages of (2) The float-sink test uses several organic solvents to divide
quickness, convenience, and high efficiency, the thermal decompo- the coal into sub-coal samples with different densities [47].
sition analytical method has become more favorable. The commer- Then, the correlation between the main component and
cial mercury analysis instruments include Hydra AA Hg Analyzer mercury content in the sub-coal samples is studied [48].
(Teledyne Leeman Labs), DMA-80 Direct Hg Analyzer (Milestone), (3) Sequential chemical extraction procedure (SCEP) adopts spe-
the AMA 254 Hg Analyzer (Leco), the Hydra-C Hg Analyzer (Tele- cific chemical solvents to extract the different mercury forms
dyne Leeman Labs), and the RA-915M Hg Analyzer equipped with in coal samples step by step based on their different solubil-
the pyrolyzer PYRO-915, etc. ity. In general, the chemical forms of mercury in coal can be
divided into six chemical species, namely, water-leachable,
3.2. Mercury content in coal ion-exchangeable, organic-bound, carbonate-bound, silicate-
bound, and sulfide-bound [49,50].
Many researchers have determined the mercury content in coal (4) Thermal treatment method is used to obtain the occurrence
around the world [32–43]. Due to the combined effects of var- mode of mercury based on the specified release temper-
ious geological factors in the depositional environment, mercury atures of the specified mercury compounds, as shown in
content in coal varies greatly in different regions, different coal- Table 3 [47,51–55].
forming periods, and different degrees of deterioration. For China, (5) Direct test analysis technology uses advanced equipment
Zhang et al. [32] measured 990 coal samples, finding that the av- (such as X-ray absorption spectroscopy (XAS) and X-ray pho-
erage mercury content in the studied Chinese coal was 0.16 mg/kg toelectron spectroscopy (XPS)) to determine the speciation
with a range of 0.003–10.5 mg/kg. Ren et al. [33], Tang and Huang and binding of mercury on coal directly. However, it is very
[34], Zheng et al. [35], and Yang et al. [36] also reported the aver- difficult to implement due to the low mercury concentra-
age concentration of mercury in Chinese coal with values of 0.20, tion in the actual application. The silicon in the coal inter-
0.1, 0.19, and 0.20 mg/kg based on the sample numbers of 1413, feres with the XPS detection results [56]. Thus, this method
1458, 1699, and 1793, respectively. Mukherjee et al. [37] collected is generally applied for the mercury sorbents, which have
the information on mercury concentration in coal from India and 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 33
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 to 27.2%, corresponding to the 50 to 200 ppmv of HCl. Agarwal
temperature, almost all the mercury in coal decomposes into Hg0 et al. [93] summarized that HCl oxidized Hg0 more effectively at
based on the mercury forms, mentioned above, in coal [74,75]. As temperatures higher than 600 °C, while Cl2 led to a stronger mer-
the flue gas cools, Hg0 can react with flue gas components, such as cury oxidation effect at temperatures below 500 °C. It has been
halogens (Cl2 , Br2 ), acid gas (HCl, HBr, NO2 ), and O2 , etc. to trans- shown that the Hg0 reaction with HCl was favorable at higher tem-
form into Hg2+ through homogeneous reactions [75–77]. Part of peratures [94,95] while it reacted favorably with Cl2 at lower tem-
the Hg0 will be catalytically oxidized to Hg2+ or absorbed on fly peratures [96–98]. Laudal et al. [97] performed bench-scale exper-
ash acting as Hgp through heterogeneous oxidation with the help iments to investigate the effects of various flue gas components on
of fly ash and flue gas components [74,78–80]. In addition, some Hg0 oxidation using the Ontario Hydro Method (OHM) and found
Hg2+ can also be absorbed on the fly ash surface as Hgp while that 10-ppmv Cl2 could realize 84.8% Hg0 oxidation at 175 °C with
some Hg0 keeps its form without transformation in the cooling flue gas components of N2 , O2 , CO2 , and H2 O. The experiments
process. Finally, the mercury emitted into the atmosphere can ex- of Agarwal et al. [99] demonstrated that Hg0 oxidation reached
ist in three forms: Hg0 , Hg2+ , and Hgp [81,82]. The general mer- above 95% as Cl2 concentration exceeded 50 ppmv. Based on the
cury transformation process, modified after [83], is shown in Fig. 6. electronic structure, Cl2 is much stronger than HCl as an oxidizing
For CFPP, Hg2+ is easily removed by wet flue gas desulfurization agent.
(WFGD) devices because of its high water solubility. The Hgp can
Cl + H ↔ HCl (1)
be captured with the use of particulate matter (PM) control de-
vices, such as an electrostatic precipitator (ESP) or fabric filter (FF). 2Cl ↔ Cl2 (2)
Due to its high volatility and water insolubility, it is very difficult
for APCDs in power plants to capture Hg0 [74–86]. Thus, under- 4Cl + 2H2 O ↔ 4HCl + O2 (3)
standing the transformation mechanism of mercury in coal com-
4HCl + O2 ↔ 2Cl2 + 2H2 O (4)
bustion is very important for the selection or development of its
removal method. Many factors can influence mercury transforma- Thermodynamic equilibrium calculations show that all the mer-
tion, such as coal types, flue gas components, flue gas temperature, cury in the flue gas exists as Hg0 at temperatures above 627 °C
combustion atmosphere, coal ash properties, etc. Based on partici- while it will be in the form of HgCl2 entirely at temperatures
pation of fly ash or not, the mercury reaction can be divided into below 452 °C for typical coals [100]. However, the measurement
homogeneous (without fly ash) and heterogeneous (with fly ash) of mercury in the flue gas with a temperature of about 127 °C
reaction, which are discussed in Sections 4.2 and 4.3. in the full-scale combustion system does not support the equilib-
rium calculations results, the reported data of which is 30−95% of
4.2. Homogeneous reaction Hg2+ [89]. The experimental data of Fry et al. [101] showed that
quench rate had obvious effects on homogeneous mercury oxida-
4.2.1. Effect of chlorine tion, in which a change from −210 to −440 K/s led to the mer-
Chlorine is considered as the key element for Hg0 oxidation cury oxidation from 34% to 86% at 300 ppmv chlorine. It indicates
[87–89]. During coal combustion, chlorine in coal will be released mercury oxidation with flue gas is kinetically controlled. Many re-
in the main form of atomic Cl, which transforms into HCl or Cl2 searchers have developed the reaction kinetic mechanisms to ex-
with flue gas cooling. The relevant transformation process can be plore the Hg0 oxidation process in the presence of Cl2 or HCl.
described by the reactions (1)–(4) [90,91]. Ghorishi [92] examined Widmer and West [102] firstly gave the rate constants in the Hg0
the effects of HCl concentration and temperature on Hg0 oxidation oxidation mechanism with chlorine, which was the eight reaction
at the gas mixture of 40 μg/m3 Hg0 , 5% CO2 , 2% O2 , and the balance paths. Due to few experiments about the rate constants, assump-
N2 , finding that the increasing concentration of HCl resulted in an tions and analogies were used by Widmer and West [102] that re-
increase in Hg0 oxidation. The Hg0 oxidation rate ranged from 9.1% 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.
constants for some of the eight Hg-Cl reactions were determined to a mercury oxidation rate of 11% at 340 °C [119], which indicated
by quantum chemistry and transition state theory (TST), such as NO2 promoted Hg0 oxidation in the Hg0 + NO2 system. Rumayor
in the works of Sliger et al. [94], Li et al. [103], Wilcox et al. [104– et al. [120] demonstrated that adding 200 and 400 ppmv of NO
108], Khalizov et al. [109], Krishnakumar and Helble [110], Liu et al. could result in 5.0% and 7.5% of Hg2+ in the atmosphere of NO
[111], and Zheng et al. [112], which helped to improve the accuracy balanced with N2 at a flue gas temperature of 150 °C, shown in
of the reaction kinetic parameters, shown in Table 4. Wilcox et al. reaction (5). With the addition of CO2 and O2 in the gas mixture,
[113] summarized that the radical combination reactions concern- the ratio of Hg2+ increased up to 14%. This might be NO reacting
ing HgCl and Cl intermediate species could be the main pathways with O2 to form NO2 and radical oxygen atoms (reaction (6)),
with the existence of chlorine radical chemistry based on theoret- which had strong oxidative properties (reactions (7) and (8)).
ical calculations. In addition, Cl2 and HOCl seemed to play a ma- Then, NO and NO2 could react with Hg0 to generate Hg(NO2 )2
jor role in mercury oxidation over HCl, while atomic Cl might be (reaction (9)) and Hg(NO3 )2 with the presence of oxygen.
in the dominant oxidation pathway, indicated by both the kinetic
and thermodynamic predications [104]. Krishnakumar and Helble 2Hg0 (g ) + 2NO(g ) → 2HgO(g ) + N2 (g ) (5)
[110] adopted high-level quantum chemistry calculations to get the
TST rate constants for the eight-step homogeneous Hg-Cl reactions. NO(g ) + O2 (g ) ↔ NO2 (g ) + O · (6)
It was found that the rate constants of Hg/HgCl reactions with
HOCl were faster or comparable to those with Cl2 , while reactions Hg0 (g ) + O · (g ) → HgO(g, s ) (7)
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- Hg0 (g ) + NO2 (g ) → HgO(g ) + NO(g ) (8)
ical dynamics software Chemkin to investigate the level of effect
of each reaction on Hg0 oxidation, finding that R1, R7, and R5 had Hg0 (g ) + NO2 (g ) → Hg(NO2 )2 (g ) + NO(g ) (9)
great impact. It can be inferred that Cl, HOCl, and HCl are the im-
portant Cl species for Hg0 oxidation. The gaseous mercury oxida- In addition, the effect of NO on Hg0 oxidation by chlorine has
tion behavior in homogeneous reaction with Cl compounds done also been investigated by some researchers. Work done by Laudal
by Naruse et al. [115] showed that Hg0 firstly reacted with Cl rad- et al. [97] showed that the addition of NO could result in a de-
icals to produce HgCl. Then, the HgCl reacted with Cl2 to form crease in the presence of oxidized mercury in the gas mixture of
HgCl2 . The Cl radical played a significant role in the relevant re- N2 , O2 , CO2 , and SO2 , which might be due to a reaction between
action chains. Qiao and Xu [116] also concluded that Cl2 was more NO and Cl2 (reaction (10)). This reaction consumed Cl2 , which was
effective than HCl for Hg0 oxidation in the Hg/O/H/Cl system. In thermodynamically favorable at temperatures near the end of a
addition, the reaction between Hg and Cl is faster than that be- typical power plant. Niksa et al. [121] predicted that lower NO
tween Hg/HgCl and Cl2 [117]. Thus, it can be summarized that the concentration (<20 ppmv) benefited Hg0 oxidation while higher
degree of effect of Cl forms on Hg0 oxidation is the Cl radical, Cl2 , NO concentration inhibited the Hg0 conversion in the presence of
and HCl in decreasing order. HCl. Auzmendi-Murua and Bozzelli [122] indicated that NO sig-
Thermodynamic equilibrium calculations show that Cl2 domi- nificantly decreased mercury oxidation with the addition of chlo-
nates HCl at temperatures below 475 °C while HCl dominates over rine (Cl = 500 ppmv). Preciado et al. [123] studied the effects of
Cl2 above that temperature for typical O2 and H2 O concentrations halogens on mercury oxidation under air- and oxygen-fired condi-
[99]. The Cl is predicted to be HCl at flame temperatures while tions in a bench-scale, methane-fired, 300 W, quartz-lined reactor,
half of it is thought to be Cl2 at the temperature of APCDs inlet by which found that the addition of NO (<300 ppmv) had little or
equilibrium calculations. However, the kinetic calculations indicate no effect on mercury oxidation by chlorine. Another explanation
that less than 1% of the Cl is converted to Cl2 at that temperature for the influence of NO on mercury oxidation with the presence of
[89]. The field test on halides emission at a 200 MW pulverized chlorine is that NO can react with OH, which takes away OH that
coal combustion boiler showed that HCl was the main Cl form in would react with H. Thus, more free H can react with Cl to produce
flue gas while Cl2 concentration was extremely low [118]. HCl, which results in little available chlorine reacting with mercury
Based on the studies above, it can be summarized that Hg0 ox- [122]. The relevant reactions are shown in reactions (11)–(13).
idation by Cl is affected by the flue gas temperature, Cl forms, and
their concentration, etc., which is summarized in Fig. 7. 2NO(g ) + Cl2 (g ) → 2NOCl(g ) (10)
4.2.3. Effect of SO2 et al. [121] concluded that H2 O was a strong inhibitor for Hg0 ox-
It has been reported that the SO2 alone does not lead to Hg0 idation. In summary, the H2 O is negative for Hg0 oxidation, which
oxidation [119]. Smith et al. [124] showed that injecting SO2 into further inhibits oxidation in the presence of SO2 or NO, or both of
the CH4 combustion flue gas resulted in Hg0 oxidation, in which them.
20% oxidation was obtained with an SO2 concentration of 100–
H2 O + Cl → OH + HCl (16)
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+
4.2.5. Effect of O2
to 5.5%. These findings indicate that the presence of O2 enhances
Hall et al. [128] investigated the Hg0 homogeneous oxidation
Hg0 oxidation by SO2 , which can be explained by reaction (14).
by O2 in the temperature range of 20–700 °C, in which no mer-
2Hg0 (g ) + 2SO2 (g ) + O2 (g ) → 2HgO(g ) + 2SO3 (g ) (14) cury oxidation was observed. However, Niksa et al. [121] argued
that O2 could weakly promote homogeneous Hg oxidation by the
In addition, it is reported that SO2 has an inhibitory effect on kinetic model. Xu et al. [129,130] adopted detailed chemical kinet-
Hg oxidation by HCl or Cl2 [93,125]. SO2 inhibits Hg0 oxidation ics to study homogeneous mercury oxidation and also found that
with the presence of HCl in the gas mixture of O2 , CO2 , and bal- O2 benefited Hg0 oxidation, especially at the low Cl2 concentra-
anced N2 at a temperature of 754 °C, in which an SO2 concen- tion; 1.5−6.0% of mercury was predicted to be present as HgO in
tration of 500 ppmv decreases the percentage of Hg2+ from 27% all cases. Based on the studies mentioned above, it can be inferred
to 20% at an HCl concentration of 200 ppmv [95]. Agarwal et al. that O2 may promote Hg0 oxidation, but the enhancement effect is
[99] indicated that adding 370 ppmv SO2 led to Hg0 oxidation de- slight.
creasing from 77% to 52% with the presence of N2 , O2 , CO2 , and
Cl2 . Meanwhile, the addition of the same concentration of SO2 de- 4.2.6. Effect of NH3
creased the Hg0 oxidation from 90% to 57% in the gas mixture of In addition to the conventional flue gas components described
N2 , O2 , CO2 , H2 O, and Cl2 . The reason for the inhibitory influence above, NH3 is also a non-negligible flue gas component after se-
of SO2 on Hg0 oxidized by Cl2 may be similar to NO, which irre- lective catalytic reduction (SCR) device in coal-fired power plants.
versibly reacts with Cl2 , as shown in reaction (15). However, mer- In the findings of Hall et al. [119], it is found that there is no re-
cury oxidation is promoted with the existence of SO2 as HCl con- action between Hg0 and NH3 for the reaction temperature ranges
centration is 200 ppmv and inhibited as HCl concentration reaches of 20–600 °C. However, the works about influence of NH3 on Hg0
555 ppmv [124]. It seems that the promotion or inhibition of SO2 homogeneous reaction with other flue gas components are little
on mercury oxidation by HCl depends on the concentration of SO2 reported, which need more studies.
and HCl. Studies in full-scale utilities indicate that SO2 had a pos-
itive correlation with Hg0 oxidation, and the interactions are af- 4.3. Heterogeneous reaction
fected by the operating conditions, chlorine content in coal, and
temperature [126]. Though some homogenous mercury oxidation mechanisms have
been proposed to predict mercury oxidation in simulated flue gas,
SO2 ( g ) + Cl2 ( g ) → SO2 Cl2 ( g ) (15)
these mechanisms are unable to accurately predict mercury oxida-
tion in actual coal-fired flue gas [79]. One reason is that the kinetic
4.2.4. Effect of H2 O parameters of the homogeneous reaction are not accurate enough
The H2 O is thought to inhibit Hg0 oxidation by chlorine (Cl2 ), as and incomplete. Another reason is the existence of heterogeneous
concluded by some researchers [93,99]. Zhao et al. [127] conducted reaction between fly ash and Hg0 in the presence of flue gas com-
mercury homogeneous oxidation experiments, the results of which ponents, which also plays an important role in mercury oxidation
showed that adding 8% H2 O resulted in a decrease in Hg0 oxida- or adsorption. Many factors can affect the heterogeneous reaction
tion rate from 38% to 4% in the presence of 200-ppmv SO2 and of fly ash on Hg0 , which include physical structure properties (sur-
13-ppmv Cl2 . Agarwal et al. [99] also thought that the existence of face area, particle sizes, etc.) of fly ash, unburned carbon, metal
H2 O intensified the inhibitory effect of SO2 and NO on mercury ox- oxides (Fe2 O3 , Al2 O3 , etc.) in fly ash, and flue gas components, as
idation by Cl2 . Auzmendi-Murua and Bozzelli [122] predicted that elaborated below.
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- 4.3.1. Physical structure properties of fly ash
acted with Cl to form OH and HCl (reaction (16)), which removed Zhou et al. [131] conducted mercury adsorption by coal-fired
Cl from HCl, and slowed the mercury conversion by chlorine. Niksa 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
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.
Fig. 11. Hg0 oxidation mechanism with HCl on Fe2 O3 surface [165]. Reprinted with permission from Elsevier, 2016.
Table 5
Gas components between air-coal and oxy-coal combustion [177].
Item Gaseous species Air-coal combustion (wet basis) Oxy-coal combustion (wet basis)
atmosphere was lower than that under O2 /N2 atmosphere, which mercury species in fly ash. In addition, mercury TPD analysis indi-
was because that conversion of SO2 to SO3 could eliminate O and cated mercury retention by fly ash was mainly by the carbon [197].
OH radicals (very important reactants for producing the main Hg0 Release behavior of mercury in a 10 kWth fluidized bed combustor
oxidant, such as Cl and HOCl). The high H2 O concentration in oxy- under a different atmosphere showed that mercury retained in fly
coal combustion inhibited Hg0 oxidation in the atmosphere of 6% ash decreased by 44% as the O2 concentration increased from 15%
O2 , 15-, 30-, 60-, and 120-ppmv HCl; 0%, 5%, 10%, 20%, 30%, and to 30%, which might be ascribed to O2 -promoted Hg0 evaporation
40% H2 O; and equilibrium gas CO2 at 900 °C, which might be due [198]. This differs from the findings of Izquierdo et al. [196]. How-
to reaction (33) [193]. The addition of SO2 in the simulated oxy- ever, the addition of H2 O favored mercury adsorption by fly ash,
coal combustion flue gas also reduced Hg0 oxidation by reaction which was caused by the generation of some active sites via reac-
(34). For the homogeneous mercury oxidation under air-coal and tion between H2 O and carbon-oxygen complexes or changes of the
oxy-coal (27% O2 in CO2 ) firing conditions conducted in a lam- surface conditions [198].
inar, methane-fired, bench-scale, quartz-lined reactor, Hg0 oxida- Based on the literature review, mercury heterogeneous trans-
tion by HCl under oxy-firing conditions was higher than that un- formation in the oxy-coal combustion atmosphere can be summa-
der air combustion. The addition of NO (less than 300 ppmv) and rized: (1) fly ash plays an important role for Hg0 oxidation; (2) SO3
SO2 (less than 400 ppmv) had little or no influence on the Hg0 ox- inhibits mercury retention by fly ash while H2 O promotes this phe-
idation by chlorine under both firing conditions [123]. Wang et al. nomenon; and (3) there is no agreement in distribution between
[194] showed that an increase in H2 O concentration would inhibit Hgp and Hgg affected by O2 . In fact, little work has been conducted
Hg0 oxidation by chlorine. More mercury oxidation in the atmo- on the mercury heterogeneous transformation with fly ash under
sphere of NO, CO2 , and O2 could be found compared to that with- oxy-coal combustion conditions. Further works should include the
out CO2 , which was due to the high proportion of NO2 production following: (1) difference in characteristics of fly ash between the
with the presence of CO2 . Meanwhile, the existence of 500-ppmv air-coal and oxy-coal combustion atmosphere, such as physical sur-
SO2 could cause mercury oxidation owing to a dramatic decrease face structure, chemical composition, and mercury compounds in
in the atmosphere of 27% O2 /CO2 by the consumption of O or OH fly ash; (2) effects of typical flue gas components on mercury re-
radicals shown in reactions (35)–(37). action by fly ash in a wide temperature range; and (3) establish-
ment of models of mercury heterogeneous transformation, which
2H2 O + Cl2 → 4HCl + O2 (33)
helps in the development of mercury prediction in actual oxy-coal
combustion flue gas.
Cl2 + SO2 + H2 O → 2HCl + SO3 (34)
sampling probe, glass filter, impinger box, vacuum line, pump, and 5.1.3. Mercury-continuous emission monitoring system
a metering console. During sampling, mercury in flue gas is with- The mercury continuous emission monitoring system (Hg-
drawn isokinetically via the probe and the filter with the tem- CEMS) can monitor the real-time concentration of different Hgg ,
perature maintained at 120 °C, followed by a series of impingers including Hgg , Hg2+ , and total Hgg . It is mainly composed of pre-
in an ice bath. The Hgp is collected at the filter in the form of treatment/conversion unit and analysis unit, the schematic dia-
particle. The first three impingers containing 1.0 mol/L KCl solu- gram of which is shown in Fig. 16. At present, the mercury an-
tion are used to adsorb Hg2+ , while the fourth impinge with 5% alyzer can only determine the Hg0 concentration. Thus, Hg2+ in
(V/V) HNO3 ·10% (V/V) H2 O2 solution and last three impingers with flue gas should be firstly transformed into Hg0 , and then be deter-
4% (w/V) KMnO4 ·10% (V/V) H2 SO4 solution are used for Hg0 cap- mined. There are two ways to transform Hg2+ into Hg0 , which are
ture. The mercury in fly ash and absorbing solution can be de- (1) wet chemical reduction method using SnCl2 solution, and (2)
termined by the relevant mercury analyzer, and the concentra- high-temperature catalyst or high-temperature heating conversion
tion of each mercury species in flue gas can be calculated by the method.
data of mercury analysis value, fly ash mass, flue gas volume, and
the volume related with absorbing solution. To ensure accuracy of 5.1.4. Comparison of OHM, US EPA Method 30B, and Hg-CEMS
the test data, OHM requires that relative standard deviation (RSD) The OHM, which has been accepted as a standard mercury sam-
should be less than 34% when mercury concentration is lower than pling method worldwide, can determine Hgp , Hg0 , and Hg2+ in the
3 μg/m3 . Otherwise, the RSD should be less than 11% if mercury flue gas. The data from this method is usually used to check the ac-
concentration is higher than 3 μg/m3 [46]. 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
5.1.2. US EPA Method 30B gas volume (about 1–2.5 m3 , dry flue gas) for each time of mercury
The US EPA Method 30B uses solid mercury adsorbent to cap- sampling. OHM can not give the real-time mercury concentration.
ture mercury in flue gas, which can adsorb the total Hgg or spe- In addition, the mercury sampling operation is complicated and
cific mercury species (Hg0 and Hg2+ ) based on the adsorbent type. needs a significant number of chemical solutions and skilled oper-
The schematic diagrams of US EPA Method 30B for Hgg and spe- ators. It is reported that Cl2 in flue gas can form hypochlorite ion
cific mercury species are shown in Fig. 15(a) [202] and Fig. 15(b) in KCl solution, which can oxidize a certain amount of Hg0 to Hg2+
[203], respectively. In general, the activated carbon (AC) modified in the solution [206]. The experiments of Linak et al. [207] showed
by halogens acts as the adsorbent to adsorb total gaseous mercury, that the low concentration of 1-ppm Cl2 in a simulated flue gas
while the oxidized mercury is adsorbed by a special adsorbent. mixture resulted in a bias of 10–20% of Hg0 misreported as Hg2+
From Fig. 15(a) and (b), it can be seen that there are two identi- for the OHM. The existence of SO2 in flue gas or the addition of
cal adsorbents in the trap for mercury adsorption, where the front Na2 S2 O3 can inhibit the oxidation in the solution [208,209]. In fact,
part is called mercury collection and the latter is called mercury the existence of SO2 in actual coal combustion flue gas eliminates
breakthrough. To ensure the accuracy of mercury data sampled by this bias of mercury speciation measurements, but it might be a
this method, the breakthrough rate (BR) and relative deviation (RD) problem for the few combustor or research works where Cl2 is
are selected as the main parameters for quality control based on present with little SO2 [207]. The obtained mercury concentration
quality assurance and quality control (QA/QC) criteria [204,205], in flue gas is affected by the sampling operation, purity of chemi-
which requires that BR and RD should be no more than 10% if cal solutions, error in recovery, and digestion of the absorption so-
total Hgg concentration is higher than 1 μg/m3 while the values lution, etc.
should be no more than 20% when the total Hgg concentration is Compared to the OHM, the sampling operation of US EPA
lower than 1 μg/m3 . The expressions of BR and RD are shown as Method 30B, which uses mercury adsorbent traps instead of the
Eqs. (1a)–(5a) [202,203]. absorption solution in OHM, is simpler. It saves the time and cost
m2 for preparation, recovery, and digestion of the absorption solution.
BRHg(g) = × 100% (1a)
m1 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
m4
BRHg(2+) = × 100% (2a) mercury concentration. Generally, it cannot determine Hgp in flue
m3 gas without collection of fly ash. Moreover, the flue gas compo-
m6 nent, such as high SO2 or NOx concentration, will affect the accu-
BRHg(0 ) = × 100% (3a) racy of the data. Thus, the method is usually applied at the outlet
m5
of FGD. The types of mercury adsorbent and adsorption efficiency
|COHM − C30B | are other factors that influence the accuracy of the data.
RD30B−OHM = × 100% (4a)
COHM With implementation of the increasingly strict emission stan-
dards for mercury from coal-fired flue gas, Hg-CEMS is encour-
|C30B1 − C30B2 |
RD30B = × 100% (5a) aged to be installed in CFPPs. Different from OHM and US EPA
C30B1 + C30B2 Method 30B, the Hg-CEMS can give the real-time mercury emis-
where, BRHg(g) , BRHg(2+) , and BRHg(0) present the breakthrough rate sion concentration, which is very important for providing immedi-
of Hgg , Hg2+ , and Hg0 , respectively, in %. m2 , m4 , and m6 rep- ate feedback for boiler operation and applied removal technology
resent the mercury mass in the second section of corresponding concerning mercury concentration. However, it can not determine
adsorbents for Hgg , Hg2+ , and Hg0 , respectively, in μg; and m1 , Hgp concentration. In addition, Hg-CEMS involves high purchase
m3 , and m5 represent the mercury mass in the first section, in and maintenance costs, as well as periodic calibration tests. The
μg. RD30B-OHM represents the relative deviation between the total comparison of OHM, US EPA Method 30B, and Hg-CEMS is shown
Hgg concentrations determined by US EPA Method 30B and OHM, in Table 6.
in %. COHM and C30B represent the total Hgg concentration deter-
mined by OHM and US EPA 30B, respectively, in μg/m3 . RD30B rep- 5.2. Co-removal efficiencies across air pollution control devices
resents the relative deviation between total Hgg concentrations de-
termined by the paired sorbent traps applied in the same sampling With more stringent emission limits on air pollutants from coal
situation, in %. C30B1 and C30B2 represent the total Hgg concentra- combustion, the install share of APCDs, such as SCR equipment,
tion determined by the paired sorbent traps, respectively, in μg/m3 . 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 [210]. However, the installed capacity of SO2 control devices and
CFPPs. Taking China as an example, almost 90% of CFPPs have been SCR equipments has accounted for 93.0% of total coal-fired gener-
equipped with ESP, while the rest have ESP+FF [2]. By the end of ating unit capacity and 85.8% of the total thermal power unit ca-
2007, the installed capacity of SO2 removal devices in total thermal pacity, respectively, by the end of 2016 [211]. It has been confirmed
power unit capacity was more than 50% with little share of SCR 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.
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.
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 rate across WFGD device is in the range of 83.45–94.53%. How-
oxidation rate is adopted. Based on the data in Table S1, the Hg0 ever, in some cases the Hg0 re-emission occurs during the Hg2+
oxidation rate across SCR device in CFPPs is in the range of 6.5– removal process in the WFGD device, which is thought to be ex-
79.9%. 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-
5.2.2. Electrostatic precipitator and fabric filter furizer. Then, Hg2 2+ reacts with OH− in seriflux to generate Hg0
The ESP and FF are good at capturing Hgp in flue gas, benefit- and HgO. SO2 in flue gas can reduce HgO to form Hg0 . This is de-
ing from the higher PM removal efficiency (>99%). With flue gas scribed by reactions (38)–(40); (2) Hg2+ dissolved in scrubber so-
cooling, some parts of Hg0 and Hg2+ will be adsorbed on fly ash lution can react with sulfite and sulfate to form HgSO3 and HgSO4 ,
to generate Hgp , and Hg0 will react with fly ash to produce Hg2+ in which sulfite and sulfate are from SO2 dissolving in scrubber
or Hgp . Compared to ESP, FF has a higher PM removal ability, espe- solution. A portion of HgSO3 and HgSO4 may further participate in
cially for fine PM. Thus, the mercury removal rate for FF is higher some reactions to release Hg0 . This is described as reactions (41)–
than that for ESP, which can be found in Zhang et al. [225] (ESP- (42). Moreover, the Hg0 re-emission is affected by the operating
11.5%, FF-52.3%), Cui et al. [199] (ESP-68.3%, FF-70.0–71.6%), and temperature, pH, O2 concentration in flue gas, transitional metal
Tian et al. [237] (ESP-33.17%, FF-67.92%) in Table S1. ions concentration, etc. It is found that high availability of excess
The mercury removal rate across ESP or FF is influenced by oxygen in the flue gas contacting with the desulfurization solution
flue gas temperature, mercury species in flue gas, fly ash compo- leads to the lower reduction of Hg2+ to Hg0 while decreasing the
nents (unburned carbon and metal oxides), capture ability of ESP slurry pH or increasing the operating temperature enhances Hg0
or FF for PM, etc. [221]. According to the data in Table S1, the Hgt re-emission significantly [250,251]. However, Wu et al. [252] found
removal rate for ESP and FF is 11.5–90.4% and 28.5–90%, respec- the opposite results by doing the Hg0 re-emission experiments in
tively. Wang et al. [249] summarized that average Hgt removal rate a lab-scale simulated scrubber, which indicated that the increase
for ESP in China, the US, South Korea, and Japan was 22%, 36%, of the slurry pH resulted in the increase in Hg0 re-emission con-
59%, and 52%, respectively. In addition, Sung et al. [233] found centration.
that more Hg2+ was generated when flue gas passed through FF, In the summary of Table S1, the Hgt removal rate of WFGD de-
compared to ESP, which benefited its removal by WFGD. Under vice is 3.9–72%.
the same conditions, installing FF between ESP and WFGD made Hg2+ + Hg0 ↔ Hg2+ (38)
2
mercury removal efficiency across the whole APCDs increase from
62.44% to 86.73%. −
Hg2+
2 + 2OH ↔ H2 O + HgO + Hg
0
(39)
5.2.4. Wet electrostatic precipitator 5.3. Emission concentration and emission factor
To meet strict emission limits, WESP is installed widely in
the ultra-low emission (ULE) power plants and has an impor- Hgt emission concentration in flue gas from the stack of CFPPs
tant role in collecting ultrafine particles and aerosols. Zhang et al. to the atmosphere has raised widespread concern. Some countries,
[229] found WESP also has the co-effect for Hgt capture with a re- such as China and the US, have issued relevant limits for mer-
moval rate of 34.52–47.42%. When the flue gas went through the cury in flue gas emitted from CFPPs, which are 30 μg/m3 (China)
WESP, concentration of both Hg2+ and Hg0 decreased. Studies by [15], 7 μg/m3 (bituminous, the US), 20–35 μg/m3 (subbituminous,
the US Department of Energy [253] indicated that the average re- the US), 60 μg/m3 (lignite, the US), and 6 μg/m3 (coal gangue, the
moval rate of Hg0 , Hg2+ , and Hgp in flue gas by WESP was 32–40%, US) [259], respectively. Based on the data in Table S2, mercury
72–82%, and 33–100%, respectively. It is known that Hg2+ and Hgp emission concentration for China and South Korea is in the range
can be collected by WESP, while there should be transformation of of 0.29–9.16 μg/m3 and 0.48–16.3 μg/m3 , respectively, while that for
Hg0 to Hg2+ or Hgp for Hg0 removal. It is inferred that electrode Poland, the Netherlands, and the US is within the range of 2.0–
of WESP can produce an electronic corona, which results in gener- 15.1 μg/m3 .
ation of free radicals, such as O, OH, O3 , Cl, and Cl2 from O2 , H2 O, To compare the mercury emission situations from different CF-
and HCl by gas discharge. Thus, the Hg0 in flue gas will be oxidized PPs, the mercury emission factor (MEF) is adopted in the work. The
into Hg2+ by free radicals and then form Hgp . The transformation MEF can be described as the ratio of the ultimate mercury emit-
process of Hg0 to Hg2+ can be interpreted by reactions (43)–(54) ted to the atmosphere to the heat value coming from the feed-
[254–258]. 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
O2 + 2e− → 2O + 2e− (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
O2 + O → O3 (44) (average 6.79) g/1012 J, respectively, while that for Poland is 0.71–
6.09 g/1012 J.
O + H2 O → OH + OH (45)
5.4. Mercury content in combustion by-products
HCl + e− → H + Cl + e− (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
Hg0 + O → HgO (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
Hg0 + O3 → HgO + O2 (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.
Hg0 OH → HgOH (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
Hg0 + Cl → HgCl (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–
HgCl + Cl → HgCl2 (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
Hg0 + Cl2 → HgCl + Cl (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
HgCl + Cl2 → HgCl2 + Cl (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
Hg0 + Cl2 → HgCl2 (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.
5.2.5. Combination of each air pollution control device In summary, the APCDs in CFPPs have a positive effect on flue
Based on the above discussion, it can be found that each APCD, gas mercury removal, in which SCR, ESP or FF, and WFGD are good
such as SCR, ESP, FF, WFGD, and WESP, has a positive effect on at Hg0 oxidation, Hgp capture, and Hg2+ removal, respectively.
flue gas mercury removal. Pudasainee et al. [221] reported the re- WESP also has the flue gas mercury removal ability. Due to the
lationship between the flue gas mercury oxidation rate of SCR or diversity and complexity in coal properties, flue gas components,
removal rate of ESP, and WFGD with the total removal rate across mercury forms in flue gas, fly ash composition, operation condi-
SCR+ESP+WFGD, which is shown in Fig. 18(a)–(c). The Hgt re- tions, etc., the Hg0 oxidation by SCR equipment, mercury removal
moval rate by SCR+ESP+WFGD has a strong relationship with mer- efficiency across APCDs, flue gas emission concentration, and
cury removed by ESP, which is followed by WFGD and SCR device. mercury content in CBPs vary widely. For mercury co-removal
Because many factors, like coal type, flue gas components, mer- and emission in CFPPs, the following studies need to be done:
cury species in flue gas, fly ash composition, and operation condi- (1) detail mercury transformation or the removal mechanism
tions, can affect the mercury removal rate by the APCD, it should across each APCD; (2) determine the way to improve the Hg0
be given specific treatment to evaluate the contribution of each oxidation rate in SCR equipment, or removal efficiency by APCDs;
APCD for the Hgt removal rate. According to summarized data in (3) obtain more mercury content data in CBPs, and give relevant
Table S1, the Hgt removal rate for ESP+WFGD, SCR+ESP+WFGD, emission limits; and (4) define the chemical species of mercury
SCR+ESP+FF+WFGD, and SCR+ESP+WFGD+WESP is 35.5–84%, in fly ash and gypsum, which is important for their utilization or
43.8–94.9%, 58.78–73.32%, and 56.59–89.07%, respectively. 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 adsorbents. Recently, some novel mercury control approaches have
been developed to improve the mercury removal efficiency and re-
Based on the mercury removal position in the CFPPs, mer- duce the mercury removal cost further, which include regenerable
cury removal technologies can be divided into pre-combustion, in- mercury removal adsorbent and multipollutant control technology.
combustion, and post-combustion mercury removal technologies. The technologies for in-combustion and post-combustion mercury
The pre-combustion technology introduced is to remove mercury removal in CFPPs are shown in Fig. 19 [81].
from coal before coal burning, which mainly includes coal wash-
ing and mild pyrolysis methods. The in-combustion technology 6.1. Pre-combustion mercury removal
includes low-NOx combustion technology, CFB combustion tech-
nology, coal blending, and the use of oxidizing chemicals in the 6.1.1. Coal washing technology
coal or furnace. The post-combustion technology mainly includes The coal washing technologies can be divided into physical
the existing APCDs, mercury oxidizing catalysts, injecting oxidizing and non-physical. The physical washing technology for mercury re-
chemicals into the flue gas, and mercury sorbents injection. Both moval is based on the density and surface physical-chemical prop-
the in-combustion and post-combustion mercury removal tech- erties of the components in the coal. Generally, mercury is mainly
nologies are to transform more Hg0 into easily capturable Hg2+ associated with pyrite and clay in coal. The washed coal is hy-
and Hgp and then remove them by the existing APCDs. Accord- drophobic while the most impurity components are hydrophilic. In
ing to the composition of adsorbents, mercury removal adsorbents the physical coal washing process, the mercury will accumulate in
can be classified into carbon-based adsorbents (AC, biochar, and flotation residue and then be removed. Physical coal washing tech-
petroleum coke), fly ash, calcium-based adsorbents, and mineral 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 47
Fig. 19. In-combustion and post-combustion mercury removal technologies in CFPPs [81]. Reprinted with permission from American Chemical Society, 2013.
increasing Cl content, which favors the transformation of Hg0 to metal oxides, such as Cr2 O3 , ZnO, CuO, NiO, and MnO, have been
Hg2+ or Hgp . Compared to these methods, putting chemicals into investigated [285], the results of which show that the impregnated
coal to remove mercury is widely studied, in which halogens are commercial SCR catalysts have a higher Hg0 oxidation ability than
the most popular oxidant. This method has the advantages of sim- their original catalysts. Zhao et al. [286] used Ce-Mn oxides to
ple operation, high mercury removal efficiency, and low cost. modify the spent TiO2 -based SCR catalysts for Hg0 removal, which
Berry [272] conducted a field test at Plant Miller to study found that the modified SCR catalysts (Ce1.00Mn/SCR1) performed
the effect of CaBr2 on mercury oxidation, the results of which the best catalytic activities with about a 92.80% Hg0 oxidation rate
showed that mercury oxidation efficiency increased from 60% to at a temperature of 150 °C. Zhao et al. [287] studied the promo-
90% under the addition of 5 mg/kg bromine to coal. Zhuang et al. tional effect of the CeO2 -modified V2 O5 -WO3 /TiO2 catalyst for Hg0
[273] found that adding 20 0–80 0 mg/kg (coal basis) of chlorine (in oxidation in a simulated coal-fired flue gas, the results of which in-
the form of CaCl2 ) into a 650 MW subbituminous CFPP equipped dicated that the introduction of CeO2 benefited Hg0 oxidation and
with SCR + FF + WFGD could achieve an overall mercury removal improved the H2 O-resistance ability. Huang et al. [288] used Fe2 O3
of 75–96%, which was only 18–32% without the addition. A series to modify the SCR catalyst, concluding that Fe2 O3 /SCR (1wt% Fe)
of spot tests conducted by the US Government Accountability Of- was the optimal catalyst, as it increased the mercury oxidation rate
fice at 14 different power plants showed that the addition of 25– from about 30% (without Fe2 O3 addition) to higher than 90% at
300 mg/kg CaBr2 to coal resulted in more than 90% of Hg0 being 350 °C in a simulated flue gas. Besides metal oxides, a study of the
oxidized in flue gas [274]. Pan et al. [275] used numerical simula- effect on Hg0 oxidation by a commercial SCR catalyst added with
tion and experimental method to study the effect of NH4 Cl injec- CaCl2 was conducted by Zhang et al. [289]. The addition of CaCl2
tion into the furnace on mercury transformation, which found that was found to significantly enhance the Hg0 oxidation activity over
the proportion of Hg0 and Hg2+ to the total mercury decreased the catalyst, which increased the Hg0 oxidation rate from 7.7% to
while that of Hgp increased as the addition amount of NH4 Cl in- 78.8% with the addition amount of 1.0 wt% CaCl2 .
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, 6.3.2. Inhibiting Hg0 re-emission in wet flue gas desulfurization
which indicated that the addition amount of 20, 50, 100, and As described in Section 5.2.3, Hg0 re-emission, namely Hg2+ re-
200 mg/kg could reduce the gas mercury emission ratio by about duction, will occur in WFGD, which reduces mercury removal effi-
20%, 30%, 60%, and 30%, respectively. Zhou et al. [277] and Zhao ciency. To suppress this phenomenon, oxidants or special chemical
et al. [278] indicated that the gaseous Hg0 concentration showed reagents are introduced in the desulfurization solution. Krzyżyńska
a decreasing trend with increasing the addition amount of CaCl2 , et al. [290] found that the extent of scrubbed mercury increased
NH4 Cl, and NH4 Br, respectively. However, all the above studies fo- from 40% to 70% with the amount of NaClO2 added in the
cus on mercury removal rate, which neglect the detailed mercury slurry increasing from 0.81 to 1.62 mol/L. The lab-scale experi-
removal mechanism. ments to achieve mercury reduction by adding aluminum sulfate
in the aqueous solutions and gypsum slurries were performed by
6.3. Post-combustion mercury capture González et al. [291], the results of which showed that the alu-
minum sulfate decreased the slurry pH to a level where the sulfite
6.3.1. Existing commercial selective catalytic reduction catalyst ions, responsible for mercury reduction, ceased to form. The ef-
improvement fects of thiocyanate ions (SCN− ) or sulfide ions (S2− and HS− ) on
SCR system has been installed widely in CFPPs, due to its ad- Hg0 re-emission from simulated WFGD solutions were conducted
vantages of high DeNOx efficiency, selectivity, and economic feasi- by Wang et al. [292], who concluded that both thiocyanate and
bility. The vanadia phase V2 O5 in typical commercial SCR catalysts sulfide ions inhibited reduction of aqueous Hg2+ to Hg0 . For the
can not only catalyze the reduction of NOx but also catalyze the thiocyanate ions addition, inhibition of mercury reduction was be-
Hg0 oxidation. Stolle et al. [279] found that the Hg0 oxidation abil- cause of the formation of a sulfite-thiocyanate- mercury complex
ity increased with increasing the concentration of V2 O5 in the SCR (HgSO3 SCN− ) and thiocyanate-mercury complex [Hg(SCN)x−(x-2)
catalyst. This finding was similar to the results of Kamata et al. (x = 2–4)]. The formation of HgS could be the main reason for
[280], which reported that the Hg0 oxidation rate showed almost inhibition of mercury reduction with sulfide ions addition. Wu
linear increasing trend with addition amount of VOx until 10 wt%. et al. [252] reported that Hg0 re-emission suppression rates could
Negreira and Wilcox [281] used two models, which represented reach 80.82% and 70.42% when adding 0.00125% (w/w) Na2 S4 and
TiO2 -supported systems with low and high loading of V2 O5 and 0.0 0 05% (V/V) trisodium salt nonahydrate (TMT15) in the simu-
WO3 , to study the influence of the surface composition and sur- lated scrubber, respectively. Omine et al. [250] demonstrated the
face coverage on the reactivity of a commercial SCR catalyst (V2 O5 - influence of sulfide-based additives on Hg0 re-emission in a sim-
WO3 -TiO2 ) on mercury oxidation. They found the increasing load- ulated batch scrubber, which showed that the suppression effec-
ing of both V2 O5 and WO3 enhanced reactivity of the SCR catalyst, tiveness of sodium hydrogen sulfide, sodium sulfide (Na2 S), TMT15,
and 75% V2 O5 -25% WO3 -TiO2 was suggested as the optimal V-W- and the Nalco-8034 reagent was 99%, 97%, 93%, and 99%, respec-
Ti composition for mercury oxidation. Though the SCR catalyst is tively. These additives benefited the precipitation of ionic mer-
effective for NOx reduction and Hg0 oxidation, it has some draw- cury as mercury sulfide. In addition, Na2 S, 2,4,6-trimercaptotiazine,
backs, such as a narrower temperature window and the potential TMT, and sodium dithiocarbamate (DTCR) were confirmed to be ef-
effect of V loss on the environment and humans during the cat- fective enough to suppress Hg0 re-emission from simulated FGD
alyst preparation and operation [282]. In addition, a low Hg0 oxi- liquors by Tang et al. [293], who found that the addition of these
dation rate is obtained in the flue gas with low HCl concentration. agents could make more than 90% of ionic mercury into a precipi-
NH3 and SO2 are reported to inhibit Hg0 oxidation over the con- tate and decreased Hg2+ reduction efficiency from 54% to less than
ventional SCR catalysts [283]. 3%. Sun et al. [294] concluded that DTCR had a better inhibitive
To overcome these disadvantages, various studies have been performance than TMT for the stabilization of mercury in flue gas
done to improve the SCR catalyst. RuO2 , which can catalytically desulfurization gypsum. In summary, the methods to inhibit Hg0
oxidize Hg0 by itself, is confirmed to work well with the SCR cat- re-emission in WFGD mainly involve adjusting the pH, or sulfite
alyst for Hg0 oxidation [284]. Moreover, Hg0 oxidation or removal ions concentration, or forming a precipitate of mercury. However,
effects by the commercial SCR catalysts impregnated with various 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 49
In summary, the main mercury control thought of injecting oxi- AC [341]. The DFT calculation of Padak et al. [342] on mercury
dizing chemicals into flue gas to remove mercury is similar to that adsorption by halide-impregnated AC showed that the sequence
of putting oxidizing chemicals into coal or furnace. The studied in- of mercury binding strength on halogenated AC was F-AC > Cl-
jected oxidizing chemicals mainly include hydrogen halogens (HF, AC > Br-AC > I-AC. This result differs from the above experimen-
HCl, HBr, and HI), ozone, and H2 O2 . The literature data shows that tal results of Zhou et al. [340], which indicates the adsorption en-
HBr has the more effective ability of Hg0 oxidation based on the ergy of mercury halide species on AC is not the only factor for
equal addition amount of oxidizing additives. mercury adsorption on halogenated AC. Rungnim et al. [343] used
the DFT method to investigate the reaction mechanisms of mer-
6.3.5. Carbon-based adsorbents cury adsorption and oxidation on halogenated AC completely, by
6.3.5.1. Activated carbon. Injecting activated carbon (AC) upstream adopting two different halogenated AC modes (namely, X-AC and
of the particle control device, such as ESP or FF, has been con- X-AC-X, X = Cl, Br, I). They showed that halide types did not influ-
sidered to be a mature and promising mercury removal technol- ence the mercury adsorption energy but affected the activation en-
ogy, the mercury removal effects of which have been evaluated ergy barrier of HgX formation significantly, which increased in the
in bench, pilot, and field-scale tests [311–315]. The pilot and field order of HgI < HgBr < HgCl. This trend agreed with experimen-
tests have shown that the mercury removal rate by AC sorbents tal results that mercury removal efficiency by halogen-impregnated
ranges from 25% to 95% with the mass ratio of carbon/mercury in- AC decreased as I-AC > Br-AC > Cl-AC. The oxidation mechanism of
creasing from 20 0 0 to 15,0 0 0 [75]. Lots of factors can affect the the mercury at (a) atop and (b) bridge sites of X-AC and X-AC-
mercury capture ability of the AC sorbents, including the surface X modes is shown in Fig. 22(a) and (b), respectively. Some tests
area, particle sizes, and pore volume of AC; mercury concentra- indicated that obtaining 90% mercury capture needed injection
tion in flue gas; flue gas temperature; flue gas components; and rates of 8.01 × 104 μg brominate AC (Br-AC) per cubic meter of
surface chemical properties; etc. [316,317]. Min et al. [318] found stack gas while the injection rate for raw AC was 16.03 × 104 –
that mercury adsorption efficiency showed a linear increase with 32.06 × 104 μg/m3 [317]. Zhong et al. [327] compared the mer-
the BET surface area increasing in the baseline gas condition. The cury removal efficiency by the AC modified with different halo-
increase in particle size would decrease the mercury adsorptive ca- gens (shown in Fig. 23) and concluded that AC modified by iodine
pacity significantly while high initial mercury concentration led to steam vapour deposition had a much better mercury removal abil-
the increase in mercury uptake [319]. Ochiai et al. [320] investi- ity than that modified by bromide deposition, as well as by NH4 Br
gated the effects of HCl and SO2 on mercury removal by AC sor- and NaBr impregnation, under the same experimental conditions.
bents in simulated coal combustion flue gas, the results of which Generally, sulfur impregnation decreases the surface area while
indicated that increasing HCl concentration benefited Hg0 removal increases the maximum Hg0 adsorption capacity compared to the
by the AC sorbents while the presence of SO2 inhibited Hg0 cap- raw AC fiber [311]. Sano et al. [344] found that the sulfur impreg-
ture with the presence of HCl. Miller et al. [321] indicated that nated AC contributed to a mercury adsorption 50- times greater
adding one of HCl, NO, or NOx at a time to the baseline gas (mix- than that of raw AC. Qiu et al. [345] showed that the mer-
ture of O2 , CO2 , N2 , and H2 O) could improve the mercury capture cury removal capacity of composite sulfurized activated carbon
rate to 90–100% from 10–20% (baseline gas conditions) by lignite- (CSAC), which was impregnated wth aqueous-phase Na2 S and fol-
based AC at 107 °C. With increasing the CO2 concentration from 0% lowed with vapour phase elemental sulfur, was 1.5 times higher
to 12% at 150 °C, the mercury adsorption efficiency of Calgon F400 than the AC impregnated with single elemental sulfur. Yan et al.
AC decreased from about 60% to 25% [322]. Li et al. [149] used [329] concluded that mercury adsorption by sulphur-impregnated
heat treatment (927 °C) in N2 , air oxidation (420 °C), and nitric acid carbon involved both physical and chemical processes. Lee and
(6 N HNO3 ) treatment to vary the surface oxygen functional groups Park [346] stated that the pore characteristics of raw AC and types
on two ACs and found that lactone and carbonyl groups might of sulfur are the main factors affecting mercury capture perfor-
be beneficial for Hg0 capture while phenol groups inhibited Hg0 mance on sulfur-impregnated AC, rather than the amount of im-
adsorption. Moreover, Liu et al. [323] confirmed that lactone, car- pregnated sulfur. Hsi et al. [347] indicated that elemental sulfur,
bonyl, and semiquinone were the active sites for Hg0 adsorption organic sulfur, and sulfate were formed on the sorbents (including
and phenol and carboxyl functional groups indicated a physisorp- AC, pistachio shell char and pistachio AC, and zeolite) in the sulfur
tion of mercury, which reduced mercury capture through DFT cal- impregnation process, in which elemental and organic sulfur were
culation. vital active sites for Hg0 and HgCl2 adsorption. In addition, Hsi
The high cost is an important reason for limiting the wide ap- and Chen [330] investigated the effects of acidic/oxidizing gases
plication of AC injection mercury removal technology; it is es- on Hg0 adsorption behavior on sulfur-impregnated AC, the results
timated that the cost for 82% mercury removal by using AC is of which showed that mercury-capture ability was promoted as
between $110,0 0 0 and $150,0 0 0 per kg of mercury [317]. Thus, one acidic/oxidizing component added in the baseline components
many methods are used to modify the AC to improve its mer- (CO2 , H2 O, and N2 ) with a declining order of NO, HCl, O2 , followed
cury removal efficiency, including halogen (Br, Cl, I) impregnation by SO2 .
or vapour deposition [324–328], sulfur impregnation [329–331], Du et al. [332] studied the catalytic oxidation and adsorption of
metal oxide or metal chloride modification [82,332–336], and non- Hg0 on neutral Al2 O3 , artificial zeolite, and AC impregnated with
thermal plasma (NTP) treatment [337–339]. Jang et al. [324] found CuCl2 . They showed that CuCl2 -impreganted AC had the best mer-
that the AC impregnated with 1% of KI and HCl solutions im- cury removal ability, and the value was over 90% for AC impreg-
proved the mercury adsorption efficiency to 80–100% and almost nated with 5% CuCl2 in the presence of 20-ppmv HCl at 140 °C in
100% within 1.5 h, respectively, whereas the mercury adsorption a 5 min test. Wang et al. [333] found that FeCl3 impregnated AC
efficiency was 60–80% for the raw AC. Zhou et al. [340] reported showed a significant performance for Hg0 capture, in which the
that NH4 Br modified AC (NH4 Br-AC) had a significantly larger mer- conversion of Hg0 to Hg2+ was promoted by the chlorine in metal
cury adsorption capability compared to the raw AC, and the mer- chlorides. Tao et al. [82] demonstrated that CeCl3 enhanced Hg0
cury removal efficiency of both the ACs increased with an in- removal by the AC, and the best CeCl3 loading amount and reac-
crease in inlet Hg0 concentration. O2 and NO in flue gas benefited tion temperature was approximately 6% and 170 °C. The presence
mercury adsorption on NH4 Br-AC while SO2 had negative effects. of NO and SO2 benefited Hg0 oxidation with the presence of O2
In general, mercury removal effects obey the increasing order of while SO2 inhibited the Hg0 capture without O2 in the flue gas.
AC < Cl-impregnated AC < Br-impregnated AC < I-impregnated 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. 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
Fig. 23. Mercury removal efficiencies by raw AC and AC modified by differ- Cl2 for 60 s) at 30 °C [339]. Reprinted with permission from American Chemical So-
ent halides (test conditions: C0 = 50 μg/m3 , m = 0.1 g, V = 7 L/min, T = 50 °C) [327]. ciety, 2016.
Reprinted with permission from Elsevier, 2017.
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 adsorption sites on the brominated petroleum cokes. The
mercury in a N2 atmosphere, the results of which indicated that inherent thiophene and organic sulfide in petroleum coke played a
the modification effect of ammonium halides on mercury adsorp- major role in mercury removal. In addition, the leaching test re-
tion performance followed the order of NH4 I (7643.1 μg/g) > NH4 Br vealed that the brominated petroleum coke showed a negligible
(842.0 μg/g) > NH4 Cl (365.3 μg/g). Based on the contrast testing and leachability of bromine and mercury from the spent sorbent, which
XPS analysis, the C-X (X: I, Br, Cl) covalent groups acted as the was safe for disposal after its use.
mercury adsorption sites and played a major role in mercury re- Common features of carbon-based adsorbents modification are
moval capacity for the modified biochars. to obtain more mercury adsorption or oxidation active sites on
In summary, halogen modification can enhance the mercury re- their surface, and to ensure a certain degree of surface physical
moval efficiency of the biochar, in which C-X (X: I, Br, Cl) and C=O structure. In addition, the flue gas components, such as O2 , NO,
may act as the major chemisorption sites for Hg0 adsorption. NO and SO2 , have a significant effect on the mercury removed by the
and O2 are beneficial for mercury removal while the effects of SO2 adsorbent.
and H2 O have a relationship with their concentration.
6.3.6. Fly ash
6.3.5.3. Petroleum coke. Petroleum coke is a low-priced carbon ob- Fly ash produced from CFPPs is considered to be a promising
tained as a byproduct from the upgrading of bitumen or petroleum sorbent for mercury capture [363]. The mercury removal efficien-
refinement [357,358]. It has a high-sulphur content, and the cies of fly ash are affected by its physical and chemical proper-
petroleum coke is usually dumped off as waste. Thus, some stud- ties, including fly ash particle size [135], surface area and average
ies propose to use it as a potential mercury sorbent after ac- pore size [137,364], UBC, and metal oxides in fly ash [137,157,168].
tivation with different chemicals. Lee et al. [357] applied high- To improve the mercury capture rate, fly ash is usually modi-
temperature pyrolysis to petroleum coke so as to bring sulfur fied by halogens or metal oxides. Zhang et al. [365] compared
to its surface, which was believed to capture gas-phase mercury. the mercury removal effects of two fly ashes impregnated with
Their result showed that the specific surface area of petroleum CaCl2 , CaBr2 , and HBr in an air-entrained-flow reactor, the results
coke increased by nearly 10 times and mercury capture was sig- of which showed that the HBr modified fly ashes had the great-
nificantly increased after pyrolysis. The pyrolyzed petroleum coke est mercury adsorption ability among the three modifiers. Both
was claimed to have high potential as a sorbent for mercury cap- the two fly ashes modified with HBr increased their mercury re-
ture. Hong et al. [359] evaluated the mercury adsorption effects of moval efficiency from 8.1% and 3.4% to 98.4% and 59.8%, respec-
petroleum coke, modified by NH4 Br solution, the results of which tively, as shown in Fig. 26. In addition, Zhang et al. [366] con-
showed that 1% NH4 Br-impregnated petroleum coke could remove firmed that HgCl2 , HgS, and HgO were the main mercury species
almost all the mercury in a fixed bed within 120 min, and the mer- on the unmodified fly ash while HgBr2 and HgO were the major
cury removal rate was more than 90% in the entrained flow reac- mercury forms in the HBr modified fly ash after Hg0 adsorption in
tor system with a temperature of 120 °C, residence time of 2 s, and the entrained-flow reactor through the determination of mercury
C/Hg ratio of 90,0 0 0. Their results highly supported that the mod- compounds by using the TPD method. HBr was thought to be the
ified high sulfur petroleum coke could be used as highly effective major factor for Hg0 oxidation. Zhou et al. [367] studied the influ-
mercury capture adsorbent for CFPPs. Cai and Jia [360] modified ence of flue gas components and ash composition on Hg0 oxidation
petroleum coke with a KOH-SO2 activation method and used it to or adsorption by NH4 Br modified fly ash (NH4 Br-FA), the results of
remove mercury from the aqueous phase. which indicated that NH4 Br modification of the fly ash enhanced
The activation processes mentioned above are energy intensive, Hg0 oxidation and adsorption, improving the Hg0 removal rate of
costly, and produce harmful pollutants. In order to overcome these 0–10% to 50% in 120 min. HgBr2 was the major adsorption specie
issues, Xiao et al. [361,362] adopted a chemical-mechanical bromi- on the NH4 Br-FA surface because of the formation of Br-containing
nation method to modify the petroleum coke for Hg0 capture from functional groups in the modification. O2 could not promote Hg0
flue gas. Their study showed that the mercury removal efficiency oxidation or adsorption, while NO enhanced Hg0 adsorption signif-
of petroleum coke was improved by 60–70% after bromination, and icantly. SO2 had negative effects on Hg0 adsorption on the NH4 Br-
bromine and sulfur in petroleum coke enhanced mercury capture. FA surface, which had little influence on Hg0 oxidation. The main
The chemical-mechanical bromination process created more active 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- 6.3.8. Mineral adsorbents
TiO2 showed excellent Hg0 oxidation performance with poor Hg0 Cai et al. [376] used KI and KBr to modify clays (named KI-
adsorption. Wang et al. [368] used halogen-modified fly ash to clays and KBr-clays) to remove Hg0 in simulated flue gas atmo-
control mercury emission in a 300 MW CFPP in China. The re- spheres, the results of which indicated that KBr and KI modifi-
sults indicated that the modified fly ash could reduce 40–50% of cation significantly enhanced Hg0 removal by the clays. Increas-
Hg0 with no obvious change in oxidized mercury. With the com- ing KI or KBr loading and adsorption temperature had positive ef-
bination of SCR, ESP, and WFGD as well as modified fly ash injec- fects on Hg0 removal. This was especially the case with the clay
tion, the total mercury removal rate could reach 75–90%. Xu et al. loaded with 3 wt% KI as it had the highest Hg0 removal efficiency
[369] indicated that fly ash modified with CaBr2 , CuCl2 , and FeCl3 of 78–89% in N2 +O2 atmosphere during the 3 h of adsorption,
possessed great mercury removal performance compared with the whereas the unmodified clay almost captured no Hg0 . The pres-
raw sample, in which both the chlorine and Cu2+ and Fe3+ pro- ence of O2 and SO2 benefited Hg0 removal while the occurrence of
moted Hg0 oxidation. Xu et al. [370] adopted a wet-impregnation H2 O inhibited the Hg0 capture by the modified clays. Both the ex-
method to load cobalt on fly ash for Hg0 removal and found that perimental results and pseudo-second-order model demonstrated
the well-dispersed Co3 O4 on the fly ash surface benefited Hg0 oxi- that KI-clays were more active than KBr-clays concerning Hg0
dation. The optimal Co loading of 9 wt% increased the Hg0 removal removal.
efficiency to 76% in a laboratory fixed-bed reactor with O2 at low Shen et al. [377] developed a new kind of titanium-pillared clay
temperatures. (Ti-PILC) impregnated by KI to capture Hg0 in the simulated flue
It can be summarized that the modified fly ash can be used for gas. With a larger BET surface area and more mesopores of 2–
mercury removal, especially with halogen modification. However, 10 nm, the KI-impregnated Ti-PILC had a greater Hg0 removal abil-
the mercury capture effects will be changed in a wide range due to ity than the original clay or the KI-impregnated clay. For the Ti-
the complexity of the physical and chemical structure of the fly ash PILC loaded with 3 wt% KI, the Hg0 removal efficiency was almost
surface from different power plants. In addition, the mixture of the 100% to 65% with an initial 300 min in 6% O2 +N2 atmosphere at
modified fly ash and original fly ash from CFPPs should be tested 80 °C. NO and SO2 promoted while H2 O inhibited Hg0 removal.
for stability and leaching of mercury and halogens before using it, Chemisorption was considered to occur between the iodine and
for example, in cement kilns, when producing brick or tiles, and Hg0 on the sorbent surface within temperatures of 80–180 °C in
when disposing off in landfills, etc. [371,372]. 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.
6.3.7. Calcium-based adsorbents Chiu et al. [378] investigated the effects of CuCl2 -impregnated
Ghorishi and Gullett [373] reported the effects of bed temper- zeolite MCM-41 (CuCl2 −MCM) on Hg0 removal. They showed that
ature, mercury concentration, acid gases (HCl and SO2 ), and wa- all the studied CuCl2 -impregnated amounts (2, 4, 8, and 16 wt%)
ter vapour on the uptake of Hg0 and HgCl2 by the Ca-based sor- could obtain the average Hg0 removal rate of 74.3–83.4% and 34.5–
bents, namely, Ca(OH)2 and mixtures of Ca(OH)2 and fly ash, in a 73.4% at an adsorption temperature of 150 °C, in N2 and flue gas at-
laboratory-scale, fixed-bed reactor. They showed that many HgCl2 mosphere (14% CO2 + 10% H2 O + 6% O2 + 50-ppmv HCl + 200-ppmv
adsorption sites existed in Ca-based sorbents. The gas-phase HgCl2 SO2 + 200-ppmv NO + balanced N2 ), respectively.
concentration had a very strong influence on its adsorption, which Shao et al. [379] compared the Hg0 removal efficiency of the
increased with an increase in HgCl2 concentration. Increasing bed KI-modified bentonite supported by starch sorbent (B-S-I) and tra-
temperature decreased the HgCl2 adsorption by the sorbents, but ditional KI-modified bentonite sorbent (B-I). They found that B-S-I
the influence was weak. HgCl2 removed by Ca(OH)2 would obvi- possessed a better Hg0 removal ability than B-I due to the iodine
ously be decreased in the presence of acid gases (10 0 0-ppmv SO2 uptake capacity between iodine and the starch on B-S-I. O2 had
and 50-ppmv HCl), and the inhibition effect of SO2 was stronger positive effects while H2 O showed a negative influence on Hg0 re-
than that of HCl. The main reason was thought to be that the moval by both the B-S-I and B-I. SO2 could promote or inhibit the
acid gases could compete with HgCl2 for available alkaline sites. Hg0 capture, which mainly depended on SO2 concentration. The
Pilot-scale tests indicated that injection of hydrated lime into fur- starch-iodine complex was thought to be able to provide I2 for Hg0
nace could get high system HgCl2 removal, with rate of 55–85% at adsorption, the product of which was mainly HgI2 on the B-I-S sur-
Ca/Hg weight ratio of 50 0 0 and 10,0 0 0, respectively. However, the face.
corresponding Hg0 capture efficiency was from 10% to 20%, even Liu et al. [380] evaluated the Hg0 removal capacity of paly-
with the Ca/Hg weight ratio as high as 30 0,0 0 0 [374]. gorskite (Pal) impregnated with the active substances CuCl2 , CuBr2 ,
Li et al. [203] used the chemical impregnation method to de- NaBr, sulfur, MnO2 , and Co3 O4 in a bench-scale fixed-bed reac-
velop a novel calcium-based sorbent synthesized from calcium ac- tor in simulated flue gas. The results showed that the active sub-
etate and mesoporous silica, the results of which indicated that the stances modification improved the mercury removal capability of
sorbent could adsorb the Hg2+ completely under N2 and a sim- Pal significantly, and the removal rate of CuCl2 and CuBr2 impreg-
ulated flue gas atmosphere, but with almost no capture of Hg0 . nated Pal (namely, CuCl2 -Pal and CuBr2 -Pal) reached 90.9% and
Wang and Duan [375] adopted different concentration of KMnO4 95.2%, respectively, with that of other modified adsorbents being
solution to modify Ca(OH)2 to form the Mnx+ /Ca(OH)2 mercury higher than 80%. For the CuCl2 -Pal and CuBr2 -Pal, O2 and HCl had
adsorbent. It was shown that the initial Hg0 removal rate for positive effects while SO2 and NO showed negative effects on mer-
Ca(OH)2 , and Ca(OH)2 impregnated with 1% and 5% KMnO4 was cury removed by them. In the preparation process of the CuCl2 -
about 20%, 30%, and 37%, respectively. As the adsorbing time in- Pal and CuBr2 -Pal adsorbents, the Pal underwent complexation
creased, the Hg0 capture rate decreased. The ultimate Hg0 ad- and adsorption by cupric halide molecules existing on its polarity
sorption amount for the three Ca-based adsorbents was 0.74, 1.05, and hydroxyl group. During heating, the cupric halide of hydrate
and 1.30 mg/kg, respectively. The mercury adsorption ability of could change into cupric oxide while some HX (X: Br, Cl) might be
Mnx+ /Ca(OH)2 was slightly higher than that of Ca(OH)2 . formed. The halogen atom from cupric halide was enough to cap-
In general, Ca-based sorbent is less effective in mercury cap- ture gaseous Hg0 and then promote the transformation of it into
ture even after activation, which is more beneficial for Hg2+ cap- Hg2+ via attaching to the active sites of Pal. The preparation and
ture than Hg0 adsorption. The presence of SO2 has a negative effect mercury removal mechanism of CuCl2 -Pal and CuBr2 -Pal is illus-
on mercury removal of the adsorbent. trated in Fig. 27 [380].
S. Zhao, D. Pudasainee and Y. Duan et al. / Progress in Energy and Combustion Science 73 (2019) 26–64 55
Fig. 28. Schematic diagram of applying regenerated FeMnOx for mercury removal
in CFPPs [385]. Reprinted with permission from Elsevier, 2017.
Fig. 27. Preparation and mercury removal mechanism of CuCl2 -Pal and CuBr2 -Pal
[380]. 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-
In brief, using the mineral as the mercury removal adsorbent tice oxygen were increased greatly by the NTP, which was signifi-
is mainly modified by the halogens. The chemisorption played an cant for mercury removal. During mercury removal, high-valence
important role in mercury adsorption by the modified adsorbent. manganese oxides and lattice oxygen were consumed. However,
In addition, the mercury removal efficiency is affected by the flue the NTP treatment could supplement it, which increased the mer-
gas components, such as O2 , HCl, SO2 , NO, and H2 O. cury removal regeneration performance compared to that with-
out NTP treatment. The mercury removal efficiency for FM-1 for
6.4. Novel mercury control approaches the first (without NTP treatment), third (with NTP treatment), and
fifth (with NTP treatment) was about 90%, 82%, and 75%, respec-
6.4.1. Non-separable regenerable mercury removal adsorbent tively. O2 and HCl benefited mercury capture by the sorbent while
Liu et al. [381] synthesized the natural chabazite-based silver NO, SO2 , and H2 O had negative effects. It is worth noting that the
nanocomposite (AgMC) to remove mercury from coal-fired flue gas, sorbents can be separated from fly ash with magnetic separation.
finding that the mercury could be captured by the AgMC com- Thus, a combination of magnetic separation, thermal regeneration,
pletely when the reaction temperature reached up to 250 °C. The and plasma treatment can make FeMnOx an excellent recyclable
nano-silver particles were confirmed to be the main active com- sorbent for mercury emission control, the schematic diagram of
ponent for mercury removal via the amalgamation mechanism. In which is shown in Fig. 28 [385].
addition, the removed mercury in the spent AgMC could be eas- Yang et al. [386] developed a new regenerable magnetic cata-
ily released for safe disposal and the sorbent could be regener- lyst by loading cobalt oxide on magnetospheres (Co-MF) from fly
ated by heating at 400 °C. Rodríguez-Pérez et al. [382] developed ash and found that the catalyst could obtain about 95% Hg0 re-
a regenerable sorbent by dispersing gold nano-particles on an AC moval efficiency at 150 °C in a simulated flue gas atmosphere with
to remove the mercury in flue gas after desulfurization units in the optimal loading of 5.8% cobalt species. The repeated oxidation-
CFPPs. It showed that the regenerable sorbent prepared by using regeneration cycles illustrated that the spent Co-MF catalyst could
5% doped gold to disperse gold nanoparticles on a carbon material be regenerated effectively by thermal treatment at 400 °C for 2 h.
could capture mercury effectively, and the mercury removal effi- Moreover, the catalyst characterization and performance evalua-
ciency could be 100% over several cycles of generation. The sorbent tion, involving reaction mechanism, regeneration performance in
could be regenerated by thermal treatment at about 240 °C, and realistic flue gas atmosphere, and the performance of sorbent
Hg0 could be recovered and collected. The main mercury capture injection in an entrained flow reactor system of the recyclable
mechanism was the mercury amalgamation with gold and oxidized CuCl2 modified magnetospheres from fly ash, were also studied
mercury retained by the AC. by Yang et al. [387–390], the results of which demonstrated that
Yao et al. [383] tried to investigate the mercury adsorption the magnetic catalyst loaded with 6% CuCl2 obtained the high-
and cyclic mercury retention on the MnOx /γ -Al2 O3 sorbent. They est Hg0 removal efficiency of 90.6% at 150 °C. The interaction be-
found that the mercury removal ability over regenerated sorbents tween Hg0 and CuCl2 was a cycle with the presence of O2 and
could not be restored through thermal desorption at high temper- HCl in the reaction system. The mercury removal capacity did not
atures, which was due to the irreversible reduction of MnO2 to vary significantly compared to a fresh catalyst after multiple re-
Mn2 O3 . Qu et al. [384] demonstrated that Ce0.5 Mn0.5 Oy had the generations through the four cycle tests of mercury adsorption-
best mercury adsorption performance at 100 °C (about 5.6 mg Hg catalyst regeneration. With the residence time of 1.61 s and sor-
/g adsorbent). The removed mercury could be released from the bent concentration of 1.09 g/m3 , the Hg0 removal rate could reach
adsorbent in the form of Hg0 by heating to 350 °C. In addition, the 80.6%.
sorbent could be generated and reused, the mercury removal abil- The magnetic adsorbent modified by metal oxides or the metal
ity of which did not show an obvious decrease after five runs of halide will be the most promising sorbent for mercury removal
adsorption and desorption. from a coal-fired flue gas, which has the advantages of high mer-
cury removal efficiency, low investment, easy separation from fly
6.4.2. Separable regenerable mercury removal adsorbent ash, mercury recovery, etc. However, the field tests of applying
The separable regenerable mercury removal sorbent is based on these adsorbents in CFPPs are sparse and the method needs fur-
magnetic material to achieve separation of the adsorbent from the 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 cal digestion analytical method. The mean mercury concentration
Flue gas cleaning technologies used today are mostly effective in the coal of China (0.20 mg/kg), the US (0.17 mg/kg), and South
in removing single pollutants: either NOx or SO2 , or PMs or met- Africa (0.20 mg/kg) is higher than that of the world (0.1 mg/kg),
als. CFPPs need to install pollutant specific control devices, which which needs more attention. Mercury forms in coal are sulfide-
require a high cost. In order to cope with this situation, there bound mercury (mainly pyritic mercury, dominant), clay-bound
have been some studies done on multi-pollutant control technolo- mercury, and organic matter-bound mercury in general. Mercury
gies, which generally employ post-combustion flue gas treatment in coal is strongly correlated with sulfur content for most coals,
technologies to simultaneously remove NOx , SO2 , and mercury. in which pyritic mercury is the typically dominant form while
Krzyżyńska et al. [290] introduced an oxidizing additive-sodium organic- and sulfide-bound mercury (mainly pyritic mercury) are
chlorite (NaClO2 ) in a limestone-based WFGD scrubber. The re- the major species in low-sulfur coals. In addition, the existing
sults showed that the extent of the scrubbed mercury amount forms of mercury in coal are affected by many factors, including
increased with an increase in the chlorite addition in the slurry, diagenetic, coalification, and post-diagenetic conditions.
which ranged from 40% (at 0.81 M NaClO2 ) to approximately 70% Mercury transformation during coal combustion can be divided
(at 1.62 M NaClO2 ). However, the selected NaClO2 only resulted in into homogeneous (without fly ash) and heterogeneous (with fly
the NO removal rate in the range of 15–30%. Ping et al. [391] used ash) reaction, which are influenced by the coal types, flue gas
urea and KMnO4 to remove Hg0 , SO2 , and NO simultaneously by components, flue gas temperature, combustion atmosphere, coal
wet scrubbing. They found that the NO and Hg0 removal rate ash properties, etc. For the mercury homogeneous reaction, chlo-
was mainly affected by the KMnO4 concentration. The highest re- rine benefits Hg0 oxidation and the oxidation degree are affected
moval efficiencies of SO2 , NO, and Hg0 could reach 98.78%, 53.05%, by the chlorine forms (Cl radical > Cl2 > HCl), flue gas tempera-
and 99.21%, respectively, under the optimal conditions. Chiu et al. ture (HCl is favorable at high temperature while Cl2 is favorable
[378] indicated that the average Hg0 oxidation rate over the MCM- at low temperature), and chlorine concentration (Hg0 oxidation
16% (zeolite MCM-41(MCM) impregnated with CuCl2 content of 16 rate increases as their concentration increases), etc. NO or NO2
wt%) was 53.7%. After CuCl2 impregnation, the SO2 removal rate are positive for Hg0 oxidation. With the addition of chlorine, the
by the modified MCM decreased from 42.3% to about 38% while effects of NO on Hg0 oxidation have not reached into a consis-
the NO removal rate increased from 62.8% to 73%. In addition, tent conclusion, which include negative, little, or sometimes pos-
Chiu et al. [392,393] adopted transition metal oxide to modified itive influence. SO2 alone can not lead to Hg0 oxidation, while
SCR catalyst and metal oxide/mesoporous SiO2 composites, respec- the existence of O2 promotes Hg0 oxidized by SO2 . The enhance-
tively, to investigate their multipollutant control effects of Hg0 , ment or inhibition of SO2 on Hg0 oxidation by HCl is affected by
SO2 , and NO. They demonstrated that Hg0 oxidation, SO2 removal, the concentration of SO2 and HCl. H2 O can inhibit Hg0 oxidation
and NO reduction of the SCR catalyst was greatly improved after mainly through consuming Cl. O2 may benefit Hg0 oxidation with
the metal oxide impregnation, which was 81.6–96.4%, 10.4–20.8%, slight enhancement. For the Hg0 heterogeneous reaction, fly ash
and 89.0–91.8%, respectively, under simulated coal-combustion flue with larger particle size is generally beneficial for mercury adsorp-
gas condition. The CuOx /SiO2 had 42.6% of the Hg0 removal rate tion, which has a relationship with the UBC and carbon types.
while the metal oxide/SiO2 composites could remove 62% NO with The mercury heterogeneous reaction on fly ash concerning UBC
NH3 injection at 350 °C. Yuan et al. [394] synthesized novel TiO2 - contains the physical adsorption and chemical reaction, in which
aluminum silicate fiber nanocomposite for the removal of multiple the physical adsorption is influenced by the particle size, surface
pollutants with the help of UV irradiation. Results indicated that area, etc. that are positive with UBC. In addition, the active sites,
the removal rates for SO2 , NO, and Hg0 at 120 °C and with UV in- including some certain unburned carbon forms (anisotropic car-
tensity of 3 mWcm−2 could reach 33%, 31%, and 80%, respectively, bon particles), oxygen function groups (C=O, OH/C–O, (O–C=O)–
in the simulated flue gas (4% O2 , 12% CO2 , 2% H2 O, 400-ppmv SO2 , O), and halogens, etc., can transform Hg0 (g) into adsorbed and
50-ppmv NO). gaseous Hg2+ . The iron oxides in fly ash promote Hg0 oxidation
The development of a novel, efficient, multi-pollutant sorbent and adsorption, which are influenced by the iron oxides type and
is extremely important, as it will reduce the cost of installing ex- reaction temperature. The Hg0 → FeHgCl(s) → HgCl2 is thought to
pensive equipment and minimize the environmental impact. How- be the main route for Hg0 oxidation by HCl on the Fe2 O3 sur-
ever, it is very difficult for the present multipollutant control tech- face. For different reaction temperatures, the Hg0 removal mecha-
nologies to realize the highest removal rate for the NO, SO2 , and nism with HCl and Fe2 O3 includes the Eley-Rideal mechanism with
Hg0 simultaneously. In addition, the effect of some additives on HCl pre-adsorption (80–280 °C), the Langmuir-Hinshelwood mech-
the equipment and the catalyst production costs should be com- anism (280–580 °C), and both the homogenous reaction of Hg0
prehensively taken into consideration. and HCl and the Langmuir-Hinshelwood mechanism (higher than
Finally, in order to provide more information about the mercury 680 °C). Chlorine and bromine in flue gas promote the Hg0 hetero-
in coal combustion process to new readers, most of the important geneous reaction with fly ash while SO2 and H2 O have inhibitory
organizations/institutes/groups in this field especially focusing on effects.
mercury emission control have been listed in Table S3. The Hgg concentration in oxy-coal combustion is higher than
that in air-coal combustion. There is no common agreement in the
7. Conclusions ratio of Hg2+ to Hgg for all the studied oxy-coal combustion condi-
tions. For the mercury homogenous transformation under oxy-coal
Mercury is a global pollutant with high toxicity, long-distance combustion, O2 promotes Hg0 oxidation with Cl2 while NO and
transport, persistence, and bioaccumulation in the environment. CO2 inhibit or do not favor that reaction. CO2 increases Hg0 oxi-
Coal has always been the major primary energy source in the dation in the atmosphere of NO and N2 . SO2 limits Hg0 oxidation
world, and it has been mainly utilized to generate electricity. CFPP while HCl has a higher oxidation effect on Hg0 than that under
is the major anthropogenic mercury emission source to the atmo- air-coal combustion conditions. The influence of H2 O on Hg0 oxida-
sphere, especially for China, India, and the US. Many countries have tion has not reached into an agreement yet, which may be related
issued stringent mercury emission limits for CFPPs. to the flue gas temperature or flue gas components. For mercury
With advantages of quickness, convenience, and high efficiency, heterogeneous transformation under oxy-coal combustion, fly ash
the thermal decomposition analytical method to determine mer- plays an important role for Hg0 oxidation. SO3 inhibits mercury re-
cury content in coal has become more favorable than the chemi- 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 57
no agreement in the distribution between Hgp and Hgg affected by and/or Hgp , including noble metal-based catalysts and non-noble
O2 . metal-based catalysts, hydrogen halogens (HF, HCl, HBr, and HI),
The generally used on-site mercury sampling methods, namely, ozone, and H2 O2 . For oxidizing chemicals, the HBr seems to be
OHM, US EPA Method 30B, and Hg-CEMS, are summarized, in- more effective for Hg0 oxidation. The last aspect is to adopt mer-
cluding the sampling or analysis principle, sampling requirements, cury removal adsorbents, including carbon-based adsorbents (AC,
and the comparsion of their advantages and disadvantages. With biochar, and petroleum coke), fly ash, calcium-based adsorbents,
more and more strict limits on pollutants emitted from CFPPs, the and mineral adsorbents. To enhance Hg0 removal efficiency by the
installation share of APCDs, which include SCR, ESP, FF, WFGD, AC, halogens, sulfur, metal chlorides, and NTP treatment have been
and WSEP, increases. The APCDs have co-beneficial effects on mer- adopted to modify the AC. Mercury removal performance by the
cury besides the conventional pollutants, like NOx , PM, SO2 , and AC follows the decreasing order of AC < Cl-impregnated AC < Br-
fine PM. The SCR equipment is good at Hg0 oxidation with rate impregnated AC < I-impregnated AC. Halogen modification can im-
of 6.5–79.9%, affected by flue gas components, boiler load, SCR prove mercury removal efficiency by the biochar, in which C-X and
space velocity, SCR catalyst structure, and service time of the C=O may be the major chemisorption sites for Hg0 adsorption. The
catalysts. With high PM removal efficiency, the ESP and FF spe- chemical-mechanical bromination process can generate more ac-
cialize in Hgp capture. The Hgt removal rate of ESP and FF is tive mercury adsorption sites on the brominated petroleum cokes,
11.5–90.4% and 28.5–90%, respectively, influenced by the flue gas which benefits Hg0 removal. The modified fly ash can be adopted
temperature, mercury species in flue gas, fly ash components, to capture Hg0 , especially by using the halogen modification. The
and their PM capture performance, etc. FF exerts a higher mer- complexity of the physical and chemical structure of the fly ash
cury removal rate than ESP, due to its higher PM capture abil- surface from different power plants results in a wide mercury re-
ity. WFGD device has high co-removal performance for Hg2+ be- moval rate. Moreover, the subsequent utilization or disposal of the
cause of its high water-solubility. The Hg2+ removal rate by WFGD fly ash adsorbents in light of the stability and leaching of mercury
is 83.45–94.53%, with the Hgt removal rate of 3.9–72%. However, and halogens should be considered. Ca-based sorbents have little
Hg0 re-emission may also occur in WFGD process, which is af- effect on mercury removal even after activation, which have more
fected by the operating temperature, pH, O2 concentration in flue Hg2+ adsorption ability than Hg0 . The mineral mercury removal
gas, transitional metal ions concentration, etc. WESP can remove adsorbent is mainly modified by the halogens, in which chemisorp-
32–40%, 72–82%, and 33–100% of Hg0 , Hg2+ , and Hgp , respec- tion plays an important role in mercury adsorption.
tively. The mercury transformation across SCR, ESP, FF, WFGD, and For the regenerable mercury removal adsorbent, the magnetic
WESP is also reviewed. ESP seems to be a stronger contributor adsorbent modified by metal oxides or the metal halide is the most
for Hgt removal by SCR+ESP+WFGD, followed by WFGD and SCR promising sorbent for the removal of mercury in coal-fired flue
device. The Hgt removal rate for ESP+WFGD, SCR+ESP+WFGD, gas compared to the noble metal and conventional metal oxides,
SCR+ESP+FF+WFGD, and SCR+ESP+WFGD+WESP is 35.5–84%, which has advantages of high mercury removal efficiency, low in-
43.8–94.9%, 58.78–73.32%, and 56.59–89.07%, respectively. The vestment, easy separation from fly ash, and mercury recovery, etc.
mercury emission concentration in the reviewed CFPPs of China, It is very difficult for the current multipollutant control technolo-
South Korea, and Poland, the Netherlands and the US is 0.29– gies to realize a higher removal rate for NO, SO2 , and Hg0 simulta-
16.3 μg/m3 . The MEF expressed as g/1012 J for the CFPPs is 0.052– neously.
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– 8. Further works
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 For mercury transformation in coal combustion process, the
WESP wastewater is higher than the relevant limits, and attention heterogeneous reaction mechanism among fly ash, flue gas com-
needs to be given to whether they are processed further or dis- ponents, and mercury is complicated compared to the mercury ho-
posed off. mogenous reaction. However, the present published studies mainly
For the pre-combustion mercury removal, physical coal wash- focus on effects of fly ash physical structure properties, unburned
ing technologies can obtain 0–65% of the mercury removal rate, carbon, and Fe2 O3 on Hg0 oxidation. The influence of flue gas com-
which is mainly affected by coal types. However, it is difficult to ponents and the wide reaction temperature range on mercury ox-
meet mercury removal requirements only by coal washing. The idation or adsorption by fly ash is rarely studied systematically,
mild pyrolysis method can remove mercury from coal to a cer- which needs further attention. The mercury emission data for oxy-
tain extent, and the mercury removal performance has a wide coal combustion is not enough, especially the concentration and
range, influenced by the thermal treatment temperature, residence distribution of various mercury species, mercury removal efficien-
time, sweep gas flow rate, and especially the mercury forms in cies by APCDs, etc. Many explanations for the effects of flue gas
coal. For in-combustion mercury removal, the low-NOx combustion components on mercury transformation in oxy-coal combustion at-
technology and CFB combustion technology enhance mercury re- mosphere are only prediction, which has no credible evidence. The
moval. Compared to these methods, putting halogens into coal to models for mercury homogeneous and heterogeneous transforma-
transform Hg0 to Hg2+ or Hgp has been widely studied to remove tion under oxy-coal combustion conditions should be developed.
mercury, which is a method that is simple to operate, highly effi- For mercury co-removal and emission in CFPPs, the following
cient, and low in cost. It can achieve a 60–96% mercury removal aspects need further study, including developing a detailed mer-
rate with little addition of halogens in field tests. Post-combustion cury transformation or removal mechanism across each APCD, es-
mercury removal can be divided into three aspects. One aspect is pecially SCR equipment; exploring the way to improve the Hg0 ox-
the improvement of the existing APCDs, such as enhancing Hg0 idation rate in SCR equipment, or the removal efficiency of APCDs
oxidation by the SCR catalyst, which can be improved through and their combination; obtaining more mercury content data in
modifying the catalyst by metal oxides such as RuO2 , Ce-Mn ox- CBPs and giving relevant emission limits; and determining the
ides, CeO2 , Fe2 O3 , and CaCl2 ; and suppressing Hg0 re-emission in chemical species of mercury in fly ash and gypsum, which is im-
WFGD by adding oxidants or special chemical reagents, such as portant for their utilization or disposal.
NaClO2 , Al2 (SO4 )3 , SCN- or S2− and HS− , Na2 S4 , TMT15, Nalco-8034 For mercury removal technologies for CFPPs, further studies
reagent, DTCR, etc. The second aspect is to use mercury oxidiz- include those investigating the inhibition of Hg0 re-emission in
ing catalysts and oxidizing chemicals to transform Hg0 into Hg2+ 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- [13] United States Environmental Protection Agency National emission standards
tives; exploring the deep mercury removal mechanism by putting for hazardous air pollutants from coal- and oil-fired electric utility steam
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[356] Li G, Wang S, Wu Q, Wang F, Ding D, Shen B. Mechanism identification of [387] Yang J, Zhao Y, Zhang J, Zheng C. Removal of elemental mercury from flue gas
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[357] Lee SH, Rhim YJ, Cho SP, Baek JI. Carbon-based novel sorbent for removing [388] Yang J, Zhao Y, Zhang J, Zheng C. Removal of elemental mercury from flue
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[358] Morris EA, Jia CQ, Morita K. Effects of O2 on characteristics of sulfur 2. Identification of involved reaction mechanism. Fuel 2016;167:366–74.
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[367] Zhou Q, Duan Y, Chen M, Liu M, Lu P, Zhao S. Effect of flue gas component Shilin Zhao: Male, born in April, 1992. Education: 2010.9–2014.6: Bachelor of En-
and ash composition on elemental mercury oxidation/adsorption by NH4 Br gineering, Thermal and Power Engineering, Nanjing Normal University, Nanjing,
modified fly ash. Chem Eng J 2018;345:578–85. China; 2014.9–present: Ph.D. candidate, Thermal Engineering, Southeast University,
[368] Wang S, Zhang Y, Gu Y, Wang J, liu Z, Zhang Y, Cao Y, Romero CE, Pan W. Nanjing, China; 2017.10–2018.10: visiting PhD student, Department of Chemical and
Using modified fly ash for mercury emissions control for coal-fired power Materials Engineering, University of Alberta, Edmonton, Canada. Publications: Has
plant applications in China. Fuel 2016;181:1230–7. published 27 journal papers including 13 SCI (first author) and 5 SCI (co-author)
[369] Xu W, Wang H, Zhu T, Kuang J, Jing P. Mercury removal from coal combustion papers with cites times of 140, and 7 international conference papers in energy, en-
flue gas by modified fly ash. J Environ Sci 2013;25(2):393–8. vironment and chemical engineering areas. Current research areas: Transformation,
[370] Xu Y, Zhong Q, Xing L. Gas-phase elemental mercury removal from emission, and control of mercury and trace elements from coal combustion.
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 Yufeng Duan: Male, born in April, 1963. Education: 1980.9–1984.6: Bachelor of En-
characteristics, thermal stability and volatility of hazardous trace elements in gineering, Thermal Engineering, Beijing University of Science and Technology, Bei-
fly ash from a coal-fired power plant. Fuel 2018;225:490–8. jing, China; 1984.9–1987.6: Master of Engineering, Thermal Engineering, Beijing
[372] Zhao S, Duan Y, Lu J, Gupta R, Pudasainee D, Liu S, Liu M, Lu J. Chemical University of Science and Technology, Beijing, China; 1987.9–1991.9: Ph.D. Ther-
speciation and leaching characteristics of hazardous trace elements in coal mal Engineering, Southeast University, Nanjing, China. Career: 1991.9–1993.12: Lec-
and fly ash from coal-fired power plants. Fuel 2018;232:463–9. turer, Thermal Engineering Institute, Southeast University, Nanjing, China; 1993.12–
[373] Ghorishi B, Gullett BK. Sorption of mercury species by activated carbons and 2002.4: Associate Professor, Thermal Engineering Institute, Southeast University,
calcium-based sorbents: effect of temperature, mercury concentration and Nanjing, China; 1995.8–1996.2: Senior visiting scholar, Korea Energy Research Insti-
acid gases. Waste Manage Res 1998;16:582–93. tute (KIER), Korea; 20 01.9–20 03.8: Visiting Professor, Institute of Combustion Sci-
[374] Stouffer MR, Rosenhoover WA, Burke FP. Investigation of flue gas mercury ence and Environmental Technology (ICSET), Western Kentucky University, USA;
measurement and control for coal-fired sources. Presented at the 89th An- 2002.4–present: Professor, Thermal Engineering Institute, Southeast University, Nan-
nual Air & Waste Management Association Meeting Nashville, TN; 1996. June jing, China; Publications: Has authored or co-authored (mostly as corresponding au-
23–2896-WP64B.06. thor) more than 300 journal papers including more than 150 SCI/EI papers with
[375] Wang Y, Duan Y. Effect of manganese ions on the structure of Ca(OH)2 and cites times of 820 and more than 30 international conference papers in energy,
mercury adsorption performance of Mnx+ /Ca(OH)2 composites. Energ Fuel environment and chemical engineering areas. Has authorized more than 30 Chi-
2011;25:1553–8. nese patents. Co-authored and edited one book. Current research areas: Mercury
[376] Cai J, Shen B, Li Z, Chen J, He C. Removal of elemental mercury by clays im- and trace elements removal technologies for coal combustion, solid waste recy-
pregnated with KI and KBr. Chem Eng J 2014;241:19–27. cling, circulating fluidized bed combustion and gasification, numerical simulation
[377] Shen B, Chen J, Yue S. Removal of elemental mercury by titanium pil- of combustion process, slurry transport and atomization, integrated removal of pol-
lared clay impregnated with potassium iodine. Micropor Mesopor Mater lutants from power station boilers, etc. Hosting research projects: 3 National Key
2015;203:216–23. Research & Development Projects (2016); 5 National Natural Science Foundations
[378] Chiu CH, Hsi HC, Lin CC. Control of mercury emissions from coal-combustion (2011, 2014, 2016, 2018); 2 National Science and Technology Support Projects (2006,
flue gases using CuCl2 -modified zeolite and evaluating the cobenefit effects 2012); 5 National “973” Third-Level Projects (1999, 20 03, 20 04, 20 06, 2010); 2 Na-
on SO2 and NO removal. Fuel Process Technol 2014;126:138–44. tional Science and Technology Research Project (1991, 1997); 1 Jiangsu Province In-
[379] Shao H, Liu X, Zhou Z, Zhao B, Chen Z, Xu M. Elemental mercury removal dustry, Education and Research Joint Innovation Fund (2013); 2 Jiangsu Environmen-
using a novel KI modified bentonite supported by starch sorbent. Chem Eng J tal Protection Research Project (2011, 2016); 3 National Key Experiment Room Open
2016;291:306–16. Fund (2010, 2010, 2011). He has undertaken more than 30 projects entrusted by
[380] Liu H, Yang J, Tian C, Zhao Y, Zhang J. Mercury removal from coal combustion enterprises.
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.