Characteristics of a biomass-based sorbent trap and its application to coal-fired
flue gas mercury emission monitoring

Hongjian Tang, Yufeng Duan, Chun Zhu, Chunfeng Li, Min She, Qiang
Zhou, Liang Cai

PII: S0166-5162(16)30564-X
DOI: doi: 10.1016/j.coal.2016.09.012
Reference: COGEL 2724

To appear in: International Journal of Coal Geology

Received date: 31 January 2016

Revised date: 18 September 2016
Accepted date: 19 September 2016

Please cite this article as: Tang, Hongjian, Duan, Yufeng, Zhu, Chun, Li, Chunfeng,
She, Min, Zhou, Qiang, Cai, Liang, Characteristics of a biomass-based sorbent trap and
its application to coal-fired flue gas mercury emission monitoring, International Journal of
Coal Geology (2016), doi: 10.1016/j.coal.2016.09.012

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 ACCEPTED MANUSCRIPT

Characteristics of a biomass-based sorbent trap and its application to coal-fired

flue gas mercury emission monitoring
Hongjian Tang, Yufeng Duan*, Chun Zhu, Chunfeng Li, Min She, Qiang Zhou, Liang Cai

Key Laboratory of Energy Thermal Conversion and Control of Ministry of Education, School of

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Energy and Environment, Southeast University, Nanjing, Jiangsu 210096, China

E-mail address: yfduan@seu.edu.cn

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ABSTRACT: A novel sorbent trap based on rice husk char (RHC) was developed. Scanning

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electron microscopy and Brunauer–Emmett–Teller analysis revealed that the raw RHC possesses a
developed pore structure and has potential for mercury adsorption after brominated impregnation
(RHC-HBr). The performance of both the raw and impregnated sorbents for Hg capture was

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investigated in a fixed bed system and compared with the performance of commercial activated
carbon (AC). RHC-HBr showed a remarkable Hg adsorption capacity (57.84 μg/g) comparable
with commercial AC. The RHC-HBr sorbent passed the analytical bias test for mercury detection
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when spiked by Hg0 and HgCl2 under both the lower and upper concentration levels. Field
verification test of the biomass-based sorbent traps was performed in a 6 kWth fluidized-bed
combustion (FBC) system. The Ontario Hydra Method (OHM) was applied as the reference
method for evaluating HgT(g) measured by the sorbent traps. The field verification test showed
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that RHC-HBr sorbent traps perform with almost the same accuracy as AC-based sorbent traps,
with 97.5 ± 2.9% field recovery rate, 3.2% breakthrough rate, and 0.6% relative deviation. HgT(g)
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field sampling based on the biomass-based traps was performed in a utility 660 MW coal-fired
unit in parallel with the OHM under two different operational loads (100% and 75%). Mercury
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migration and the removal characteristics of existing air pollution control devices (APCDs) were
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evaluated using the biomass-based sorbent traps. The final Hg emissions from the stack were
determined to be 0.65 and 1.54 μg/Nm3 for 100% and 75% operational loads, respectively,
indicating that a high load operation condition could be beneficial for mercury control by existing
AC

APCDs.

Keywords: Biomass-based sorbent traps; Coal-fired flue gas; Mercury field sampling; Mercury

emissions; Air pollution control devices

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1. Introduction
Mercury and its compounds have attracted global attention because of their effects on both the
environment and human health (Mukherjee et al., 2008). Burning of coal remains one of the most

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significant anthropogenic sources of mercury emitted into the atmosphere. According to the
Global Mercury Assessment 2013 of the United Nations Environment Programme, 24% of global

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total mercury emissions are generated by coal combustion, and more than 85% of them come from
power generation and industrial boilers (United Nations Environment Programme, 2013).

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Therefore, control and prevention of mercury pollution from coal-fired boilers has become a

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crucial issue for mitigating global mercury release. The United States Environmental Protection
Agency (US EPA) developed the Mercury and Air Toxics Standards to reduce coal-fired mercury
pollution in December 2011 (US EPA, 2011). In China, from January 2015, mercury emission

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from coal-fired power plants is limited to 30 μg/Nm3 (GB 13223-2011, 2011). To objectively
evaluate the current situation of mercury emission and design corresponding control techniques, it
is imperative to develop highly accurate and expedient mercury monitoring techniques for
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coal-fired flue gas.
Wet chemistry based the Ontario Hydro Method (OHM) is considered to be the reference
method for artificial vapor phase mercury (Hg(g)) speciation measurement in flue gas (ASTM
Standard D6784-02, 1999), while the Mercury Continuous Emission Monitoring System
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(Hg-CEMS) specializes in monitoring real-time Hg emissions from the stack (US EPA, 2010).
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Both methods are mainstream methods for field Hg(g) sampling and testing in North America and
Europe (Laudal et al., 2000; López-Antón et al., 2012). Almost all of the existing studies on
monitoring mercury emissions from electric utility units are based on the OHM (Wang et al., 2009;
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Yokoyama, et al., 2002) and Hg-CEMS (Tao et al., 2010). EPA Method 30B (Laudal, 2009; US
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EPA, 2008) is currently certified as the most suitable method for sampling and testing total Hg(g)
in flue gas in which chemical-treated activated carbon (AC) is used as the mercury sorbent.
Because of its convenient operation, high precision, and rigorous quality assurance procedures for
AC

field sampling, it is highly recommended by the US EPA as an effective alternative to the

cumbersome OHM (Chen et al., 2009). However, the drawback for its large-scale industrial
application in China is the exorbitant import price of sorbent traps padded with prominent AC. As
a consequence, it is essential to search for economic alternatives to AC.
As a renewable resource derived from agricultural residue, biomass waste can be processed into
biomass char by pyrolysis, and biomass char possesses an abundant porous structure and highly
active functional groups on its surface, similar to AC. Previous studies have reported that the
surface functionality of biomass char dominates mercury adsorption while the surface area does
not show any significant effect on the mercury retention capacity (Fuente-Cuesta et al, 2012; Zhu
et al, 2016). Further studies have found that modification with halogens is effective for promoting
Hg removal by carbon-based sorbents (De et al., 2013; Lee et al., 2009). Olson et al. (2004)
indicated that the presence of halogens (i.e., bromine, chlorine, and iodine) promotes oxidation of
Hg on carbon surfaces. Bisson et al. (2013) found that at high temperature the Hg adsorption
capacity of brominated biomass ash is comparable with that of brominated AC. Consequently,
biomass char shows potential as an alternative sorbent for mercury trapping in flue gas after
halogenation treatment.
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In this study, a novel sorbent trap was developed based on rice husk char (RHC). A brominated
RHC (RHC-HBr) sorbent was prepared by hydrogen bromide impregnation and its surface
structure and properties were characterized by scanning electron microscopy (SEM) and
Brunauer–Emmett–Teller (BET) analysis. The mercury adsorption capacities of both the raw RHC
and RHC-HBr were investigated in a fixed bed system. Analytical bias tests for mercury detection

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were performed in the laboratory to investigate the potential of RHC-HBr for quantifying the
mercury concentration. To assess its reliability for monitoring HgT(g) emissions in coal-derived

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flue gas, a preliminary verification test of the biomass-based sorbent trap was performed in a 6
kWth FBC coal combustion system and compared with AC-based sorbent traps. The

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biomass-based traps were then applied to field HgT(g) sampling in a 660 MW demonstration

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coal-fired unit. The mercury removal performance of existing air pollution control devices
(APCDs) is also discussed according to the HgT(g) concentration data measured by the novel
biomass-based sorbent traps.

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2. Materials and Methods
2.1. Sorbent preparation and characteristics
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Fresh air-dried rice husk (RH) was crushed and sieved to an average diameter of 0.6–1.2 mm.
The raw RH particles were pyrolyzed at 600 °C for 10 min, and they were then modified with HBr
solution for 2 h (Khezami et al., 2005; Nabais et al., 2008). After filtering and drying at 45 °C in
an oven for about 6 h, all of the samples were cooled to room temperature in a drying dish. The
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cooled samples are labeled as RHC-HBr. AC for comparison was divided into two samples. One
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sample (AC-HBr) was sieved and modified by the same method mentioned above. The other
sample (AC-KI) was derived from imported sorbent traps (Ohio Lumex Inc, OH, USA). The
nitrogen adsorption and desorption isotherms for all of samples were determined at 77 K on an
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automatic nitrogen adsorption analyzer (BELSORP-mini II, BEL Japan Inc., Japan). The specific
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surface areas and pore volumes of the raw and impregnated sorbents were determined on the basis
of the BET isotherm equation. The surface structures and morphologies of the biomass sorbents
were characterized by SEM (Sirion 200, FEI, Netherlands).
AC

2.2. Fixed bed system

Mixing and Preheating Chamber Bypass Flue Gas Analyzer

Computer
Triple Valve
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Hg0 Analyzer
Flow Flow
Meter Meter

N2 Exhaust
O2 CO2N2 SO2 NO
Waterbath
Tail Gas
Hg0 Generator Fixed-bed Reactor Teflon Tees
Treatment Unit

Fig. 1. Schematic diagram of the fixed bed Hg0 adsorption system.

The Hg0 adsorption capacities and breakthrough rates of the samples were tested in a fixed-bed
reactor at 150 °C. As shown in Fig. 1, stable gaseous mercury (Hg0(g)) was generated from a
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mercury permeation tube (VICI Metronics Inc., USA) with the temperature controlled by a water
bath. The N2 flow (200 mL/min) through the U-shaped quartz tube stably carrying the Hg0(g) was
mixed with other gaseous components in a borosilicate glass chamber. The simulated gas (6 vol.%
O2, 12 vol.% CO2, 1200 ppmv SO2, 300 ppmv NO, with the remainder being N2 and Hg0(g)) then
flowed into the borosilicate fixed bed reactor with two sorbent layers, each containing 50 mg of

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the sorbent. The sorbents were separated by mercury-free fiberglass. A mercury analyzer
(VM3000, Mercury Instruments GmbH, Germany) was used to continuously detect the Hg0(g)

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concentration. Initial calibration of the Hg concentration was performed before each test through
the bypass. The initial mean Hg0(g) concentration in this study was 35 ± 0.1 g/m3.

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The Hg adsorption capacity (q, μg/g), Hg breakthrough rate (BHg, %), and Hg mass equilibrium

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rate (EHg, %) of the samples were calculated by
t
Qg
C  Cout  dt
m
q in (1)
0

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m2 nd
BHg   100% (2)
m1st
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m1nd  m2 nd
EHg   100% (3)
mq

where Cin and Cout (μg/Nm3) are the inlet and outlet Hg0 concentrations at time t (min), Qg
(m3/min) is the gas flow rate, m (g) is the total mass of sorbent, m1st (μg) is the mass of Hg
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adsorbed by the first layer of sorbent, and m2nd (μg) is the mass of Hg adsorbed by the second
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layer of sorbent.
2.3. Mercury sorbent trap sampling system
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EPA Method 30B (published by the US EPA in 2007) describes a procedure for measuring total
Hg(g) emissions from coal-fired sources using extractive sampling through sorbent traps that are
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subsequently analyzed (Laudal, 2009; US EPA, 2008). As shown in Fig. 2, the flue gas is
extracted at an isokinetic target rate from the stack through a heated probe lined with Pyrex tube,
preventing condensation of water vapor and adhesion of mercury vapor to the tube inner surface.
AC

The sampling gas should be dried before it enters the diaphragm pump. The auxiliary equipment
(i.e., digital indicator, flow-control devices, condenser and power supply) are integrated in the
sampling console.
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Mercury Sorbent
` Thrmocouple

Duct Wall Collection Breakthrough

A Vacuum
Gauge

Temperature Heated Condensers

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Sensor Probe Sampling
Flanges Line
Gas Inlet

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B Isolation
Probe Valve Flow
Control
Sorbent
Trap

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Discharge `
Gas Flow Meter
Gas
Pump

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Sampling
Console

Fig. 2. Schematic diagram of the sorbent trap sampling system.

The paired sorbent traps are the core components of the dual sampling system. The sorbent
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traps were made of Pyrex (heat-resistant glass) to maintain in-stack sampling and a mercury-free
inner face. Each trap consisted of two sorbent sections loaded with 500 mg of sorbent (front
section for Hg collection and back section for Hg breakthrough) insulated by mercury-free
fiberglass.
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Compared with the OHM, EPA Method 30B is much simpler but equally accurate because of its
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rigorous quality assurance procedures. According to the quality assurance and quality control
(QA/QC) criteria (Laudal, 2009; US EPA, 2008), the breakthrough rate (RB, %) of the sorbent
trap and relative deviation (RD, %) are the main parameters for quality control:
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m2
RB   100% (4)
m1
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COHM  C30 B
RD   100% (5)
COHM
AC

where m1 (μg) is the mercury mass in the Hg collection section, m2 (μg) is the mercury mass in the
Hg breakthrough section. COHM (μg/Nm3) is the total Hg(g) concentration measured by the OHM,
C30B (μg/Nm3) is the total Hg(g) concentration measured by EPA Method 30B. The QA/QC
criteria (Laudal, 2009; US EPA, 2008) require RB and RD ≤ 10% if the Hg(g) concentration is
above 1 μg/Nm3 or RB and RD ≤ 20% if the Hg(g) concentration is below 1 μg/Nm3.
In addition, an analytical bias test and a field recovery test are essential for accuracy control of
sorbent trap sampling systems. Analytical bias test was performed on a mercury analyzer in the
laboratory to accurately quantify mercury from the RHC-HBr media. The test was performed by
spiking sorbents at the lower (100–500 ng) and upper (1000–3000 ng) expected Hg amount levels.
Traceable Hg0 and HgCl2 standards by National Institute of Standards and Technology (NIST)
were used for the spiking. Field recovery test was performed to verify the performance for onsite
sampling. One of the traps in each pair was spiked with a known amount of gaseous Hg0
(NIST-traceable) while the other was unspiked. Hg was recovered from the traps and analyzed
after sampling, and the spike recovery was calculated by comparing the analytical results of the
expected value (50%–150% of the actual mass collected):
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mre cov ered

R  100% (6)
mspiked

where mrecovered (μg) is the recovery Hg mass, mspiked (μg) is the spiked Hg mass. The QA/QC
criteria (Laudal, 2009; US EPA, 2008) require constraints of 100 ± 10% and 100 ± 15% for the
average recovery rate to pass the analytical bias test and field recovery test, respectively.

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2.4. Bench-scale coal-fired unit

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Contradistinctive Hg sampling tests were performed between biomass-based sorbent traps and
AC-based sorbent traps on a bench-scale coal-fired unit. The OHM was used to assess the

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accuracy of the HgT(g) sampling data. As shown in Fig. 3, the flue gas was generated by a 6 kWth
FBC coal combustion system. Double coal hoppers were installed to ensure continuous feeding

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and stable running. Combustion air was provided by an air compressor, which was forced to enter
the mixing chamber after degreasing and dehumidifying. The furnace was made of stainless steel,
allowing continuous operation at 950 °C or higher. Four sampling points were orderly located

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along the gas stack before the fabric filter, enabling parallel sampling by sorbent traps and the
OHM. During the field sampling test, both the sorbent traps and OHM sampling of Hg(g) in flue
gas were filtered by a two-stage dedusting device, which was heated to 160 °C to prevent mercury
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vapor condensation. After field testing, solid samples from the sorbent traps were analyzed by a
Hydra II C mercury analyzer (Teledyne Technologies Inc., USA), and the liquid samples from the
OHM were digested and analyzed by a Hydra AA mercury analyzer (Teledyne Technologies Inc.,
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USA).
FBC Boiler
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OHM
T6 Two-stage
Dedusting Device Sampling Console
ΔP
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Sample Gas
T5 Pump
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Sampling
point A
T4 Ice Bath
Sampling
Solution Impringers
AC

point B

T3

Sample
Gas FF WFGD
T2 Heated
Line

Coal Heated Probe

T1 Two-stage Condenser
Feeder Dedusting Device

Filtered Mercury sorbents

Flue Gas
Secondary Circulating Paired Sorbent Traps Pump
Air Primary Sampling Console
Air Ash Tube
Slagging Method 30B
Tube

Air
Mixing Chamber

Fig. 3. Schematic diagram of the 6 kWth coal-fired FBC combustor system.

2.5. Full-scale coal-fired unit

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The biomass-based traps were used for onsite mercury emission monitoring in a demonstration
coal-fired unit in north China with the 660 MW boiler maximum continuous rating (BMCR).
Differing from Hg sampling in the bench-scale test, only RHC-HBr traps were used for the HgT(g)
measurement compared with the OHM. The demonstration unit was equipped with a selective
catalytic reduction (SCR) system for nitrogen oxide control, an electrostatic precipitator (ESP), a

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wet flue gas desulfurization (WFGD) system, and a wet electrostatic precipitator (WESP). Two
types of constant power loads (100% of the BMCR (100%-BMCR) and 75% of the BMCR

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(75%-BMCR)) were offered by the power plant throughout the duration of testing. The sampling
locations are shown in Fig. 4. The Hg(g) sampling tests were simultaneously performed at five

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locations: the front and rear of the SCR system (A and B, respectively), the front and rear of the

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WFGD system (C and D, respectively), and the outlet duct of the WESP leading to the stack (E).
Table 1 gives the results of the proximate and ultimate analyses of the burned coals under the two
power loads. The Hg mass balance ( b , %) was calculated by

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mT
b  (7)
mC
where mT (g/h) is the measured total mercury mass (sum of gaseous Hg and particulate Hg) in the
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flue gas, mC (g/h) is the calculated total mercury mass in the flue gas obtained by calculating all of
the mercury contents (i.e., Hg in the feeding coal, bottom ash from the boiler, and ESP, gypsum
and slurry from the WFGD system, and feedwater and drainage from the WESP). The results are
acceptable only when b is between 70% and 130% (Yokoyama, et al., 2002).
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Exhaust
Flue Gas

Hg(g) Hg(g)
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in Flue Gas in Flue Gas

Flue Gas
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A
Boiler
Hg in ESP WESP
SCR WFGD
D
Coal E
B C
AC

GAH

Hg in
fly ash Hg in
Hg in gypsum and slurry
bottom ash

Fig. 4. Sampling locations in the 660 MW demonstration coal-fired unit with ultra-low emissions.
Table 1. Proximate and ultimate analyses of the burned coals (as-received basis).
Proximate analysis (wt.%) Ultimate analysis (wt.%)
Condition
Mar Aar Var FCar Car Har Oar Nar Sar Hgar
100%-BMCR 13.01 14.19 26.69 46.11 58.36 3.49 9.86 0.82 0.27 8.45×10-8
75%-BMCR 15.21 10.84 27.97 45.98 57.99 3.69 11.01 0.8 0.47 8.03×10-8

3. Results and Discussion

3.1. Sorbent characteristics
Fig. 5 shows SEM images of the raw and impregnated RHC sorbents. The porous structures of
the sorbents are clearly observed in the SEM images. It is commonly considered that micropores
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increase upload of the impregnation agent and diffusion of gaseous mercury during the adsorption
process. In addition, porous structures have been reported to positively affect Hg0 capture by
directly increasing its physical interaction with the sorbents (Diamantopoulou et al., 2010; Zheng
et al., 2012).
BET analysis was performed to determine the specific surface area and pore volume of the

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RHC-based sorbent and compare them with AC-based sorbents. The BET results summarized in
Table 2 indicate that the porous structures are retained in both the RHC and AC sorbents after

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impregnation. We showed in our previous work that the porous structures are not destroyed by
brominated impregnation (Zhu et al., 2016). The BET analysis also suggests that the specific

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surface area and micropore volume of raw AC are nearly 2.5 times greater than those of raw RHC,

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so impregnation of RHC is necessary to offset its natural disadvantage for mercury capture.

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D
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(a) Raw RHC (b) RHC-HBr

Fig. 5. SEM images of RHC.

Table 2. BET analysis of raw and impregnated RHC and AC.

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BET surface Micropore surface Micropore volume Total pore Average pore
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samples 2 2 3 3
area (m /g) area (m /g) (cm /g) volume (cm /g) size (nm)
Raw AC 624.22 460.68 0.21 0.31 2.01
AC

Raw RHC 254.39 245.84 0.11 0.13 2.07

AC-HBr 622.49 468.98 0.22 0.31 1.97
AC-KI 690.913 421.290 0.192 0.348 2.01
RHC-HBr 235.36 218.82 0.23 0.34 2.44

3.2. Analytical bias test for the mercury analyzer

As illustrated in Fig. 6, RHC-HBr analyzed by the Hydra II C mercury analyzer showed
excellent spike recoveries. Both Hg0 and HgCl2 met the 100 ± 10% constraint required by the
QA/QC criteria, indicating that the Hydra II C mercury analyzer is capable of accurately
quantifying mercury from the RHC-HBr media. Because the AC-based sorbent passed the test in
our previous work, the tests were not repeated in this study.
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120 120
0
Hg -Spiking upper limit (+10%) HgCl2-Spiked upper limit (+10%)
115 100% Recovery lower limit (- 10%) 115
100% Recovery lower limit (-10%)
110 110
Recovery rate (%)

Recovery rate (%)

105 105
100 100

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95 95

90 90

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85 85

80 80
0 500 1000 1500 2000 2500 3000

R
0 500 1000 1500 2000 2500 3000
Spike level (ng) Spike level (ng)

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(a) (b)

Fig. 6. Analytical bias test for RHC-HBr: (a) Hg0 spiked and (b) HgCl2 spiked.

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3.3. Hg adsorption performance in the fixed bed system
The Hg adsorption performance of RHC and AC before and after impregnation was determined
in the fixed-bed system, and the results are shown in Table 3. For the raw RHC sample, after a 120
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min adsorption test, the initial mercury adsorption capacity was only 5.127 μg/g. Hg0
breakthrough was observed in the second sorbent layer because of the low uptake ability of raw
RHC. Raw AC showed a higher mercury adsorption capability (22.76 μg/g) but the 44.66% Hg0
breakthrough rate is unsatisfactory. In contrast, the brominated sorbents showed good mercury
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uptake ability and almost no Hg0 breakthrough occurred during the 120 min test. The RHC-HBr
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adsorption capacity is comparable with those of the other two AC-based sorbents under the
simulated flue gas conditions. It was conclusive in our previous work (Zhu et al., 2016) that
enrichment of the bromine functionality played the dominant role in enhancing the mercury
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adsorption capacity of RHC, which could overcome its lower porosity than AC. Therefore, the
RHC-HBr sorbents are suitable for trapping HgT(g) in flue gas.
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Table 3. Hg adsorption capacities of RHCs and ACs in the fixed bed system.

Sorbents q (μg/g) m1st (μg) m2nd (μg) EHg (%) BHg (%)
AC

Raw AC 22.76 1.705 0.762 108.39 44.66

Raw RHC 5.127 0.265 0.203 91.32 76.81
AC-KI 57.60 5.152 0.053 109.64 1.03
AC-HBr 57.84 5.515 0.081 103.25 1.46
RHC-HBr 57.84 4.680 0.038 118.43 0.81

3.4. Bench-scale mercury sampling test

The parallel Hg sampling results of sorbent traps and the OHM in the 6 kWth coal-fired FBC
are compared in Table 4 and Fig. 7. The fluctuations of the measured mercury concentration data
are reasonable because the coal type varied with the sampling run. All of the b values are within
the acceptable range (70%–130%), showing that the Hg concentration data measured by the OHM
are acceptable. The contrast sampling results agree with the expectation that the measuring results
by the sorbent trap are consistent with those obtained by the OHM. Considering EPA Method 30B,
the affirmative recovery rate (R) ranged from 97.5% to 105.3%, confirming that the sorbent
trapping runs passed the field recovery test. Furthermore, both the RB and RD passed the QA/QC
criteria, verifying the results measured by the sorbent traps. Further comparing the biomass-based
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sorbent trap (RHC-HBr) with the AC-based sorbent traps (AC-KI and AC-HBr), it is noticeable
that the RHC-HBr sorbent trap possesses the equivalent accuracy. The higher RD for AC-KI
sorbent trap can be explained by the low Hg concentration in the flue gas (0.715 μg/Nm3), but it is
still acceptable.
Table 4. Parallel Hg sampling results of sorbent traps and the OHM in the 6 kWth coal-fired FBC (6% O2

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normalized).

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C30B COHM
Sampling run RB (%) RD (%) Field R (%) b (%)
(μg/Nm3) (μg/Nm3)

R
#1 (AC-HBr/OHM) 4.039 4.806 9.0 8.67 105.3±3.1 95.47

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#2 (AC-KI/OHM) 0.715 0.985 1.65 15.9 101.6±1.7 104.72
#3 (RHC-HBr/OHM) 2.463 2.434 3.2 0.60 97.5±2.9 128.98
4
Method 30B

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OHM
Hg concentration (g/Nm )
3

3
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2

1
D

0
#1 #2 #3
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Fig. 7. Parallel Hg sampling of sorbent traps and the OHM in the 6 kWth coal-fired FBC.

3.5. Full-scale mercury sampling test

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Owing to the outstanding performance of the RHC-HBr traps in Hg field testing in the
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bench-scale coal-fired unit, only RHC-HBr traps were used for onsite sampling in the 660 MW
demonstration pulverized coal unit. The parallel Hg measurement results are shown in Table 5.
The Hg concentration data obtained by the OHM are credible because all of the b values are
AC

within the constraint (70%–130%) for the two unique boiler outputs. As shown in Fig. 8, the
RHC-HBr traps passed the field recovery test for both 100%-BMCR and 75%-BMCR, with the
recovery rates within the limits (100% ± 15%). The RHC-HBr traps have relatively poor field R
values at locations A and E, which probably resulted from the high fly ash content in flue gas
sampling at A and the low Hg(g) concentration in the flue gas at E. The adverse effect of the low
Hg(g) concentration can be observed in Fig. 9 when calculating the RD between the sorbent traps
and the OHM. The RHC-HBr traps performed well at locations A and B, where the ash content in
the flue gas was relatively high. This can be attributed to the filter membrane installed at the head
of probe to protect the sorbent traps from ash blocking. As showed in Figs. 9 and 10, both RB and
RD met the QA/QC criteria, and the sampling results in Fig. 11 for the RHC-Br traps agree well
with those of the OHM, indicating satisfactory mercury concentration data at each sampling
location by the RHC-HBr traps.
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100%-BMCR Field Spike +15% upper limit 75%-BMCR Field Spiking +15% upper limit
120 100% Recovery -15% lower limit 120 100% Recovery - 15% lower limit

110 110
Recovery rate (%)

Recovery rate (%)

100 100

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90 90

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80 80

A B C D E A B C D E

R
Sampling location Sampling location

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(a) (b)

Fig. 8. Field recovery test for the RHC-HBr sorbent trap in the 660 MW coal-fired unit: (a) 100%-BMCR and (b)

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75%-BMCR.
Table 5. Parallel Hg sampling results of sorbent traps and the OHM in the 660 MW coal-fired unit (6% O2 normalized).
100%-BMCR 75%-BMCR
Sampling
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C30B COHM C30B COHM
location b (%) b (%)
3 3 3
(μg/Nm ) (μg/Nm ) (μg/Nm ) (μg/Nm3)

A 13.21 12.63 77.08 10.02 9.42 76.29

B 11.59 12.31 79.62 9.88 10.38 88.25

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C 6.17 5.71 93.92 6.72 7.18 94.45

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D 3.76 4.1 75.4 3.28 3.55 74.23

E 0.65 0.8 71.56 1.54 1.41 73.12

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30%
RD RD
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20%
Target RD < 20%3
CHg (g) ≤ 1 μg/Nm
Relative Deviation

Relative Deviation

20%

Target RD ≤ 10%
3
Target RD ≤ 10% 3 CHg (g) > 1 μg/Nm
CHg (g) > 1 μg/Nm 10%
AC

10%

0% 0%
A B C D E A B C D E
100%-BMCR 75%-BMCR

(a) (b)

Fig. 9. RD between the biomass traps and the OHM in the 660 MW coal-fired unit: (a) 100%-BMCR and (b)

75%-BMCR.
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25%
Target RB ≤ 20%
Breakthrough Rate of Sorbent Traps
RB

Breakthrough Rate of Sorbent Traps

3 RB
CHg (g) ≤ 1 μg/Nm
20% 20%

15%
Target RB ≤ 10% Target RB ≤ 10%
3 3
CHg (g) > 1 μg/Nm CHg (g) > 1 μg/Nm
10% 10%

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5%

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0% 0%
A B C D E A B C D E

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100%-BMCR 75%-BMCR

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(a) (b)
Fig. 10. RB between the biomass traps and the OHM in the 660 MW coal-fired unit: (a) 100%-BMCR and (b)
75%-BMCR.

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14 12
OHM Method 30B
12 Method 30B 10 OHM
Hg (g) concentration (g/Nm )

Hg (g) concentration (g/Nm )

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10
8
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8
6
6
4
4
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0 0
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A B C D E
100%-BMCR 75%-BMCR

(a) (b)
Fig. 11. Parallel Hg sampling of the sorbent traps and the OHM in the 660 MW coal-fired unit: (a) 100%-BMCR
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and (b) 75%-BMCR.

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3.6. Mercury removal by existing APCDs

From the perspective of the HgT(g) concentrations through air pollution control devices, the
concentration variation reflected the mercury removal efficiencies of the APCDs. As shown in
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Table 6, the HgT(g) concentrations measured in the front and rear of the SCR are slightly different
under 100%-BMCR and 75%-BMCR unit loads, which is reasonable because the SCR was able to
catalyze and oxidize Hg0(g) but only a small portion of Hg2+(g) in the flue gas adsorbed to the
catalyst. The SCR has removal efficiencies of 12.33% and 1.41% for gaseous mercury, which
agrees with existing research on mercury speciation and removal across a SCR (Richardson et al.,
2002). However, the SCR+ESP combination shows excellent mercury removal ability (53.17%
and 32.98% for 100%-BMCR and 75%-BMCR, respectively), indicating mercury oxidation rather
than adsorption through the SCR (Kamata et al., 2008; Li et al., 2011; Pudasainee et al., 2012).
The removal efficiencies of the single ESP are 46.60% and 32.0% for 100%-BMCR and
75-BMCR, respectively, which are close to the reported level (Pudasainee et al., 2012; Srivastava
et al., 2006). WFGD system can absorb 80% to 90% of the Hg2+(g) by its wet slurry but show
hardly any Hg0(g) removal (Pavlish et al., 2003). In contrast, the WESP is capable of effectively
dissolving Hg2+(g) and oxidizing Hg0(g) to a certain level because of the electrocatalytic oxidation
process (McLarnon et al., 2005). Therefore, the mercury capture efficiencies of the single WFGD
system are lower than those of the WESP (39.29% and 51.19% compared with 82.69% and
52.75%). The ESP+WFGD system is the most widely used APCDs in China. In this study, the
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average mercury removal efficiency of the ESP+FGD system is 67.2%, which is consistent with
the results reported by other researchers (29%–74%) (Srivastava et al., 2006; Wang et al., 2010).
The SCR+ESP+WFGD and SCR+ESP+WFGD+WESP systems have high mercury removal
efficiencies (67.28%–71.57% and 84.54%–95.08%, respectively), demonstrating that an
appropriate combination of APCDs is capable of controlling mercury emissions from coal-fired

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power plants. Variation of the mercury removal efficiency with the unit load is clearly observed in
this study, and the results suggest that APCDs perform better for mercury capture under the upper

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unit load than the lower unit load.

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Table 6. Mercury removal by existing APCDs (based on results measured by RHC-Br traps).

Gaseous mercury removal efficiency (%)

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ACPDs
100%-BMCR 75%-BMCR
SCR 12.33 1.41

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ESP 46.60 32.01
WFGD 39.29 51.19
WESP 82.69 52.75
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SCR+ESP 53.17 32.98
ESP+WFGD 67.58 66.81
SCR+ESP+WFGD 71.57 67.28
SCR+ESP+WFGD+WESP 95.08 84.54
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Previous studies have reported some Hg emission data from coal-fired power plants. Guo et al.
(2007) reported Hg emissions of 13–21 μg/Nm3 from a 300 MW coal-fired power plant equipped
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with a cold-side ESP (CS-ESP) (0.33 mg/kg Hg in the coal). Lee et al. (2006) reported Hg
emissions ranging from 1.03 to 2.41 μg/Nm3 in a 500 MW power plant equipped with a CS-ESP
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and a WFGD system (with 0.043–0.078 mg/kg Hg in the coal). Pudasainee et al. (2012) applied
the OHM to 600 and 500 MW boilers equipped with a SCR, a CS-ESP, and a WFGD system. The
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Hg concentrations in the flue gas at the stack ranged from 0.26 to 4.70 μg/Nm3 by burning coal
with 0.046 mg/kg Hg. With advanced APCDs like the WESP, the ultimate mercury emissions from
the stack under 100%-BMCR and 75%-BMCR loads were 0.65 and 1.54 μg/Nm3, respectively,
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which are substantially lower than the reported values above, agreeing with the ultra-low emission
purpose.
4. Conclusion
In this study, a novel sorbent trap was developed based on RHC. The removal efficiency of
cost-efficient RHC-HBr as the media in sorbent traps was investigated by the mercury adsorption
capacity test in a fixed bed system. A field verification test of the biomass-based trap was
performed in a 6 kWth FBC coal combustion system and compared with AC-based sorbent traps
by the OHM. The biomass-based trap was ultimately applied for field HgT(g) sampling in a 660
MW demonstration coal-fired unit. The existing APCD performance for mercury removal was
reported by the RHC-HBr sorbent traps. The main conclusions of this study are as follows:
(1) The mercury capture ability of raw RHC can be substantially improved by brominated
impregnation. The comparable Hg adsorption capacity with impregnated AC shows the potential
of the biomass-based sorbent for trapping HgT(g) in flue gas.
(2) The HgT(g) emission data measured by sorbent traps was consistent with that by the OHM
in a bench-scale FBC boiler. All of the sorbent traps passed the field recovery test with recovery
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rates from 97.5 ± 2.9% to 105.3 ± 3.1%, which are within the QA/QC criteria. The accuracy of
RHC-HBr sorbent traps for HgT(g) emission monitoring was confirmed and it is comparable with
AC-based sorbent traps.
(3) Under the 100% and 75% of the BMCR of the full-scale coal-fired unit, the HgT(g)
sampling results by RHC-HBr traps were consistent with those by the OHM. The RB and RD of

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RHC-HBr traps are within the QA/QC criteria, showing the valid sampling by the novel sorbent
traps.

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(4) Different mercury migration and emission characteristics across single APCDs are reported
by the biomass-based sorbent traps. Mercury oxidation rather than adsorption through the SCR

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was confirmed. The WFGD system was capable of effectively dissolving Hg2+(g), while the

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WESP possesses the addition ability for Hg0(g) oxidization through the electrocatalytic effect. The
combined APCDs system achieved high mercury removal rates of 95.08% and 84.54% for
100%-BMCR and 75%-BMCR, respectively. A 660 MW coal-fired unit obtained lower mercury

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emission under 100%-BMCR (0.65 μg/Nm3) than under 75%-BMCR (1.54 μg/Nm3).
Acknowledgements
This study was supported by the National Natural Science Foundation of China (51376046,
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51576044), the Fundamental Research Funds for the Central Universities, Graduate Student
Research and Innovation Program of Jiangsu Province (CXZZ13_0093, KYLX_0115,
KYLX_0184, KYLX15_0071), and the Scientific Research Foundation of Graduate School of
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Southeast University (YBJJ1505)

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Exhaust
Sorbent trap Flue Gas
Flue Gas RHC-HBr
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Collection Breakthrough
Flue Gas

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SCR B
660MW power
Hg in WESP
unit AH ESP

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Coal Stack
Boiler WFGD

QA/QC verification Field Hg monitoring Hg migration analysis

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RHC-HBr
preparation

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Cost-efficient
Fixed bed
investigation
Novel
Bench-scale sorbent Convenient
verification

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trap
AC trap
comparison Equivalent
accuracy
OHM parallel
evaluation
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Graphical abstract
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Highlights
 A novel biomass-derived sorbent trap was developed for HgT(g) monitoring
 The trap was based on rice husk char and impregnated with bromine (RHC-HBr)
 The RHC-HBr trap was comparable with commercial AC trap for HgT(g) monitoring
 High accuracy field sampling by the RHC-HBr trap was confirmed by QA/QC


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The RHC-HBr trap was used to report Hg migration through existing APCDs.

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