Fuel 239 (2019) 830–840

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Removal of elemental mercury using large surface area micro-porous corn T

cob activated carbon by zinc chloride activation
⁎
Xue-Lei Duan, Chun-Gang Yuan , Tian-Tian Jing, Xiao-Dong Yuan
Department of Environmental Science & Engineering, North China Electric Power University, Baoding 071000, China

A R T I C LE I N FO A B S T R A C T

Keywords: It is a big challenge to effectively remove elemental mercury (Hg0) from coal fired flue gas with affordable
Corn cob adsorbents. To explore new adsorbents with low cost and high capacity for mercury removal is urgently de-
Activated carbon manded. On the other hand, it will be a good way to reduce the environmental burden by beneficially utilizing
Removal agricultural waste. In this study, one kind of agricultural waste, corn cob, was beneficially used for Hg0 control.
Elemental mercury
The corn cob activated carbon (CCAC) with large surface area was prepared by chemical activation using ZnCl2
Flue gas
and was employed to remove elemental mercury (Hg0) from simulated flue gas (SFG) for the first time. The
results demonstrated that the corn cob activated carbon performed high mercury removal efficiency up to 91.4%
at 150 °C. The effects of activator, reaction temperature and main flue gas components were studied. Brunauer-
Emmett-Teller (BET), X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy with energy
dispersive X-ray spectrometry (SEM-EDX) were used to characterize the physicochemical properties of the ad-
sorbents. The possible mechanism of mercury removal was discussed based on XPS analysis and characterization.
The results indicated that ZnCl2 could not only activate microporous structures of carbon but also played an
important role for removal of elemental mercury. The produced AC can be used as an effective adsorbent with
low cost for mercury pollution control in flue gas.

1. Introduction highly anticipated.

Mercury is one of the most hazardous metals because of its prop-
erties of persistence, long-distance migration, and bio-accumulation
[1]. Natural release and anthropogenic discharge are the main sources
of mercury. It was estimated that about 30% of anthropogenic mercury
discharge was from coal combustion in China [2,3]. Moreover, Wang
et al. [4] reported that China contributed 25%–40% to the global
mercury emissions. There are three states of mercury in coal-fired flue
gas: elemental mercury (Hg0), oxidized mercury (Hg2+) and particu-
late-bound mercury (HgP) [5,6]. Hgp can be efficiently captured by
electrostatic precipitators (ESPs) and fabric filters (FFs), and Hg2+ can
also be removed by wet flue gas desulfurization systems (WFGDs) with
high efficiency [6,7]. Nevertheless, Hg0 is difficult to be removed by air
pollution control devices because of its high volatility and insolubility
in water [8]. In order to remove Hg0, several methods had been de-
veloped [9]. Among these techniques, the activated carbon injection
(ACI) technology was regarded as a practical and effective technology
to treat mercury pollution in power plants [2,9]. However, high cost,
low efficiency and poor selectivity of traditional AC limited its wide
applications [2,10]. Thus, the effective adsorbents with low cost are
Agricultural waste is a renewable, economical and abundant re-
source for biochar production [11,12]. There are many kinds of agri-
cultural waste that have been used to prepare bio-chars or activated
carbons [13–19]. Giraldo et al. [20] prepared activated carbon from
coffee waste and applied it to treat Hg2+ from aqueous solution, and
the adsorption capacities was from 0.002 to 0.38 mmol/g. Tan et al.
[21] prepared AC from bamboo and applied it to treat Hg0 from si-
mulated flue gas (SFG), and the AC presented good performance for Hg0
removal efficiency (Above 88%). Liu et al. [22] prepared AC from
seaweed and applied to treat elemental mercury from SFG, and the
average Hg0 removal efficiency (RE) was 85%. Wheat straw chars were
also prepared and employed to remove Hg0 from SFG [2]. Although
some kinds of biomass or their products had been applied for elemental
mercury removal, the adsorption capacity and selectivity are needed to
be enhanced. It is necessary to explore more kinds of biomass activated
carbon for flue control.
Activated carbon can be prepared by both chemical activation and
physical activation processes. The chemical activation is a single step
during which carbonization and activation processes are simulta-
neously carried out [10]. The popular chemicals used as activation

⁎
Corresponding author.
E-mail address: cgyuan@ncepu.edu.cn (C.-G. Yuan).

https://doi.org/10.1016/j.fuel.2018.11.017
Received 16 August 2018; Received in revised form 29 October 2018; Accepted 3 November 2018
Available online 29 November 2018
0016-2361/ © 2018 Elsevier Ltd. All rights reserved.
X.-L. Duan et al.
reagents are mainly alkali (NaOH, K2CO3, KOH and Na2CO3)
[20,23,24], acids (H3PO4, HNO3, HClO4 and H2SO4) [6,16,23,25] and
some metal salts (FeCl3, ZnCl2). The activation reagents promote the
decomposition of carbonaceous material in biomass and increase the
carbon yield. In order to get high specific surface area and good se-
lectivity to mercury ions, ZnCl2 was used as activating reagent. Yang
et al. [26] prepared activated carbon from pistachio nut shell using
ZnCl2 under nitrogen and vacuum conditions. The mesoporous acti-
vated carbon which had a BET surface area of 2527 m2/g was prepared
with ZnCl2 impregnation ratio of 1.5, furnace temperature of 500 °C and
a hold time of 2 h under vacuum condition. Biomass AC was also pre-
pared from cattle-manure compost, and it was successfully used to
adsorb phenol which exhibit the high adsorption capacity due to its
high BET surface area (2170 m2/g) and large total pore volume
(1.70 cm3/g) [27]. In another study, high surface area activated carbon
was also produced from tomato processing solid waste [11]. High sur-
face area of 1093 m2/g was achieved with the total pore volume of
1.569 cm3/g. These previous studies suggested that ZnCl2 could be used
as an effective activation reagent for biomass to produce functional AC
with high surface area and porous structures. These two characters are
regarded as very important for adsorption of pollutants. In addition to
that, the previous studies [18,25] reported that Cl element was strongly
supportive for AC to adsorb Hg0 because Hg0 could be possibly oxidized
to HgCl2 by Cl element during the adsorption process. The CeCl groups
had strong adsorption energy for mercury, which could convert ele-
mental mercury to HgCl2 form [1,26]. On the other hand, zinc is re-
garded as a special element which has high affinity to mercury and
enhancement property to catalytic activity [28]. Moreover, Hu et al.
[29] suggested that chemically activated activated carbon using ZnCl2
had higher Hg0 RE than AC modified by steam. The selectivity and
adsorption capacity for elemental mercury can be enhanced when ZnCl2
is used as activator to prepare activated carbon. Therefore, activated
carbon prepared with ZnCl2 as activation reagent from biomass is as-
sumed to have the potential to effectively remove elemental mercury.
In this study, corn cob was employed as a precursor material for
activated carbon preparation. Corn cob is abundant with huge pro-
duction of about 218 million tons in 2013 in China per year [30]. Most
of them was burned as household fuel without any pollution control
device, which caused serious air pollution. Therefore, producing acti-
vated carbon from corn cob would not only be an effective way for its
beneficial utilization but also reduce the environmental burden caused
by huge amount of agricultural waste. Furthermore, it was demon-
strated that corn cob activated carbon was prepared with chemical
activation using H3PO4 (Sych et al.) and KOH (Liu et al.), which had
larger surface areas than other biomass such like Peanut shell (activa-
tion by H3PO4) (Li et al.) and grape seeds (by KOH) (Okman et al.)
[14,16,30,31]. To the best of our knowledge, there was no report about
elemental mercury removal by activated carbon prepared from corn cob
using ZnCl2 activation. The primary objectives of our study are (1) to
provide a method for the preparation of activated carbon from corn cob
using ZnCl2 activation, (2) to obtain an adsorbent for elemental mer-
cury removal from flue gas with low cost and high efficiency, and (3) to
explore one new route to beneficially use this kind of agricultural waste
and to release the burden of air pollution.
2. Experimental
2.1. Preparation of activated carbon
2.1.1. Preparation of corn cob activated carbon
The corn cob was collected from a countryside in Hebei province,
China. The optimal conditions for the preparation of activated carbon
were selected by orthogonal experiments (The experimental process
and results were shown in Tables S1 and S2 in Supporting information).
The experimental factors included the type and concentration of acti-
vators, solid-liquid radios, activation temperatures and time. After
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Fuel 239 (2019) 830–840
optimization, ZnCl2 was selected as the most effective activation re-
agent with the activation concentration of 20%. The liquid-solid radio
was 3:1. The activation temperature was 600 °C for 2 h. The activated
carbon was prepared as the following steps: First, the corn cob was
washed with distilled water to remove all the impurities. Then, the
granular corn cob was grounded and sieved through a 40 mesh sieve
and the corn cob powder was placed in a tube furnace under N2 at-
mosphere at 400 °C for 30 min. After that, the pyrolytic corn cob was
impregnated in the solution of activation reagent with a certain solid-
liquid ratio for 24 h at room temperature. The impregnated material
was heated in an oven at 110 °C for 24 h. After activation, the material
was calcined in a tube furnace under N2 atmosphere at a high tem-
perature of 600 °C for 2 h. Finally, 10% of HCl solution and distilled
water were used to wash the residues on the surface of the prepared
activation carbon in series until the washing water reach a pH value
about 7.0. The sample prepared were denoted as 3-20CCACz, where 3
represents solid-liquid radio (3:1), 20 represents activation reagent
with the activation concentration of 20%, and CCAC represents corn
cob activated carbon, z represents ZnCl2.
2.1.2. Sample impregnation
In order to compare the effectiveness of different ACs and to discuss
the role of ZnCl2 during the removal process, the commercial AC were
also employed. The commercial activated carbon (CAC) used in this
study was purchased from Hua Dong carbon Industry, Tianjin, China.
The used CAC was prepared by steam activation from coal. Firstly, the
CAC were pulverized and sieved into 200 mesh. Then, the CAC was
washed with deionized water and dried at 110 °C. Secondly, 0.21 mol/L
ZnCl2 (A1), 0.42 mol/L ZnCl2 (A2), 0.42 mol/L KCl (A3), 0.84 mol/L
KCl (A4), 0.21 mol/L Zn (CH3COO)2 (A5) and 0.42 mol/L Zn(CH3COO)2
(A6) were added into beakers with CAC, respectively. The liquid-solid
ratio was 4:5 (volume to mass). Then all solid-liquid mixtures were well
stirred and stood in darkness for 24 h. After impregnation, the samples
were dried in an oven at 110 °C for 24 h. Finally, all samples were
cooled down to room temperature and stored for use.
2.1.3. Sample elution
In order to obtain the materials with different contents of Zn, the
prepared AC (3-20CCACz) was used as the raw material. At first,
deionized water, 500 mL of 1 M HNO3 and 500 mL of 3 M HNO3 were
added into a beaker with 500 mg prepared AC, respectively. The solid-
liquid mixture was stirred for 3 h at 25 °C. After separation of solid-
liquid, the supernatant was removed (the process is repeated three
times). All AC samples were washed by deionized water to neutral and
dried at 90 °C in a vacuum oven for 24 h. When the AC samples cooled
down to room temperature, they were pulverized and sieved through a
200 mesh for use. The raw AC was used for blank experiment which was
used to reckon the total amount of zinc in the prepared AC. The blank
was denoted as “a”. The prepared AC named as 3-20CCACz which was
respectively flushed with deionized water, 1 M HNO3 and 3 M HNO3
and the flushed ACs were denoted as “b”, “c” and “d”.
2.2. Characterization
Brunauer-Emmett-Teller (BET) was performed by nitrogen adsorp-
tion at −196 °C on a Micromeritics 3 Flex Surface Characterization
Analyzer to determine the specific surface area and porosity of the
prepared AC. The average pore diameter and pore volumes were also
obtained. All CCACx were degassed prior to BET measurements.
To analyze the morphology and surface structure of the AC samples
were carried out using (quanta F250, Thermo Fisher, USA) scanning
electron microscopy (SEM) coupled with the energy dispersive X-ray
spectrometry (EDX). The semi-quantitative elemental analysis of
sample could be supported with high resolution.
X-ray photoelectron spectroscopy (XPS) analysis was performed at
room temperature on an ESCALAB 250Xi with an Al/Mg X-ray source.
X.-L. Duan et al.
Fig. 1. Schematic of the experimental system. (1) Generator of water vapor; (2–4, 6–7) SO2/NO/CO2/N2 cylinders; (5) Mercury vapor generator; (8) Heat tape; (9)
Gas mixer; (10) fixed bed reactor; (11) temperature controller; (12) Exhaust gas treatment; (13) Hg0 analysis; (14) Gas adsorb.
2.3. Experimental setup and procedure
2.3.1. Elemental mercury adsorption
A fixed-bed reactor was applied to evaluate the performances of Hg0
removal by CCAC. The experimental setup was shown in Fig. 1. It
contained four parts: flue gas generation and control part, reaction part,
sampling and detecting part, exhaust gas purification part. The simu-
lated flue gas (SFG) contained 800 ppm SO2, 300 ppm NO, 10% CO2,
5% O2 and 3% H2O. The balance gas was N2. Moisture was added to the
gas flow by a nitrogen flow through a gas-washing bottle to carry steam.
The flow of N2 was adjusted to change the concentration of water vapor
in the gas flow. The total flow rate of flue gas was controlled at 1 L/min
using a mass flow controller. Hg0 was generated through a mercury
permeation tube (VICI Metronics, USA). The fixed-bed reactor was
composed of a digital temperature controller and a quartz tube with an
inner diameter of 8.0 mm and a length of 40 cm. 10 mg of sample was
packed into the quartz tube and used as the adsorbent. The con-
centration of Hg0 in gas flow was monitored online by a mercury
analyzer (QM201, Suzhou Qingan instrument Co., Ltd, China). The
exhaust gas from the mercury analyzer was introduced into the ab-
sorption solution (2%H2SO4 + 0.1%KMnO4) before being expelled into
the atmosphere. Prior to mercury analyzer, the flue gas passed through
10% NaOH solution to minimized the adverse effects of CO2, SO2 and
NO on measurement and the detector.
The Hg0 removal efficiency was defined as (Eq. (1)):
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Fuel 239 (2019) 830–840
0 0 0
E= (Hgin − −Hgout )/Hgin × 100% (1)
where E is mercury removal efficiency (%); Hg0inand Hg0out
represent the
concentration of Hg0 at the inlet and outlet of the reactor, respectively.
2.3.2. Sample digestion
Each sample (a, b, c, d) were digested by microwave (MWD-800,
Shanghai Meta Analysis Instrument Co., Ltd. China), then were diluted
40 times with deionized water which was tested using Atomic
Absorption Spectroscopy (AAS) (AA-6800, Shimadzu, Japan). An
overview of the procedure was shown in Fig. S1 (Supporting informa-
tion). The microwave program used was shown in Table S3 (Supporting
information) and operational parameters of AAS was showed in Table
S4 (Supporting information).
3. Results and discussion
3.1. BET analysis
The larger BET surface area of activated carbon is, the better the
activated carbon performs for the physical adsorption. In order to op-
timize the activator which can make the activated carbon with high
specific surface area, BET analysis was conducted for the ACs treated by
different activators including ZnCl2, H2SO4 and H3PO4.
Table 1 showed the textural properties of samples. The surface area
X.-L. Duan et al. Fuel 239 (2019) 830–840

Table 1 with pores. The white spots on the surface indicated that there were
BET measurement and pore parameters of the samples. some ZnCl2 particles attached on AC. The results of the SEM-EDX
Sample 1-20CCACz 3-20CCACz 3-20CCACs 2-20CCACp 3-40CCACz analysis (Table 2) confirmed the existence of Zn and Cl.

2
SBET (m /g) 616 1270 556 553 828 3.3. Performance of elemental mercury removal
Smic (m2/g) 499 701 380 130 728
(%) 81.0 55.2 68.3 23.5 87.9
Sext (m2/g) 117 569 176 423 101 3.3.1. Effect of activation reagent
Vtot (cm3/g) 0.29 0.67 0.33 0.32 0.36 In order to investigate the effects of different activators on Hg0 re-
Vmic (cm3/g) 0.19 0.28 0.15 0.045 0.28 moval, the Hg0 removal efficiencies (RE) of the adsorbents produced
(%) 67.3 41.8 46.2 14.4 77.1 with different activators were investigated. The results were shown in
Vext (cm3/g) 0.094 0.39 0.18 0.27 0.082
Fig. 5. It was found that CCACz performed a very good removal effi-
DP (nm) 1.87 2.10 1.09 2.28 1.74
ciency of 99.4% in 1 h. H2SO4-activation activated carbon (CCACs) was
SBET: The total surface area; Smic: Micropore specific surface area; (%): less effective (RE 80%) than CCACz. H3PO4-activation activated carbon
Micropore proportion; Sext: Outer (mesopores and macropores) specific surface (CCACp) had the worst performance (RE 45%). Therefore, it could be
area; Vtot: Totall pore volume; Vmic: Micropore pore volume; Vext: Outer space concluded that ZnCl2 was the best choice for elemental mercury re-
pore; DP: Average pore size. moval. Compared with the other samples, CCACz had high SBET
(1269.8 m2/g) and large pore volume (0.67 m3/g). The specific surface
of the sorbents was as follows: 3–20% ZnCl2/AC (3-20CCACz) > area of the adsorbent played a key role in physical adsorption. Higher
3–40% ZnCl2/AC (3-40CCACz) > 1–20%ZnCl2/AC (1-20CCACz) > surface area promoted Hg0 capture [6]. In addition to physical ad-
3–20% H2SO4/AC (3-20CCACs) > 2–20% H3PO4/AC (2-20CCACp). It sorption, chemical adsorption may also occur when ZnCl2 was used as
could be seen that 3-20CCACz owned the biggest surface area the activator. Rungnim et al. [35] reported that chlorine on the surface
(1270 m2/g) and the highest total pore volume (0.67 cm3/g). of AC was able to oxidize Hg0. The reaction process could be proposed
Fig. 2 showed the N2 adsorption-desorption isotherms of the pre- as follows [36] (Eqs. (2)–(5)):
pared AC. The adsorption-desorption isotherm increased rapidly at a
Hg 0 (g) + C→ Hg 0 (adsorption) (2)
relatively low pressure (P/P0 ≤ 0.01), and then reached a horizontal
plateau at P/P0 ≥ 0.20. The phenomenon was in accordance with the Cl− + C→ C− Cl(ad) (3)
type I isotherm. The result indicated that the samples had large number
of micro-pores and some mesopores on its surface [10]. According to Hg 0 (ad) + C− Cl → HgCl (4)
the potential energy theory of Polanyi-Dubinin [32] and molecular
HgCl + C− Cl → HgCl 2 (5)
sieving effect [33], these micro-pores played an indispensable role
during the adsorption.
According to Nonlocal Density Functional Theory (NLDFT) [34], the 3.3.2. Effect of temperature
pore size distributions of these samples were shown in Fig. 3. It could be For most plants, the outlet temperatures of air preheaters are gen-
seen that 3–20 CCACz had higher peak value than the other ACs in the erally between 120 and 200 °C. Temperature is a key factor to be
pore width of 0.5–2 nm. Therefore, it demonstrated that micro-pores considered when AC is projected for mercury removal [9]. The typical
were distributed on the AC with ZnCl2 activation. Thus, it could be temperature is about 150 °C before ESP, so the researchers mainly
concluded that five samples mainly had micro-pores, and ZnCl2 could conducted element mercury removal experiments and evaluated the
act as an effective activator. The obtained large surface area activated performances of AC at 150 °C or below. In order to compare the effects
carbon was comparable to the surface areas of commercially available of temperature in different situations, the experiments were conducted
ACs typically ranging from 500 to 2000 m2/g [10]. BET surface areas of in both pure N2 and SFG. The results in pure N2 were shown in Fig. 6(a,
the ACs obtained in our work were compared with the literatures (Table b, c). The activated carbons performed the similar effectiveness at
S5 in Supporting information). 150 °C and 30 °C under pure N2 (about 99.9% and 99.7%, respectively)
during the first 2 h. The sorption dynamics of elemental mercury to 3-
3.2. SEM-EDX characterization 20CCACz was evaluated by adsorption in pure N2 at 150 °C. The Hg0
removal efficiencies of 3-20CCACz at 30 °C and 150 °C could both keep
As shown in Fig. 4, the surface of the 3-20CCACz was rough and above 99% and 93% for 10 h (data not shown). The adsorption capacity
for Hg0 was 13.14 mg/g at 150 °C under pure N2. The results indicated
that the adsorption process was dominated by physical adsorption
under pure N2. High temperature would weaken Van der Waals force
between the target element and the adsorbent, which in turn decreased
the efficiency. The previous literature clarified that Hg0 reacted with
chlorine with exothermic behaviors in pure N2 [7]. Therefore, higher
temperature might inhibit the function of chlorine with the increase of
temperature, and the physical adsorption could also be decreased as
well.
However, it was interesting that the higher removal efficiency (RE)
was obtained under SFG conditions (5%O2, 10%CO2, 800 ppm SO2,
300 ppm NO) at 150 °C rather than 30 °C. The results were shown in
Fig. 6(d). The adsorbent exhibited outstanding Hg0 RE (about 91.4%) at
150 °C under SFG, while about 86.7% at 30 °C. The results were in
accordance with the experimental observation by De et al. [37]. Che-
mical adsorption could dominate during the course in SFG. The acti-
vation energy was an important descriptor for the adsorption reactivity
to Hg0 [35]. Bozzelli et al. [38] reported that the activation energy
barrier of Hg0 with chloride was high. High temperature provided po-
Fig. 2. The nitrogen adsorption-desorption isotherms. sitive effects on the chemical reaction between chloride and Hg0 in SFG

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X.-L. Duan et al.
Fig. 3. Pore size distribution of (a) 2–20%H3PO4/AC, (b) 3–20%H2SO4/AC, (c) 1–20%ZnCl2/AC, (d) 3–20%ZnCl2/AC and (e) 3–40%ZnCl2/AC.
atmosphere.
According to Fig. 6(a, d), it was observed that the activated carbon
showed lower RE under SFG than pure N2 at 30 °C. Fig. S2 (Supporting
information) showed that SO2 and NO in the flue gas could also be
adsorbed at 150 °C and the adsorption capacities for them were ap-
proximately 960 mg/m3 and 370 mg/m3, respectively. The experi-
mental data indicated that the components in SFG (especially SO2 and
NOx) could compete with elemental mercury for the adsorption sites on
the surface of the 3-20CCACz, which resulted in lower RE under SFG
than pure N2. However, the adsorption was mostly controlled by phy-
sical adsorption at lower temperature (30 °C) rather than higher tem-
perature (150 °C). The RE decrease was more obvious at 30 °C than
150 °C (Fig. 6(d)).
3.3.3. Effects of flue gas components
In order to investigate the possible effects of the components in flue
on the removal efficiency, the adsorption experiments were carried out
under both SFG and pure N2 conditions. The results were compared to
figure out the effects and roles of the components under different si-
tuations (SFG and N2). SEG was applied to show that the produced AC
could be used as an effective adsorbent for mercury pollution control in
flue gas.
3.3.3.1. Effect of O2. In order to better understand the effect of gas-
phase oxygen on the Hg0 removal performance, the removal efficiency
834
Fuel 239 (2019) 830–840
of 3-20CCACz were examined at both 30 °C and 150 °C under SFG. As
shown in Fig. 7(a). The Hg0 removal efficiency (RE) was about 81.5%
(30 °C) and 87.5% (150 °C) without O2. When the content of O2 in flue
gas rose to 10%, the Hg0 RE values were about 89% (30 °C and 150 °C).
This result implied that O2 could promote the removal of elemental
mercury. This was in line with the conclusion of Li et al. [39]. Qiao
et al. [40] reported that Hg0 adsorbed on the surface of the adsorbent
could react with lattice oxygen to form chemical adsorption site, which
could improve Hg0 RE. In addition, when O2 was present, NO and SO2
in flue gas could participate in Hg0 oxidation reaction and produce
mercuric compounds such like Hg(NO3)2 and HgSO4. These chemical
reactions could improve the removal efficiency. However, when the
content of O2 increased to 15%, there was no obvious increase of
mercury removal efficiency. It could be concluded that low O2
concentration would achieve the supplement of the lost lattice O and
promote the removal procedure [7].
However, the results were different under pure N2 conditions.
Fig. 7(b) showed that when the adsorption was conducted under pure
N2, Hg0 removal efficiencies of 3-20CCACz decreased from about 99.9%
and 99% to 95% and 95.5% when O2 concentration increased from 0 to
5% at 30 °C and 150 °C, respectively. The phenomenon could be due to
the O2 compete with elemental mercury for the adsorption sites on the
surface of the 3-20CCACz. When the concentration of O2 increased from
about 5% to 15%, no obvious changes of mercury adsorb efficiency was
observed. Li et al. [6,7] reported that AC had an immense capacity for
X.-L. Duan et al. Fuel 239 (2019) 830–840

Fig. 4. SEM photos of 3-20CCACz with different magnification factors.

Table 2 phenomenon was also reported by the other researchers [41].

EDX analysis of 3-20CCACz.
Levels Element quantity of sample (wt%) 3.3.3.2. Effect of CO2. The effect of CO2 on the RE was also examined
(Fig. 7(a)). The experiments were carried out at both 150 °C and
C N O Si Cl K Zn 30°Cunder SFG. When the content of CO2 increased from 0% to 12%,
the mercury RE decreased from about 91.4% to 83.8% at 150 °C, and
1 84.76 3.11 7.24 0.28 3.01 0.23 1.38
2 83.39 3.50 9.66 0.21 2.12 0.23 0.89 from about 89.2% to 86.5% at 30 °C. When the adsorbent was tested at
3 85.68 2.86 6.32 0.50 2.98 0.32 1.34 150 °C and 30 °C under pure N2 (Fig. 7(b)) without CO2, the RE was
Average 84.61 3.17 7.74 0.33 2.70 0.26 1.20 about 99% during 1 h. However, when the content of CO2 rose to 12%,
RE reduced to about 92.1% and 91.6% at 30 °C and 150 °C, respectively.
It was reported that the distribution of pore size in 0.5–1.7 nm was
the ideal pore range for adsorption of CO2 on AC. The diameter of Hg0 is
0.157 nm [42]. Therefore, low RE was attribute to that CO2 competed
with Hg0 for adsorption sites due to the similar pore size during the
process of adsorption. Lopez-Anton et al. [42] reported that high pro-
portion of CO2 in flue gas might occupy a lot of active sites on the
surface of activated carbon and reduce the possibility of interaction
between active sites with mercury. Thus, it could be concluded that CO2
inhibit the Hg0 RE.

3.3.3.3. Effect of NO. NO had been proved to play a dominant role in

Fig. 5. Effect of activation reagent. Conditions: Reaction temperature 30 °C; the
concentration of activator concentration, 20%.
storing oxygen and consumption of oxygen in oxidation process during
the experimental period. Under pure N2 without NO and SO2, O2 not
only had no chance to promote the oxidation reaction of NO and SO2,
but also occupied adsorption sites instead of Hg0. The similar
Hg0 removal. Dunham et al. [43] reported that the presence of NO
could improve the mercury oxidation, but some researchers suggested
that the presence of NO would inhibit the removal of Hg0 [21]. Fig. 7(a)
showed when the content of NO increased from 0 to 100 ppm, the
mercury removal efficiency increased from about 89.3% to 90.2% at
150 °C. This could be attributed to the formation of NO2 on the surface
of adsorbents. Moreover, Yang et al. [2] reported that NO2 could
promote mercury oxidation efficiency. Tao et al. [7] concluded that NO
participated in the Hg0 oxidation reaction and volatile mercuric
compounds, like Hg(NO3)2, were generated which improved Hg0 RE.
The possible pathway was summarized below (Eqs. (6)–(8)):
NO + 1/2O2 → NO2 (6)
Hg 0 + NO2 → HgO + NO (7)

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X.-L. Duan et al. Fuel 239 (2019) 830–840

Fig. 6. Effect of temperature on Hg0 removal efficiency. Conditions: a, b, c, d reaction temperature, 30 °C and 150 °C; a, b, c under pure N2; d, under SFG.

2NO2 + Hg 0 + O2 → Hg(NO3 )2 (8) surface of activated carbon. The newly formed substances, such as
aromatic sulfate species and sulfuric acid, could also enhance the RE
However, when the content of NO kept increasing from 100 ppm to
[44]. However, with the content of SO2 continuously increase up to
500 ppm, the RE reduced from about 90.2% to 84.3%. The oxygen and
1200 ppm, the RE reduced to about 89.2%. The low RE was possibly
bound water which could react with mercury on the surface of AC could
caused by the competitive adsorption between high concentration of
be consumed rapidly when the concentration of NO was too high. In
SO2 and Hg0 for the active sites.
addition, some researchers also reported that high concentration of NO
Fig. 7(b) showed the capture of Hg0 by the adsorbent under pure N2.
in flue could scavenge OH radicals and prohibit the oxidation of Hg0
When the content of SO2 increased from 0 to 1200 ppm, the RE de-
[21]. Another reason for the decrease of Hg0 RE could be that high
creased from about 99.5% to 94.5% at 150 °C. It could be attribute to
content of NO competed the active sites on the surface of AC with Hg0.
the suppression was caused by competitive adsorption between SO2 and
The maximum RE in pure N2 was about 99% (Fig. 7(b)). However,
Hg0. The subtotal active sites on the adsorbent could be occupied by
When the content of NO increase from 0 ppm to 500 ppm, the RE re-
high content of SO2 [7]. Moreover, the existence of SO2 had a severe
duced from about 99% to 92.9%. This could be attribute to the NO
poisoning effect on Hg0 removal [45]. Thus, SO2 inhibited Hg0 removal
covered the active sites and consumed surface oxygen and/or hydroxy.
under pure N2.
Hence, NO inhibited Hg0 oxidation and furthermore decreased Hg0 RE
under N2.
3.3.3.5. Effect of H2O. Water-resistance is an important parameter to
assess the real application possibility of adsorbent in flue gas. The
3.3.3.4. Effect of SO2. Yang et al. [12] reported that SO2 favored
content of water vapor (0, 1%, 3% and 6%, m/v) were continuously
mercury removal particularly in the presence of oxygen. While the
introduced into SFG. As shown in Fig. 7(a). It cloud be found that the
other studies conceived that SO2 hindered mercury adsorption by
RE was about 89.5% without water vapor. When the content of water
activated carbon [6]. In this study, the effects of SO2 were
vapor increased from 0% to 3%, the RE increased to about 98.6% at
investigated and the results were shown in Fig. 7(a). When the
150 °C. The results noted that water vapor at low content could
content of SO2 increased from 0 to 400 ppm, the RE increased from
facilitate Hg0 removal as report in previous studies [46]. The effect of
about 91.2% to 94% at 150 °C under SFG. The results indicated that SO2
water vapor might be attributed to the various function group – active
could promote Hg0 RE. This could be attribute to the SO2 could react
sites and chemical substances generated in the process of chemical
with O2 to produce SO3, and the HgSO4 could be formed due to the
reaction. The reaction equation could be described as follows (Eqs.
reaction between SO3 and Hg0 [7]. The reaction could be described as
(12)–(17)):
follows [21] (Eqs. (10) and (11)):
NO + O2 → NO2 (12)
SO2 + 1/2O2 → SO3 (10)
3NO2 + H2 O→ 2HNO3 + NO (13)
Hg 0 + 1/2O2 + SO3 → HgSO4 (11)
SO2 could react with the functional groups and other gas on the Hg 0 + O2 → HgO (14)

836
X.-L. Duan et al.
Fig. 7. (a) Effect of individual flue gas component under simulated flue gas on
Hg0 removal efficiency of 3-20CCACz. Reaction conditions: 150 °C and 30 °C; O2
concentration, 0–15%; CO2concentration, 0–12%; NO concentration:
0–500 ppm; SO2 concentration: 0–1200 ppm; H2O concentration, 0–6%; Hg0
concentration: 280 ng/g. (b) Effects of individual flue gas components under
pure N2 on Hg0 removal efficiency of 3-20CCACz.
2HNO3 + HgO → Hg(NO3 )2 + H2 O
SO2 + H2 O+ 1/2O2 → H2 SO4
HgO + H2 SO4 → HgSO4 + H2 O
Morris et al. [47] stated that the formation of H2SO4 on the surface
of the AC did not lead to blockage of the pores but improved Hg0 ad-
sorption via oxidation on the surface. The acidic materials could in-
crease the quantity of micro-pore and enlarge surface area and im-
proved the RE. The carbonyl and quinone groups were possibly
responsible for mercury oxidation and retention in the ACs [48].
However, when the content of H2O increased to 6%, the RE slightly
reduced to about 97.6%. It could be attribute to the competitive ad-
sorption between high concentration of H2O and Hg0 on the AC, and
H2O covered on AC surface result in Hg0 could not get in touch with
active sites on the surface of prepared AC which could inhibit mercury
removal.
Fig. 7(b) showed the capture of Hg0 under pure N2. When the
content of H2O increased from 0 to 6%, the RE decreased from about
99.5% to 87.7% at 150 °C, and from about 99.9% to 93.7% at 30 °C. It
could be due to the competition between water vapor and Hg0 [12].
Fuel 239 (2019) 830–840
Lopez-Anton et al. [42] advocated that H2O molecules in pure N2 might
be adsorbed into the micro-pores of the activated carbon, so reduced
the number of active sites for mercury adsorption. Hence, water vapor
could inhibit the Hg0 removal under N2.
3.4. Mechanism of the enhancement by ZnCl2
Activated carbon produced by ZnCl2-activation had been reported
in many literatures [29,49–51]. These products had been applied to
adsorb Hg0 from flue gas, and remove Pb(II), As(III), Dye from aqueous
solution. However, to the best of our knowledge, there was no report
about removing Hg0 using activated carbon prepared from corn cob by
ZnCl2 activation under SFG. Some researchers used metal chlorate to
modify carbon materials and to enhance the capacity of elemental
mercury removal [7,21,52]. It was proved that Cl played an important
role in the process of mercury removal. In addition, zinc salt was also
employed for the promotion of Hg0 removal [21,51]. These literatures
reported that the presence of zinc salt greatly enhanced Hg0 RE.
However, the effect of Zn2+ on the removal of elemental mercury is still
not very clear. Our experimental results demonstrated that the prepared
CCAC by ZnCl2 activation in this study had good capacity for elemental
mercury removal rather than by other activators. Therefore, it is ne-
cessary to clarify the role of ZnCl2 in the removal process.
3.4.1. Analysis of mechanism of Zn and Cl
Tan et al. [21] reported that AC had excellent Hg0 RE due to the
existence of ZnCl2 which could produce new active sites. The existence
of ZnCl2 contribute to the increase of micropore surface area and mi-
cropore volume of AC, which might be one reason for that it exhibited
the outstanding performance. In order to evaluate the possible role of
Zn and Cl during the removal process in this study, the removal effi-
ciencies of CAC which was saturated with different zinc/chlorate
compounds and different concentrations. The experimental results were
given in Fig. 8. The average Hg0 RE of samples (A1-6) were about
76.5%, 87.5%, 70.2%, 53.7% and 52.9% under pure N2 during 3 h,
respectively. Compared with impregnated samples by KCl (A3, A4) and
Zn (CH3COO)2 (A5, A6), the AC impregnated with ZnCl2 (A1, A2) had
better Hg0 removal ability, and the RE were up to about 82.5% and
89%. ZnCl2 significantly enhanced the Hg0 RE of CAC. The mercury
removal performance of ZnCl2-impregnated (A1, A2) and KCl-im-
pregnated (A3, A4) were compared. The contents of Cl in A1 and A3
was same, it is the similar for A2 and A4. The results revealed that zinc
played critical roles in the enhancement of elemental mercury RE. The
mercury removal performance of ZnCl2-impregnated (A1, A2) and Zn
(CH3COO)2-impregnated (A5, A6) were compared, the contents of Zn in
(15)
A1 and A5 was same, it is the similar for A2 and A6. The experimental
(16)
(17)
Fig. 8. Efficiency-time curves of activated carbon at 150 °C.
837
X.-L. Duan et al.
Fig. 9. (1) XPS spectra of activated carbons before and after mercury adsorption and spectral regions of (2) Cl2p, (3) O1s, (4) Hg4f.
results revealed that chloride also played an important role in the en-
hancement of elemental mercury removal. The roles of Zn and Cl were
further discussed below.
3.4.2. Role of Cl
To confirm the role of Cl in the process of Hg0 removal using the
prepared activated carbon, the chemistry valence states of the elements
on AC were analyzed by XPS. C1s, O1s, Cl2p and Hg4f were analyzed by
XPS and as shown in Fig. 9. XPS spectra of the prepared AC before and
after mercury adsorption were recorded. There were two strong peaks
at 284.5 eV and 530.0 eV in Fig. 9(1), which was ascribed to C1s and
O1s, respectively. It could be found that C1s peaks decreased and O1s
speaks increased after mercury adsorption. The phenomenon might be
due to the C]C, CeC and CeH groups on the sample surfaces could be
broken and form new functional groups containing oxygen, such as
CeO, C]O and COOH [53].
As shown in Fig. 9 (2), two main peaks centered at 198.6 eV and
200.3 eV for Cl2p were found. The peak at 198.6 eV was ionic chlorine
(Cl−) [54]. The Cl− possibly existed as HgCl2 at 198.9 eV [7]. There-
fore, the band of 198.6 eV corresponded to HgCl2. In order to verify the
hypothesis that Cl plays an important role during the process of ele-
mental mercury removal, Hg4f was further monitored. Fig. 9(4) showed
that the two strong binding energies were found at 101.6 eV and
104.4 eV. The two peaks of Hg4f could be attributed to HgO (104.4 eV)
and HgCl2 (102.0 eV) [55]. Thus, it was confirmed that the performance
of removal mercury was influenced by Cl species. During the adsorp-
tion, Hg0 could be oxidized into its oxide.
The O1s fitting peaks which could be used to judge the formation of
838
Fuel 239 (2019) 830–840
oxygen-containing groups were shown in Fig. 9(3). The binding energy
of 532.6 eV was ascribed to the adsorbed water species [7]. The peak at
530.0 eV was ascribed to the lattice oxygen (O2−) in the metal oxide.
The peak at 531.7 eV represented the chemisorbed oxygen or weakly
bonded oxygen species, which was regarded as the most active oxygen
in reaction of mercury oxidation. Some reports inferred that HgO could
be formed during the progress of reaction due to the existence of
oxygen-containing functions [7]. Furthermore, HgO was found in Hg4f
fitting peaks (with the peak at 104.4 eV) in this work. Thus, it could be
concluded that Hg0 removal was influenced by O species or oxygen
functional groups on the surface of AC.
3.4.3. Role of zinc
In order to investigate the positive role of Zn on mercury removal,
the content of Zn in four treated AC samples (a, b, c and d, see them in
part 2.1.3) were determined. The results were shown in Fig. S3(1). The
content of Zn of samples were 3904.2 µg/g, 2898.0 µg/g, 1584.7 µg/g
and 1637 µg/g, respectively. The Hg0 RE of four samples were also
tested, and the results were shown in Fig. S3(2). The Hg0 RE of samples
were about 99% 65%, 36.9% and 37%, respectively. The results in-
dicated there was a positive correlation and dose-dependent relation
between zinc content and mercury RE. Li et al. [56] reported that the
optimal content of Zn could improve the tensile strength, water ad-
sorption and water tolerance of the biodegradable material result from
the hydroxyl group could coordinate with Zn2+ to form complex.
Henning et al. [28] reported that the zinc exhibit enhanced catalytic
activity. Based on these findings, it could be assumed that the state of
Zn might be Zn2+, Zn (OH)+ and [ZnCl2(OH)2]2+ on the surface of AC
X.-L. Duan et al.
which might improve the Hg0 RE. Therefore, the Zn element was
strongly supportive for activated carbon to adsorb Hg0 as well as
chlorate. Here, we need to point out that the activated carbon surface
could etched after oxidizing by nitric acid, which might result in the
decrease of surface area and the increase of pore sizes [57]. So, the
samples washed with nitric acid had poor Hg0 RE.
4. Conclusion
A method for the preparation of porous activated carbon using the
agricultural waste (corn cob) with low cost was proposed. The prepared
AC was with large surface area and high elemental mercury removal
capacity. Compared with H2SO4 and H3PO4, ZnCl2 was the best choice
to be used as the activator for elemental mercury removal. The pre-
pared AC (3-20CCACz) exhibited excellent Hg0 removal capacity from
SFG with RE up to about 91.4% at 150 °C. O2 and the low concentration
of SO2, NO and H2O were beneficial to mercury removal under SFG.
However, CO2 and high concentration of SO2, NO and H2O inhibited
the Hg0 RE under the same situation. The results of XPS indicated that
chloride function groups on the surface of the prepared AC and Hg0
were mainly in the forms of HgO and HgCl2. Cl played an important
role during the removing process. A positive relation between Zn con-
tents and mercury removal efficiencies were also found in our experi-
ment. Zn was also certified to play an important role during the course.
The prepared AC can be used as an effective adsorbent for Hg0 removal
from flue gas with low cost and high capacity. This study not only
provided a method for the preparation of adsorbent for Hg0 removal but
also a new route for beneficial utilization of agricultural waste (corn
cob) and releasing the environmental burden caused by huge amount
agricultural waste.
Acknowledgements
This study was supported by the National Natural Science
Foundation of China (91543107), China and the Fundamental Research
Funds for the Central Universities (2017ZZD07), China.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.fuel.2018.11.017.
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