Chemical Engineering Journal 408 (2021) 127888

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Chemical Engineering Journal

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γ-Fe2O3 decorated attapulgite composite modified with CuCl2 as

magnetically separable sorbents for Hg0 removal from coal combustion
flue gas
Lu Dong a, Hai Wang b, Yaji Huang a, *, Jianrui Zha a, Haoqiang Cheng a, Lingqin Liu a,
Zhicheng Zhu a, Hao Chen a, Shouyi Ding a, Sheng Wang c
a
Key Laboratory of Energy Thermal Conversion and Control of Ministry of Education, School of Energy and Environment, Southeast University, Nanjing 210096, China
b
GD Power Development CO., LTD., Zhejiang Branch, Hangzhou 310012, China
c
State Power Environmental Protection Research Institute, Nanjing 210031, China

A R T I C L E I N F O A B S T R A C T

Keywords: To remove Hg0 from coal combustion flue gas efficiently and economically, a magnetically recoverable sorbent
CuCl2 fabricated by incorporating γ-Fe2O3 into attapulgite and subsequently being loaded with CuCl2 was developed
Elemental mercury removal and employed for Hg0 removal in a fixed-bed reactor. Results indicated that 0.05CuFA could eliminate more than
Attapulgite
88% of Hg0 from the SFG with HCl or not at 150 ◦ C under GHSV of 2 × 106h− 1. The surface O* and Cl* species
Coal combustion flue gas
were responsible for Hg0 oxidation, and the products of mercury were mainly HgO and HgCl2. O2 contributed to
Magnetic
Hg0 removal by regenerating the consumed O* and re-oxidizing the Cu+ and Fe2+. NO and SO2 both insignifi­
cantly affected Hg0 removal over 0.05CuFA, because CuCl2 could hinder the reaction of NO and SO2 with the
surface-active sites, leading to no nitrite species and few sulfate species produced on the surface. The reaction
between HCl and the sorbent surface, and the generation of active Cl* was less sensitive to SO2. The co-presence
of HCl and O2 was conducive to recovering the spent sorbent to its raw ability, and made the 0.05CuFA sustain 6
regeneration cycles. From the above advantageous aspects, this work provides an approach for cost-effectively
utilizing mineral for Hg0 decontamination in coal combustion flue gas, and a universal mindset for exploring
the Hg0 removal mechanism.

1. Introduction
Mercury was considered as a global pollutant and a great threat to
eco-system as a fact of its extremely toxicity, bioaccumulation, and
persistence [1,2]. Coal-fired power plants have now become the world’s
largest anthropogenic mercury emission source [3,4]. Several stringent
mercury standards to restrict Hg emission in industries, such as Mina­
mata Convention on Mercury, have been enacted in both China and the
United States [5]. Three forms of Hg exist in the coal combustion flue
gas: elemental mercury (Hg0) [6], oxidized mercury (Hg2+) [7], and
particulate mercury (Hgp) [8]. Hg2+ and Hgp can be cooperatively
captured by the existing air pollution control devices (APCDs) [9].
Whereas, Hg0 is difficult to be removed by the APCDs owing to its high
volatility and low aqueous solubility [10]. Hence, the development of
technologies for effectively removing Hg0 from coal combustion flue gas
is becoming increasingly important.
Amidst the technologies trialed for Hg0 removal, activated carbon
injection (ACI) emerges as one of the most encouraging approaches,
attributing to the large specific surface area and favorable pore size
characters of activated carbon (AC) [2]. With the help of particulate
control devices installed in most coal-fired power plants to remove
particulate matters from flue gas, the injected AC adsorbed with mer­
cury can be synergistically collected. Nonetheless, the main drawbacks
associated with the ACI that limit its extensive industrial applications
were attributed to the high operating cost and low operating tempera­
ture. Besides, the carbon-based sorbents injection will impede fly ash’s
reusability of by increasing its carbon content [11]. Therefore, it is
imperative to develop an environmentally and economically non-carbon
based sorbent to control mercury removal from coal combustion flue
gas. Up to now, various non-carbon sorbents related to, i.e., fly ash
[12,13], chalcogenides [14,15], and mineral clay [16,17], have been
widely utilized to control Hg0 emission in flue gas effectively. However,

* Corresponding author.
E-mail address: heyyj@seu.edu.cn (Y. Huang).

https://doi.org/10.1016/j.cej.2020.127888
Received 28 October 2020; Received in revised form 23 November 2020; Accepted 24 November 2020
Available online 30 November 2020
1385-8947/© 2020 Elsevier B.V. All rights reserved.
L. Dong et al.
a common problem faced by these sorbents is that the injected sorbents
loaded with mercury will be simultaneously collected by particulate
devices along with fly ash, which would also contaminate the fly ash by
the captured mercury. To alleviate this situation, various magnetic
sorbents prepared by incorporating magnetic material (Fe3O4 or
γ-Fe2O3) to zeolite [18], graphene oxide [19], and biomass activated
carbon [20], have been well developed, which make them efficiently
separated from fly ash by an external magnetic field. Dong et al. syn­
thesized a magnetic composite by incorporating Fe3O4 into zeolite and
further being loaded with silver nanoparticles, which presented a good
Hg0 retention ability from gas stream with almost mercury being
removed at temperatures up to 200 ◦ C [18]. Yang et al. incorporated
selenide [21] and CuS [22,23] with Fe3O4 to prepare the sorbents with
an extremely high mercury decontamination ability, and the Hg0
removal mechanism was proposed. Yang et al. [23] prepared
Fe3− xMnxO4/CNF sorbents for Hg0 elimination from the gas stream, the
results showed that more than 90% of Hg0 was removed from flue gas at
the reaction temperature of 150–200 ◦ C. As can be seen, extensive at­
tempts to use magnetic sorbents have been widely investigated for Hg0
removal. Yet it is still highly desirable and challenging to further
develop low-cost and high-efficiency mercury removal sorbents to
satisfy the increasing demands for Hg0 purification in coal combustion
flue gas. It has been reported that the cost of attapulgite is extremely low
with the price of only 15–20 USD/ton [24], while that of AC is 1050
USD/ton [25]. Recently, attapulgite has been utilized in pollutant pu­
rification processes, such as selective catalytic reduction of NOx [26,27],
catalytic oxidation of formaldehyde [28], and mercury removal from
flue gas [16], since it possesses a rod-like structure and a large surface
area [9]. In our previous researches, attapulgite incorporated with
γ-Fe2O3 (0.5Fe/1ATT) was prepared and used as a magnetic sorbent to
evaluate its Hg0 performance in a fixed-bed reactor system, indicating
that this magnetic sorbent has the potential to be applied in Hg0 removal
from coal-fired power plant flue gas [29,30]. However, the mercury
removal efficiency of 0.5Fe/1ATT was only 75.3% at a relatively low
hourly space velocity (about 4.0 × 105h− 1) at 150 ◦ C. Hence, it is
necessary to further improve the mercury removal activity over 0.5Fe/
1ATT to reduce the cost of this approach. Several strategies, such as
modifying with transition metal oxides [30], halogen [17,31], and metal
halide [32,33], have been used to promote mercury removal. Among
them, the metal halide modification on a sorbent surface, especially
CuCl2, has been demonstrated to be one of the most efficient strategies
for the enhanced mercury removal performance. Yang et al. [34-37]
adopted CuCl2 to modify magnetospheres to prepare a cost-effective
sorbent for removing Hg0 from flue gas, and the activity and mecha­
nism over this sorbent were systematically investigated. Besides, the
industrial scale activity test at a 50 MWth coal-fired power plant has also
been carried out. Zhou et al. [38] used CeO2-ZrO2 as a support and
loaded with CuCl2 to prepare a highly efficient Hg0 sorbent. The fixed-
bed experiments showed that this sorbent could capture 89.6%-97.1%
of Hg0 at a temperature of 100–300 ◦ C without HCl. Zhou et al. [39]
prepared 7 wt% CuCl2 modified TiO2 catalysts for Hg0 elimination, and
found that only 20% of Hg0 was eliminated from the gas stream in the
presence of N2 + O2, while the Hg0 removal efficiency could be achieved
to about 95% with the aid of HCl. As it is known that a high energy
barrier is needed to be overcome at low temperatures during the oxi­
dization of Hg0 over CuCl2 through providing a lattice Cl atom [38]. The
Cl*, which serves as the active site responsible for Hg0 oxidation, could
be obtained by the activation of lattice chlorine atom existing in CuCl2
with the help of chemisorbed oxygen species, and the chemisorbed ox­
ygen species present good activity in low temperature reactions [40]. On
account of lacking surface oxygen species over CuCl2, using supports
with chemisorbed oxygen species is necessary to elevate the Hg0
oxidation ability. As evidenced by our report that the γ-Fe2O3 based
sorbent (0.5Fe/1ATT) was confirmed to possess surface chemisorbed
oxygen, which showed a good Hg0 oxidation activity at 150 ◦ C [29]. The
presence of γ-Fe2O3 in a CuCl2 containing sorbent should be beneficial to
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Chemical Engineering Journal 408 (2021) 127888
activate chlorine atom in CuCl2 for promoting Hg0 removal. It has been
reported that CeO2-ZrO2 solid solution with a superior chemisorbed
oxygen species was suitable to support CuCl2 for efficient oxidation of
Hg0 [38]. Although the storage of adsorbed oxygen species on the sur­
face of γ-Fe2O3 is not as large as that of CeO2-ZrO2 solid solution. The
magnetic property of γ-Fe2O3 allows the sorbent to be recycled for reuse,
thereby reducing the cost of Hg0 removal. It can be inferred that the
introduction of CuCl2 into 0.5Fe/1ATT has three benefits. One is that
CuCl2 can provide active chlorine with stronger Hg0 oxidation ability.
The second is that γ-Fe2O3 can provide surface chemisorbed oxygen and
make the sorbent magnetic. The third is that the attapulgite has a rod-
like structure and larger specific surface area, resulting in a better
dispersion of active components and a larger contact area between
sorbent and Hg0, which is favorable for Hg0 retention. Hence, it is
extremely significant and worthwhile to construct 0.5Fe/1ATT with
CuCl2 to evaluate the Hg0 removal performance from coal combustion
flue gas. Additionally, it should be noted that CuCl2 will be reduced to
CuCl during Hg0 oxidation process, which causes the CuCl2 based sor­
bent/catalyst to lose Hg0 removal ability [38,39]. Fortunately, the
presence of HCl and O2 has the ability to regenerate CuCl [35]. Thereby
it is also necessary to investigate the regeneration performance of CuCl2
modified 0.5Fe/1ATT sorbent with the help of O2 and/or HCl.
In this study, the CuCl2 modified magnetic attapulgite (xCuFA) was
prepared via impregnation method with loading CuCl2 onto 0.5Fe/1ATT
composite, and employed for Hg0 removal from the coal combustion flue
gas in a fixed-bed reaction system. The role of flue gas components such
as O2, NO, SO2, H2O and HCl in the Hg0 removal were systematically
examined. Besides, the regeneration performance of the sorbent was
evaluated under different treating conditions. Various characterization
methods, including XRD, SEM, BET, XPS, VSM, and in situ DRIFT, were
used to determine the physical properties and chemistry state of the
sorbents, as well as explore the involved reaction mechanisms for Hg0
removal. This work can not only provide some references for the
development of low-cost magnetic sorbents for Hg0 removal, but also
present a universal mindset for exploring how the Hg0 could be removed
by other kinds of sorbent or catalysts.
2. Experimental
2.1. Sorbent preparation
The preparation process of the xCuFA samples is depicted in Fig. 1,
and the synthesized procedures are illustrated in Supplementary mate­
rial. Please refer to the Supplementary material.
2.2. Sorbent characterization
Please refer to the Supplementary material.
2.3. Hg0 removal activity tests
The evaluation of Hg0 removal activity over the as-prepared samples
was carried out using a fixed-bed reaction system consisting of a quartz
tube, a gas supply system, an elemental mercury generation system, and
a tube program temperature furnace, as described in Fig. S1. The total
volume gas flow rate of 2 L/min was composed of 12% CO2, 5%/10%
O2, 300/600 ppm NO, 400/800 ppm SO2, 5%/10% H2O, 5/10 ppm HCl,
and balanced N2. A stable concentration of Hg0 was provided by a
mercury permeation tube (VICI Metronics Inc, USA). The carrier gas
consisted of 400 ml/min N2 purged through the mercury tube to intro­
duce a stable Hg0 (about 95 μg/m3) to the reactor. A certain concen­
tration of water vapor was introduced by a micro-injection pump and
injected into the Teflon tube, which was heated to 110 ◦ C by using
heating tapes to generate a desired concentration of water vapor. The
inner diameter and length of the quartz tube were 8 mm and 800 mm,
respectively. The sorbents used in each test were 50 mg with particle size
L. Dong et al. Chemical Engineering Journal 408 (2021) 127888

Fig. 1. Schematic illustration for the synthesis of xCuFA samples.

ranging from 0.25 to 0.425 mm, corresponding to a gas hourly space Where Cin and Cout (μg/m3) represented the inlet and outlet Hg0 con­
velocity (GHSV) of 2 × 106h− 1. The flue gas was first flowed into the centrations of the reactor, respectively.
bypass line to stabilize the inlet Hg0 concentration before each test, then
diverted to pass through the sorbent to start the adsorption test for 120 3. Results and discussion
min. The concentration of Hg0 in the gas stream was detected by an
online VM3000 mercury analyzer (Mercury Instruments, Germany). 3.1. Sample characterization
The experimental conditions are summarized in Table 1. The effects
of CuCl2 loading amount and reaction temperature on Hg0 removal To demonstrate the successful loading of CuCl2 onto the FA surface,
performance were summarized in Set I and II. Set III was used to eval­ the phase structure of the virgin FA and xCuFA were characterized by
uate the effects of flue gas components such as O2, NO, SO2, H2O and HCl XRD results, as shown in Fig. 2. The attapulgite diffraction peaks
on Hg0 removal over 0.05CuFA. Besides, the regeneration ability of occurred at 2θ = 13.7◦ , 19.9◦ , 26.7◦ , and 35.3◦ (JCPDS No. 00-021-
0.05CuFA was also investigated, which is listed in set IV. 0550) [42,43], and the diffraction peaks for γ-Fe2O3 at 2θ values of
Generally, the Hg0 removal over CuCl2 based sorbent/catalyst can be 30.3◦ , 57.4◦ , and 62.9◦ (JCPDS No. 39-1346) [44,45] were detected for
divided into three categories: (I) a part of Hg0 is physically adsorbed on raw FA. After modified with CuCl2, the intensity of the characteristic
the sorbent/catalyst [38,41]; (II) a part of Hg0 is oxidized to Hg2+ and peaks of FA were weakened apparently, suggesting the existence of an
subsequently chemisorbed on the sorbent/catalyst surface [41]; (III) a interaction between FA and active ingredient. For 0.01CuFA and
part of Hg0 is catalytically oxidized into Hg2+ and failed to be captured 0.05CuFA, no visible peaks ascribed to copper species CuCl2 were
by the surface-active sites, hence, released to flue gas [34]. Therefore, observed, suggesting a well dispersion of CuCl2 and an amorphous phase
absorption efficiency, oxidation efficiency, and removal efficiency of of CuCl2 in the sorbent. With the increasing of CuCl2 loading amount to
Hg0 are often used to evaluate the mercury removal performance of the 0.1 or more, the peaks assigned to CuCl2⋅2H2O at 2θ values of 16.2◦ and
sorbent/catalyst. It should be noted that Hg2+ is water-soluble and could 33.9◦ (JCPDS No. 34-0775) could be obviously observed [32], indicating
be easily removed by the downstream wet flue gas desulfurization sys­ that a high loading value of CuCl2 would impede the dispersion of CuCl2
tem. Thus, considering the reduction value of Hg0 instead of the amount on the sample surface and strengthen the crystallinity of the active
of the Hg0 oxidation of the sorbent is sufficient for evaluating the ac­ components. Besides, two peaks associated with Cu2(OH)3Cl at 2θ =
tivity of the sorbent/catalyst. In this work, the Hg0 removal efficiency 32.5 and 39.9 were observed for 0.05CuFA, 0.1CuFA, and 0.15CuFA,
Erem (%) and average Hg0 removal efficiencyEave (%) were determined which could be attributed to the hydrolysis of CuCl2⋅2H2O [31,46]. It
by the equations (1) and (2), respectively: has been reported that Cu2(OH)3Cl is unstable and easily decompose to
Erem = (1 − Cout /Cin ) × 100% (1) CuCl2 by losing hydroxyl groups, resulting in promoting Hg0 oxidation
[46,47].
∑t ∑t
0 Cin− 0 Cout
The morphology of CuCl2 on the FA surface can further be revealed
Eave = ∑t × 100% (2) by SEM-EDS results, as shown in Fig. 3. Comparing virgin FA with
0 Cin
xCuFA, an obvious difference could be observed. For virgin FA (Fig. 3
(a)), the rod-like structure of the attapulgite can be seen, and some small
particles attributed to iron oxide exist on the surface of the rod-like
Table 1 structure. After CuCl2 doped, a rougher surface can be observed in
Experimental conditions. Fig. 3b-e, and a large amount of particulate matter aggregated on the
Experiment Samples Gas components Reaction surface, indicating the successful loading of CuCl2. Besides, with
temperature (oC) increasing content of CuCl2, such as 0.1CuFA and 0.15CuFA, the surface
Set I xCuFA N2 + 5% O2 150 of the sample would become more compact, indicating the pore struc­
Set II 0.05CuFA N2 + 5% O2 100, 150, 200, 250, ture has been blocked to some extent, and the active components on the
300 surface may be aggregated. The EDS analysis of the red circled area in
Set III 0.05CuFA N2 150
N2 + 5%/10% O2
Fig. 3c was performed to verify the elements in the 0.1CuFA sample, as
N2 + 300 ppm NO, N2 + 5% O2 shown in Fig. 3f. The peaks of Al, Mg, and Si are derived from atta­
+ 300/600 ppm NO pulgite, Fe peak is ascribed to iron oxide, and the peaks of Cu and Cl
N2 + 400 ppm SO2, N2 + 5% O2 confirm the successful loading of CuCl2 on the attapulgite.
+ 400/800 ppm SO2
The nitrogen adsorption–desorption isotherms of the as-prepared
N2 + 5% H2O, N2 + 5% O2 +
5%/10% H2O samples at 77 K are shown in Fig. 4. Comparing with virgin FA, the
N2 + 5 ppm HCl, N2 + 5% O2 + nitrogen uptake of CuCl2 loaded samples did not change obviously,
5/10 ppm HCl which indicated that all of the samples possess a similar pore structure.
SFG, SFG + 5 ppm HCl According to the IUPAC classification, all of the curves can be classified
Set IV 0.05CuFA SFG 150
as type II hysteresis loop, indicating a mesoporous structure [42].
SFG: N2 + 5% O2 + 12% CO2 + 300 ppm NO + 400 ppm SO2 + 5% H2O.

3
L. Dong et al.
Fig. 2. XRD patterns of FA and xCuFA (x = 0.01, 0.05, 0.1, and 0.15) samples.
According to previous studies, the mesopores are conducive to mercury
removal since the mesopores are favorable for the transportation of
mercury into the inner surface of the sorbent [38,48]. The SBET, average
pore size, and total pore volume of the as-prepared sorbents were further
analyzed, as shown in Fig. S2. When the FA impregnated with CuCl2, its
SBET and total pore volume were reduced, and the higher the CuCl2
loading, the more the SBET and total pore volume decreased. The prob­
able reason is that the internal pore structures of FA might be occupied
by CuCl2 particles during impregnation, which would result in a poor
developed pore structure of the sorbents. Besides, it can be seen that the
average pore diameter increased with increasing in CuCl2 loading
amount, which can be explained by the reason that micropores were
partly occupied by the excessive CuCl2. Meanwhile, the excessive
loading of CuCl2 could result in the formation of macropores on the
surface of the samples. It should be noted that the prepared 0.05CuFA
sample in this study possesses a relatively high SBET (more than 120 m2/
g), which is higher than that of the reported non-carbon CuCl2 based
sorbents and catalysts [32,34,38]. In general, for Hg0 removal, Hg0 at
gaseous state collides with the active sites of the sorbent/catalyst and
reacted with the active species to form oxidized mercury, wherein a
larger surface area could provide more active sites and channels for Hg0
adsorption/oxidation, then the Hg0 retention could be enhanced.
Thereby, it can be deduced that 0.05CuFA might possess a good mercury
removal ability.
It was claimed in previous literatures that the Cu and Cl species on
the sorbent surface act as active sites in Hg0 oxidation [34,49], as well as
O species that existed in metal oxides always participate in Hg0 oxida­
tion [38]. Herein, the chemical state of Cu, Cl, and O atom on the
0.05CuFA surface was identified by XPS analysis. The atom composi­
tions on the surface of the sample are shown in Table 2. As observed
from Fig. 5a, the binding energies at around 935.8 eV for Cu 2p3/2 and
955.6 eV for Cu 2p1/2 are the characteristics of Cu2+ species [31]. Be­
sides, the peak of Cu 2p3/2 at 933.5 eV and Cu 2p1/2 at 953.3 eV ev­
idence the existence of Cu+ [10], which is in agreement with the
previous report that CuCl was prone to be generated at a low CuCl2
loading amount [38]. In regard to Cl 2p XPS spectra as shown in Fig. 6a,
the peak at about 198.2 eV could be ascribed to Cl- ion in CuCl2 [50],
4
Chemical Engineering Journal 408 (2021) 127888
while the other peak at about 200.0 eV was recognized as active chlorine
atom (Cl*) [51]. The O 1 s spectra for the fresh 0.05CuFA as shown in
Fig. 7a can be deconvoluted into three main peaks, the first peak at
around 530.6 eV was corresponded to the lattice oxygen (OL) [52], the
second peak at around 531.9 eV can be attributed to the chemisorbed
oxygen (O*) [31,53], and the third peak at higher binding energy
(533.6 eV) generally accepted as hydroxyl species in adsorbed water
species (OH) [54]. As reported in previous literature that the sorbent,
with respect to using metal oxide as a support, after applied to Hg0
removal, the variation of metal cation valence could be observed [38].
Such valence change could produce active oxygen species which is
favorable for Hg0 oxidation [40]. Thereby, the Fe 2p XPS spectra was
also investigated as exhibited in Fig. S3, which can be deconvoluted into
four peaks. The peaks at about 711.6, 714.0, and 718.6 eV can be
ascribed to Fe3+ [55,56], the peak at a lower binding energy (710.3 eV)
can be identified as Fe2+ [57]. The fact that the existence of Fe2+ with a
lower valence, together with the aforementioned literature [38], it can
be inferred that the production of O* might be partly ascribed to the
reduction of Fe3+ to Fe2+ via the reaction (3). As the fact that the
characteristic peaks of mercury species silicon always overlap with each
other [58], it is necessary to determine the binding energy of silicon. As
evidenced in Fig. S4, the peak centered at about 102.4 eV can be iden­
tified as Si 2p of SiO2 in the support (attapulgite) [58].
Fe2 O3 →2FeO + O* (3)
The magnetization curves of the virgin FA and 0.05CuFA are
exhibited in Fig. S5. As demonstrated in Fig. S5, in comparison with the
raw FA, the 0.05CuFA with a 5 wt% CuCl2 loading possess the same
saturation magnetization value. No coercivity could be observed from
the curves, which indicated that the prepared sorbents were super­
paramagnetic materials [34]. The good magnetization characteristics
with a low coercivity of 0.05CuFA can prevent itself from being
permanently magnetized under an external magnetic field environment.
Hence, the aggregation of 0.05CuFA particles will not occur when the
external magnetic field disappears [59]. Besides, the saturation
magnetization value of 0.05CuFA is about 18.0 emu/g, which enables it
to be easily separated from fly ash in an external magnetic field.
L. Dong et al.
Fig. 3. SEM images of FA (a), 0.01CuFA (b), 0.05CuFA (c), 0.1CuFA (d), 0.15CuFA (e), and EDS analysis of 0.05CuFA (f) samples.
3.2. Mercury removal performance
3.2.1. Effect of CuCl2 content in the sorbent
The effects of CuCl2 loading on Hg0 removal performance over
xCuFA in N2 plus 5% O2 atmosphere at 150 ◦ C were investigated, as
presented in Fig. S6. It can be seen that when the CuCl2 was modified on
the FA surface, all the resultant xCuFA sorbents exhibited a remarkably
higher Hg0 removal activity than the virgin FA sorbent. For instance,
virgin FA sorbent eliminated no more than 40% of Hg0 from the gas
stream within 2 h, while the minimal Hg0 removal efficiency had more
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Chemical Engineering Journal 408 (2021) 127888
than 60% over xCuFA sorbents. As illustrated in BET analysis, the SBET of
xCuFA samples is all lower than the virgin FA sample, and it has been
reported that a higher SBET will result in a better physisorption of mer­
cury [60]. Therefore, the pore structure which takes part in the Hg0
physisorption over sorbents shows no effect on the Hg0 removal activity
of xCuFA, and the chemisorption of Hg0, which is determined by the
active components (CuCl2) on xCuFA surface, dominates the Hg0
retention. It should be noted that approximately 40% of Hg0 could be
removed by FA, while raw attapulgite could only capture less than 5%
Hg0. It has been validated in our previous study that the introduction of
L. Dong et al. Chemical Engineering Journal 408 (2021) 127888

Fig. 4. N2 sorption–desorption isotherms of FA and xCuFA (x = 0.01, 0.05, 0.1, and 0.15) samples.

insignificant increase of active sites on the xCuFA surface in contact with

Table 2
mercury. Besides, excessive loading amount of CuCl2 addition to the
Surface atomic ratios of different samples (Obtained from XPS).
sorbent surface may cause multilayer impregnation and block its pores
Samples Cu 2p Cl 2p O1s Fe 2p that allow Hg0 access into, which goes against the Hg0 adsorption [61].
Cu2+/Cu+ Cl*/Cl- O*/ OT OL/OT Fe3+/Fe2+ It is evidenced that the Hg0 removal performance of 0.1CuFA and
0.05CuFA fresh 3.28 0.92 0.63 0.33 3.71 0.15CuFA was comparable to that of 0.05CuFA, however, the cost of the
0.05CuFA N2 0.72 0.45 0.41 0.53 2.43 prepared sorbents increased. Hence, the conclusion can be made
0.05CuFA O2 1.96 0.63 0.54 0.41 3.02 regarding the above results that the 0.05CuFA sorbent, with 5 wt%
0.05CuFA SO2 1.16 0.81 0.35 0.62 1.96 loading of CuCl2, could be chosen as a representative to investigate the
OT represents OL + O* + OH. Hg0 removal activity of xCuFA under different reaction conditions in the
following studies.
the γ-Fe2O3 into attapulgite resulted in surface chemisorbed oxygen
species that was served as active sites for Hg0 removal [29]. In order to 3.2.2. Effect of the reaction temperature
illustrate the beneficial effect of γ-Fe2O3 in xCuFA sorbent for Hg0 The effect of temperatures in the range of 100–300 ◦ C on Hg0
removing, a fixed-bed Hg0 removal test was carried out for the removal activity over 0.05CuFA under N2 + 5% O2 atmosphere was
0.05CuATT sorbent, as exhibited in Fig. S7. It is interesting that studied as displayed in Fig. S6. A positive correlation was found between
0.05CuATT could only remove 76.2% of Hg0 from the flue gas, the Hg0 removal activity and temperature when the temperature is no more
performance of which was far inferior to that of 0.05CuFA, although than 250 ◦ C. The reaction temperature enhanced Hg0 removal as the Hg0
both of the sorbents have the same CuCl2 loading amount, implying that elimination efficiency within 2 h increased from 84.3% to 92.4% with
interaction of CuCl2 and FA might result in the generation of more active the increase of temperature from 100 to 250 ◦ C, which indicated that
species. Besides, the SBET of 0.05CuATT is 150.7 m2/g (was not exhibited elevating temperature promoted the chemical reaction between mer­
in Fig. S2), which was greater than that of 0.05CuFA (123.6 m2/g). It can cury and sorbent [62]. Besides, Cu2(OH)3Cl existed in 0.05CuFA was
be inferred that the higher Hg0 removal activity of 0.05CuFA was observed from XRD results, and would be decomposed to CuCl2 at a high
ascribed to the existence of γ-Fe2O3, in which the generated chem­ temperature, and, subsequently, contributed to Hg0 removal [46]. It can
isorbed oxygen species could activate Cl atom in CuCl2 for enhancing also be observed that 0.05CuFA exhibited a good Hg0 removal efficiency
Hg0 removing, and the 0.05CuATT sorbent was lack of such surface at a relatively low temperature (100 ◦ C), which could be ascribed to the
oxygen species. This observation confirms our above assumption. existence of active Cl species (Cl*) on the surface of 0.05CuFA (as dis­
The sorbent with a CuCl2/FA mass ratio of 0.05 exhibited high ac­ cussed in section 3.1) showing a high Hg0 oxidizability [51]. However, a
tivity and removed more than 90.8% of mercury from the flue gas. decrease in mercury removal efficiency can be found when the reaction
Nevertheless, it is noteworthy that the increase of CuCl2 loading amount temperature further increased to 300 ◦ C. The inhibition of Hg0 removal
did not improve the mercury removal performance of the xCuFA sor­ at 300 ◦ C might be interpreted by the following possible reasons: (I)
bents linearly. Further increase of the CuCl2/FA mass ratio to 0.1 and High temperature would inhibit the adsorption process of Hg0 on the
0.15 led to a slight increment of Hg0 removal efficiency for xCuFA, at sorbent surface [60]; (II) Surface adsorbed mercury species could
0.9% and 1.6%, respectively. As discussed in the sample characteriza­ release, and mercury oxide on the sorbent surface could decompose at a
tion section, poor dispersion of CuCl2 on the sample surface (Fig. 2), the high temperature [63]; (III) The decomposition of CuCl2 and loss of
aggregation of the active ingredients on the surface of xCuFA (Fig. 3), active Cl species on the surface of sorbent might be occurred at a high
and the reduction of the SBET and pore volume (Fig. S2) were observed temperature [32]. Considering that the sorbent was generally injected
with an increasing CuCl2 loading amount, thus leading to an into the flue gas upstream of the particulate control devices in a coal-

6
L. Dong et al.
Fig. 5. XPS spectra of Cu 2p over the fresh 0.05CuFA (a), and the spent 0.05CuFA sorbent reacted with Hg0 in N2 (b), 5% O2 (c), and 800 ppm SO2 (d) contain­
ing atmosphere.
fired power plant, the temperature of which is always less than 200 ◦ C,
together with that the Hg0 removal activity at 150 ◦ C over 0.05CuFA is
high. Therefore, a temperature of 150 ◦ C was chosen to conduct the
following experiments in the later work.
3.2.3. Effect of flue gas components
3.2.3.1. Effect of O2. As is known that O2 is an essential ingredient in
coal-fired flue gas, which plays an important role in Hg0 removal pro­
cess. Fig. 8 shows the Hg0 removal efficiency over 0.05CuFA under three
O2 concentrations (0, 5% and 10%). It can be found that 0.05CuFA could
remove 84.4% of mercury from the gas stream without O2, indicating a
good Hg0 removal activity of 0.05CuFA sorbent. The elimination of Hg0
on 0.05CuFA in pure N2 atmosphere could be ascribed to the reaction
between Hg0 and stored Cl species and oxygen species on the sorbent
surface (as shown in Fig. 6a and Fig. 7a), which possessed a good ability
to oxidize Hg0 without the assistance of O2. Li et al. have employed the in
situ DRIFT method to investigate the interaction mechanism between gas
components and Hg0, and found that different characteristic peaks in
DRIFT spectra for CeO2–WO3/TiO2 varied with being treated with
different flue gas components while introducing Hg0 into the IR cell,
which could then be detected by IR [51]. In order to reveal the under­
lying mechanism concerning Hg0 removal under the pure N2 atmo­
sphere, the in situ DRIFT analysis was also adopted to examine the
variation of the chemistry state on the sorbent surface after Hg0
7
Chemical Engineering Journal 408 (2021) 127888
retention. Although it is known that in situ DRIFT cannot detect the
mercury reaction directly, the alteration of relevant active functional
groups might be measured and can be used to prove the mercury reac­
tion. The in situ DRIFT experiment in a flow of about 350 ug/m3 Hg0 +
N2 stream passed through the 0.05CuFA sample as a function of time was
performed, as presented in Fig. 9. Before the mercury was introduced,
the 0.05CuFA sample had been swept with N2 for 2 h at 150 ◦ C to make
sure no peak can be observed in spectra (Fig. 9a). It is evidenced from
the curves that the characteristic peak at 1629 cm− 1 immediately
appeared after the sample contacted with Hg0 in 5 min, which indicated
that the hydroxyl group in the adsorbed H2O was generated on the
surface of 0.05CuFA [64]. As the duration of the sorbent exposed to Hg0
increased, the intensity of this peak strengthened and then kept con­
stant. The results demonstrated that the reaction between the mercury
and sample indeed occurred (reactions (4, 5)), which was in line with
the previous report that the surface-active species (O*) participated in
Hg0 oxidation process for CuCl2 based sorbent/catalyst [32,38]. In order
to further elucidate the adsorption reaction mechanism, and identify the
role of Cl species in Hg0 oxidation, the XPS characterization was
employed to investigate the chemistry state of active species on the
surface of 0.05CuFA after the Hg0 retention test as depicted in Figs. 5-7b
and Fig. S3b. Combined with the content ratios of Cu, Cl, O and Fe listed
in Table 2, compared to the fresh sorbent, the mole ratios of Cu2+/Cu+,
O*/OT, Cl*/Cl-, and Fe3+/Fe2+ all decreased after Hg0 removal reaction
over 0.05CuFA in pure N2 atmosphere. This result firstly validated the in
situ DRIFT analysis that the reaction between Hg0 and the sorbent
L. Dong et al.
Fig. 6. XPS spectra of Cl 2p over the fresh 0.05CuFA (a), and the spent 0.05CuFA sorbent reacted with Hg0 in N2 (b), 5% O2 (c), and 800 ppm SO2 (d) contain­
ing atmosphere.
surface indeed occurred, and secondly indicated that a large amount of
Cl* and O* had been consumed by Hg0 oxidation via reactions. It is well
admitted that Cl* could oxidize adsorbed Hg0 into HgCl2 directly (re­
action (8)) [39], which was responsible for Cl* consumption. It should
be mentioned that the existence of Cl* might be partly produced by the
reduction of CuCl2 to CuCl during the impregnation process (reaction
(6)) [32], as well as partly be originated from the activation of Cl- by the
surface O* (reaction (7)) [38]. As to O*, its consumption during Hg0
oxidation could also be explained by two reasons: For one thing, O*
could oxidize adsorbed Hg0 into HgO (reaction (10)); for another, O*
was participated in the activation of Cl- into Cl* (as aforementioned)
[38]. As is known that Cu2OCl2 is unstable and easily decomposed to
CuCl (reaction (9)). The decrement of Cu2+ and Fe3+ should be attrib­
uted to their reduction into a lower valence state (Cu+ and Fe2+) to
provide Cl* and O*, respectively, to sustain the Hg0 oxidation. Besides,
the HgCl2 and HgO were detected by XPS (Fig. S4b) with the charac­
teristic peaks appeared at about 101.5 eV and 104.2 eV, respectively,
which further confirmed that Hg0 was oxidized by the surface-active
sites, i.e., Cl* and O*.
As observed from Fig. 8, the addition of 5% O2 increased the Hg0
eliminate efficiency by 6.4% as compared to the case when no O2 was
added. It can be concluded that O2 played an important role in
enhancing Hg0 retention. As illustrated above, surface O* was consumed
by being participated in the conversion of Cl- to Cl*, and in the oxidation
of Hg0 to Hg2+. Consequently, O2 could regenerate the consumed
8
Chemical Engineering Journal 408 (2021) 127888
oxygen during Hg0 removing, thereby favoring Hg0 oxidation, as
described in reaction (11) [40]. As evidenced by XPS spectra showed in
Fig. 6c and 7c and atomic content listed in Table 2 that the content of Cl*
and O* on 0.05CuFA surface in 5% O2 runs was higher than that in N2-
only runs. Furthermore, the lower valence metal cations such as Cu+ and
Fe2+ on the sorbent surface would be re-oxidized by O2 [65], which was
also verified by the XPS analyses as shown in Fig. 5c and S3c. The HgCl2
and HgO could also be observed from the XPS spectra (Fig. S4c). It
should be noted that the intensity of the two characteristic peaks was
higher than that of the sorbent when reacted with pure N2 (Fig. S4b),
indicating that more Hg0 was oxidized with the aid of O2. Upon raising
the O2 concentration to 10% in the flue gas, no obvious increase of Hg0
removal efficiency (91.6%) was observed compared to that observed in
5% O2. This indicated that a low concentration of O2 (5%) was enough to
replenish the consumed oxygen, and a higher O2 concentration made
little difference.
CuCl2⋅H2O→Cu(OH)2+Cl-Cu-OH (4)
2Cl-Cu-OH+Hg0(ad)+O*→CuO+HgCl2+H2O (5)
CuCl2→CuCl+Cl* (6)
2CuCl2+O*→Cu2OCl2+2Cl* (7)
0
2Cl*+Hg (ad)→HgCl2 (8)
L. Dong et al.
Fig. 7. XPS spectra of O 1 s over the fresh 0.05CuFA (a), and the spent 0.05CuFA sorbent reacted with Hg0 in N2 (b), 5% O2 (c), and 800 ppm SO2 (d) contain­
ing atmosphere.
Cu2OCl2→CuCl+1/2O2 (9)
Hg0(ad)+O*→HgO (10)
O2(g)→2O*(ad) (11)
3.2.3.2. Effect of NO. It is well-recognized that the inclusion of NO in
the reaction atmosphere might result in the regeneration of new active
species, for instance, NO2 and nitrate species, which then oxidize the
surface adsorbed Hg0 in a sorbent/catalyst into Hg(NO3)2 or HgO
[58,66]. From this point of view, the presence of NO is beneficial to Hg0
removal. However, as shown in Fig. 8, after 300 ppm NO added into N2
and N2 + 5% O2 atmosphere, the Hg0 removal efficiency was only
increased by 2.2% and 1.6%, respectively. Further increasing NO con­
tent to 600 ppm in O2 containing atmosphere resulted in a slightly
decrement of 1.1% compared with that of under 5% O2 + 300 ppm NO
atmosphere. This observation indicated that NO exhibited insignificant
effects on the Hg0 retention activity over 0.05CuFA. For the purpose of
exploring the surface chemistry characteristics associated with the in­
duction of NO, a series of in situ DRIFT were carried out for 0.05CuFA
sorbent under the treating atmosphere of 300 ppm NO. As depicted in
Fig. 10, when 300 ppm NO was introduced into the IR cell, no
9
Chemical Engineering Journal 408 (2021) 127888
remarkable change was observed in the infrared curves, indicating that
no new nitrogen-related functional groups formed on the 0.05CuFA
surface within 10 min treating. However, after the sorbent was exposed
to NO for 15 min, an obvious peak appeared at 1626 cm− 1, which can be
identified as NO2 adsorbed on the surface [50,67]. When 0.05CuFA was
treated in NO atmosphere for 30 min, the intensity of NO2 peak was
strengthened, whereas no peak attributable to the nitrite species be­
tween 1200 and 1600 cm− 1 [67,68] appeared, indicating that the gen­
eration of nitric species, which exhibits strong Hg0 oxidization ability
[50], did not occur on the surface of 0.05CuFA. Related studies indicated
that NO could be oxidized into NO2 by the active oxygen species on the
surface of iron oxide [65,69], and the presence of NO2 is beneficial to
Hg0 removal by reacting with adsorbed Hg0 to produce HgO and Hg
(NO3)2 [50]. Notwithstanding, the formation of NO2 species was
confirmed by in situ DRIFT, such promotion effect of NO was not
observed in the activity tests (Fig. 8), which can be explained by the
following reasons. One thing is that the competitive adsorption of NO
and Hg0 could occur due to the reason that NO would react with Cu
related active sites, resulting in the reduction of active sites for Hg0
adsorption [70]. The other thing is that the generated NO2 would also
compete for the adsorption sites for Hg retention over CuCl2 containing
sorbents reported by Chiu et al. [61]. To explore whether such
competitive adsorption occurs, a desorption experiment was deliber­
ately carried out in this study, which has been used to investigate the
L. Dong et al. Chemical Engineering Journal 408 (2021) 127888

Fig. 8. Effect of flue gas components on Hg0 removal performance over the 0.05CuFA sorbent at150 ◦ C.

Fig. 9. The in situ DRIFT spectra of the 0.05CuFA sorbent treated with 350 ug/m3 Hg0 (a), and 50 ppm HCl (b) at 150 ◦ C.

competitive adsorption of SO2/H2O and Hg0 as reported by Yang et al.
[71]. Firstly, 0.05CuFA was exposed to N2 + Hg0 for 1 h. Whereafter, the
mercury supply was terminated, left the sorbent swept with pure N2 for
about 50 min until there is almost no Hg0 can be detected by VM3000,
which indicated that the surface weakly bonded Hg0 was totally
removed. Finally, 300 ppm NO was introduced into the reactor. As
shown in Fig. S8, a high value of Hg0 concentration achieved to 22.3 ug/
m3 was immediately detected and then rapidly decreased to less than 5
ug/m3 while the NO was injected, indicating that part of the weakly
chemisorbed Hg0 desorbed from the sorbent surface. As evidenced from
this observation that 300 ppm NO could repel Hg0 out of 0.05CuFA
pretreated with Hg0, verifying the competitive adsorption between Hg0
and NO. Therefore, the insignificant effect of NO on Hg0 removal ac­
tivity can be understood as a compromise between the promotion effect
of the formed NO2 on Hg0 oxidation and the competitive adsorption of
NO and Hg0.
For the sake of better understanding the influence of NO on sorbent’s
surface chemistry properties, the tests associated with the effect of NO
on Hg0 removal over CuOFA were performed, and the in situ DRIFT
experiments in the NO containing atmosphere were conducted as well.
As depicted in Fig. S7, an addition of 300 ppm NO into the gas stream
with or without O2 both resulted in a marked improvement in Hg0
eliminate activity, with an increment of Hg0 removal efficiency at 23.6%
and 20.3%, respectively. It can be observed from the fixed-bed

10
L. Dong et al.
Fig. 10. The in situ DRIFT spectra of 0.05CuFA and CuOFA sorbents treated with 300 ppm NO at 150 ◦ C.
Fig. 11. The in situ DRIFT spectra of 0.05CuFA and CuOFA sorbents treated with 800 ppm SO2 (a), and SO2 pre-treated 0.05CuFA sorbent reacted with HCl at
150 ◦ C (b).
experiments that the presence of NO plays different roles in Hg0 removal
process over 0.05CuFA and CuOFA sorbents, which can be ascribed to
the different chemical production on the surface whilst being exposed to
NO. From the curve of in situ DRIFT, as depicted in Fig. 10, several peaks,
including 1626 cm− 1 appeared after CuOFA was exposed to 500 ppm NO
for 30 min. The band at 1290 cm− 1 was ascribed to monodentate nitrate
species [72]. The peaks at 1310, 1341 cm− 1 can be identified as the N-O
stretching in bidentate nitrite species [73], whereas the peaks centered
at 1510 and 1540 cm− 1 were assigned to nitrito (O-bound NO2) and
nitrate (NO3) species [74]. This observation verified the formation of
nitrate and nitrito species on CuOFA surface with exposure to NO, which
served as active sites responsible for the promoting effect of NO on Hg0
removal. It can be inferred that the presence of CuCl2 on the 0.05CuFA
surface might hinder the interaction between NO and the iron oxide sites
on sorbent surface, hence interrupting the production of nitrate species.
11
Chemical Engineering Journal 408 (2021) 127888
A similar phenomenon was observed in the previous report that the
CuCl2 in CuCl2-modified cobalt catalyst supported on Ti-Ce composite
inhibited the reaction of NO with CoOx sites [32]. The conclusion can be
drawn with respect to the behavior of in situ DRIFT for 0.05CuFA and
CuOFA treating with NO that the insignificant effect of NO on the Hg0
elimination over 0.05CuFA should be partly ascribed to no nitrate spe­
cies formation on 0.05CuFA surface.
3.2.3.3. Effect of SO2. The effect of SO2 on Hg0 adsorption over
different sorbents was complicated and still not conclusive. Either
detrimental or promotional effects of SO2 on Hg0 removal was obtained
in previous reports [75,76]. It is hence imperative to ascertain the in­
fluence of SO2 on mercury elimination over the 0.05CuFA sorbent. As
shown in Fig. 8, the inhibition effect of SO2 on Hg0 removal activity for
0.05CuFA was observed whether in the presence of O2 or not. Several
L. Dong et al.
conclusions have been made in previous literatures that the negative
effect of SO2 could be attributed to the following three aspects
[33,76,77]: (I) The competitive adsorption of SO2 and Hg0 for the same
active sites on a sorbent/catalyst surface as a consequence of the affinity
of which for SO2 was much higher than that for Hg0. (II) The surface
chemisorbed oxygen species, which is beneficial to Hg0 oxidation as well
as able to activate Cl- into active Cl* species, could be consumed via
reacting with SO2. (III) The sulfation of a sorbent/catalyst could occurr
with the inclusion of SO2. To check the negative effect of route (I), a
similar desorption test (see in section 3.2.4.2) was performed by using
SO2 as a desorption gas. As depicted in Fig. S8, almost no Hg0 could be
detected at the outlet of reactor after the SO2 injection, suggesting that
SO2 was incapable of repelling the surface bounded Hg0 out of the Hg0
pretreated sorbent. It can be inferred that the competitive adsorption
between SO2 and Hg0 played an insignificant role in the SO2 induced
reduction of Hg0 elimination activity. We further introduced O2 to the
gas stream to check the route (II), as seen from Fig. 8. When there was no
O2 in the flue gas, the addition of 400 ppm SO2 resulted in a decrement
of 8.3% in the Hg0 removal efficiency. However, with the aid of 5% O2,
the inhibitory effect of SO2 could be obviously alleviated with an
increment of Hg0 removal efficiency by 10.1% as compared to that
without O2. It seemed that route (II) was responsible for the deactivation
of Hg0 removal ability of the sorbent as the consumed oxygen species by
SO2 on the sorbent surface can be recovered in the presence of O2. To
verify whether the deterioration of Hg0 removal activity was completely
resulted from the route (II), a SO2 transient response experiment was
conducted over the 0.05CuFA sorbent. As shown in Fig. S9, the Hg0
removal efficiency of 0.05CuFA in the atmosphere of Hg0 plus 5% O2
gradually decreased to 91.3% at the 40th min. When 400 ppm SO2 was
introduced into the gas stream at the 40th min, a negative trend was
observed as the Hg0 removal efficiency decreased to 84.9% with 60 min
reaction. However, when the inclusion of SO2 in the gas stream was
terminated at the 100th min, the Hg0 removal efficiency was only
restored a bit (89.6%) and subsequently declined gradually to 86.0% at
the 160th min. This observation shows that the inhibitory effect of SO2
could not be completely eliminated after SO2 was cut-off even if O2 was
still existed in the gas stream, although the presence of O2 could recover
the surface oxygen species which were consumed by reacting with SO2.
Consequently, the negative effect of route (II) was not sufficient to
explain the deactivation caused by SO2 addition alone. In addition, route
(III) should also be taken into consideration. Related studies show that
some inert species such as sulfates are generated on a sorbent/catalyst
after its exposure to SO2 [77], which are in favor of the possibility of the
route (III). In this section, XPS and in situ DRIFT were employed to
0.05CuFA sorbent’s surface chemistry state as a result of treating with
SO2. The 0.05CuFA sorbent was pre-treated with 800 ppm SO2 + Hg0 for
6 h, and then be used to conduct an XPS characterization. From the
combination of the XPS spectra showed in Figs. 5-7b and S3, and surface
atom content ratios listed in Table 2, several conclusions can be made.
The first thing is that the content of O* and Cl* on the sorbent surface
was less than that on the sorbent treated without SO2, which should be
attributed to the reaction of O* and SO2 resulting in the consumption of
O*, and then hindered the activation of Cl- to Cl*. The other thing is that
a new peak located at around 712.8 eV for Fe 2p spectra and a new peak
centered at about 523.4 eV for O 1 s spectra were observed, suggesting
the generation of Fe2(SO4)3 and SO2- 4 [78], respectively. Hence, it is well
accepted that the surface O* consumption and sulfation could be
responsible for the slight decrease in Hg0 removal efficiency in the
presence of SO2. The in situ DRIFT of SO2 adsorption experiments were
conducted to elucidate the SO2 adsorption behavior on 0.05CuFA.
Fig. 11 records the in situ DRIFT spectra of SO2 adsorption on the
0.05CuFA sorbent at 150 ◦ C as a function of time. With the sorbent
exposure to 800 ppm SO2 for 5 min, several bands at 1340 and 1373
cm− 1 appeared, which were ascribed to the asymmetric stretching vi­
bration of O = S = O in sulfate [79,80]. With the increasing treating
time, some new peaks at the band of 1240 and 1263 cm− 1 were
12
Chemical Engineering Journal 408 (2021) 127888
observed, which could be attributed to the sulfate [81] and the splitting
of triply degenerate asymmetric (ν3) stretching vibration of S-O bond in
sulfate [79], respectively. It is evidenced from this observation that the
sulfation of 0.05CuFA surface has indeed happened in the presence of
SO2. Additionally, we cut-off the SO2 stream and left N2 flowed into the
IR cell sweeping the 0.05CuFA sample for 30 min, the corresponding in
situ DRIFT spectra was shown in Fig. 11b. As observed from the spectra
that the peaks at 1240 and 1263 cm− 1 were still remained while the
peaks at 1340 and 1373 cm− 1 were disappeared, indicating that some
sulfur related sulfate species was weakly adsorbed on the surface and
could partly be blown off the surface by N2. This observation could
explain the results in the SO2 transient response experiment that the
demercuration performance could be restored to some extent after SO2
was cut-off.
To better understand the role of CuCl2 on 0.05CuFA surface in the
reaction of the sorbent with SO2, a series of Hg0 elimination tests and an
in situ DRIFT experiment for CuOFA, without any Cl species on the
surface of which, was performed in the SO2 containing atmosphere as a
comparison. As shown in Fig. S7, the Hg0 removal efficiency of CuOFA in
the atmosphere of 5% O2 + 400 ppm SO2 and 5% O2 + 800 ppm SO2 was
decreased by 16.3% and 21.5%, respectively, compared to that in the
5% O2-only atmosphere. These results indicated that the poisoning ef­
fect of SO2 on Hg0 removal activity over 0.05CuFA was inferior to that
over CuOFA. We assume that this difference in Hg0 removal perfor­
mance of the two sorbents caused by SO2 may be due to the different
sulfur species generated on the sorbent surface under the reaction of
SO2. To confirm this proposal, we deliberately conducted an in situ
DRIFT adsorption of 800 ppm SO2 at 150 ◦ C to reveal the states of sulfate
species for exploring the interaction between SO2 and CuOFA. As shown
in Fig. 11a, after CuOFA was sulfated by SO2 for 30 min, various peaks
located at in the range of 1000–1600 cm− 1 can be found on the sulfated
sorbent. Among these peaks, the bands at 1240, 1263, 1340, and 1373
cm− 1 that appeared in the DRIFT spectra of 0.05CuFA were also
observed for CuOFA, whereas the peak at 1240 cm− 1 for 0.05CuFA was
not observed for CuOFA. Additionally, some new peaks at 1180, 1210,
1294, and 1315 cm− 1 were observed for CuOFA. Among them, bands at
1180, 1294, and 1315 cm− 1 could be attributed to bulk-like sulfates
[82,83], while the peak at 1210 cm− 1 was ascribed to bidentate sulfate
complex [84], indicating that more sulfur related species were produced
on the CuOFA surface compared to 0.05CuFA. It should also be noted
that the bulk-like sulfates were unfavorable to the catalytic oxidation
activity, and exhibited more harmful impacts on the oxidation activity
compared to the sulfate species as reported in previous literatures
[83,85]. An interesting situation could be seen that the peak at 1641
cm− 1 assigned to the adsorbed H2O was appeared [64,86], which was
generated by the reaction of SO2 and surface groups over CuOFA [84].
However, such a feature was not found for 0.05CuFA, indicating that
more SO2 reacted with CuOFA than that with 0.05CuFA, which might be
attributed to the existence of CuCl2 on the surface of 0.05CuFA prevents
the bonding of SO2 to its surface. Besides, we further conducted an XPS
characterization of CuOFA sorbent, which was pretreated in Hg0 + 800
ppm SO2 for 6 h as shown in Fig. S10. A new peak could be fitted at
around 936.5 eV from the Cu 2p spectra indicating the formation of
CuSO4 [32,87], which further confirmed that CuOFA was more sus­
ceptible to sulfur poisoning than 0.05CuFA due to the fact that such peak
ascribed to CuSO4 was not found in the XPS spectra of 0.05CuFA
(Fig. 5d). According to the results of the XPS and in situ DRIFT, the better
Hg0 removal ability of 0.05CuFA compared to that of CuOFA can be
interpreted as follows that the presence of CuCl2 could alleviate the
affinity of SO2 to sorbent surface, as well as prevent the bulk-like sulfate
formation on the sorbent surface.
Furthermore, increased SO2 concentration to 800 ppm in 5% O2
containing atmosphere led to a further slight decrease of Hg0 removal
activity (Fig. 8). The results were attributed to the reason that a higher
content of SO2 would speed up the sulfation of the sorbent as well as the
surface oxygen species consumption [32], hence, resulting in the loss of
L. Dong et al.
Hg0 oxidation activity. It should be noted that 0.05CuFA could still
eliminate more than 84% of Hg0 from the flue gas, showing a good sulfur
resistance performance.
3.2.3.4. Effect of H2O. H2O inevitably exists in the coal-fired power
plants flue gas and always impedes Hg0 removal. Therefore, it is
important to investigate the effect of H2O on the activity of 0.05CuFA.
As depicted in Fig. 8, when 4% H2O was introduced into the gas stream
with or without O2, both a slight inhibitory effect on Hg0 removal per­
formance could be observed. Increasing the H2O concentration to 8% in
O2 containing atmosphere led to a decrease of Hg0 removal efficiency to
87.2%. The negative effects of H2O might be ascribed to the competitive
adsorption between H2O and Hg0 [88]. This can be clarified by a
desorption experiment similar to a NO desorption test (see in section
3.2.4.2) as exhibited in Fig. S8, from which a Hg0 concentration peak
can be clearly observed, suggesting that the competitive adsorption
happened as a consequence of the adsorbed mercury on the sorbent
surface could be partly expelled by H2O. It is worth noting that the Hg0
removal efficiency under the H2O containing atmosphere was not much
reduced compared to that under the H2O-free atmosphere with a
maximum decrement of 3.4%, suggesting a good H2O resistance per­
formance for the 0.05CuFA sorbent.
3.2.3.5. Effect of HCl. In the coal-fired flue gas, HCl is always consid­
ered as an important factor for the control of Hg0. Especially for the Cl-
based sorbents/catalysts that Cl species on the surface serves as active
sites for Hg0 oxidation and is consumed during the Hg0 oxidation pro­
cess. The presence of HCl in the gas stream can enhance Hg0 oxidation
and replenish the consumed Cl species on the sorbents/catalysts’ sur­
face, and the latter aspect was of benefit to Hg0 oxidation, too [32,35].
Therefore, it is imperative to investigate the role of HCl in Hg0 elimi­
nation process over 0.05CuFA sorbent. As evidenced in Fig. 8, the
introduction of 5 ppm HCl into N2 shows a marked improvement in Hg0
retention activity, with about 93% of Hg0 being eliminated from the gas
stream. This result was in line with previous reports that the presence of
HCl facilitates Hg0 elimination over a sorbent/catalyst [32,34]. To
explore the removal mechanism of Hg0 in the presence of gas HCl over
0.05CuFA, the in situ DRIFT and XPS were carried out. Although the Cl
related groups cannot be identified by IR detector, the variation of
surface functional groups except for Cl might be detected, if such
changes occurred in treating with HCl. Hence, we recorded the in situ
DRIFT spectra for 0.05CuFA in 50 ppm HCl flow at 150 ◦ C as a function
of time, in which the HCl concentration was several times of that in the
Hg0 removal test for the sake of allowing enough HCl to react with the
sorbent surface. Hence the generated groups could be detected by IR
quickly. As demonstrated in Fig. S11, after 0.05CuFA treating with HCl
for 10 min, an obvious peak appeared at 1626 cm− 1 could be assigned to
the hydroxyl in adsorbed H2O [64]. This observation indicated that the
reaction between HCl and the surface of 0.05CuFA sorbent really
happened, which might be interpreted by the reactions (12–13) that at
one hand, the CuCl would react with HCl to produce CuCl2 and H2O
(reaction (12)) [32,39], on the other hand, the adsorbed HCl would be
activated by surface O* to generate active Cl* and H2O (reaction (12))
[40]. Besides, an XPS analysis over 0.05CuFA was conducted after 6 h
adsorption of Hg0 in the presence of 10 ppm HCl, the spectra of which
with respect to Cu and Cl were correspondingly exhibited in Figs. S12a
and b. In contrast to the sorbent adsorbing Hg0 in the N2 only, the peak
of Cu2+ was much stronger, suggesting that HCl contributed to re-
chlorinate CuCl to CuCl2 to regain the Hg0 retention ability for
0.05CuFA [49]. With respect to the analysis of Cl spectra, the area of Cl*
characteristic peak was also larger than that of the sorbent treated
without HCl, indicating the Cl* on the sorbent surface could be attained
by the activation of adsorbed HCl with the help of O*. From the Hg 4f
spectra of the sorbent treated within HCl, the peak of HgCl2 was much
stronger than that of HgO, indicating that a greater proportion of HgCl2
13
Chemical Engineering Journal 408 (2021) 127888
is generated on the surface (Fig. S12c). The results of XPS analyses were
well confirmed the Hg0 removal mechanism in the presence of HCl
elucidated by in situ DRIFT.
2CuCl+2HCl(ads)→2CuCl2+H2O (12)
2HCl(ads)+O*→2Cl*+H2O (13)
As obtained from the above investigation, SO2 could impair Hg0
removal ability of 0.05CuFA in the absence of HCl, therefore, it is
meaningful to explore the effect of SO2 on demercuration activity in the
presence of HCl. As shown in Fig. 8, adding 400 ppm SO2 into 5 ppm HCl
atmosphere led to a decrease of Hg0 removal efficiency at 2.1%, whereas
introducing 400 ppm SO2 to 5% O2 atmosphere resulted in a decrease in
Hg0 removal activity of 4.6%. This observation indicated that the
inhibitive effect of SO2 on Hg0 elimination activity over 0.05CuFA in
HCl containing atmosphere was inferior to that in O2 containing atmo­
sphere. This might be due to the assumption that SO2 could seldom
hinder the activate process of HCl on the sorbent surface. To confirm this
speculation, the in situ DRIFT was also conducted as depicted in Fig. 11b.
At first, the sorbent SO2 pretreated sorbent (as depicted in section
3.2.4.3, see from Fig. 11a) was swept with N2 for 30 min. Then HCl was
introduced into the IR cell. It can be seen that the peak at 1623 cm− 1
immediately emerged after the sorbent was contacted with HCl, and the
peak intensity strengthened with exposure time. The observation was
similar to the behavior of HCl treatment on 0.05CuFA without SO2, as
recorded in Fig. S11. The results suggested that the reaction between
HCl and sorbent might not be disturbed by SO2 pretreatment, which also
verified our assumption. Both Hg0 retention fixed-bed test results and in
situ DRIFT analysis were consistent with previous reports that the active
Cl* generated on the sample’s surface in the presence of HCl was less
sensitive to SO2 [89,90].
However, when HCl concentration further increased to 10 ppm from
5 ppm, an insignificant increase of Hg0 removal efficiency increased
with an increment of 2.1%. This result indicated that a low HCl con­
centration would achieve the supplement of the consumed Cl species
and the re-oxidization of Cu+ to Cu2+, increasing the content of HCl in
flue gas showed insignificant improvement of the Hg0 removal ability.
As it is known that the composition of the flue gas is complicated and
it is necessary to evaluate the Hg0 removal activity over 0.05CuFA under
the simulated coal combustion flue gas atmosphere for the possible
application in actual coal-fired power plants. Hence, the Hg0 removal
activities over 0.05CuFA in the SFG and SFG + 5 ppm HCl atmosphere
were evaluated, and the results are shown in Fig. 8. It can be found that
85.7% of Hg0 could be eliminated from flue gas under the SFG atmo­
sphere, which performed better than that under the pure N2 atmosphere.
As reported in previous studies, although SO2 and H2O in flue gas could
inhibit the Hg0 removal ability of 0.05CuFA, the presence of NO could,
to some extent, alleviate this inhibitory effect [30]. Besides, when 5 ppm
HCl was added into SFG atmosphere, a better Hg0 removal performance
could be acquired with 92.4% of Hg0 being removed within 2 h, indi­
cating a promotion effect on Hg0 removal induced by HCl. The conclu­
sion can be deduced through all the forenamed results, that is, 0.05CuFA
has the potential to be used as a sorbent to applied in Hg0 removal from
the coal-fired power plant flue gas whether in the presence of HCl or not.
3.3. Regeneration ability of the sorbent
Although the as-prepared 0.05CuFA sorbent exhibited a highly
effective Hg0 removal performance, the regeneration behavior of the
sorbent is of considerable importance for industrial application. There­
fore, a recycling test on the Hg0 removal activities under SFG atmo­
sphere of the 0.05CuFA sorbent was performed. Based on the
aforementioned results, mercury species, such as HgO and HgCl2, were
formed on the 0.05CuFA sorbent surface. Besides, HgSO4 might be
generated on the sorbent surface in reacting with a SO2 containing at­
mosphere, although it was not detected in the XPS analyses (Fig. S4d). In
L. Dong et al.
order to regenerate the spent sorbent, it needs to be firstly heated to
decompose the mercury species on its surface for releasing sites that
bind to mercury, and then pretreated with an O2 and/or HCl containing
atmosphere to regenerate the active sites for Hg0 capture. As reported in
the previous study, a regeneration temperature of 400 ◦ C was appro­
priate to decompose most mercury species without decomposition and
volatilization of CuCl2/CuCl [91]. Additionally, the mercury on the
sorbent’s surface could be released and collected via the thermal
regeneration method, benefiting the mercury recovery for the sake of
avoiding the secondary pollution caused by mercury. In this study, the
spent 0.05CuFA sorbent was heated at 400 ◦ C for 2 h under the N2 + 5%
O2, N2 + 20 ppm HCl, and N2 + 5% O2 + 20 ppm HCl atmosphere, and
the corresponding regenerated adsorbents were denoted as 0.05CuFA-R,
0.05CuFA-NCl-R, and 0.05CuFA-Cl-R, respectively. After each regener­
ation step, 0.05CuFA-R, 0.05CuFA-NCl-R, and 0.05CuFA-Cl-R were then
separately placed in the fixed-bed reactor to adsorb Hg0 under the SFG
atmosphere to evaluate their activity, and the results are shown in
Fig. S13. For 0.05CuFA-R and 0.05CuFA-NCl-R, their mercury removal
efficiency gradually decreased with increasing regeneration times, only
70.1% and 78.6% of Hg0 could be removed from the flue gas after six
regeneration times. The poor regeneration performance of 0.05CuFA-R
and 0.05CuFA-NCl-R could be interpreted by the reason that the CuCl
and Cl* species, which were reduced by CuCl2 and consumed, respec­
tively, during the Hg0 oxidation, could not be effectively re-oxidized to
CuCl2 by O2 and HCl separately. However, as to 0.05CuFA-Cl-R, no
obvious reduction of Hg0 removal efficiency appeared after six cycles of
adsorption, indicating that CuCl could be totally re-oxidized and re-
chlorined to CuCl2, as well as the consumed Cl* could be recovered by
the co-existence of O2 and HCl. In order to further illustrate the effect of
HCl on 0.05CuFA surface, an in situ DRIFT experiment on Hg0 pre-
treated sorbent (as depicted in section 3.2.4.1, see from Fig. 9a)
within the inclusion of HCl was performed. The sorbent in the IR cell was
firstly purged with N2 to blow the reactants off the surface, as shown in
Fig. 9a, the peak at 1629 cm− 1 became smaller after 10 min and dis­
appeared after 30 min. After the sorbent purged with N2 for 100 min, a
negative peak at 1629 cm− 1 appeared, indicating that the hydroxyl
groups generated after the adsorbent surface adsorbed Hg0 had dis­
appeared, and the surface chemical state was indeed changed. Next, HCl
was introduced into the IR cell and observed the changes in functional
groups on the surface of the adsorbent. As exhibited in Fig. 9b, the
negative peak at 1629 cm− 1 was immediately weakened once the sample
in contact with 50 ppm HCl, indicating the occurrence of reaction be­
tween HCl and the sorbent surface. Since the peak appeared in the
spectra attributed to the adsorbed H2O on the sorbent surface that had
been purged by N2, hence, the reduction of the peak suggested that the
surface adsorbed H2O might be replenished via the treatment of HCl,
which can also be interpreted by reactions (12–13). However, it can also
be observed from Fig. 9b that the peak at 1629 cm− 1 almost no longer
decreased after 30 min with the HCl treatment, indicating that the HCl
alone cannot recover the sorbent surface the original state. Conse­
quently, we introduced 5% O2 into the IR reaction cell to detect the
variation of the sorbent surface, and the in situ DRIFT spectra was also
recorded as shown in Fig. 9b. It can be found that the intensity of the
peak associated with adsorbed H2O monotonically decreased with time
and finally almost disappeared after treated with 20 min, which implied
that the presence of O2 replenished and regenerated the surface-active
oxygen species on the surface and hence contributed to recover the
used sorbent to the original state. The combination of the fixed-bed
experiments and in situ DRIFT results indicated that both HCl and O2
were required to regenerate the Hg0 pre-treated 0.05CuFA sorbent,
which is in accordance with the previous report that both HCl and O2 are
indispensable to the regeneration of CuCl to CuCl2 as illustrated by re­
action (14) [49]. It should be pointed out that although the effect of flue
gas components, e.g. NO, SO2, and H2O, as well as the regeneration
temperature on the Hg0 retention performance over 0.05CuFA were not
taken into consideration when we conducted the in situ DRIFT
14
Chemical Engineering Journal 408 (2021) 127888
experiments with respect to treating with HCl, the results obtained
above could still explain to a certain extent that the co-existence of HCl
and O2 in the gas stream are conducive to recover the spent sorbent to its
raw Hg0 removal ability.
2CuCl+1/2O2+2HCl→2CuCl2+H2O (14)
In addition, the magnetic property of the regenerated sorbent should
be taken into consideration to explore whether it can be effectively
separated from the fly ash by applying an external magnetic field after
injection into the flue gas. As depicted in Fig. S5, the saturation
magnetization of the 0.05CuFA-Cl-R sorbent with 6 regeneration times
showed an ignorance decrease comparing with the fresh sorbent.
Therefore, 0.05CuFA has the ability to be recycled for Hg0 removal from
the coal combustion flue gas with high activity and magnetic, and the
cost of Hg0 removal can be significantly reduced. Together with the
results of Hg0 removal over 0.05CuFA tested in various conditions
aforementioned above, it can be concluded that 0.05CuFA was trust­
worthy at least under laboratory test conditions. In the future work, the
0.05CuFA sorbent will be tested in a pilot-scale coal-fired facility, a
0.3MWth circulating fluidized bed combustion boiler which has been
successfully used to test our as-prepared NH4Br-modified rice husk char
injection into the flue duct before a fabric filter to capture mercury from
flue gas [92], to further investigate its stability and explore its possibility
of industrial application.
4. Conclusion
A magnetic support (FA) with a high specific surface area was pre­
pared by incorporating γ-Fe2O3 into attapulgite, further introducing
CuCl2 into FA via impregnation method could synthesize an effective
and recyclable sorbent (xCuFA) for Hg0 removal from coal-fired flue gas.
The activity of the sorbent was evaluated in a laboratory-scale fixed-bed
system, and the mechanism underlying the effect of flue gas components
on removal of Hg0 was determined by various characterization methods
such as XRD, SEM, BET, XPS, VSM, and in situ DRIFT. Results indicated
that the 0.05CuFA sorbent with a 5 wt% CuCl2 loading amount was
proved to be eligible for Hg0 removal as a result of its high activity and
cost effectiveness. More than 88% of Hg0 at 150 ◦ C was eliminated from
the SFG in the absence and presence of HCl with a GHSV as high as 2 ×
106h− 1. The active oxygen species (O*) on the sorbent surface, provided
by γ-Fe2O3, played a key role in contributing to Hg0 oxidation and Cl-
activation. O* was consumed during Hg0 retention process. The addition
of O2 was beneficial to Hg0 removal as a result of regenerating the
consumed O* and re-oxidizing the Cu+ and Fe2+. The negligible effect of
NO on Hg0 removal activity was attributed to a compromise between the
promotion effect of the formed NO2 on Hg0 oxidation and the compet­
itive adsorption of NO and Hg0. Besides, the presence of CuCl2 on
0.05CuFA surface might hinder the interaction between NO and the iron
oxide sites on the sorbent surface, which hindered the generation of
nitrate species. The detrimental effect of SO2 on Hg0 elimination activity
over the 0.05CuFA sorbent in the absence of O2 could be attributed to,
on the one hand, the consumption of O*, which would weaken the Hg0
oxidation and inhibit the activation of Cl to Cl*, and, on the other hand,
the sorbent surface sulfation, i.e., the generation of Fe2(SO4)3. However,
the presence of O2 could alleviate this negative effect as a result of
regenerating and replenishing the consumed O*. It is interesting to note
that although the inhibition effect of SO2 on Hg0 activity was observed,
the 0.05CuFA sorbent still retained a well Hg0 eliminated ability
whether in the presence of O2 or not. This could be ascribed to the reason
that the CuCl2 existed on the surface alleviated the affinity of SO2 and
the surface-active sites, as well as prevented the sulfation of copper and
the formation of bulk-like sulfate, as observed from XPS and in situ
DRIFT results. H2O in the gas stream inhibited Hg0 retention due to the
competitive adsorption between H2O and Hg0. HCl benefited Hg0
oxidation removal due to the fact that the adsorbed HCl could be
L. Dong et al.
activated by surface O* to regenerate the consumed Cl* species on the
sorbent surface, as well as re-chlorinate CuCl to CuCl2. More HgCl2 was
generated on sorbent surface in the presence of HCl compared to the case
when no HCl was present. SO2 in the flue gas exhibited an insignificant
effect on Hg0 elimination activity in the presence of HCl. This was
ascribed to the reason that SO2 could hardly impair the reaction between
HCl and sorbent, and the active Cl* generated on the sample’s surface in
the presence of HCl was less sensitive to SO2. The spent sorbent cannot
be restored to the original activity by regeneration in O2 and HCl
separately, whereas the co-existence of HCl and O2 in the gas stream was
conducive to recover the spent sorbent to its raw Hg0 removal ability. As
stated above, CuCl2 modified magnetic attapulgite sorbent possesses
certain advantages related to its high Hg0 decontamination activity,
sound SO2 resistance ability, good magnetism, and excellent regener­
ability that render it environmentally and cost-effectively promising for
Hg0 decontamination in coal-fired power plants flue gas. What’s more,
the methods used in this study, i.e., activity tests combined with XPS and
in situ DRIFT characterization, to reveal the mechanism for Hg0 capture
over the 0.05CuFA sorbent and the effect of flue gas components on Hg0
removal, is universal, which can also be employed to explore how other
kinds of sorbents or catalysts remove Hg0 in the flue gas.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgements
This work was financially supported by the National Key R&D Pro­
gram of China (2018YFC1901200), the National Natural Science
Foundation of China (51976036), the Jiangsu Province Natural Science
Foundation (BK20181281), the Scientific Research Foundation of
Graduate School of Southeast University (3203009703)
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.cej.2020.127888.
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