Fuel Processing Technology 159 (2017) 266–271

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Fuel Processing Technology

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Research article

Heterogeneous reaction kinetics of mercury oxidation by HCl over

Fe2O3 surface
Yingju Yang, Jing Liu ⁎, Zhen Wang, Feng Liu
State Key Laboratory of Coal Combustion, School of Energy and Power Engineering, Huazhong University of Science and Technology, Wuhan 430074, China

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

Article history: Fe2O3 is one of the catalytically active compositions present in fly ash for mercury oxidation. Fe2O3 sample was
Received 22 August 2016 prepared by a precipitation method. The textural property and surface chemical state of Fe2O3 sample were char-
Received in revised form 14 January 2017 acterized by Brunauer-Emmett-Teller (BET) surface area and X-ray photoelectron spectroscopy (XPS), respec-
Accepted 19 January 2017
tively. A series of experiments were conducted in a fixed-bed reactor to investigate the heterogeneous
Available online xxxx
mercury oxidation by HCl on Fe2O3 surface. Fe2O3 can obtain a maximum mercury oxidation efficiency of
Keywords:
89.5% at 100 °C. Heterogeneous Hg0 oxidation by HCl over Fe2O3 surface occurs through the gas-solid reaction
Mercury oxidation between gas-phase Hg0 and active surface chlorine species generated from the dissociation of HCl. Based on
Heterogeneous kinetic model the experimental results, a detailed eight-step heterogeneous reaction kinetic model of mercury oxidation
Kinetic calculations over Fe2O3 was proposed to predict mercury oxidation in the presence of Fe2O3 and HCl. This heterogeneous
Fe2O3 model was validated by comparison to different experimental data. The results of kinetic calculations show
that model prediction is in good agreement with experimental results obtained by two research groups. Mercury
oxidation process over Fe2O3 surface can be described using this heterogeneous kinetic model.
© 2017 Elsevier B.V. All rights reserved.

1. Introduction
Mercury (Hg), a global hazardous atmospheric pollutant, has
attracted considerable public concern due to its toxicity, high volatility,
persistence, and bioaccumulation in the ecosystem and food chain
[1–3]. In recent years, the total anthropogenic mercury emissions
have been dominated by coal-fired power plants [4–6]. In 2013, the
U.S. Environmental Protection Agency (EPA) updated the mercury
emission limits for existing power plants under the Mercury and Air
Toxics Standards (MATS) with a maximum emission concentration
between 1.4 and 4.1 μg/m3 (STP, dry) at 6 vol.% O2 [7]. Therefore, it is
an urgent concern to make efforts to effectively control mercury emis-
sions from coal-fired power plants.
Mercury removal efficiency of coal-fired power plants is highly af-
fected by mercury speciation in flue gas [8–10]. Mercury in coal-fired
flue gas mainly exists in three forms: elemental mercury (Hg0), oxi-
dized mercury (Hg2+) and particulate bound mercury (Hgp) [11–13].
During coal combustion, mercury is released from coal in its elemental
form which is difficult to be captured and removed by the existing air
pollution control devices because of its water insolubility and chemical
inertness [14,15]. As flue gas is cooled, some of Hg0 is oxidized into
Hg2 + through a lot of homogeneous reactions and heterogeneous
gas-solid interactions [14,16]. Water-soluble Hg2 + is easily captured
⁎ Corresponding author.
E-mail address: liujing27@mail.hust.edu.cn (J. Liu).
by the wet flue gas desulfurization (WFGD) system. Hg2+ can also be
adsorbed on fly ash as Hgp and subsequently collected by particulate
control devices such as electrostatic precipitators (ESP) and fabric filters
(FF) [17,18]. Mercury transformation (homogeneous and heteroge-
neous reactions) in flue gas is kinetically limited [8,16]. Therefore, the
fundamental investigation for the reaction kinetics of mercury transfor-
mation is critical for the effective mercury emission control.
To date, a lot of homogeneous reaction kinetic models have been
proposed to predict the homogeneous mercury oxidation in simulated
flue gas [8,9,19–21]. However, the homogeneous kinetic model is inca-
pable of predicting successfully mercury oxidation in coal combustion
flue gas, because the suspended fly ash particles can exhibit catalytic
effects on mercury oxidation [22,23]. In the post furnace regions, the
heterogeneous reaction kinetics plays an important role in mercury
transformation in coal-fired flue gas [16,24]. A three-step heterogeneous
reaction kinetic model was proposed to describe mercury oxidation by
HCl over unburned carbon (UBC) surface [22,23]. However, the catalytic
activity of Fe2O3 present in fly ash was not considered in this heteroge-
neous model. Thus, this model is unable to interpret the distinctive
mercury oxidation over fly ash with high contents of iron oxides.
Several studies [25–27] have been conducted to investigate the
effects of Fe2O3 present in fly ash on mercury oxidation. Bhardwaj
et al. [28] reported that Fe2O3 within fly ash exhibits catalytic oxidation
activity for mercury oxidation. It was found that 90% mercury oxidation
efficiency could be attained by exposing model fly ash containing Fe2O3
to simulated flue gas stream at 250 °C [29]. In the absence of Fe2O3, the

http://dx.doi.org/10.1016/j.fuproc.2017.01.035
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 Y. Yang et al. / Fuel Processing Technology 159 (2017) 266–271
extent of mercury oxidation decreased from 90% to 10%. However, it is
difficult to investigate the heterogeneous mercury oxidation over
Fe2O3 in these experiments, because mercury oxidation is also affected
by other fly ash compositions, such as unburned carbon and copper
oxide. Therefore, it is necessary to design experiments to separate the
catalytic effects of Fe2O3 on mercury oxidation. Mercury removal by
nanoparticle Fe2O3 sorbent was investigated at a single temperature of
80 °C [30], however, the effect of reaction temperature on mercury ox-
idation was not considered. Moreover, the chemical reaction kinetics of
mercury oxidation over Fe2O3 was also not investigated. Therefore, the
understanding of mercury oxidation process over Fe2O3 surface is still
uncertain because of the lack of knowledge about the detailed reaction
kinetics.
In this work, the heterogeneous mercury oxidation experiments
were conducted at different reaction temperatures. The corresponding
experiments were designed to verify the mechanism of mercury
oxidation by HCl over Fe2O3. Based on the experimental results, a
detailed kinetic model was developed for mercury oxidation over
Fe2O3 and validated by comparison to experimental data. This study
aims to understand the chemical reaction kinetics of mercury oxidation
in coal-fired flue gas.
2. Experimental and computational methods
2.1. Fe2O3 preparation and characterization
Fe2O3 samples were synthesized by a precipitation method [31]. Ap-
propriate amount of Fe(NO3)3·9H2O was dissolved in deionized water
under stirring, and a stoichiometric amount of aqueous ammonia was
added to the aqueous solution of Fe(NO3)3 as a precipitating agent.
The precipitate was filtrated and washed three times with deionized
water. The collected precipitate was dried in an oven maintained at
110 °C for 12 h and subsequently calcined at 550 °C in air for 3 h. Finally,
the calcined Fe2O3 samples were ground and sieved to 180 mesh.
The Brunauer-Emmett-Teller (BET) surface area of Fe2O3 samples
was determined using a nitrogen adsorption apparatus (ASAP-2020,
Micromeritics). Prior to BET measurement, the synthesized Fe2O3 sam-
ples were degassed at 200 °C for 2 h. X-ray photoelectron spectroscopy
(XPS) analysis was carried out on a Thermo ESCALAB 250 instrument
with Al Kα (hv = 1486.6 eV) as the excitation source. The binding
energy was calibrated using C 1s peak at 284.6 eV.
2.2. Catalytic performance tests
Mechanistic investigations will most likely require laboratory-scale
tests conducted under simulated flue gas conditions, because the com-
plexity of real coal-derived flue gas under the commercial operating
Fig. 1. Schematic diagram of the experimental system for mercury oxidation.
267
conditions may prevent the investigation of reaction mechanism [16].
Therefore, a series of oxidation experiments were conducted in a
laboratory-scale fixed-bed quartz reactor (i.d. 10 mm) placed in a tem-
perature controlled tubular furnace. The schematic diagram of experi-
mental system is shown in Fig. 1. N2 was used to introduce Hg0 from
mercury permeation device into the simulated flue gas (4% O2, 12%
CO2, 30 ppm HCl, N2 as the balance gas). To provide a constant Hg0 con-
centration (about 45 μg/m3), mercury permeation device was placed in
a sealed U-shaped tube immersed in a fixed temperature (45 °C) water
bath. The total flue gas flow rate was 1 L/min, which corresponded to a
gas volume hourly space velocity (GHSV) of about 5 × 104 h−1. Some
Fe2O3 in fly ash are combined with other substituted aluminosilicates,
but the aluminosilicates usually impart a very lower intrinsic reactivity
for mercury oxidation in actual coal-fired flue gas [28]. Therefore, the
aluminosilicates were not considered in the heterogeneous mercury ox-
idation experiments. 0.5 g of Fe2O3 samples and 1.5 g of quartz sand
were used during each experiment. Quartz sand, an inactive material,
was used as diluent to mix with ground powder Fe2O3. Quartz sand in-
creased the height of heterogeneous reaction zone, thereby increasing
the residence time of flue gas. The length of heterogeneous reaction
zone for mercury oxidation was approximately 16 mm. A continuous
mercury analyzer (VM3000, Mercury Instruments, Germany) was
used to monitor gas-phase Hg0 concentration in simulated flue gas.
At the beginning of every mercury oxidation experiment, the simu-
lated flue gas stream was switched to bypass to obtain a stable inlet Hg0
concentration (Hg0in). After the experimental system obtained a stable
Hg0in for 30 min, the gas stream was switched to reactor to measure
the outlet Hg0 concentration (Hg0out). The gas stream was switched
from reactor to bypass to verify the Hg0in when Hg0out stabilized for
30 min. Prior to experiments, Fe2O3 samples were first saturated by N2
gas stream containing Hg0 at room temperature to avoid the possible
bias caused by Hg0 adsorption. During the saturation experiments,
Fe2O3 was quickly penetrated within 2 min when N2 gas stream
including 45 μg/m3 Hg0 passed through it, indicating that Hg0 adsorp-
tion capacity of Fe2O3 is negligible. Therefore, during the oxidation ex-
periments, the loss of Hg0 across Fe2O3 samples was attributed to Hg0
oxidation rather than Hg0 adsorption. Accordingly, the Hg0 oxidation
efficiency (Eoxi) was calculated using the following equation:
 
Eoxi ð%Þ ¼ 1– Hg0out =Hg0in  100% ð1Þ
2.3. Kinetic calculations
Mercury oxidation in flue gas involves homogeneous and heteroge-
neous reactions. Homogeneous reaction kinetic model with 279
268 Y. Yang et al. / Fuel Processing Technology 159 (2017) 266–271

elementary reactions has been described in detail in our previous work

[32]. In the present work, heterogeneous reaction kinetics of mercury
oxidation by HCl over Fe2O3 was investigated. Kinetic calculations
were performed using Perfectly Stirred Reactor (PSR) and Plug Flow Re-
actor (PFR) of CHEMKIN-PRO software [33]. Thermodynamic data of
Fe2O3 was taken from thermochemical database [34].
A method was proposed to determine the surface site density of
Fe2O3. This calculation method is based on the following procedures:
(1) the surface site density can be determined by the ratio of active
surface atoms number to surface area. (2) A surface atom can be defined
as the active one if the reactants prefer to adsorb on this atom. (3) The
above second step is performed by density functional theory (DFT)
calculations, because the DFT calculations can reveal the active surface
atom by comparing the adsorption energies of reactants on different
surface atoms [35,36]. (4) The surface area is determined by lattice Fig. 2. Pore size distribution of Fe2O3 samples.
parameters. Based on this method, the initial iron site density
(2.66 × 10−9 mol/cm2) of Fe2O3 can be obtained. Fe2O3 samples at higher temperatures leads to the decline of mercury
Sticking coefficients were used to specify the kinetic parameters of oxidation efficiency. Similar finds were obtained in the earlier study in
the heterogeneous surface reactions. The sticking coefficient represents which mercury removal efficiency of iron oxide decreased with increas-
the reaction probability of a collision between gaseous species and solid ing calcinations temperature from 110 to 300 °C [31].
surface [37]. The sticking coefficient of heterogeneous reaction (R2) was
determined by fitting to our experimental data obtained at 100 °C. For
other heterogeneous reactions, the sticking coefficients were obtained 3.3. Hg0 oxidation mechanism on Fe2O3
from reference [32]. The heterogeneous kinetic model was validated
by performing the kinetic modeling of experiments conducted by two To date, Langmuir-Hinshelwood mechanism and Eley-Rideal mech-
different groups. No sticking coefficients were adjusted when the kinetic anism have been proposed to interpret heterogeneous mercury oxida-
modeling of different experiments were carried out. tion by HCl over different catalyst surface. For Langmuir-Hinshelwood
Sticking coefficients can be converted to the usual kinetic rate mechanism, mercury oxidation reaction occurs between two species
constants [38], as shown in Eq. (2). adsorbed on solid surface. For Eley-Rideal mechanism, mercury oxida-
   0:5 tion reaction occurs between gas-phase (or weakly adsorbed) species
γ ∏ j¼1 σ νj RT and catalyst-bound species [12]. In this study, Fe2O3 samples pretreated
kf ¼ ð2Þ
1−γ=2 ðГtot Þm 2πW k with HCl were used to identify the Hg0 oxidation mechanism on Fe2O3.
Fe2O3 was first exposed to a N2 stream containing 30 ppm HCl for
kf is rate constant, mol/(cm2·s); γ is dimensionless sticking coeffi- 30 min and then flushed by pure N2 stream at the same temperature
cient; Гtot is the total surface iron site density, mol/cm2; m is the sum for 10 min. XPS analysis was used to determine the surface chemical
of all the stoichiometric coefficients of reactants that are surface species; state of Fe, O and Cl present in pretreated Fe2O3. The XPS analysis results
σj is the number of sites that the surface species occupies; ν is the reac- of Fe2O3 pretreated with HCl at 100 °C are shown in Fig. 4. The O 1 s XPS
tion order for that species; Wk is the molecular weight of the gas-phase spectra shows two peaks at 529.68 and 531.32 eV. The peak at 529.68 eV
species, g/mol; R is the universal gas constant, J/(K·mol). T is reaction is attributed to the lattice oxygen of transition metal oxides. Another
temperature, K. peak at 531.32 eV is ascribed to the hydroxyl groups (\\OH), which in-
dicates that HCl dissociates on Fe2O3 surface and produces hydroxyl
3. Results and discussion groups during HCl pretreatment. Five peaks were observed in Fe 2p
XPS spectra. The peak centered at 710.82 eV is attributed to Fe3 + in
3.1. Characterization analysis iron-chlorine compounds [41], suggesting the strong interaction be-
tween HCl and Fe2O3 samples. The other four peaks are attributed to
The measured BET surface area of Fe2O3 samples is about 7.1 m2/g. It Fe3+ in Fe2O3. The peak with a binding energy of 198.72 eV was found
was reported that the surface area of fly ash is in the range of in Cl 2p XPS spectra and attributed to Cl− in iron-chlorine compounds
0.70–5.42 m2/g [39]. Therefore, the specific surface area of prepared [42], indicating the interaction between Cl atoms and Fe atoms.
Fe2O3 samples is comparable to that of actual fly ash. The measured
BET surface area can be used to determine the available surface area of
heterogeneous reaction over Fe2O3. The pore size distribution of Fe2O3
samples is shown in Fig. 2. It can be seen that the prepared Fe2O3 pos-
sesses a bimodal porous structure with a narrow pore diameter range
of 2–4 nm and a broad pore diameter range of 20–100 nm. The average
pore diameter is 39.28 nm, which indicates that the prepared Fe2O3
sample is a kind of mesoporous materials.

3.2. Hg0 oxidation performance of Fe2O3

Hg0 oxidation efficiency over Fe2O3 at temperatures ranging from 50

to 300 °C is shown in Fig. 3. Eoxi increased with increasing temperature
from 50 to 100 °C. The maximum Eoxi of 89.5% was observed at 100 °C.
Eoxi decreased from 89.5% to 49.1% when the reaction temperature
was further increased from 100 to 300 °C. This decline may be attributed
to the decomposition of active surface chlorine species at higher tem-
peratures [40]. On the other hand, the possible sintering effect of Fig. 3. Hg0 oxidation efficiency over Fe2O3 at temperatures ranging from 50 to 300 °C.
 Y. Yang et al. / Fuel Processing Technology 159 (2017) 266–271
Fig. 4. O 1s, Fe 2p and Cl 2p XPS spectra of Fe2O3 pretreated with HCl.
XPS results indicate that iron-chlorine compounds are formed on
the HCl pretreated Fe 2 O 3 surface. Fe 2 O 3 pretreated with HCl was
further used to investigate the mercury oxidation on its surface.
The Hg0 breakthrough curves over HCl pretreated Fe2O3 at different
reaction temperatures are presented in Fig. 5. Hg 0 oxidation effi-
ciency should decrease with increasing reaction temperature if the
adsorbed Hg 0 reacts with surface chlorine species (Langmuir-
Hinshelwood mechanism), because higher temperature is unfavor-
able for Hg0 adsorption [43]. However, as shown in Fig. 5, Hg0 oxida-
tion efficiency increased as the reaction temperature increased from
50 to 100 °C. Therefore, it can be deduced that Hg0 oxidation by HCl
over Fe 2O 3 surface occurs through the Eley-Rideal mechanism, in
which HCl is first adsorbed on Fe2O3 surface and generates surface
chlorine species to react with gas-phase Hg0. In addition, Hg0 oxida-
tion efficiency declined when the reaction temperature was further
increased to 150 °C. The possible reason is that the active chlorine
species over Fe2 O3 surface are thermally unstable and decompose
at relatively higher temperature, which is unfavorable for mercury
oxidation.
269
Fig. 5. Hg0 breakthrough curves over HCl pretreated Fe2O3.
3.4. Kinetic calculations
3.4.1. Model development
The abovementioned XPS results indicate that HCl are dissociatively
adsorbed on Fe2O3 surface to form active chlorine species for mercury
oxidation. Moreover, the experimental results of mercury oxidation
mechanism indicate that gaseous Hg0 reacts with active surface chlorine
species over Fe2O3 surface. Therefore, based on the XPS results and mer-
cury oxidation mechanism, a heterogeneous kinetic model of mercury
oxidation by HCl over Fe2O3 surface was developed using the following
surface reactions:
FeðsÞ þ HCl→FeClðsÞ þ H ðR1Þ
FeClðsÞ→FeðsÞ þ Cl ðR2Þ
FeClðsÞ þ Cl→Cl2 þ FeðsÞ ðR3Þ
FeClðsÞþHg0 →FeHgClðsÞ ðR4Þ
FeClðsÞþHg0 →FeðsÞ þ HgCl ðR5Þ
FeClðsÞ þ HgCl→FeðsÞþHgCl2 ðR6Þ
FeHgClðsÞ þ HCl→FeðsÞþHgCl2 þ H ðR7Þ
FeClðsÞþHgCl2 →FeHgClðsÞþCl2 ðR8Þ
Fe(s), FeCl(s), and FeHgCl(s) denote unoccupied, chlorinated, and
Hgp sites on Fe2O3 surface, respectively. In (R1), gas-phase HCl is
dissociatively adsorbed on the unoccupied iron sites and form chlorinat-
ed sites. The chlorinated sites may be thermodynamically unstable and
decompose at higher temperature (R2). The chlorinated sites can react
with Cl radicals to form gas-phase Cl2 (R3). Hg0 can be oxidized into
HgCl2 by gas-phase Cl2 through homogeneous reactions [32]. In (R4)
and (R5), gas-phase Hg0 is first oxidized into intermediate products
(solid-phase FeHgCl(s) or gas-phase HgCl). Subsequently, these inter-
mediate products are further oxidized into HgCl2 through (R6) and
(R7). Moreover, the fully oxidized gas-phase HgCl2 can also back adsorb
into the Hgp species on the Fe2O3 surface (R8).
3.4.2. Kinetic modeling of experiments conducted by this work
The proposed heterogeneous kinetic model was combined with our
previous homogeneous kinetic model [21] and incorporated into Per-
fectly Stirred Reactor (PSR) to predict mercury oxidation on Fe2O3 sur-
face. The reaction conditions of PSR were obtained from the
experiments. The residence time of flue gas in PSR was calculated
from gas volume hourly space velocity (GHSV) of mercury oxidation ex-
periments. The simulated flue gas compositions (4% O2, 12% CO2,
270 Y. Yang et al. / Fuel Processing Technology 159 (2017) 266–271
Fig. 6. Comparison between model predictions and experimental data.
30 ppm HCl, N2 as the balance gas) in experiments were used for this ki-
netic calculation. The reaction volume of PSR was calculated from the
reaction zone (0.5 g Fe2O3 + 1.5 g quartz sand). The available surface
area for heterogeneous reaction was obtained from the measured BET
surface area of Fe2O3 samples and Fe2O3 weight.
Fig. 6 presents the comparison between model predictions and ex-
perimental data. It can be seen that kinetic calculation results are consis-
tent with experimental results, especially at the temperatures ranging
from 150 to 300 °C. The slight deviation is observed at 50 and 100 °C.
The comprehensive mercury oxidation process over Fe2O3 surface is
controlled by mass transfer and chemical reaction. Mass transfer was
omitted for lack of gas transport data, which may be a cause for the
deviation.
3.4.3. Kinetic modeling of experiments conducted by Helble et al.
Helble et al. [44] carried out a series of heterogeneous Hg oxidation
experiments in a bench scale flame-based flow reactor by injecting
Fe2O3 particles. In the experimental system, the simulated flue gas
was supplied by a methane-fired burner. The residence time of methane
fired flue gas in flow reactor is approximately 5 s. The thermal history of
flue gas was obtained from the experiments. The major flue gas
compositions (9.1% CO2, 18.2% H2O, 0.9% O2, 200–555 ppm HCl, N2 as
the balance gas) were used for kinetic calculations. The initial Hg0
concentration in flue gas is 52.2 μg/m3. Fe2O3 particles with an average
specific surface area of 45 m2/g were used during heterogeneous
experiments. Fe2O3 particle loading in flue gas was expressed as a
surface-to-volume ratio (Fe2O3 surface area to flue gas volumetric
flow rate). This simulation was carried out using Plug Flow Reactor
(PFR).
Fig. 7. Comparison between predicted and measured extents of mercury oxidation.
The comparison between model predictions and experimental data
is shown in Fig. 7. The results show clearly that kinetic calculations are
in good agreement with experimental data. Even though the kinetic
model slightly over predicts mercury oxidation (ratio = 622 m2/m3,
HCl = 400 ppm), the kinetic calculation results are generally within
the measurement uncertainties of experimental data. In summary, the
kinetic modeling is consistent with experimental data obtained by
two independent research groups. Therefore, mercury oxidation by
HCl over Fe2O3 surface can be described using this heterogeneous kinetic
model.
4. Conclusions
A combination of experiment and kinetic calculations was used to
identify the detailed reaction kinetics of heterogeneous mercury oxida-
tion on Fe2O3 in the presence of HCl. Fe2O3 can obtain a maximum mer-
cury oxidation efficiency of 89.5% at 100 °C. Hg0 oxidation by HCl over
Fe2O3 surface occurs through the gas-solid reaction between gas-
phase Hg0 and active surface chlorine species generated from the disso-
ciation of HCl. The detailed eight-step heterogeneous kinetic model of
mercury oxidation on Fe2O3 can display a reasonable agreement to ex-
perimental data. Mercury oxidation process over Fe2O3 surface can be
described using the proposed reaction kinetic model. It is noteworthy
that the comprehensive mercury oxidation process includes mass trans-
fer process and intrinsic reaction kinetics. In the future study, the effect
of mass transfer process will be incorporated into the kinetic model.
Moreover, NOx, SOx and moisture will be independently added to the
simulated flue gas to investigate their effects on mercury oxidation by
HCl over Fe2O3 surface.
Acknowledgments
This work was supported by National Natural Science Foundation of
China (51376072), National Key Research and Development Program
(2016YFB0600604), Natural Science Foundation of Hubei Province
(2015CFA046).
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