Fuel Processing Technology 216 (2021) 106747

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Fuel Processing Technology

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Research article

Behavior of mercury in chemical looping with oxygen uncoupling of coal

Jinchen Ma a, Xin Tian a, Bo Zhao b, Xiaoshan Li a, Yongchun Zhao a, Haibo Zhao a, *,
Chuguang Zheng a
a
State Key Laboratory of Coal Combustion, Huazhong University of Science and Technology, Wuhan 430074, PR China
b
Hubei Key Laboratory for Efficient Utilization and Agglomeration of Metallurgic Mineral Resources, Wuhan University of Science and Technology, Wuhan 430081, PR
China

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

Keywords: Mercury pollution is a critical point in chemical looping with oxygen uncoupling combustion (CLOU) of coal.
Chemical looping with oxygen uncoupling This work aims to investigate the behavior of mercury and the role of oxygen carrier (OC, CuO@TiO2-Al2O3) in
Oxygen carrier the CLOU of Pingdingshan (PDS) anthracite. The average CO2 yield was 93.9% during the 15 redox cycles. The
Coal
mercury balance was 119.0% ± 0.49 in the CLOU test (8 min, 4 repeated redox cycles). The distribution of
Mercury
Hg0(g) and Hg2+(g) was 0.033 ± 0.9*10− 5 μg and 0.054 μg within the reduction process, respectively. The
removal efficiency of Hg0(g) by the OC was 60.71%. Moreover, the Hg(p) was adsorbed on the OC with an
adsorption capacity of 0.281 μg/g and was composed of 23.48% and 76.52% for Hg0 and Hg2+. The decreasing
removal efficiency of Hg0 was listed as: OC + the complicated atmosphere of CLOU > OC + 5 vol% O2 > the
completely oxidized OC > the partially reduced OC. The oxidation of Hg0(g) was promoted by sufficient active
sites, absorbed oxygen and lattice oxygen of the OC. A long reduction time in the fuel reactor reduced the
mercury released in the air reactor.

1. Introduction
Carbon capture utilization and storage (CCUS) could be the key for
achieving near -zero emissions worldwide and is focused on low-cost
and high-efficiency CO2 capture. Chemical looping combustion (CLC)
is a representative technology for CO2 capture and is regarded as one of
the most promising methods due to its inherent CO2 separation [1]. In
CLC, inherent CO2 separation was achieved by the lattice oxygen pro­
vided by the oxygen carrier (OC). However, the reaction rate was
restricted by the gasification rate of the char in the CLC technology [2],
especially for high-rank anthracite. Some transition metal oxides (Cu
[3], Mn [4,5], Co [6]) have the characteristic of releasing gaseous O2,
which is beneficial for improving the char gasification rate [7]. At the
same time, lattice oxygen also participated in heterogeneous reactions
between volatiles and the products of char gasification. As a result, the
advantages of CLOU were the small bed inventory (125 kg/MWth for Cu-
based OC [8] vs 500–1000 kg/MWth for Fe-based OC [9,10]) and re­
sidual char of anthracite or coke in the fuel reactor [11,12].
To date, the foci of CLOU has been the design and operation of
suitable reactors [13], the selection and evaluation of oxygen carriers
[8,14], and the emission control of sulfur, nitrogen, and chlorine
[15–17]. All these achievements have laid a solid foundation for
developing CLOU technology. Some toxic trace metals, such as mercury,
should be considered in the second stage of research due to their bio­
toxicity [18] and accumulation during CO2 purification [19]. Currently,
the only investigation of mercury in CLOU was carried out by Pérez-
Vega et al. [16]. The distributions of the gas phase mercury (Hg(g)) in
the fuel reactor (FR) and air reactor (AR) were 18.6% and 22.0% with
Hg0 to Hg2+ ratios of 0.86 and 0.5, respectively. Moreover, the solid
phase mercury (Hg(p)) accounted for 59.4% of the total Hg. The mer­
cury released in the AR was derived from the transportation of the
reduced oxygen carrier and residual char. The behavior of mercury is
obviously different in other CLC technologies such as chemical looping
combustion (CLC) and chemical looping gasification (CLG). The mer­
cury in the coal was mostly released as Hg(g) (99.2% by Mendiara et al.
[20,21] and 99.5% by Ma et al. [22]) in CLC and solid phase mercury
was rarely detected. However, 24.14% of the mercury in the coal
migrated to the OC (CuFe2O4) with the form of Hg0, HgO, and HgCl2 in
CLG [23].
Although various distributions of mercury were caused by the
configuration of the reactor, the type of coal and oxygen carrier, the
extension technology of chemical looping, and the oxidation of Hg0 to

* Corresponding author.
E-mail address: hzhao@mail.hust.edu.cn (H. Zhao).

https://doi.org/10.1016/j.fuproc.2021.106747
Received 29 November 2020; Received in revised form 23 December 2020; Accepted 5 January 2021
Available online 24 February 2021
0378-3820/© 2021 Elsevier B.V. All rights reserved.
J. Ma et al. Fuel Processing Technology 216 (2021) 106747

Table 1
Proximate analysis, ultimate analysis and Hg in PDS anthracitea.
Proximate analysis/(%) Ultimate analysis/(%)

M V A FC C H N S Ob Hgc

1.88 14.98 16.87 66.27 64.73 3.99 1.08 0.30 11.15 0.390
a
Air-dried basis.
b
By difference.
c
μg/g.

Table 2
Experimental operating conditionsa.
Test Bed inventory (g) Coal Flow rate (L/ Reaction
(g) min) atmosphere

No. SiO2 (6) 0.213 2.0 Redox cyclesb

1
No. OC (15) 0.213 2.0 Redox cyclesb
2
No. OC (67%Cu2O + 33% – 1.0 100 vol% N2
3 CuO, 0.5)
No. OC (100% CuO, 0.5) – 1.0 100 vol% N2
4
No. OC (Inability to release – 1.0 5 vol% O2 + 95 vol
5 O2, 0.5) % N2
a
The operating temperature was 900 ◦ C for all the tests.
b
Redox cycles: (1) 40 vol% CO2 (N2 balance) for the reduction process in the
CLOU test (gasification process for reference test No. 1); (2) 100 vol% N2 for the
purification process; (3) 8.5 vol% O2 (N2 balance) for the oxidation process.

Fig. 1. Sketch map of the batch fluidized bed reactor.
Hg2+ were generally promoted by the large bed inventory of the OC in
the FR. Two pathways for the oxidation of Hg0 were identified by
Density Functional Theory (DFT) calculations: (i) Hg0 adsorption on the
reduced Fe2O3[104] surface was promoted by more possible active sites
[24]; (ii) Hg0 was oxidized by the adsorbed Cl2 [25]. The highest
removal efficiency of Hg0 was achieved by the Cu-based catalysts [26].
The favorable factors for Hg oxidation were: the regeneration of the
catalyst by gaseous O2 [27], the existence of Cl2 [26,28], and the in­
termediate states (Cl-Cu-OH, NO+ or NO2) on the surface of the catalysts
[29]. However, the inhibited factors were CO2 and SO2 in coal com­
bustion [30]. Thus, Hg oxidation could be favorable in CLOU. Mercury
could be released in the two flue gases of the FR and AR, which resulted
in an increased cost for mercury removal.
In this work, we aim to investigate the CLOU performance of
CuO@TiO2-Al2O3 as an oxygen carrier and the distribution of mercury
(Hg0(g), Hg2+(g) and Hg(p)). Second, the effects of the reduction time/
gasification time and the reduction degree of the oxygen carrier on the
removal efficiency of Hg0 were evaluated. Third, the fraction of Hg0 and
Hg2+ in the used OC was determined. Finally, fresh and used CuO@­
TiO2-Al2O3 were characterized for the crystal phase, surface composi­
tion, element distribution and apparent morphology by X-ray
fluorescence (XRF), X-ray diffraction (XRD), X-ray photoelectron spec­
troscopy (XPS) and scanning electron microscopy with energy dispersive
spectroscopy (SEM + EDX). At last, suggestions for reducing the mercury
in the air reactor were proposed.
2. Material and methods
2.1. Materials
Cu-based oxygen carriers were prepared according to the production
process [3,11]. Al2O3 was used as the inert composition, however, Al2O3
could react with CuO to form CuAl2O4. When the external of Al2O3
microparticles were coated with nano-TiO2, the formation of CuAl2O4
could be interrupted. The OC particles were sieved to 0.15–0.35 mm,
and the true density was 5634 kg/m3 (AccuPyc II 1330, Micromeritics
instrument, America). The active composition (CuO) in the fresh oxygen
carrier was 78.02 ± 0.21 wt%, as shown in Table 3. The mercury in the
fresh OC was zero, as detected by a Mercury Analyzer (RA-915 M +
PYRO915+, Lumex, Russia). The minimal fluidization gas velocity of the
oxygen carrier was 0.07 m/s based (air at 900 ◦ C) on fluidization theory
[31].
Pingdingshan (PDS) anthracite was prepared according to the stan­
dard GB474–2008 using a size range of 0.3–0.5 mm. The proximate and
ultimate analysis of the PDS anthracite as well as the mercury content
are shown in Table 1. The composition of the ash sample (prepared
following the redox processes in reference test 1 without SiO2 as bed
inventory) was 39.62 wt-% Al2O3, 48.86 wt-% SiO2, 5.58 wt-% CaSO4,
and 5.94 wt-% CaAl4Fe8O19 and the mercury content was 0.335*10− 3
μg/g.
2.2. Experimental setup
The inner diameter and height of the batch fluidized bed reactor
were 20 mm and 100 mm, respectively. (See Fig. 1.) The sintered plate
was used as the distributor with an aperture diameter of 0.07 mm. The
total flow rate into the reactor was 2.0 L/min, corresponding to 5.6 Umf
for the oxygen carrier. The 40 vol% CO2 (N2 balance), 100 vol% N2 and
8.5 vol% O2 (N2 balance) were used for the reduction process (gasifi­
cation process for reference test No. 1), purification process and oxida­
tion process, respectively. The agglomeration of the Cu-based OC could
be alleviated by the mild oxidation of OC under a relatively low con­
centration of O2. The bed inventory of the OC was 15 g and the mass of
the coal was 0.213 g (2.80 for the oxygen to fuel ratio [32]), as shown in
Table 2. Tests No. 3–5 were conducted to identify the effects of the
reduction degree (CuO) and gaseous O2 on the removal efficiency of
Hg0(g) in the fixed bed reactor using specific kinds of gases containing a
constant Hg0(g) stream, which was described in previous work [33].

2
J. Ma et al. Fuel Processing Technology 216 (2021) 106747

Fig. 2. CO2 gasification of PDS anthracite at 900 ◦ C: (a) gas concentration vs

time; (b) CO/CH4/CO2 yields and carbon residue rate vs gasification time. Fig. 3. CLOU tests of PDS anthracite at 900 ◦ C: (a) gas concentration vs time;
(b) carbon balance and CO2/CO/CH4 yields.

CuO (67%) was reduced to Cu2O in test No. 3, prepared by the reduction
of H2 in the thermogravimetric analysis (TGA). Fully oxidized fresh OC ∫ ttotal

was investigated in test No. 4, and 5 vol% O2 (N2 balance) was used to mHg0 = Fi ⋅yHg0 dt (1)
0
simulate the low concentration of O2 in the CLOU test, set as test No. 5.
The real-time concentration of Hg0(g) was analyzed by an online where i represents the reduction process, purification process and
VM3000 (MI, Germany). Moreover, the average amount of Hg2+(g) was oxidation process, and ttotal represents the different duration times for
absorbed by an 1 mol/L KCl solution based on the OHM method [34] process i.
within the reaction and oxidation processes. Solid-phase mercury (Hg The amount of Hg2+(g) released from the coal was calculated based
(p)) was detected by Lumex RA-915 M + PYRO915+ for the mixed ash on the ion concentration of Hg2+(g) (ci, Hg2+) in the OHM method as
and SiO2 in the reference test (No. 1), and the mixed ash and the used OC shown in Eq. (2).
from the 15th cycle of the CLOU test (No. 2). The concentrations of the
conversional gases (that is, CO2, CO, CH4, H2 and O2) were measured by mHg2+ = ci,Hg2+ ⋅Vs (2)
an online gas analyzer (Gasbroad 3000, Cubic, China). Vs is the volume of solution, which was 1 L in every test.
The amount of Hg (p) released from the coal was given based on the
2.3. Data evaluation mass of the sample taken from the different stages.

The carbon balance, carbon conversion and CO2/CH4/CO yields mHg(p) = cj,Hg(p) ⋅mj (3)
were calculated based on the previous work [3]. The residual carbon
was calculated according to the amount of the carbonaceous gases where, cj, Hg(p) is the mercury fraction of the samples, and j represents
released in the oxidation process and the carbon residue rate was the the different samples, i.e., the ash from the reference test, the sample of
value of the residual carbon dividing the carbon in coal. mixed ash and used OC after 15 redox cycles.
The amount of Hg0(g) released from the mercury in coal was inte­ The conversion of Hg0(g) and Hg2+(g) from the mercury in the coal
grated by the concentration of Hg0(g) (vHg0) and the flow rate of the flue are represented by wHg0 and wHg2+ and were calculated as the amounts of
gas (Fi), as shown in Eq. (1). Hg0(g) and Hg2+(g) released to the total mercury in coal fed into the
reactor (mHg(p), coal).
/
wHg0 = mHg0 mHg(p),coal (4)

3
J. Ma et al. Fuel Processing Technology 216 (2021) 106747

Fig. 4. Hg0(g) concentration in the CO2 gasification process (a) and CLOU (b) of PSD anthracite at 900 ◦ C.

/ 3. Result and discussion

wHg2+ = mHg2+ mHg(p),coal (5)

The mercury balance was calculated as show in Eq. (6), 3.1. CLOU performance
( )/
B = mHg0 + mHg2+ + mHg(p) mHg(p),coal (6) In the CLOU test, the bed inventory of the OC was 15 g and the total
0
The removal efficiency of Hg (g) in the flue gas by the OC was flow rate of the fluidization gas was 2.0 L/min at 900 ◦ C. Coal (0.213 g)
calculated based on the difference in the amount of Hg0(g) released in was fed into the reactor by a pulse of high-pressure N2. In the reference
the CLOU test and the reference test, as shown in Eq. (7). test, SiO2 was used as the bed inventory with the same high static bed
( )/ (17 mm) and the other parameters were the same. In the CO2 gasifica­
EHg0 = mHg0SiO − mHg0CuO mHg(p),coal (7) tion process of the PDS anthracite in the reference test, coal was injected
into the reactor when the CO2 concentration was steady at 39.3 vol%.
2 2

where, mHgSiO20 and mHgCuO20 are the amounts of Hg0(g) released during
the reaction process in the reference test and CLOU test, respectively.
The peaks of CH4 and H2 were 1.25 vol% and 1.24 vol%, respectively, in
the initial test, which was the main composition of the volatiles. (See
Fig. 2(a)). A broad peak of CO was observed within the whole gasifi­
cation process because part of CO was derived from volatiles and the
other part was generated by char gasification (C + CO2 = 2CO). The CO

4
J. Ma et al.
Fig. 5. Mercury distribution and balance.
concentration was decreased to 0.25 vol% even though the gasification
time lasted 8 min. This result indicated that the high-rank anthracite was
difficult to gasify at a later stage due to the dense shell surrounding the
char [35]. O2 (8.4 vol%) was intruded into the reactor to oxidize the
residual char at the end of the purification process. A mass of CO2 was
generated with a high peak of 6.83 vol%. The results demonstrated that
the residual char of anthracite from the gasification process was more
than that of lignite [32,36]. A small amount of CO and H2 escaped in the
oxidation process, which was attributed to incomplete combustion.
A key issue was the residence time of coal for carbon conversion
[37], especially when using high-rank anthracite as fuel. Thus, the effect
of the various gasification times on the CLOU indexes is shown in Fig. 2
(b). The CO yield was increased from 21.5% to 31.5% when the duration
time was extended by 12 min. The increase resulted from the deep
gasification of the char. However, the CH4 yield nearly stable between
1.1% and 1.9% because it mainly resulted from volatiles. Moreover, the
carbon residue rate noticeably decreased from 31.4% to 23.7% with the
additional period for the gasification process (from 8 min to 20 min).
With respect to the CLOU of PDS anthracite using CuO@TiO2-Al2O3
as the oxygen carrier, the coal was fed into the reactor at a steady CO2
concentration of 39.3 vol% and an O2 concentration of approximately
1.5 vol% (the equilibrium partial pressure of O2 was 1.52 vol% for CuO
Fig. 6. Carbon and Hg0(g) conversion in every minute.
5
Fuel Processing Technology 216 (2021) 106747
at 900 ◦ C [2]) in Fig. 3(a). At first, the CO2 concentration dropped
slightly due to the CO2 concentration diluted by N2 added with coal.
Subsequently, the CO2 concentration increased rapidly to 44.5 vol%,
which was generated from both the heterogeneous reactions between
CO/CH4 and CuO (CO + CuO = CO2 + Cu2O, CH4 + CuO = CO2 + H2O
+ Cu2O) and the homogeneous reaction between CO/CH4 and O2 (CO +
O2 = CO2, CH4 + O2 = CO2 + H2O). The peaks of the unconverted gases
were 0.51% and 0.49% for CO and CH4, respectively, and obviously
decreased compared with the peaks from chemical looping combustion
(CLC) [32]. A low concentration of O2 (0.5 vol%) was detected during
the reduction process, which was explained by the capacity of the
released O2 by the unreduced CuO. In the oxidation process, the peak of
CO2 was just 0.12 vol% indicating that the complete conversion of
anthracite was achieved in the reduction process and providing an ev­
idence that the OC could promote char gasification. Two explanations
were listed: the gasification rate and degree of char were effectively
improved by the assistance of gaseous O2 [8], and the reaction balance
of char gasification tended to move to the right (C + CO2 = 2CO) with
the consumption of CO.
The CO2 yield was higher than 92.1% during the 15 repeated redox
cycles, except for the 8th –10th cycles in Fig. 3(b). The steady CO2 yields
showed a stable reactivity of OC, which coincided with the stable
morphology of the OC (Section 4.3). In the 8th–10th cycles, more CO
and CH4 were unconverted due to the insufficient contact of the OC and
coal in a new reactor (the addition point of the coal was located in the
upper part of the OC bed inventory). The conversion of the PDS
anthracite can be divided in two parts: the gasification by the CO2 and
the incomplete combustion under the low concentration of O2. Thus, CO
was generated via. C + CO2 = 2CO and C + O2 = 2CO. As a result, the
CO2 yield was relatively low. The carbon balance ranged from
94.7–107.7%, which was in the confidence interval. The >100% carbon
balance was attributed to the fluctuation of the CO2 flow rate into the
reactor. The average key indexes (carbon balance and CO2/CO/CH4
yields) were 102.33 ± 0.05, 93.90 ± 4.05, 4.13 ± 1.95 and 1.02 ± 0.05.
The low standard deviation demonstrated good repeatability of the tests.
3.2. Behavior of Hg in CLOU
3.2.1. Characteristic of released Hg0 (g)
The Hg0 (g) concentration soon reached the pinnacle during the
initial 2–3 s in Fig. 4(a), which was independent of the gasification time
J. Ma et al. Fuel Processing Technology 216 (2021) 106747

Fig. 7. Effect of the degree of reduction of CuO on the removal efficiency of Hg0 (g).

the reduction process of the CLOU test (the reduction time of 8 min were
repeated for 4 times, named 8 (1–4)), as shown in Fig. 4(b), and
appeared before the CO peak. At other reduction times, the Hg0 (g)
concentrations were 107.6 μg/Nm3 and 121.5 μg/Nm3 at 10 min and 12
min. The Hg0 (g) concentration rapidly increased and then declined
down to zero within 1.5 min. This result indicated that the existence of
the OC facilitated the conversion of Hg0 (g). In the oxidation process, the
Hg0 (g) concentration gradually increased to 2.2 μg/Nm3. The residual
char was very small in the oxidation process of CLOU. Thus, the small
amount of residual char was explained by the absorption of Hg0(g) or
Hg2+(g) on the active sites of the reduced OC surface. Furthermore, Hg
was detected on the reoxidized OC by XPS analysis (Section 3.3). The
desorption of Hg0(g) occurred by the competition of O on the active
sites. The result also provided an explanation for the released Hg(g) in
the air reactor [16], which was transported by the residual char and OC.

Fig. 8. XPS spectra of Hg 4f for the used OC.
in the reference test due to the effumability of the mercury in the coal
[38]. The peak of Hg0 (g) was 206.6 μg/Nm3 in the reference test
(gasification time of 8 min). The Hg0 (g) peak appeared ahead of the CO
peak in Fig. 2(a). In the oxidation process in the reference test, the Hg0
(g) concentration decreased from 3.8 μg/Nm3 to 0.7 μg/Nm3 as the
gasification time was increased from 8 min to 20 min. The results
showed that the longer the gasification time was, the less Hg(p) was in
the residual char, which was similar to the fate of mercury in the CLC
and CLG [21–23]. Hg0 (g) was released along with the oxidation of the
char due to absorption by residual char or ash (magnetic oxide, Fe3O4)
[39].
The average peak of Hg0 (g) dropped to 115.5 ± 8.5 μg/Nm3 during
3.2.2. Role of OC
The distribution of mercury in the reference test and CLOU test is
shown in Fig. 5, and a gasification or reduction time of 8 min is taken as
an example. The mercury balances were 117.6% ± 0.07 and 119.0% ±
0.49 in the reference test and CLOU test (4 repeated cycles), respec­
tively, which was in the confidence interval of 70–130% [40].
The amounts of Hg0(g) and Hg2+(g) released were 0.033 ± 0.9*10− 5
μg and 0.054 μg, respectively, in the reduction process of the CLOU test.
These values decreased by 0.051 μg for Hg0(g) and increased by 0.040 μg
for Hg2+(g) compared to the reference test. The removal efficiency of
Hg0(g) by the OC was 60.71%, indicating significant promotion of the
oxidation of Hg0(g) by gaseous O2 and lattice oxygen [3,11] via the
Mars-Maessen mechanism [27,41]. Moreover, an inhibitory factor in
Hg0(g) removal (the reducing atmosphere, CO and H2) [42] was elimi­
nated. The Hg2+(g)/Hg0(g) ratio was 62/38 in the reduction process of
CLOU, which was higher than the ratio in CLC (Fe-based OC) [22].
In the oxidation process, the amounts of Hg0(g) and Hg2+(g) released
were obviously decreased, that is, 0.002 ± 2.3*10− 5 μg and 0.003 μg in
the CLOU test and 0.001 ± 2.8*10− 7 μg and 0.002 μg in the reference

Table 3
Composition and BET of the OC samples.
Oxygen carrier CuO TiO2 Al2O3 SiO2 Fe2O3 CaO BET Average pore diameter
(wt%) (wt%) (wt%) (wt%) (wt%) (wt%) (m2/g) (nm)

Fresh sample 78.02 ± 0.21 5.95 ± 0.12 13.60 ± 0.17 2.43 ± 0.08 – – 4.97 6.22
Used sample 78.55 ± 0.22 4.58 ± 0.10 15.52 ± 0.18 4.70 ± 0.10 0.86 ± 0.04 0.37 ± 0.02 6.91 10.16

6
J. Ma et al.
Fig. 9. XRD patterns and compositions of the fresh and used OC samples.
test. However, the carbon residual rate was 9.01*10− 6 vs 0.314 for these
two tests. The amount of mercury in the carbon residual was small, and
some mercury (the mercury absorbed on the surface of OC) was released
in the oxidation process. The details were proven by XPS analysis of the
used OC (Section 3.3).
The Hg(p) in the ash and the ash and OC mixture were 0.001 μg and
0.066 μg, respectively. A part of the mercury, released in the reduction
process was absorbed by the OC. The Hg(p) in the used OC (15 cycles)
was 0.002 μg/g.
3.2.3. Effect of the duration time
The CO2 gasification rate of the high-rank anthracite char was rela­
tively slow [43]. Thus, the carbon conversion was evaluated at the
longer gasification/reduction time of anthracite. The carbon and Hg0(g)
conversion every minute is shown in Fig. 6. The carbon conversion was
effectively improved by gaseous O2 in the CLOU test (XC = 52.32%),
which was 3.1 times to the carbon conversion in the reference test. The
Hg0(g) conversion was 55.34% and 13.68% at the 1st min and 2nd min,
respectively, which demonstrated the effumability of mercury at a
relatively high temperature in the CLOU test [38]. The Hg0(g) conver­
sion was completed within 10 min. However, the carbon conversion
decreased gradually from 1.90% at 11 min to 0 at 22 min and the carbon
residue rate was 23.7%.
The removal efficiency of Hg0(g) was approximately 50% at the 1st
min because of the sufficient active sites and O2 provided by the
completely oxidized OC. The lowest removal efficiency of Hg0(g) was
17.40% at the 4th min. During this time, a vast amount of lattice oxygen
and O2 was consumed by the reducing gases (CO, CH4 and H2). Then, the
removal efficiency of Hg0(g) showed an uptrend from 43.00% at the 5th
min to 98.99% at the 8th min. The active phase CuO exhibited a strong
oxidizability to Hg0(g) if the competitive adsorption of the reducing
gases was attenuated [26]. In addition, the finishing time of the Hg0(g)
conversion was brought forward to 10 min. Thus, a sufficient residence
time for coal in the fuel reactor was suggested for reducing the released
mercury in the air reactor.
3.2.4. Effect of the reduction degree of CuO
The removal efficiency of Hg0(g) could be affected by the oxidation
state of Cu, the absorbed O*, and the O2 on the surface of the OC during
the reduction process. Thus, tests No. 3–5 were conducted to identify
these effects on the removal efficiency of Hg0(g).
7
Fuel Processing Technology 216 (2021) 106747
It was found that the removal efficiency of Hg0(g) in No.3 test higher
than that in No.4 test in the initial test. The explanation was that more
active sites exposed when a part of CuO was reduced in the No.3 test,
which was favor for the oxidation of the element mercury. However, the
Hg0(g) concentration increased due to the consumption of the lattice
oxygen provided by the oxygen carrier. The drop of the Hg0(g) con­
centration was 15.1 μg/Nm3 at 30 min in the test No. 4, which was larger
than the drop of the Hg0(g) concentration in test No. 3, as shown in
Fig. 7. Hg0(g) was inclined to be oxidized by high valence state CuO
rather than by low valence state Cu2O. However, the oxidability of CuO
was restricted by the reduced active lattice oxygen and absorbed O2 on
the surface of the OC, which was proven by the increasing Hg0(g) con­
centration late in test No. 4. At the same time, a large amount of O2 was
released, regarded as almost no absorbed O* and an incapacity to release
O2 by the OC. Thus, 5 vol% O2 was introduced into the fixed bed reactor
at the end of the test No. 4. The Hg0(g) concentration gradually
decreased to 26.3 μg/Nm3 with a drop of 30.3 μg/Nm3. The function of
the active lattice oxygen and absorbed O2 on the surface of the OC was
more powerful than the function of the fully oxidized CuO on the
oxidation of Hg0(g) by comparing tests No. 4 and No. 5 [27]. The
removal efficiency of Hg0(g) was sorted in descending order: CLOU test
(test No. 2) > test No. 5 > test No. 4 > test No. 3. In the CLOU test, the
highest removal efficiency of Hg0(g) was achieved because of the
favorable gases for oxidizing Hg0(g) (O2, NO, HCl, etc.) in the envi­
ronment [44,45].
3.3. Mercury on OC
The mercury on the oxidized OC (taken from the oxidation process at
15 cycles) was analyzed by XPS, as shown in Fig. 8. The peaks at 99.8,
101.9, and 104.0 eV belonged to Hg0, Hg2+ (HgS, HgCl2, and HgO) [46],
and Hg0, respectively, according to the Nist XPS database. Lattice oxy­
gen (O− ) and absorbed O2 were observed on the surface of the OC
(Section 4.2) and the latter was more favorable for oxidizing Hg0 to Hg2+
[29], forming HgO. HgS was generated by the reactions between the
elemental sulfur on the surface of the OC and Hg0 [47] or the reaction of
H2S and HgO (H2S + HgO = HgS + H2O) [23]. HgCl2 was formed mainly
by the reaction of HCl and Hg0 on the surface of CuO due to its high
binding energy with CuO(111) [48]. The fractions of Hg0 and Hg2+ were
23.48% and 76.52%, respectively, in the used OC. The unfilled orbital
structure of Cu iron could promote the generation of intermediate
J. Ma et al. Fuel Processing Technology 216 (2021) 106747

Fig. 10. XPS spectra of Cu, O, and Al for the fresh and used OC samples.

8
J. Ma et al.
Fig. 11. SEM images and EDS analysis of the fresh and used OC samples.
products, which played a key role in Hg0 oxidation [26].
4. Characterization of OC
4.1. XRF, BET, and XRD
The oxidized sample was taken after 15 redox cycles. The elements in
ash (Fe and Ca) were detected in the used sample and the Fe/Ca dis­
tribution on the OC was measured by EDS (Section 4.3). There was no
wastage of CuO during the redox cycles in Table 3. The specific surface
area and the average pore diameter of the used sample were increased
by 39.0% and 63.3%, respectively, compared to those of the fresh
sample. The possibility of contact between reducing gases and CuO was
improved, which was beneficial for enhancing the CO2 yield. The BET
9
Fuel Processing Technology 216 (2021) 106747
results indicated that anti-sintering CuO@TiO2-Al2O3 could be a suit­
able choice for industrial CLOU plants.
CuO and CuAl2O4 were the main active phases in the XRD results.
The CuAl2O4 was a new crystalline phase formed by the calcination of
CuO and Al2O3. The addition of nano-TiO2, which wrapped the Al2O3
microparticles, could interrupt the calcination of CuO and Al2O3 and
maintain the crystalline phase of CuO during multiple cycles. The
addition of nano-TiO2 effectively prevented the decay of the OC activity.
4.2. Surface compositions
The surface compositions were identified by XPS, as shown in
Fig. 10. CuO was the main component in the fresh OC with a peak of
934.1 eV and an accompanying peak of 952.7 eV, as shown in Fig. 10(a).
J. Ma et al.
CuSO4 (peak at 936.0 eV) was formed on the surface of the OC and the
mole fraction of Cu in the CuSO4 was 8.72% of the total Cu in the OC. It
was attributed to the finite sulfur tolerance of CuO [49] and the sulfate
(CuSO4) could be reduced by decorating CaO [50].
The absorbed oxygen (O− , O2− , and O, the peak range of
532.5–532.8 eV) was obviously decreased and the lattice oxygen (the
peak range of 529.0–530.9 eV) was increased in the used OC in Fig. 10
(b). The high activity of the absorbed oxygen first reacted with the
reducing gases, and oxygen vacancies were then formed. The inner
lattice oxygen was second transported to the surface of the OC to
replenish the oxygen vacancy in the late reduction process.
The fractions of Al in Al2O3 were 99.19% and 95.83% for the fresh
and used OCs, respectively, as shown in Fig. 10(c). This result indicated
that a small amount of Al2O3 was converted to CuAl2O4, which was
consistent with the XRD results of the used OC (Fig. 9). The peak of
CuAl2O4 (934.7–935.0 eV) was not found in the split peak of Cu in
Fig. 10(a), which could be covered by abundant CuO (934.1 eV).
4.3. Morphology and elements distribution
The sphericity of the fresh OC was desirable and the porous structure
was sufficient for good contact for the gas-solid reaction. The micro­
particles of Al2O3 formed the skeleton, which was adhered by the clus­
ters of TiO2 and CuO. Spherical morphology and developed porous
structure were also observed for the used OC. Channels (a diameter of 2
μm) were formed during the release process of O2, which diffused out­
wards from the inner OC particles [51]. The TiO2 and CuO clusters were
kept well on the surface of OC, which suffered exothermic oxidation and
the temperature was higher than the ambient temperature [2], as shown
in Fig. 11b (2). The stable structure of the OC was maintained well, and
the stability of the reactivity was accordingly ensured.
Cu was well dispersed with mass fractions of 78.62 wt% and 77.19 wt
% in the fresh (Fig. 11a (3)) and used (Fig. 11b (3)) OCs, respectively.
The mass fractions of Ti and Al increased to 6.51 wt% and 14.07 wt%,
respectively, in the used OC, indicating that Cu migrated inward [51] or
the deposition of ash (Al2O3, main composition in the PDS ash) on the
surface of the OC.
5. Conclusions
The distribution and fate of mercury were investigated in chemical
looping with oxygen uncoupling of anthracite. The CuO@TiO2-Al2O3
oxygen carrier exhibited good reactivity (CO2 yield >92.1%) and a
stable physiochemical structure. The existence of the OC accelerated the
carbon and mercury conversion in the reduction process. The amounts
of Hg0(g) and Hg2+(g) released were 0.033 ± 0.9*10− 5 μg and 0.054 μg
during the reduction process, and 0.002 ± 2.3*10− 5 μg and 0.003 μg
during the oxidation process, respectively. The removal efficiency of
Hg0(g) was 60.7% using the Cu-based OC and decreased to 18.3% using
the reduced OC (67% Cu2O). Under 5 vol% O2, a 53.7% removal effi­
ciency of Hg0(g) was achieved due to the recovery of the active sites, the
absorbed O, and the lattice oxygen. The ratio of Hg0 to Hg2+ in the used
OC was 23.48/76.52 by XPS. In summary, a high fraction of Hg2+ in the
fuel reactor and a lower mercury content in the air reactor could be
achieved by increasing the reduction time and supplying sufficient
oxygen.
Credit authorship contribution statement
Jinchen Ma: Conceptualization, Methodology, Validation, Formal
analysis, Investigation, Visualization, Data curation, Writing-Original
draft, Writing-Reviewing and Editing.
Xin Tian: Data curation, Writing-Original draft, Writing-Reviewing
and Editing.
Bo Zhao: Methodology, Investigation, Visualization, Data curation.
Xiaoshan Li: Investigation, Visualization, Data curation.
10
Fuel Processing Technology 216 (2021) 106747
Yongchun Zhao: Resources and Data curation.
Haibo Zhao*: Conceptualization, Resources, Writing-Reviewing and
Editing, Supervision, Project administration, Funding acquisition.
Chuguang Zheng: Resources and Data curation, Writing-Reviewing
and Editing.
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.
Acknowledgment
This work was funded by “National Natural Science Foundation of
China [52025063, 51806076, and 51906182]” and Program for HUST
Academic Frontier Youth Team. Meanwhile, the staff from the Analyt­
ical and Testing Center, Huazhong University of Science and Technol­
ogy, are appreciated for the relevant analytical work.
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