Chemical Engineering Journal 428 (2022) 132110

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Chemical Engineering Journal

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Ni-CaO dual function materials prepared by different synthetic modes for

integrated CO2 capture and conversion
Guodong Wang a, Yafei Guo a, *, Jun Yu a, Fanghua Liu a, Jian Sun a, Xinru Wang b, Tao Wang b,
Chuanwen Zhao a, *
a
School of Energy and Mechanical Engineering, Nanjing Normal University, No. 2, Xuelin Road, Qixia District, Nanjing, Jiangsu 210023, PR China
b
State Key Laboratory of Clean Energy Utilization, Zhejiang University, Hangzhou 310027, China

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

Keywords: Dual-functional materials (DFMs) present broad prospects in CO2 capture and in-situ conversion to value-added
CO2 capture and conversion products using renewable energy. Herein, we proposed and demonstrated three different synthetic modes for
Ni-CaO preparing Ni-CaO DFMs using carbide slag as calcium precursor. CO2 sorption and in-situ hydrogenation per­
Dual function materials
formance of the Ni-CaO DFMs was evaluated using a fixed-bed reactor. Results indicated that CO2 sorption
Synthetic modes
capacity and CO productivity of the synthesized Ni-CaO DFMs depended on the synthetic modes. The desired Ni/
Reverse water–gas shift
CS-P30-C synthesized by acid pretreatment of carbide slag followed by citric acid complex exhibited a high CO2
sorption capacity (13.28 mmol/g DFMs) and a great CO productivity (5.12 mmol/g DFMs) under the isothermal
testing temperature of 650 ◦ C. The sample also showed stable CO2 uptake and CO productivity within 17 cycles.
The good CO2 sorption and in-situ hydrogenation performance were associated with the better textural prop­
erties, smaller particle size and more uniform dispersion of Ni species, which were resulted from propionic acid
pretreatment and citric acid complex processes. In addition, Ni-CaO pellet with high mechanical strength (2.88
MPa) and abrasion ability (weight loss of 2.36% after 3000 rotations). had also been prepared by the extrusion-
spheronization method. The pelletization process adversely affected the CO2 sorption and in-situ hydrogenation
performance, but the pellet exhibited good stability in cyclic operations.

1. Introduction combining CO2 conversion and renewable energy utilization [13–15].

DFMs are generally consisted of a CO2 adsorbent and a catalytic
The increasingly severe energy crisis and environmental issues component that are well dispersed on porous supports with large surface
resulted from the massive burning of fossil fuels have remained as un­ areas. One typical DFM contains nano-sized Ru and CaO supported on
precedented challenges for human beings [1–3]. As a result, effective γ-Al2O3 for CO2 capture and methanation [16]. CO2 is firstly captured
measures are critically necessary to reduce CO2 emissions and mitigate from flue gas stream at 320 ◦ C by the CaO adsorbent. The captured CO2
the impacts of global warming [4,5]. Carbon capture and utilization is then regenerated in H2 stream, accompanied by in-situ methanation
(CCU) that aims at capturing CO2 from flue gas or atmosphere and over the Ru sites. Despite that highly-active Ru catalyst is involved in
converting it into value-added products, has been considered as a DFM, the methane yield is far from expectation. This is because methane
promising strategy for relieving energy crisis and environmental issues yield to some extent depends on CO2 captured and released. While the
while achieving a carbon–neutral society [6–9]. On the other hand, wind CO2 capture capacity of the Ru-CaO has been limited by the low CaO
and solar energy resources feature volatility and intermittence, and their loading. In addition, the scale-up applications of Ru-based DFMs have
scale-up applications therefore have been limited [10,11]. Conse­ also been restricted by the high cost and limited reserve of Ru.
quently, there is a growing interest in converting the captured CO2 into In this framework, Ni has been regarded as a potential alternative to
value-added products using renewable energy [12]. Ru for composing DFMs, due to its comparable activity, low cost, and
Dual-functional materials (DFMs) that enable CO2 capture and in- plentiful reserve [17]. Miguel et al. packed a commercial K-promoted
situ conversion to synthetic fuels, serve as an important link in hydrotalcite CO2 adsorbent and Ni-based methanation catalyst in a

* Corresponding authors.
E-mail addresses: [email protected] (Y. Guo), [email protected] (C. Zhao).

https://doi.org/10.1016/j.cej.2021.132110
Received 31 May 2021; Received in revised form 20 August 2021; Accepted 25 August 2021
Available online 1 September 2021
1385-8947/© 2021 Elsevier B.V. All rights reserved.
G. Wang et al. Chemical Engineering Journal 428 (2022) 132110

Fig. 1. Schematic diagram of the procedures for synthesizing the different Ni-CaO DFMs.

sorptive reactor for integrated CO2 capture and conversion. CO2 sorp­ ratio in the products. Tailoring the composition of syngas is important
tion capacity and CH4 productivity of such configuration were 0.38 for the synthesis of downstream products: CO/H2 = 1:2 for methanol
mmol CO2/g DFMs adsorbent and 0.35 mmol CH4/g DFMs, respectively production, CO/H2 = 2:1 for Fischer-Tropsch synthesis, and CO/H2 =
[18]. Kim et al. combined the Ni/MgO-Al2O3 catalyst with CaO adsor­ 1:1 for dimethyl ether production [10,33]. Here, Ni-CaO DFMs were
bent for integrated CO2 capture and in-situ dry reforming of methane, synthesized for CO2 capture and in-situ hydrogenation to syngas.
and they demonstrated the process was feasible and economically Textural structure of the Ni-CaO DFMs is critically important, since
attractive [19]. It is noticed that CO2 sorption capacities of the reported developed pore structure enables fast CO2 diffusion for enhanced CO2
configurations are far from expectation, and the yields of the target capture capacity and large surface area promotes Ni dispersion on CaO
products therefore are limited. for improved catalytic activity. It is worth noting that the good textural
Efforts have been devoted to promoting the CO2 sorption capacities structure of the Ni-CaO DFMs depends on the synthesis methods. Thus,
and the yields of target products. Tian et al. combined the Ni-based Ni-CaO DFMs were synthesized in this work via three different modes: I)
catalyst and CaO adsorbent as an integrated DFM, and the DFM wet-mixing; II) acidification/impregnation; III) acidification/impreg­
allowed CO2 capture via calcium-looping and in-situ dry methane nation combined with citric acid complexation. The objective of this
reforming to yield syngas with a high productivity (10.4 mmol/g DFMs) work is to study the effect of synthesis mode on the structure–activity
at 800 ◦ C [20]. Sun et al. constructed the cerium modified CaO-Ni DFMs relationships of the Ni-CaO DFMs for CO2 capture and in-situ hydroge­
via the sol–gel method, and the DFMs were capable of capturing CO2 and nation to syngas. The results will provide significant guidance for
hydrogenation to CO with a high yield of 7.3 mmol/g DFMs at 650 ◦ C designing highly efficient DFMs and lay the groundwork for their scale-
[21]. up application in CO2 capture and conversion.
The above analysis indicates that Ni-CaO DFMs show potential for
CaO + CO2 ↔ CaCO3 , △Hr, 298k = - 178 kJ/mol (1)
integrated CO2 capture and conversion [22,23]. CaO as the key
component in the DFMs, plays pivotal roles in determining the CO2
CaCO3 + H2 ↔ CaO + CO + H2 O, △Hr, 298k = + 219.2 kJ/mol
sorption capacity and product yield. Considerable efforts have been
made to improve the CO2 sorption performance of CaO-based adsor­ (2)
bents. Particularly, synthetic CaO adsorbents derived from waste cal­
cium precursors have attracted increasing attention [24–28]. Carbide 2. Experimental
slag as one typical calcium precursor, shows particularly potential in
fabricating CaO adsorbents for cost-effective CO2 capture [29–32]. 2.1. Raw materials
Meanwhile, carbide slag should also be a promising candidate for Ni-
CaO DFMs. Carbide slag (CS) sampled from Hunan Province, China, was
In this work, carbide slag was employed as calcium precursor for employed as the calcium precursor. The results of X-ray fluorescence
synthesizing Ni-CaO DFMs for integrated CO2 capture (Eq. (1)) and (XRF) analysis in Table S1 indicate the CaO content in the carbide slag is
conversion (Eq. (2)). Reverse water gas shift (RWGS) plays an important as high as 70.6 wt%. The results of laser particle size analysis show that
role in CO2 hydrogenation. One feature of RWGS is the tunable CO/H2 the median particle size [d (0.5)] of the carbide slag is 46.6 μm. Nickel
nitrate (Ni(NO3)2⋅6H2O, AR, 98.0%) was selected as catalytic active

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G. Wang et al. Chemical Engineering Journal 428 (2022) 132110

stream was switched to 10% CO2/N2 (180 ml/min) and preserved for 30
min for CO2 sorption. Once the sorption process was completed, the
stream was switched to pure N2 to purge the reactor for 5 min. In-situ
hydrogenation test was then performed by regenerating the DFM in
5%H2/N2 (180 ml/min). Once the hydrogenation process finished, the
reactor was purged in a pure N2 stream for 5 min. By repeating the
above-mentioned CO2 sorption and hydrogenation procedures, cyclic
CO2 sorption and in-situ hydrogenation tests can be performed to
evaluate the working stabilities of the Ni-CaO. Change of gas concen­
tration in CO2 sorption and hydrogenation processes was recorded by
the on-line gas analyzer (MRU) connected to the outlet of the reactor.
Fig. S2 shows the flowchart of the cyclic CO2 sorption and hydrogena­
tion tests. CO2 sorption capacities and CO productivities of the DFMs are
calculated via Eq. (3) and Eq. (4) [34].
∫ t( )
Q Cin − Cout
qCO2 = × dt (3)
m × Vm 0 1 − Cout
∫ t
Q
qCO = × (CCO )dt (4)
Fig. 2. Gas concentration curves of integrated CO2 sorption and in-situ hy­ m × Vm 0
drogenation behaviors of Ni/CS, Ni/CS-P30 and Ni/CS-P30-C at 650 ◦ C.
In which, qCO2 (mmol CO2/g DFMs) is the CO2 sorption capacity, Q
(ml/min) is the gas flow rate, m (g) is the mass of DFMs, Vm is molar
component. Propionic acid (C3H6O2, AR, 99.5%) was selected as acid
volume of gas, Cin and Cout are the inlet and outlet CO2 concentrations,
modified solvent. Citric acid monohydrate (C6H8O7⋅H2O, GR, 99.8%)
qCO (mmol CO/g DFMs) is the CO productivity, CCO is the outlet CO
was determined as complexes or dispersant.
concentration.

2.2. Preparation of DFMs 2.4. Characterization

Ni-CaO DFMs were prepared by three different synthetic modes: I) Crystalline structures of the DFMs were investigated using the D8
wet-mixing; II) acidification/impregnation; III) acidification/impreg­ Advance X-ray diffraction (XRD) instrument. Textural properties of the
nation combined with citric acid complexation. The schematic diagram samples were obtained from nitrogen adsorption–desorption isotherms
of the synthesis procedures of Ni-CaO DFMs is illustrated in Fig. 1. conducted at − 196 ◦ C using the ASAP 2460 instrument. The specific
Mode I: wet-mixing surface areas and pore size distributions were determined by BET
A certain gram of carbide slag was mixed with nickel nitrate and (Brunauer-Emmett-Teller) and BJH (Barrett-Joyner-Halenda) methods.
distilled water, and then the slurry was stirred for 4 h to achieve uniform The surface morphologies of the DFMs were studied by recording the
mixing. The theoretical NiO loading in the DFM is 10 wt%. The mixtures scanning electron microscopy (SEM) images using the Hitachi SU8100
were then dried at 110 ◦ C for 12 h in a muffle furnace at 850 ◦ C (ramping instrument. The transmission electron microscopy (TEM) images were
rate: 3 ◦ C/min) for 5 h. The obtained DFM was labelled as Ni/CS, in recorded and elemental mapping was conducted using the JEOL-2100F
which CS denoted carbide slag. instrument. The atomic concentrations and valence states of the DFMs
Mode II: acidification/impregnation were determined by X-ray photoelectron spectroscopy (XPS) analysis
A certain gram of carbide slag was mixed with propionic acid (sol­ using the EscaLab 250xi instrument. H2-chemisorption tests were per­
id–liquid ratio 1:20) under stirring for 2 h to extract Ca ions. Nickel formed on AutoChem II 2920 to analyze Ni dispersion. The sample was
nitrate was then added to the filtrate, and the mixtures were further reduced for 1 h in 10% H2 at 300 ◦ C, and then cooled to 50 ◦ C. Ar gas was
stirred for 2 h. The mixtures were then subject to drying and calcination used to purge, and then passing in pulse gas for testing. Ni dispersion (D)
under the same conditions to Mode I. The obtained DFM was labelled as and Ni specific surface area (S) and Ni mean particle size (d) were
Ni/CS-P30, in which P30 denoted the concentration of propionic acid calculated via Eqs. (5), (6) and (7), respectively [35].
(30%).
Mode III: acidification/impregnation combined with citric acid 2V × NA/V
D= m
× 100 (5)
complexation. m × ω × NA/
M
Ca ions were firstly extracted from carbide slag with the assistance of
propionic acid using the same method in Mode II. Nickel nitrate and 2V × NA × σNi
S= (6)
citric acid were added to the Ca-rich filtrate and stirred for 2 h at 80 ◦ C m 0 × Vm × ω
for complexation. The stoichiometric ratio of citric acid and Ca ions was
1:1. The obtained complex was then subject to drying and calcination 6 × 103 × ω
d= (7)
under the same conditions to Mode I. The samples were labelled as Ni/ ρNi × S
CS-P30-C, in which C denoted citric acid.
In which, D (%) the Ni dispersion, S (m2/g) is the Ni specific surface
area, d (nm) is the Ni particle size. V (mL) is the amount of hydrogen
2.3. Integrated CO2 sorption and in-situ hydrogenation test adsorbed on the surface of the sample, NA is the Avogadro’s number, M
(58.7 g/mol) is the molar mass of a Ni atom, Vm (22.4 L/mol) is the
The integrated CO2 sorption and in-situ hydrogenation tests were molar volume of hydrogen, m is the mass of DFMs, m0 is the mass of NiO
carried out in a fixed-bed reactor. The schematic diagram of the particles. ω is the load of NiO particles. ρNi (8.902 g/cm3) is the density
experimental setup is illustrated in Fig. S1. The specific procedures for of the Ni atom and σNi (0.0649 nm2) is the cross sectional area of the Ni
testing were as follows. 0.5 g of the sample was placed in the fixed-bed atom.
reactor and the reactor was heated to 650 ◦ C in pure N2 (180 ml/min)
with 10 ◦ C/min. The sample was then pretreated in 5%H2/N2 (180 ml/
min) for 2 h, followed by N2 purge for 5 min. Subsequently, the gas

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G. Wang et al. Chemical Engineering Journal 428 (2022) 132110

Fig. 3. Integrated CO2 sorption and in-situ hydrogenation behaviors of Ni/CS, Ni/CS-P30 and Ni/CS-P30-C at 650 ◦ C (a) CO2 sorption capacity and (b) CO
productivity.

(below 600 ◦ C) is quite necessary. However, at lower temperatures,

Table 1
RWGS process is always accompanied by methanation, which makes it
CO2 sorption and in-situ hydrogenation performance of different Ni-CaO DFMs
hard to achieve with high selectivity. In addition, the optimum tem­
at the first cycle.
perature range for carbonation of calcium carbide slag is 650–700 ◦ C
DFMs CO2 sorption capacity, CO productivity, CO2 conversion, [37]. Therefore, 650 ◦ C is optimal for CO2 sorption and in-situ hydro­
mmol/g mmol/g %
genation of Ni-CaO DFMs. The integrated CO2 sorption and in-situ hy­
Ni/CS 3.56 0.78 21.90 drogenation performance of the DFMs prepared with different modes
Ni/CS- 8.40 2.86 34.00
was evaluated at 650 ◦ C in a fixed-bed reactor. Fig. 2 shows the dynamic
P30
Ni/CS- 13.28 5.12 38.60 concentration curves of CO2, CO and H2 in the first cycle. In the initial
P30-C carbonation stage, CO2 is completely captured by the CaO in the DFMs
within 1.8 ~ 3.4 min, then fast dynamic CO2 sorption breakthrough can
be observed, followed by the slow growth in outlet CO2 concentration
until equilibrium adsorption. After the CO2 sorption is completed, pure
N2 is introduced to purge the reactor. Subsequently, a flow of 5%H2/N2
(180/min) is introduced for regeneration and in-situ hydrogenation.
During this stage, the desorbed CO2 reacts with H2, and CO is released
slowly within the long time span of 35 ~ 95 min.
CO2 sorption capacities and CO productivities of the different DFMs
over the 5 cycles are calculated using Eqs. (3) and (4), and the results are
illustrated in Fig. 3 and Table 1. The initial CO2 sorption capacities of
Ni/CS, Ni/CS-P30 and Ni/CS-P30-C are 3.56, 8.40, 13.28 mmol/g DFMs,
respectively. Their CO productivities are 0.78, 2.86, 5.12 mmol/g DFMs,
respectively. Amongst, the Ni/CS-P30-C exhibits the maximum CO
productivity with the CO2 conversion of 38.55% and a nearly 100% CO
selectivity. Catalytic performance of the DFMs in this work has been
compared to those of the Ni-based catalysts for RWGS. As indicated in
Table S2, CO2 conversions of the 5%Ni/CeO2 and 10%Ni/MgO catalysts
at 650 ◦ C are 40% and 38%, and their CO selectivity are 97% and 95%
[38,39]. Besides, the inherent RWGS activity of Ni/CS-P30-C was eval­
uated at 650 ◦ C under the co-feed H2-CO2 stream (5%CO2, 20%H2/N2,
180 ml/min). The CO2 conversion rate and CO selectivity of Ni/CS-P30-
C is 57.2% and 100% at 650 ◦ C, which is higher than those of the 5%Ni/
CeO2 and 10%Ni/MgO catalysts mentioned above. Hence, the desired
Fig. 4. XRD patterns of the fresh Ni-CaO DFMs. Ni/CS-P30-C sample shows comparable catalytic performance to the
reported Ni-based catalysts. CO2 sorption capacity of the desired Ni/CS-
3. Results and discussion P30-C catalyst drops to 8.87 mmol CO2/g DFMs after 5 cycles. However,
the CO productivity over the 5 cycles keeps stable at 5 mmol CO/g DFMs
3.1. Performance evaluation of the different DFMs with a high CO2 conversion of 56.14%. The CO2 sorption and in-situ
hydrogenation performances of the Ni/CS and Ni/CS-P30 are similar
The RWGS process is thermodynamically beneficial at higher tem­ to that of the Ni/CS-P30-C. CO productivities of Ni/CS and Ni/CS-P30
peratures owing to its endothermic nature [36]. Increasing the reaction are maintained at 1.2 and 2.9 mmol CO/g DFMs within 5 cycles,
temperature to 900 ◦ C and the H2/CO2 ratio to 4 can only harvest 84% of which are far less than that of Ni/CS-P30-C. Hence, it is concluded that
the CO2 conversion. Therefore, the RWGS process at lower temperatures Ni/CS-P30-C shows good RWGS activity and exhibits good CO2 sorption

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G. Wang et al. Chemical Engineering Journal 428 (2022) 132110

Fig. 5. N2 adsorption–desorption isotherms and pore size distributions of the fresh DFMs. (a) N2 adsorption–desorption isotherms, (b) pore size distributions.

Ni/CS-P30 and Ni/CS-P30-C show diffraction peaks for CaO (JCPDS No.
Table 2
37–1497). The diffraction peaks detected at 2θ = 43.2◦ could be
Physicochemical properties of the different Ni-CaO DFMs.
assigned to the (2 0 0) crystal plane of NiO (JCPDS No. 04–0835) [40].
DFMs BET BJH Pore Ni Ni specific Ni particle Besides, diffraction peaks for Ca(OH)2 can also be observed, which is
surface volume dispersion surface area size (nm)
associated with the hydration of CaO due to the expose of the DFM to
area (m2/ (cm3/g) (%) (m2/gNi)
g) moisture.
Fig. 5 depicts the N2 adsorption–desorption isotherms and pore size
Ni/CS 7.27 0.01 6.4 54.4 15.1
Ni/CS- 12.93 0.03 7.6 64.7 12.7
distributions of the different DFMs. According to the IUPAC classifica­
P30 tion, all the samples present typical IV-type isotherm with H3 hysteresis
Ni/CS- 21.62 0.04 18.5 123.8 5.2 loop, indicating the presence of mesopore structure with slit pore in the
P30- DFMs [41]. The samples exhibit similar pore size distribution, as the
C
majority of the pores located in the pore diameter range of 2–100 nm.
This indicates the DFMs contain mesopores and macropores, and the
and in-situ hydrogenation performance. pores in the 2–100 nm range have been proved important in the
carbonation process of CaO [42].
Textural parameters of the different DFMs are listed in Table 2. The
3.2. Characterization of the DFMs BET surface area and pore volume of Ni/CS are 7.27 m2/g and 0.01 cm3/
g. With propionic acid pretreatment and citric acid complex, the textural
XRD patterns of the DFMs are shown in Fig. 4. XRD profiles of Ni/CS,

Fig. 6. SEM, TEM and elemental mapping images of the fresh DFMs (a, d) Ni/CS, (b, e) Ni/CS-P30 and (c, f, g) Ni/CS-P30-C.

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G. Wang et al. Chemical Engineering Journal 428 (2022) 132110

Fig. 7. XPS spectra of the fresh DFMs (a) survey spectra; (b) O 1 s spectra; (c) Ca 2p spectra; (d) Ni 2p spectra.

Fig. 8. Schematic illustration of the integrated CO2 sorption and in-situ hydrogenation over the desired Ni/CS-P30-C.

structure of the Ni-CaO DFM has been significantly promoted, as indi­ visible on the surface of the samples, as depicted by their SEM images
cated by the higher BET surface areas and pore volumes of Ni/CS-P30 (Fig. 6a-c). The well-developed pore structure of Ni/CS-P30-C can be
and Ni/CS-P30-C. The increased surface area and expanded pore ascribed to the following aspects. On the one hand, propionic acid
structure will favor CO2 diffusion and adsorption, and the Ni/CS-P30 pretreatment of the carbide slag precursor will induce pore-expanding
and Ni/CS-P30-C samples therefore exhibit higher CO2 sorption effect for higher porosity. On the other hand, citric acid complex of
capacities. the calcium and nickel salts will produce low-density foam, which will
Fig. 6 shows the high magnification SEM, HRTEM and elemental be decomposed under the high calcination temperature. The released
mapping images of the different DFMs. Porous structure can be clearly gas will contribute to secondary pore-expanding. HRTEM images in

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G. Wang et al. Chemical Engineering Journal 428 (2022) 132110

Fig. 9. Integrated CO2 sorption and in-situ hydrogenation performance of (a) Ni/CS, (b) Ni/CS-P30-C and (c) Ni/CS-P30-C-P at 650 ◦ C within 17 cycles.

Fig. 6d-f show that both the surface morphology and dispersing NiO in images of Ni/CS and Ni/CS-P30 in Figs. S3 and S4 show relatively un­
the DFMs vary from their synthesis modes. For the Ni/CS sample, NiO even distribution of Ni and Ca elements. It is usually postulated that the
particles show uneven distribution on the CaO matrix. In contrast, the even dispersion of active components is beneficial for preventing the
nano-sized NiO particles are dispersed more uniformly on CaO for Ni/ aggregation of CaO and Ni particles and postponing the grain sintering
CS-P30 and Ni/CS-P30-C [43]. The insets in Fig. 6d-f show the parti­ [11]. The enlarged HRTEM images in Fig. S5 show that obvious lattice
cle size distributions of NiO in the different DFMs. The average particle fringes with different d-spacing values for Ni/CS, Ni/CS-P30 and Ni/CS-
sizes of NiO are calculated as 18.3, 12.7 and 13.6 nm for Ni/CS, Ni/CS- P30-C. The lattice fringes of 0.234–0.238 nm and 0.199 nm should be
P30 and Ni/CS-P30-C, respectively. Notably, Ni/CS-P30-C shows much attributed to the (2 0 0) and (1 1 1) lattice plane of NiO. Overall, propi­
more uniform dispersion of NiO, as the majority of the NiO nanoparticles onic acid pretreatment and citric acid complex (Mode III) benefit the Ni/
(NPs) are distributed in the range of 10 ~ 16 nm. Fig. 6(g) shows the CS-P30-C sample not only developed pore structure for improved CO2
EDX elemental mapping images of O, Ca and Ni for Ni/CS-P30-C. Results sorption capacity but also more uniform dispersion and smaller grain
indicate that the O, Ca and Ni elements achieve homogeneous mixing. In size of NiO NPs for enhanced CO yield.
other words, the active NiO NPs are uniformly dispersed over the CaO Surface compositions and valence states of the different DFMs are
adsorbents, which is of great significance for improving both adsorption examined by XPS analysis, and the results are depicted in Fig. 7. The
and catalytic activity [44]. On the contrary, the EDX elemental mapping survey spectra of the different DFMs in Fig. 7(a) include Ni 2p, O 1 s, Ca

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G. Wang et al. Chemical Engineering Journal 428 (2022) 132110

accommodate and anchor Ni species and enable their uniform disper­

sion. On the other hand, the citric acid complex process will complex Ni
metallic ions, inhibit the growth of Ni crystallite as well as prevent
particle agglomeration, and thus will benefit the sample minimized Ni
particle size [52].
Compared to the Ni/CS and Ni/CS-P30 samples synthesized by Mode
I and Mode II, the desired Ni/CS-P30-C DFMs prepared by Mode III
shows better physicochemical properties and CO2 sorption and in-situ
hydrogenation performance. The promoting roles of propionic acid
pretreatment and citric acid complexing are further illustrated in Fig. 8.
The propionic acid pretreatment and citric acid complexing possess a
double functionality, namely, to improve the microstructures of Ni-CaO
DFMs for enhanced CO2 sorption performance due to the pore-
expanding effect in heat and gas release, and to enable uniform
dispersion of Ni NPs for reinforced hydrogenation due to the strong
anchoring of Ni species over the surface or within the channels of CaO.
Furthermore, NiO does not react with CaO to form new phase and the
dispersed NiO will prevent the growth and agglomeration of CaO grains
through isolation. This has further endowed the Ni/CS-P30-C with better
Fig. 10. CO2 sorption capacities and CO productivities of (a) Ni/CS, (b) Ni/CS-
P30-C and (c) Ni/CS-P30-C-P at 650 ◦ C within 17 cycles. microstructures (uniform dispersion, enhanced porosity and optimized
pore size distribution) and improved CO2 adsorption performance and
cycle stability [53]. The highly dispersed NiO NPs have offered a high Ni
2p and C 1 s XP profiles. The O1s XP profiles in Fig. 7(b) can be
specific surface area for Ni/CS-P30-C, and more surface active sites can
deconvoluted into three peaks, which correspond to three different ox­
thus be exposed for enhanced CO2 hydrogenation activity [21].
ygen species (O1, O2 and O3). The peaks observed at the binding en­
ergies of 530.6 and 531.3 eV are associated with the lattice oxygen (O1)
3.3. Cyclic CO2 sorption and in-situ hydrogenation performance
and oxygen vacancy (O2), respectively. The peak presents at the binding
energy of 532.1 eV can be assigned to the surface adsorbed oxygen
For practical application, twin fluidized beds are suitable for the
species (O3) [45,46]. It is well perceived that oxygen mobility plays an
operation of consecutive CO2 sorption and hydrogenation. However, the
important role in catalytic redox reactions [47]. XPS results indicate that
practical CO2 sorption and hydrogenation performance would be limited
the oxygen species are primarily presented as lattice oxygen (O1) and
considering the loss of DFMs materials due to elutriation under a high
oxygen vacancy (O2). Particularly, O2 accounts for 40%, 39% and 38%
fluidized velocity [54]. One effective strategy to overcome such problem
in the oxygen species for Ni/CS-P30-C, Ni/CS-P30 and Ni/CS, respec­
is the pelletization of the DFMs [55]. Therefore, the Ni/CS-P30-C-P
tively. The Ni/CS-P30-C and Ni/CS-P30 samples show slightly higher O2
pellets with particle size ranging from 0.9 to 1.25 mm were prepared
ratios, indicating they exhibit better oxygen mobility. The high resolu­
via the extrusion-spheronization method reported in literature [56].
tion XP spectra of Ca 2p in Fig. 6(c) show the characteristic peak for Ca
High mechanical strength and abrasion ability, which are critically
2p3/2 at 346.7 eV and a satellite peak for Ca 2p1/2 at 350.3 eV, which
important for the consecutive operations of the DFMs pellets in twin
indicate that Ca(II) is the valence state for calcium species [11,48]. As
fluidized-bed reactors. Therefore, it is meaningful to test the mechanical
depicted in Fig. 6(d), the XP profiles of Ni 2p show characteristic peaks
strength and abrasion ability. The LYYS-1000 N mini-type precision
for Ni 2p3/2 and Ni 2p1/2 at 854.8 and 873.2 eV, respectively. The
compression tester was used to test the peak force required to crush a
peaks at 861.2 and 879.3 eV are shake-up satellite peaks [49]. The peak
single DFMs pellet. The attrition properties of the Ni/CS-P30-C-P were
separation between the two main peaks of Ni 2p3/2 and Ni 2p1/2 is
measured using the CS-2 friability tester with a rotating speed of 25 rpm.
18.4 eV, which is in good agreement with that reported in literatures,
The Ni/CS-P30-C-P were put in the drums and then was operated for
indicating that the observed peaks at 854.8 and 873.2 eV are associated
3000 rotations. The average compressive strength of the Ni/CS-P30-C-P
with NiO [50,51]. Besides, the different Ni-CaO DFMs exhibit different
pellets is 2.88 MPa, which is close to that of the carbide slag pellets
ratios of Ni2+ to Ni3+. Ni/CS shows a low Ni2+/Ni3+ ratio of 0.48. In
(3.17 MPa), as an indicative of good abrasion resistance in repeated
contrast, the Ni2+/Ni3+ ratios of Ni/CS-P30 and Ni/CS-P30-C increase to
cycles. Ni/CS-P30-C-P pellets exhibits good abrasion performance, with
0.66 and 0.83. A higher Ni2+/Ni3+ ratio means that the catalyst can offer
the weight loss of 2.36% after 3000 rotations, which possess a better
abundant active sites to achieve a higher catalytic activity [21,45].
abrasion ability with the carbide slag pellets doped with microcrystal­
H2 chemisorption tests are conducted to further study the dispersion
line cellulose, with the weight loss of 2.78% after 2000 rotations [26].
of Ni NPs in the different DFMs reduced at 10% H2/N2, and the results
Fig. 9 and Fig. 10 show the CO2 sorption and hydrogenation per­
are summarized in Table 2. The Ni/CS and Ni/CS-P30 samples show
formance of Ni/CS, Ni/CS-P30-C and Ni/CS-P30-C-P pellets in 17 cycles.
close Ni dispersion (6.4% vs. 7.6%) and Ni specific surface area (54.4 vs.
CO2 sorption capacities and CO productivities of the samples at the first
64.7 m2/g Ni). With propionic acid pretreatment of the carbide slag and
and last cycles are summarized in Table S3. CO2 sorption capacity and
citric acid complex, surface area and pore structure of Ni/CS have been
CO productivity of Ni/CS-P30-C are much higher than those of Ni/CS,
improved, and Ni dispersion and Ni specific surface area have been
which indicates that propionic acid pretreatment and citric acid com­
significantly increased to 18.5% and 123.8 m2/g Ni, respectively. Be­
plex promote the CO2 sorption and in-situ hydrogenation performance
sides, the Ni particle sizes of Ni/CS and Ni/CS-P30 are close (15.1 vs.
of Ni-CaO DFM. CO2 sorption capacities of Ni/CS-P30-C and Ni/CS-P30-
12.7 nm), while the Ni/CS-P30-C sample exhibit the minimum Ni par­
C-P decrease by 48.6% and 25.7% respectively within the first 6 cycles
ticle size of 5.2 nm. Thus, the propionic acid pretreatment and citric acid
and then show no significant change in the next 11 cycles. The change in
complex would endow the desired Ni/CS-P30-C with not only better Ni
CO productivity of the two samples over repeated cycles shows similar
dispersion but also minimized Ni particle size for enhanced catalytic
trend. Notably, CO2 sorption capacity and CO productivity of the Ni/CS-
activity for higher CO yield. This can be further associated with the
P30-C-P are lower than those of Ni/CS-P30-C, indicating that pelleti­
following aspects. On the one hand, the propionic acid pretreatment of
zation process adversely affect the CO2 sorption and in-situ hydroge­
the carbide slag precursor contributes to extending surface area and
nation performance of Ni-CaO DFM. Besides, the working stability of Ni/
expanding pore structure, which will provide more space to
CS-P30-C-P is comparable to that of Ni/CS-P30-C, which implies that

8
G. Wang et al. Chemical Engineering Journal 428 (2022) 132110

Fig. 11. SEM, TEM and elemental mapping images of the different Ni-CaO DFMs (a) fresh Ni/CS-P30-C-P, (b) spent Ni/CS-P30-C-P, (c, e, g) spent Ni/CS and (c, f, g)
spent Ni/CS-P30-C.

Table 3
A comparison of CO2 sorption capacity of the desired Ni-CaO to similar DFMs reported in literatures.
DFMs Method Reaction Testing conditions CO2 uptake, mmol/g Productivity, mmol/g Refs.
T, CO2 sorption CO2 DFMs DFMs
o
C conversion

10Ni-10CaO/Al2O3 impregnation methanation 400 9.5% CO2/Ar 10% H2/Ar 0.31 0.14 [59]
10Ni/CaO sol–gel method methanation 500 10% CO2, 10% H2O 90% H2/N2 8.96 8.34 [60]
/N2
15Ni-15Ca/Al2O3 wet impregnation methanation 520 10% CO2/Ar 10% H2/Ar 0.17 0.14 [44]
Ca1Ni0.1Ce0.033 sol–gel RWGS 650 15% CO2/N2 5% H2/N2 14.1 7.2 [21]
combustion
Ca1Ni0.1 sol–gel RWGS 650 15% CO2/N2 5% H2/N2 15.0 6.9 [21]
combustion
Ni20@(K − Ca)50/ sol − gel DER 650 10% CO2/N2 5% C2H6/N2 0.99 0.95 [61]
(γ-Al2O3)50 procedure
CaO + Ni/MgO-Al2O3 coprecipitation DRM 820 20% CO2/N2 2.4% CH4/N2 7.05 \ [19]
Ni/CS-P30-C sol–gel RWGS 650 10% CO2/N2 5% H2/N2 13.86 5.52 this
combustion work
Ni/CS-P30-C-P sol–gel RWGS 650 10% CO2/N2 5% H2/N2 8.95 5.33 this
combustion work

9
G. Wang et al. Chemical Engineering Journal 428 (2022) 132110

pelletization exerts no remarkable influence on its working stability. 10Ni-10CaO/Al2O3, 15Ni-15Ca/Al2O3 and 10Ni/CaO reported in liter­
Fig. 11 displays the SEM images of the fresh and spent Ni/CS-P30-C-P atures. Besides, the values are also comparable to those of the Ca1N­
and the SEM, TEM and elemental mapping images of the Ni/CS and Ni/ i0.1Ce0.033 and Ca1Ni0.1 DFMs reported by Sun et al. Thus, the desired
CS-P30-C samples after 17 cycles. The fresh Ni/CS-P30-C-P shows Ni/CS-P30-C shows potential in CO2 sorption and in-situ hydrogenation
clearly visible spherical morphology with relatively smooth surfaces to syngas. In addition, the valorization of carbide slag for fabricating Ni/
(Fig. 11(a-1)). The loose surface and well-developed pore structure of CS-P30-C for CO2 capture and conversion shows economic and envi­
the fresh Ni/CS-P30-C-P will benefit the pellets facilitated CO2 diffusion ronmental implications.
and sorption (Fig. 11(a-2)). However, compared to the fresh Ni/CS-P30-
C, part of the porous structure required for CO2 diffusion has been 4. Conclusion
destroyed in the pelletization process for Ni/CS-P30-C-P [31,57]. In
addition, in the inner of the spherical particle exists intra-particle Ni-CaO DFMs were synthesized from the carbide slag precursor using
diffusion resistance, which hinders the mass transfer process [26,54]. the three synthetic modes of wet mixing (Mode I), acidification/
Thus, CO2 sorption capacity of Ni/CS-P30-C-P is adversely affected. For impregnation (Mode II), and acidification/impregnation combined with
the spent Ni/CS-P30-C-P sample after 17 cycles, no obvious cracks could citric acid complexation (Mode III). CO2 sorption and in-situ hydroge­
be observed on the surface (Fig. 11(b-1)), indicating the as-synthesized nation performance of the as-prepared Ni-CaO DFMs were evaluated.
DFMs pellets show good heat resistance at high temperature. The Effect of synthetic modes on the structure–property-activity relation­
enlarged SEM image in Fig. 11(b-2) shows the Ni/CS-P30-C-P suffers ships of the Ni-CaO DFMs was demonstrated. The desired Ni/CS-P30-C
obvious sintering after 17 consecutive operations. Fig. 11(c-1) and (c-2) prepared by Mode III showed outstanding CO2 uptake (13.86 mmol
show that Ni/CS suffers more severe sintering, as evidenced by the CO2/g DFMs) and high CO productivity (5.52 mmol CO2/g DFMs). Ni/
obvious particle fusion and agglomeration and pore structure blockage. CS-P30-C also exhibited good working stability within 17 consecutive
In contrast, the spent Ni/CS-P30-C sample remains developed porous CO2 sorption and in-situ hydrogenation cycles. Propionic acid pre­
structure (Fig. 11(d-1) and (d-2)), implying that propionic acid pre­ treatment and citric acid complex had benefitted the Ni/CS-P30-C
treatment and citric acid complex will promote pore formation and extended surface area and expanded pore structure for accommoda­
inhibit grain sintering and will thus endow the Ni/CS-P30-C sample with ting and anchoring Ni species and enabling their uniform dispersion. On
stabilized CO2 sorption and hydrogenation performance in repeated the other hand, the citric acid complex process had immobilized Ni
cycles. metallic ions, inhibited Ni crystallite growth and prevented particle
TEM image of the spent Ni/CS sample in Fig. 11(e) shows a compact agglomeration, and would benefit the sample minimized Ni particle size.
block structure, which is consisted of large particles and particle The good textural properties would promote CO2 diffusion and sorption
agglomeration can be clearly observed. In contrast, TEM image of the for enhanced CO2 sorption performance, while the uniform dispersion of
Ni/CS-P30-C in Fig. 11(f) shows that the average Ni particle size is 14.0 Ni particles and the minimized particle size could provide considerable
nm and the majority of the Ni NPs are distributed in the range of 11 ~ active sites for reinforced hydrogenation performance. To satisfy the
18 nm, which is smaller than that of Ni/CS, and this is beneficial for requirement of scale-up application, Ni-CaO DFMs pellets had been
retaining relatively high CO productivity of Ni/CS-P30-C in repeated fabricated by the extrusion-spheronization method. The Ni/CS-P30-C-P
cycles. This has also been proved from the elemental mapping of Ni/CS pellets possessed outstanding mechanical strength (2.88 MPa) and good
and Ni/CS-P30-C in Fig. 11(g) and (h). The consecutive CO2 sorption abrasion ability (weight loss of 2.36% after 3000 rotations). The
and in-situ hydrogenation operations have induced the growth of Ni and pelletization process adversely affected the CO2 sorption and in-situ
CaO particles of Ni/CS and Ni/CS-P30-C [58]. Compared with the fresh hydrogenation performance. The Ni/CS-P30-C-P pellets exhibited good
Ni/CS-P30-C, a slight aggregation of Ni species can be observed for the stability within 17 cycles. Overall, the as-synthesized Ni-CaO DFMs
spent Ni/CS-P30-C. The sintering and pore-plugging process of CaO showed promise for cost-effective CO2 capture and conversion to value-
grains and the aggregation of Ni species is the main reason for the decay added products.
of CO2 sorption and CO productivity over repeated cycles.
Declaration of Competing Interest
3.4. A comparison of CO2 sorption performance of Ni-CaO to similar
DFMs reported in literatures The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
CO2 sorption performance of Ni-CaO has been compared to similar the work reported in this paper.
DFMs reported for integrated CO2 sorption and methanation [44,59,60],
reverse water–gas shift (RWGS) [21], dry ethane reforming (DER) [61] Acknowledgements
and dry reforming of methane (DRM) [19]. Table 3 summarizes the
synthesis, testing conditions and CO2 sorption performance of the The work was funded by the National Natural Science Foundation of
different Ni-CaO DFMs. 10Ni-10CaO/Al2O3 [59] and 15Ni-15Ca/Al2O3 China (51806108) and the State Key Laboratory of Clean Energy Utili­
[44] DFMs were prepared for CO2 capture and isothermal methanation zation (Open Fund Project ZJUCEU2020009) and Graduate Research
application. CO2 sorption capacities of the two DFMs were rather low as and Innovation Projects of Jiangsu Province (KYCX21_1379).
0.37 and 0.17 mmol/g DFMs. Although the γ-Al2O3 support contributes
to the uniform distribution of Ni and CaO, their CO2 sorption capacities Appendix A. Supplementary data
are limited by the CaO content and the CH4 productivities are therefore
far from expectation. Jo et al. synthesized a novel 10Ni/CaO DFM via Supplementary data to this article can be found online at https://doi.
sol–gel combustion for CO2 capture and methanation. The sample org/10.1016/j.cej.2021.132110.
exhibited a high CO2 uptake of 8.96 mmol/g DFMs and a great CH4
productivity of 8.34 mmol/g DFMs, which were associated with the high
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