Waste Management 107 (2020) 244–251

Contents lists available at ScienceDirect

Waste Management
journal homepage: www.elsevier.com/locate/wasman

Facile use of coal combustion fly ash (CCFA) as Ni-Re bimetallic catalyst
support for high-performance CO2 methanation
Xinxin Dong, Baosheng Jin ⇑, Songshan Cao, Fanyue Meng, Tong Chen, Qifeng Ding, Chao Tong
Key Laboratory of Energy Thermal Conversion and Control of Ministry of Education, School of Energy & Environment, Southeast University, Nanjing 210096, People’s Republic of China

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

Article history: The industrial waste coal combustion fly ash (CCFA) was used as a cheap catalyst support and by facile co-
Received 25 November 2019 impregnation method, the active component Ni and promoter Re was loaded to form a bimetallic catalyst
Revised 1 April 2020 for high-performance CO2 methanation. The physico-chemical properties of the prepared catalyst were
Accepted 7 April 2020
further measured by a series of characterizations such as X-ray fluorescence (XRF), N2 isothermal
Available online 19 April 2020
adsorption-desorption, X-ray diffraction (XRD), H2 temperature-programmed reduction (H2-TPR) et al.
The effect of reaction temperature and gas hourly space velocity (GHSV) on the catalytic performance
Keywords:
was carefully investigated on a continuous fixed-bed reactor. The results showed that in comparison with
Fly ash
Waste treatment
the non-promoted monometallic Ni/CCFA catalyst, the bimetallic Ni-Re/CCFA catalyst displayed a supe-
Methanation rior activity, which could achieve 99.55% of CO2 conversion and 70.27% of CH4 selectivity under the con-
Ni-based catalyst dition of 400 °C, 2000 h
1, 1 atm and H2:CO2:N2 = 4:1:0.5, possibly owing to the higher Ni dispersion and
Rhenium more active sites in Ni-Re/CCFA. Besides, the addition of Re promoter was beneficial to enhance the cat-
alyst anti-sintering and anti-coking abilities as reflected by the smaller Ni particle size growth and less
carbon deposition amount in Ni-Re/CCFA. The in-situ diffuse reflection infrared Fourier transform spec-
trum (in-situ DRIFTS) was finally carried out to determine the CO2 adsorption state and its methanation
intermediates, from which a loop mechanism of CO2 methanation process was proposed and depicted.
Ó 2020 Elsevier Ltd. All rights reserved.

1. Introduction 2015). The diverse sorbents including CaO, MgO as well as

Coal combustion remains the major way to generate electricity
in China at the present stage of development. The large consump-
tion of coal in thermal power plants can cause heavy burden of fly
ash emission, a type of solid waste whose production amount con-
tinues to expand annually. It is estimated by a government forecast
that from 2016 to 2021, the amount of coal combustion fly ash
(CCFA) will approximately reach 560–610 million tons per year
(Zhang et al., 2019a). Though nearly 70% of the CCFA is utilized
in many aspects such as construction cement, pavement bricks
and soil conditioner (Mandpe et al., 2019), the rest 30% is carelessly
discarded and thus accumulated due to poor management and
treatment (Xue et al., 2019). The inappropriate disposal of CCFA
may cause atmospheric pollution, water contamination and further
threaten the living environment of human (Zhou et al., 2019a).
Therefore, a novel and efficient using method of CCFA is urgently
required in the face of the current treatment situation.
The large CO2 emission from coal combustion has driven people
to either capture or convert CO2 (Hu et al., 2019a; Zarghami et al.,
⇑ Corresponding author.
E-mail address: bsjin@seu.edu.cn (B. Jin).
advanced materials like MOFs and Li4SiO4 have contributed a lot
to CO2 capture (Li et al., 2020; Hu et al., 2019b). Unlike chemical
capture of CO2, a thermal conversion method called CO2 methana-
tion, also known as Sabatier reaction (CO2 + 4H2 = CH4 + 2H2O,
DH =
165 kJ/mol), is getting more and more attention recently
because it not only can convert CO2 into renewable energy product
like synthetic natural gas (SNG) but also is regarded as an viable H2
storage technology (Vrijburg et al., 2019; Ricca et al., 2019). The
above reaction could mitigate the CO2 emission derived global
warming issue as well as produce high energy density CH4, which
can be directly used in the existing natural gas pipeline infrastruc-
ture. The reaction of CO2 hydrogenation into CH4, namely CO2
methanation, usually proceeds through thermal catalysis by cer-
tain catalysts (Alarcón et al., 2019). Lots of researchers have put
much effort to the design, development and improvement of
high-performance catalyst in order to favor the reaction both ther-
modynamically and/or kinetically. For example, Navarro-Jaén and
co-authors employed the polyol method to prepare a 5 wt% Ru/
c-Al2O3 catalyst through hydrothermal process and its CO2 metha-
nation activity including CO2 conversion and CH4 yield was highly
related to the Ru nanoparticle size (Navarro-Jaén et al., 2019).
Mihet et al. utilized popular metal organic framework (UiO-66

https://doi.org/10.1016/j.wasman.2020.04.014
0956-053X/Ó 2020 Elsevier Ltd. All rights reserved.
 X. Dong et al. / Waste Management 107 (2020) 244–251
and MIL-101) as catalyst support and effectively encapsulated Ni
nanoparticles for CO2 methanation (Mihet et al., 2019). The cata-
lyst revealed the best activity in the case of Ni@MIL-101 sample,
which obtained 56.4% of CO2 conversion and 91.6% of CH4 selectiv-
ity at 320 °C and H2/CO2 = 8:1. Some other advanced technologies
are also applied to prepare high-performance CO2 methanation
catalysts. For instance, Kierzkowska-Pawlak et al. designed a CoOx-
based nano-catalyst by the plasma–enhanced chemical vapor
deposition method. The obtained superior performance of high
CO2 conversion (73%) and selectivity to methane (94%) was attrib-
uted to the special structure of CoO in graphite-like matrix
(Kierzkowska-Pawlak et al., 2019). However, the above mentioned
catalysts generally are on the basis of noble metals (such as Ru) or
the preparation process is complicated and consumes massive
chemicals (such as MOFs) or even energy-intensive (plasma
enhanced deposition method), which no doubt limits their applica-
tion in practical productions. Hence, in this scenario, a facile cata-
lyst preparation method based on inexpensive active metals is thus
needed.
Nickel-based catalyst is regarded as one of the most promising
catalysts for Sabatier reaction because of its high activity, satisfac-
tory product selectivity, low cost and easy accessibility (Su et al.,
2016; Sreedhar et al., 2019; Younas et al., 2016). As a result, it
has been widely investigated and commonly used for industrial
purpose. The chemical composition of CCFA includes silica, calcium
oxide, alumina, iron oxide and many other inorganic compounds.
Therefore, CCFA can be intrinsically considered as a composite to
some extent. Moreover, its abundant pores and considerable sur-
face area has qualified it to be a natural adsorbent for waste water
treatment and remediation (Wang et al., 2019b; Mushtaq et al.,
2019) as well as versatile catalyst support in various reaction fields
such as supporting Pd for p-nitrophenol reduction (Park and Bae,
2019), sustaining CeOx for low-temperature selective catalytic
reduction (SCR) of NOx (Wang et al., 2019c) and loading MnO2
for dye degradation (Li et al., 2019). The dual advantage of CCFA
support is to lower the catalyst production cost and meanwhile
discover a new path to use and treat this environmental waste.
However, to our best knowledge, the utilization of CCFA as catalyst
support for CO2 methanation has never reported in exposed
literatures.
In this work, we proposed a facile using method to transform
CCFA as CO2 methanation catalyst support and successfully loaded
Ni as active component and Re as promoter by impregnation
method. The rhenium promoter was reported to favor hydrogena-
tion reaction both electronically and structurally and meanwhile
exhibit high activity to cleave the CAO bond (Kong et al., 2020).
The prepared Ni-Re bimetallic catalyst was thoroughly character-
ized by diverse techniques including XRF, N2 isothermal
adsorption-desorption, XRD, H2-TPR, H2-TPD, SEM, TEM and TG.
Its catalytic activity was further tested in a tubular fixed-bed reac-
tor and the effect of reaction temperature and GHSV on the CO2
methanation performance was investigated. The reaction path of
CO2 methanation was also probed with the aid of in-situ DRIFTS.
The novel strategy of this study may provide a new route towards
CCFA treatment as well as develop a cheap but high-performance
CO2 methanation catalyst for potential industrial application.
2. Materials and methods
2.1. Materials
CCFA was obtained from a local thermal power plant and was
used directly as received without any processing. The active metal
precursor Ni(NO3)26H2O (AR, 500 g) was purchased from Nanjing
WANQING Chemical Glass Ware & Instrument Co., Ltd and the pro-
245
moter precursor NH4ReO4 (AR, 50 g) was purchased from Hunan
RHENIUMET Alloy Material Co., Ltd. The reactant gas used in the
catalyst performance tests including H2, CO2 and N2 (99.999%
grade) as well as H2 and He (99.999% grade) for the gas chromatog-
raphy was all ordered from Nanjing Shangyuan Industrial Gas Co.,
Ltd.
2.2. Catalyst preparation and testing
The catalyst preparation process and performance test flow was
shown in Fig. 1a and b, respectively. As can be seen in Fig. 1a, the
obtained CCFA powder was first mixed with the solution of Ni
(NO3)2 and NH4ReO4. Then the mixture was placed in a water bath
at 60 °C for 12 h in order to ensure sufficient impregnation. Subse-
quently, the mixture was dried in an oven overnight at 110 °C and
then transferred to a temperature programmed muffle furnace for
four-hour calcination at 400 °C. The obtained bulk catalyst sample
was ground into fine powders in a mortar and further pressurized
into tablets under 20 MPa. Then the tablet catalysts were carefully
crushed and sieved to produce the final particle catalyst with size
of 8–10 meshes, which at this stage was denoted as Ni-Re/CCFA.
For comparison, the monometallic Ni catalyst supported on CCFA
was also prepared using the same method as above and was even-
tually marked as Ni/CCFA. The designed content of Ni and/or Re in
the both catalysts were 15 and/or 1 wt%, respectively. The mor-
phology of the as-prepared catalyst in each period was shown in
Fig. S1.
The catalyst testing procedure was presented in Fig. 1b. In each
test, the reactor was packed with 50 mL catalyst particles. The cat-
alyst was first pre-reduced using pure H2 flow with a gas hourly
space velocity (GHSV) of 1000 h
1 under 450 °C for 4 h. Subse-
quently, the reactant gas flow with a composition of H2:CO2:
N2 = 4:1:0.5 and a total GHSV of 2000 h
1, adjusted and controlled
by three individual mass flow meters, was first mixed and pre-
heated to 200 °C in a preheater and then passed downwards in a
tubular fixed bed reactor. The catalyst bed temperature was mea-
sured and controlled by a K-type thermocouple inserted in the
middle of catalyst bed. The product gas then washed through a
cold trap and a U-type tube filled with silica gel to remove the
moisture in the gas. The final product gas was collected in a gas
bag and then subjected to a gas chromatography for its composi-
tion determination. Structurally, the gas chromatography was
equipped with a packed bed column and a molecular sieve column
coupling with a TCD and FID detector. The CO2 conversion (X) and
CH4 selectivity (S) was calculated according to the following equa-
tions (Tan et al., 2019; Wolf et al., 2019), where F stands for the gas
molar flow rate (mol/min), subscript in and out represents the inlet
and outlet of the reactor, respectively. The detailed description of
catalyst characterization and the related facility introduction was
listed in the Supplementary Material.
½F CO2 in
½F CO2 out
X¼  100% ð1Þ
½F CO2 in
½F CH4 out
S¼  100% ð2Þ
½F CO2 in
½F CO2 out
3. Results and discussion
3.1. Characterization
The compositions of CCFA were detected by XRF and the corre-
sponding content of each component was listed in Table S1. As can
be seen, CCFA is composed of multiple inorganic compounds such
as SiO2, Al2O3, Fe2O3 et al. According to the content, the component
246 X. Dong et al. / Waste Management 107 (2020) 244–251
Fig. 1. Schematic diagram of catalyst preparation and performance testing: (a) catalyst preparation process and (b) catalyst testing process.
could be classified into three types: major, minor and micro. The
major components refer to SiO2 and Al2O3, which comprise over
84% of the whole weight. The minor components include Fe2O3,
CaO, TiO2 and K2O, which is basically in the range of 1.0–6.0 wt%.
The last three chemicals including MgO, P2O5 and Na2O constitute
the micro components. Such compositions resemble the character-
istics of natural minerals and thus possess the function of catalyst
support (Park et al., 2019). The actual content of the active compo-
nent Ni and promoter Re in the as-prepared catalysts were deter-
mined by ICP and the results were compiled in Table S2. It can
be seen that the actual content of Ni in the Ni/CCFA and Ni-Re/
CCFA respectively is 15.05 wt% and 16.02 wt% while the actual
Re content in the Ni-Re/CCFA is 1.15 wt%, which demonstrates that
Ni and Re are successfully loaded on the support in accordance
with the designed content. The N2 isothermal adsorption-
desorption was carried out later and the isotherms were shown
in Fig. 2a. It can be observed that the N2 adsorption amount for
the two catalysts is around 60 cm3/g, which is much more larger
than CCFA support in the inserted figure (~9 cm3/g). This is due
to the enlarged pore volume after Ni and Re are loaded on the sup-
port (Table S2). In addition, the isotherm patterns of the catalysts
are quite different from CCFA support. For pure CCFA, its isotherm
type accord well with type II according to the IUPAC classifications,
implying that the support is nearly non-porous. However, Ni/CCFA
and Ni-Re/CCFA are supposed to accord with type IV isotherm with
a type H3 hysteresis loop, indicating the formation of mesoporous
structure after Ni and Re loading that can be further proven by the
pore size distribution in Fig. S2. The last column in Table S2 shows
that the two catalysts have relatively larger average pore diameter
than pure CCFA, which is owing to the newly emerged mesopores
centered at around 10 and 14 nm in Fig. S2. Finally, the derived
surface area calculated according to Brunauer-Emmett-Teller
(BET) method was also compiled in Table S2. In comparison with
CCFA, the surface area of the two catalysts is increased specifically
from 10.43 m2/g to 17.56 and 23.53 m2/g, respectively. This phe-
nomenon maybe originates from the stacking between the small
particles of Ni and Re species (Li et al., 2019).
The XRD patterns of the as-prepared and reduced catalysts were
shown in Fig. 2b. As can be seen, the numerous but distinct diffrac-
tion peaks in CCFA are attributed to typical mullite (also known as
aluminum silicate, xAl2O3ySiO2), which is formed by partial fusion
between SiO2 and Al2O3 during high-temperature coal combustion.
The rest of SiO2 (quartz) can be detected in XRD as proven by the
two diffraction peaks at 2h = 20.8° and 26.6° (PDF#03-0427). The
small diffraction peak at 2h = 29.4° is ascribed to K2FeO4
(PDF#03-0650) that is also derived from high temperature fusion
between Fe2O3 and K2O. However, the other inorganic compounds
listed in Table S1 such as CaO, TiO2 et al. cannot be observed in XRD
patterns of CCFA due to their relatively low content or peak over-
lapping. After loading Ni and Re, the XRD patterns of as-prepared
Ni/CCFA and Ni-Re/CCFA catalysts are changed. There are five
new diffraction peaks emerged at 2h = 37.3, 43.3, 62.9, 75.4 and
79.4°, which are attributed to typical NiO species (PDF#04-0835)
from the thermal decomposition of nickel nitrate. Subsequently,
the XRD patterns of reduced catalysts are changed further. The
three Ni(1 1 1), (2 0 0) and (2 2 0) crystal planes at 2h = 44.6,
51.9 and 76.8° can be clearly observed (PDF#01-1260), which indi-
cates the successful reduction from NiO oxides to Ni metals
(NiO + H2 ? Ni0). Nevertheless, the Re species in the both as-
prepared and reduced Ni-Re/CCFA catalysts cannot be detected
by XRD, possibly due to its high dispersion on the CCFA support
(Dong et al., 2018).
The H2-TPR and H2-TPD were employed to characterize the
types of NiO species and reduced Ni clusters. The XRF results in
Table S1 showed no signs of CeO2 or ZrO2 in CCFA and the main
components Al2O3 and SiO2 were quite difficult to be reduced, thus
the reducibility of the support was neglected here. The obtained
results were shown in Fig. 2c. As can be seen, the H2-TPR curves
 X. Dong et al. / Waste Management 107 (2020) 244–251
Fig. 2. Characterization results: (a) N2 adsorption isotherms of as-prepared catalysts, (b) XRD patterns, (c) H2-TPR plus H2-TPD curves and (d) SEM plus TEM morphologies of
reduced catalysts. The sequence number (1)-(5) in XRD patterns represents CCFA, as-prepared Ni/CCFA, as-prepared Ni-Re/CCFA, reduced Ni/CCFA and reduced Ni-Re/CCFA,
respectively.
of the two catalysts both present a broad peak ranging from 250 to
600 °C and could be further fitted by three reduction peaks through
mathematical deconvolution with R2 > 0.999, namely a, b and c.
According to some literatures (Xia et al., 2018; Meng et al., 2017;
Nataj et al., 2018), a and b peak are ascribed to NiO species that
have respectively weak and strong interactions with support while
c peak stands for NiO species that form a unique spinel structure
with support. The detailed information of each reduction peak
was compiled in Table S3. As can be seen, the reduction tempera-
ture of each peak for Re-promoted catalyst (Ni-Re/CCFA) is lower
than non-promoted catalyst (Ni/CCFA), implying that adding Re
as promoter could decrease the reduction temperature of the Ni-
based catalyst, leading to an increased proportion of Ni metals
under the reduction condition of 450 °C. The H2-TPD curves of
the two catalysts are similar, which both present two abreast peaks
locating at medium and high temperature, respectively. The des-
orption peak (P1) at around 280 °C is regarded as the hydrogen che-
misorbed on highly dispersed Ni particles with large surface
defects while the second desorption peak (P2) at around 580 °C is
considered as the hydrogen chemisorbed on poorly dispersed Ni
bulks (Liu et al., 2013; Zhang et al., 2019c). The amount of hydro-
gen consumption in H2-TPR and hydrogen chemisorbed in H2-TPD
as well as the derived Ni dispersion were also listed in Table S3.
Calculating Ni dispersion through combination of H2-TPR and H2-
TPD has been adopted and examined by a lot of reported work
(Han et al., 2019; Wang et al., 2019d; Zhou et al., 2019b; Zhang
247
et al., 2019c). As it shows, the Ni dispersion of Ni-Re/CCFA is
14.8%, which is higher than Ni/CCFA (9.7%), indicating that Re addi-
tive could promote Ni dispersion on the support. Furthermore, the
Ni particle size of the two reduced catalysts in Table S3 shows that
Ni-Re/CCFA has smaller Ni particle than Ni/CCFA, which is consis-
tent with the Ni dispersion data. At last, Fig. 2d displayed the mor-
phologies of reduced Ni-Re/CCFA and Ni/CCFA catalysts. The SEM
images under 500 nm scale seem to show that Ni-Re/CCFA has
smaller Ni particle size and through TEM analysis, it can further
prove that Ni/CCFA presents larger Ni clusters than Ni-Re/CCFA,
which is in according with the Ni dispersion and Ni particle size
in Table S3. The SEM mapping images of the two catalysts are
shown in Fig. S3. Apart from the main element Si and Al of the
CCFA support, it can be seen that the supported Ni and Re is rela-
tively homogenous on the support, which proves that the Ni active
species and Re promoter interact with the support in a dispersive
way.
3.2. CO2 methanation
The effect of reaction temperature on the CO2 methanation per-
formance was examined in the range of 350–450 °C and the results
were shown in Fig. 3a and b. As can be seen, in the whole temper-
ature range, CO2 conversion and CH4 selectivity for the two cata-
lysts is both higher than 94% and 55%, respectively. CO2
conversion in Fig. 3a for both catalysts shows the same pattern,
248 X. Dong et al. / Waste Management 107 (2020) 244–251

Fig. 3. The effect of reaction temperature (a, b) and GHSV (c, d) on the CO2 conversion and CH4 selectivity. Characterization results of spent catalysts: XRD patterns (e) and TG
curves (f). The conditions of reaction temperature test are H2:CO2:N2 = 4:1:0.5, GHSV = 2000 h
1 and 1 atm. The conditions of GHSV test are H2:CO2:N2 = 4:1:0.5, 375 °C and
1 atm.

which first increases with reaction temperature and then reaches
the maximum at 400 °C and further decreases from 400 °C to
450 °C due to the dual function of thermodynamics and kinetics
(Moon et al., 2020). Specifically, the maximum CO2 conversion
for Ni/CCFA and Ni-Re/CCFA at 400 °C is 97.87% and 99.55%, respec-
tively. CH4 selectivity in Fig. 3b seems unordered with reaction
temperature. However, it can be noted that the gap between Ni/
CCFA and Ni-Re/CCFA expands as temperature ascends. The CH4
selectivity of the two catalysts are almost overlapped at 350 °C
but the gap gradually become enlarged after increasing the reac-
tion temperature, indicating that Ni-Re/CCFA performs better than
Ni/CCFA at higher temperature. The results of effect of GHSV on the
CO2 methanation performance were shown in Fig. 3c and d. As can
be observed, CO2 conversion for both catalysts decreases with
GHSV due to more incomplete reaction causing from less residence
time of reactant gas (Mikhail et al., 2019). Nevertheless, GHSV has
 X. Dong et al. / Waste Management 107 (2020) 244–251
less impact on CH4 selectivity as Fig. 3d shows. The CH4 selectivity
of Ni/CCFA and Ni-Re/CCFA basically fluctuates around 55% and
70%, demonstrating that the catalysts are stable to some extent.
Through careful observation and comparison, it can be seen that
in the whole temperature range of 350–450 °C and GHSV range
of 1000–3000 h
1, the CO2 conversion and CH4 selectivity for Ni-
Re/CCFA are always larger than Ni/CCFA, implying that the addition
of Re promoter is beneficial to the reaction. This may be on account
of the smaller Ni particle size and more active sites in Ni-Re/CCFA
as proved by XRD and H2-TPR results. Apart from the above struc-
tural promotion effect, the electronic effect of Re additive can also
promote hydrogenation reaction. According to some studies
(Bawornruttanaboonya et al., 2018; Ma et al., 2019; Yuan et al.,
2018), the ample electron transfer from Re to Ni could enhance
the Ni electron cloud density thus further accelerate the activation
and breakage of the chemical bonds in adsorbed reactants. The
structural and electronic dual function of Re promoter may jointly
lead to higher CO2 conversion and CH4 selectivity for Ni-Re/CCFA
catalyst.
The spent Ni/CCFA and Ni-Re/CCFA catalysts were also charac-
terized by XRD and TG. The obtained results were shown in
Fig. 3e and f, respectively. The XRD patterns of the two spent cat-
alyst are similar to each other and compared to the XRD patterns
of reduced ones in Fig. 2b, there is no new diffraction peak
emerged, indicating that the chemical compositions of the cata-
lysts are not altered after reaction and the catalysts are chemically
stable to some extent. However, by calculating the Ni particle size
after reaction, it shows that it grows from 19.7 nm to 20.8 nm
(+1.1 nm) for Ni-Re/CCFA and increases from 24.1 nm to 25.3 nm
(+1.2 nm) for Ni/CCFA. In addition, through comparison, the
high-resolution TEM (HRTEM) images of the two spent catalysts
in Fig. S4 show that the spent Ni-Re/CCFA present more dispersed
Fig. 4. In-situ DRIFTS spectra (a, b, c) of CO2 adsorption and methanation over reduced Ni-Re/CCFA and proposed reaction mechanism (d).
249
and smaller Ni bulks than spent Ni/CCFA. Thus it can be safely sug-
gested that the Re additive can slightly suppressing Ni sintering
during reaction. The TG curves in Fig. 3f show the weight loss sit-
uation of the two spent catalysts. As can be seen, the TG curve
slightly declines from room temperature to around 200 °C, which
is attributed to the evaporation of adsorbed water on the catalyst
surface. Then as the temperature increases to around 400 °C, the
TG curves shows a tiny upward trend due to the oxidation of Ni
metals (Ni0 + O2 ? NiO). The following sharp descending part from
400 °C to 800 °C is attributed to the removal of deposited carbon on
the support (C + O2 ? CO2), which is usually utilized to measure
the carbon deposition amount. By this standard, the carbon depo-
sition amount of Ni-Re/CCFA is calculated as 6.51%, which is smal-
ler than Ni/CCFA (8.06%), demonstrating that Re additive is also
positive in suppressing carbon deposition. Moreover, from the
inserted SEM pictures in Fig. 3f, the spent Ni/CCFA shows more
roughness on the surface than spent Ni-Re/CCFA, which is in accor-
dance with the TG analysis results that the former catalyst has
more deposited carbon. Interestingly, in spite of the carbon depo-
sition evidence from TG analysis, there is no diffraction peak in
XRD patterns ascribing to deposited carbon phases, possibly due
to their amorphous characteristics (Wang et al., 2019a).
3.3. Reaction mechanism
The in-situ DRIFTS characterization could be helpful to reflect
the adsorption state and detect reaction intermediates that lead
to possible reaction mechanism. In this work, the CO2 adsorption
and methanation in-situ DRIFTS was carried out and the obtained
spectra were shown in Fig. 4. As shown in Fig. 4a, from 5 min to
30 min for pure CO2 adsorption, the distinct IR band at
2341 cm
1 is related to CO2 gas phase (Yu et al., 2018). However,
250 X. Dong et al. / Waste Management 107 (2020) 244–251
it can be carefully observed that in the range of 3500–4000 cm
1,
there are some subtle bands that may reveal the information
related to CO2 adsorption on the catalyst surface. Thus, this region
was amplified and the corresponding spectra were inserted in the
upper left edge. As it shows, the bands at 3600 and 3700 cm
1 are
attributed to CO2 overtones and bands at 3640 and 3740 cm
1 are
ascribed to bicarbonates OH, which was formed by the reaction of
CO2 with hydroxyl groups on the support surface (Proaño et al.,
2019). The hydroxyl groups from adsorbed moisture were usually
strongly linked with SiO2 and Al2O3 and the XRF results in
Table S1 shows that CCFA has large proportion of SiO2 and Al2O3.
Subsequently, when the gas was switched from CO2 to H2, the
spectra were changed. At 35 min, the residual CO2 gas phase at
2341 cm
1 still can be detected while bands at 3600, 3640, 3700
and 3740 cm
1 were largely shrunk, indicating that the introduc-
tion of H2 starts to influence the existence of bicarbonates. With
continuous flowing of H2 from 40 min to 60 min, the spectra
become complicated. As Fig. 4b shows, except for band at
2341 cm
1, some new IR bands are emerged. The band at
1403 cm
1 corresponds to the isomerized bicarbonates that have
bridged connection with metal atoms on the support surface
(OAMAO, M = Al or Si) (Jia et al., 2019). With more hydrogen flows
beyond catalyst, it can be observed that from 40 min to 60 min the
IR band at 2341 cm
1 are getting gradually smaller, implying that
the CO2 gas phase is being diluted and on the contrary, the bands at
1310, 1335, 1162, 1450 and 3018 cm
1 become more conspicuous.
The adjacent IR bands at 1310 and 1335 cm
1 are ascribed to
OACAO and CAH in bidentate formate and bands at 1162 and
1450 cm
1 are related to linear CAO and CAH in methoxy group
(Solis-Garcia et al., 2017; Jia et al., 2019). Moreover, the unique
band at 3018 cm
1 is the characteristic reflection of CH4 gas phase
(Zhang et al., 2019b), demonstrating that the CO2 is hydrogenated
into methane on the catalyst surface.
From 65 min to 90 min, the flow gas was CO2 plus H2 and the in-
situ DRIFTS spectra was shown in Fig. 4c. Because of high reactant
concentration, the reaction is quickly finished and the spectra
looks comparatively brief. Except the IR band at 3018 and
2341 cm
1 that refers to CH4 and CO2 gas phase, the broad band
at around 3300 cm
1 belongs to the moisture product and the IR
band at 1304 cm
1 is attributed to CAH vibration. Besides, the IR
band at 1633 cm
1 is ascribed to ACO3 group in bicarbonates
(Takano et al., 2016). The gradually enlarged band of each species
is due to the accumulation in the reaction cell from 65 min to
90 min. According to the above analysis, a whole loop mechanism
of CO2 methanation over reduced Ni-Re/CCFA was proposed in
Fig. 4d. Firstly, the CO2 molecule is adsorbed and further reacted
with the abundant hydroxyl group on the catalyst surface to form
bicarbonate. Then the structurally unstable bicarbonate is rapidly
transformed into its isomeride, which has a steady structure of
bridged bonding with catalyst surface metal atoms. Then hydrogen
molecule is adsorbed on the Ni clusters and subsequently split into
two hydrogen radicals due to the promotion effect of ReOx, which
could further react with the bicarbonate isomeride to produce one
water molecule and bidentate formate. As H2 is continuously
adsorbed and split into radicals, the bidentate formate keeps react-
ing with the radicals to form methoxyl group and another water
molecule. Finally, the last hydrogen molecule continues to attack
methoxyl group, the methane is produced and leaves a new hydro-
xyl group on the catalyst surface to complete a whole loop of CO2
methanation reaction (CO2 + 4H2 = CH4 + 2H2O).
4. Conclusion
In the present work, coal combustion fly ash (CCFA) was readily
used as Ni-Re bimetallic catalyst support for CO2 methanation,
under which circumstance three goals could be achieved simulta-
neously: reduce the environmental impact of the industrial waste,
alleviate the global warming from CO2 emission and produce syn-
thetic natural gas (SNG) as renewable energy. The catalyst was pre-
pared by a facile co-impregnation method and was further
examined by a series of material characterizations. Its catalytic
CO2 performance was tested in a continuous fixed-bed reactor
and the effect of reaction temperature and gas hourly space veloc-
ity (GHSV) was investigated. It was concluded that CO2 conversion
reached maximum at 400 °C due to thermodynamic and kinetic
limitations and also decreased with GHSV because of insufficient
residence time. Moreover, compared with non-promoted Ni/CCFA
catalyst, the bimetallic Ni-Re/CCFA catalyst showed a higher CO2
methanation activity as proved by the larger CO2 conversion and
CH4 selectivity in the whole reaction temperature and GHSV range,
possibly due to the larger Ni dispersion in the latter catalyst.
Besides, it was also found that Re promoter was beneficial to
enhance the catalyst anti-sintering and anti-coking ability. With
the insight of in-situ DRIFTS, the intermediates of CO2 methanation
over Ni-Re/CCFA catalyst was detected and a possible loop reaction
mechanism involving surface hydroxyl group, bicarbonate, biden-
tate formate and methoxyl group was proposed in the end.
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared
to influence the work reported in this paper.
Acknowledgements
This work was supported by the National Key R&D Program of
China (2018YFC1901200) and the Scientific Research Foundation
of the Graduate School of Southeast University (YBJJ1803).
Appendix A. Supplementary material
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.wasman.2020.04.014.
References
Alarcón, A., Guilera, J., Díaz, J.A., Andreu, T., 2019. Optimization of nickel and ceria
catalyst content for synthetic natural gas production through CO2 methanation.
Fuel Process. Technol. 193, 114–122.
Bawornruttanaboonya, K., Laosiripojana, N., Mujumdar, A.S., Devahastin, S., 2018.
Catalytic partial oxidation of CH4 over bimetallic Ni-Re/Al2O3: kinetic
determination for application in microreactor. AIChE J. 64, 1691–1701.
Dong, X., Jin, B., Sun, Y., Yu, L., 2018. Urban gas production from low H2/CO biogas
using Re-promoted Ni catalysts supported on modified manganese sand. Fuel
220, 60–71.
Han, Y., Quan, Y., Hao, P., Zhao, J., Ren, J., 2019. Highly anti-sintering and anti-coking
ordered mesoporous silica carbide supported nickel catalyst for high
temperature CO methanation. Fuel 257, 116006.
Hu, Y., Liu, W., Yang, Y., Qu, M., Li, H., 2019a. CO2 capture by Li4SiO4 sorbents and
their applications: Current developments and new trends. Chem. Eng. J. 359,
604–625.
Hu, Y., Qu, M., Li, H., Yang, Y., Yang, J., Qu, W., Liu, W., 2019b. Porous extruded-
spheronized Li4SiO4 pellets for cyclic CO2 capture. Fuel 236, 1043–1049.
Jia, X., Zhang, X., Rui, N., Hu, X., Liu, C., 2019. Structural effect of Ni/ZrO2 catalyst on
CO2 methanation with enhanced activity. Appl. Catal. B 244, 159–169.
Kierzkowska-Pawlak, H., Tyczkowski, J., Balcerzak, J., Tracz, P., 2019. Advances in
plasma produced CoOx-based nanocatalysts for CO2 methanation. Catal. Today
337, 162–170.
Kong, L., Zhang, L., Gu, J., Gou, L., Xie, L., Wang, Y., Dai, L., 2020. Catalytic
hydrotreatment of kraft lignin into aromatic alcohols over nickel-rhenium
supported on niobium oxide catalyst. Bioresour. Technol. 299, 122582.
Li, H., Qu, M., Hu, Y., 2020. Preparation of spherical Li4SiO4 pellets by novel agar
method for high-temperature CO2 capture. Chem. Eng. J. 380, 122538.
Li, X., Yi, L., Zhu, Q., Zhao, L., Xu, Y., Liu, M., Liu, T., Wu, Q., 2019. Synthesis of coal fly
ash supported MnO2 for the enhanced degradation of Acid Red 73 in the
presence of peroxymonosulfate. Environ. Technol., 1–12
 X. Dong et al. / Waste Management 107 (2020) 244–251
Liu, J., Li, C., Wang, F., He, S., Chen, H., Zhao, Y., Wei, M., Evans, D.G., Duan, X., 2013.
Enhanced low-temperature activity of CO2 methanation over highly-dispersed
Ni/TiO2 catalyst. Catal. Sci. Technol. 3, 2627.
Ma, L., Yan, L., Lu, A., Ding, Y., 2019. Effects of Ni particle size on amination of
monoethanolamine over Ni-Re/SiO2 catalysts. Chinese J. Catal. 40, 567–579.
Mandpe, A., Paliya, S., Kumar, S., Kumar, R., 2019. Fly ash as an additive for
enhancing microbial and enzymatic activities in in-vessel composting of
organic wastes. Bioresource Technol. 293, 122047.
Meng, F., Li, X., Li, M., Cui, X., Li, Z., 2017. Catalytic performance of CO methanation
over La-promoted Ni/Al2O3 catalyst in a slurry-bed reactor. Chem. Eng. J. 313,
1548–1555.
Mihet, M., Grad, O., Blanita, G., Radu, T., Lazar, M.D., 2019. Effective encapsulation of
Ni nanoparticles in metal-organic frameworks and their application for CO2
methanation. Int. J. Hydrogen Energy 44, 13383–13396.
Mikhail, M., Wang, B., Jalain, R., Cavadias, S., Tatoulian, M., Ognier, S., Gálvez, M.E.,
Da Costa, P., 2019. Plasma-catalytic hybrid process for CO2 methanation:
optimization of operation parameters. React. Kinet. Mech. Catal. 126, 629–643.
Moon, D.H., Chung, W.J., Chang, S.W., Lee, S.M., Kim, S.S., Jeung, J.H., Ro, Y.H., Ahn, J.
Y., Guo, W., Ngo, H.H., Nguyen, D.D., 2020. Fabrication and characterization of
Ni-Ce-Zr ternary disk-shaped catalyst and its application for low-temperature
CO2 methanation. Fuel 260, 116260.
Mushtaq, F., Zahid, M., Bhatti, I.A., Nasir, S., Hussain, T., 2019. Possible applications
of coal fly ash in wastewater treatment. J. Environ Manage. 240, 27–46.
Nataj, S.M.M., Alavi, S.M., Mazloom, G., 2018. Modeling and optimization of
methane dry reforming over Ni-Cu/Al2O3 catalyst using Box-Behnken design. J.
Energy Chem. 27, 1475–1488.
Navarro-Jaén, S., Navarro, J.C., Bobadilla, L.F., Centeno, M.A., Laguna, O.H., Odriozola,
J.A., 2019. Size-tailored Ru nanoparticles deposited over c-Al2O3 for the CO2
methanation reaction. Appl. Surf. Sci. 483, 750–761.
Park, J., Bae, S., 2019. Highly efficient and magnetically recyclable Pd catalyst
supported by iron-rich fly ash@fly ash-derived SiO2 for reduction of p-
nitrophenol. J. Hazard. Mater. 371, 72–82.
Park, J., Hwang, Y., Bae, S., 2019. Nitrate reduction on surface of Pd/Sn catalysts
supported by coal fly ash-derived zeolites. J. Hazard. Mater. 374, 309–318.
Proaño, L., Tello, E., Arellano-Trevino, M.A., Wang, S., Farrauto, R.J., Cobo, M., 2019.
In-situ DRIFTS study of two-step CO2 capture and catalytic methanation over
Ru, ‘‘Na2O”/Al2O3 Dual Functional Material. Appl. Surf. Sci. 479, 25–30.
Ricca, A., Truda, L., Palma, V., 2019. Study of the role of chemical support and
structured carrier on the CO2 methanation reaction. Chem. Eng. J. 377, 120461.
Solis-Garcia, A., Louvier-Hernandez, J.F., Almendarez-Camarillo, A., Fierro-Gonzalez,
J.C., 2017. Participation of surface bicarbonate, formate and methoxy species in
the carbon dioxide methanation catalyzed by ZrO2-supported Ni. Appl. Catal. B
218, 611–620.
Sreedhar, I., Varun, Y., Singh, S.A., Venugopal, A., Reddy, B.M., 2019. Developmental
trends in CO2 methanation using various catalysts. Catal. Sci. Technol. 9, 4454–
4478.
Su, X., Xu, J., Liang, B., Duan, H., Hou, B., Huang, Y., 2016. Catalytic carbon dioxide
hydrogenation to methane: a review of recent studies. J. Energy Chem. 25, 553–565.
Takano, H., Kirihata, Y., Izumiya, K., Kumagai, N., Habazaki, H., Hashimoto, K., 2016.
Highly active Ni/Y-doped ZrO2 catalysts for CO2 methanation. Appl. Surf. Sci.
388, 653–663.
Tan, J., Wang, J., Zhang, Z., Ma, Z., Wang, L., Liu, Y., 2019. Highly dispersed and stable
Ni nanoparticles confined by MgO on ZrO2 for CO2 methanation. Appl. Surf. Sci.
481, 1538–1548.
251
Vrijburg, W.L., van Helden, J.W.A., Parastaev, A., Groeneveld, E., Pidko, E.A., Hensen,
E.J.M., 2019. Ceria–zirconia encapsulated Ni nanoparticles for CO2 methanation.
Catal. Sci. Technol. 9, 5001–5010.
Wang, F., Zhang, J., Chen, Z., Lin, J., Li, W., Wang, Y., Chen, B., 2019a. Water-saving
dry methanation for direct conversion of syngas to synthetic natural gas over
robust Ni0.1Mg0.9Al2O4 catalyst. J. Catal. 375, 466–477.
Wang, N., Han, Y., Li, S., 2019b. Adsorption characteristic of Cr(VI) onto different
activated coal fly ashes: kinetics, thermodynamic, application feasibility, and
error analysis. Water Air Soil Pollut. 230, 154.
Wang, S., Chen, Z., He, B., Yan, Z., Wang, H., Liu, L., Wang, X., 2019c. In situ DRIFTS
investigation on CeOx catalyst supported by fly-ash-made porous cordierite
ceramics for low-temperature NH3-SCR of NOx. Catalysts 9, 496.
Wang, X., Zhu, L., Zhuo, Y., Zhu, Y., Wang, S., 2019d. Enhancement of CO2
methanation over La-modified Ni/SBA-15 catalysts prepared by different
doping methods. ACS Sustain. Chem. Eng. 7, 14647–14660.
Wolf, M., Schüler, C., Hinrichsen, O., 2019. Sulfur poisoning of co-precipitated Ni-Al
catalysts for the methanation of CO2. J. CO2 Util. 32, 80–91.
Xia, D., Chen, Y., Li, C., Liu, C., Zhou, G., 2018. Carbon dioxide reforming of methane
to syngas over ordered mesoporous Ni/KIT-6 catalysts. Int. J. Hydrogen Energy
43, 20488–20499.
Xue, Y., Yu, W., Mei, J., Jiang, W., Lv, X., 2019. A clean process for alumina extraction
and ferrosilicon alloy preparation from coal fly ash via vacuum thermal
reduction. J. Clean. Prod. 240, 118262.
Younas, M., Loong Kong, L., Bashir, M.J.K., Nadeem, H., Shehzad, A., Sethupathi, S.,
2016. Recent advancements, fundamental challenges, and opportunities in
catalytic methanation of CO2. Energy Fuels 30, 8815–8831.
Yu, Y., Bian, Z., Song, F., Wang, J., Zhong, Q., Kawi, S., 2018. Influence of calcination
temperature on activity and selectivity of Ni-CeO2 and Ni-Ce0.8Zr0.2O2 catalysts
for CO2 methanation. Top. Catal. 61, 1514–1527.
Yuan, H., Zhu, X., Han, J., Wang, H., Ge, Q., 2018. Rhenium-promoted selective CO2
methanation on Ni-based catalyst. J. CO2 Util. 26, 8–18.
Zarghami, S., Hassanzadeh, A., Arastoopour, H., Abbasian, J., 2015. Effect of steam on
the reactivity of MgO-based sorbents in precombustion CO2 capture processes.
Ind. Eng. Chem. Res. 54, 8860–8866.
Zhang, S., Dai, S., Finkelman, R.B., Graham, I.T., French, D., Hower, J.C., Li, X., 2019a.
Leaching characteristics of alkaline coal combustion by-products: A case study
from a coal-fired power plant, Hebei Province, China. Fuel 255, 115710.
Zhang, Z., Tian, Y., Zhang, L., Hu, S., Xiang, J., Wang, Y., Xu, L., Liu, Q., Zhang, S., Hu, X.,
2019b. Impacts of nickel loading on properties, catalytic behaviors of Ni/c-Al2O3
catalysts and the reaction intermediates formed in methanation of CO2. Int. J.
Hydrogen Energy 44, 9291–9306.
Zhang, Z., Wei, T., Chen, G., Li, C., Dong, D., Wu, W., Liu, Q., Hu, X., 2019c.
Understanding correlation of the interaction between nickel and alumina with
the catalytic behaviors in steam reforming and methanation. Fuel 250, 176–
193.
Zhou, H., Bhattarai, R., Li, Y., Li, S., Fan, Y., 2019a. Utilization of coal fly and bottom
ash pellet for phosphorus adsorption: Sustainable management and evaluation.
Resour. Conserv. Recycl. 149, 372–380.
Zhou, J., Ma, H., Liu, C., Zhang, H., Qian, W., Ying, W., 2019b. Ni based catalysts
supported on Ce modified MgAl spinel supports for high temperature syngas
methanation. Catal. Lett. 149, 2563–2574.