Applied Catalysis B: Environmental 224 (2018) 310–321

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Applied Catalysis B: Environmental

journal homepage: www.elsevier.com/locate/apcatb

Hydroxyapatite supported bimetallic cobalt and nickel catalysts for syngas MARK
production from dry reforming of methane
Thanh Son Phan, Abdoul Razac Sane, Bruna Rêgo de Vasconcelos, Ange Nzihou, Patrick Sharrock,
⁎
Didier Grouset, Doan Pham Minh
Université de Toulouse, Mines Albi, UMR CNRS 5302, Centre RAPSODEE, Campus Jarlard, F-81013 Albi cedex 09, France

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

Keywords: Hydroxyapatite (HAP, Ca10(PO4)6(OH)2) has all the criteria of a catalyst support, in particular its high thermal
Hydroxyapatite stability. However it is still less studied in the heterogeneous catalysis. For the first time, hydroxyapatite sup-
Cobalt ported bimetallic Co-Ni catalysts were prepared and evaluated in the dry reforming of methane (DRM) process.
Nickel Nanoparticles containing both nickel and cobalt were well formed on the surface of HAP by conventional im-
Bimetallic catalyst
pregnation methods. No modification of HAP structure was observed after metals deposition. DRM reaction was
Dry reforming of methane
carried out at 700–750 °C and around 1.6 bar, using a fixed-bed reactor which was fed with a mixture of 20%vol
CH4, 20%vol CO2 and 60%vol N2. CH4 and CO2 conversion reached up to 60 and 68% at 700 °C, respectively,
and 73 and 79% at 750 °C, respectively during long reaction times of 50–160 h. Water as a by-product could be
quantified along the catalytic reaction indicating the implication of reverse water-gas-shift reaction. TEM-EDX
analysis of the used catalysts recovered after catalytic tests showed that coke deposition was limited and there
was slight modification of metals particle size. The results obtained were very promising for the design of an
efficient catalytic system for DRM process.

1. Introduction Biogas reforming includes various processes such as steam re-

forming, dry reforming, partial oxidation, and auto-thermal oxidation.
Waste management is up-to-date dominated by incineration and They generally need a solid catalyst. In fact, because of the chemical
landfill technique. However, most of incinerators and landfill sites are stability of CO2 and CH4, biogas reforming needs high temperature
not equipped with an energy or matter recovery system. In order to (usually > 700 °C). Thus, side reactions such as Boudouard reaction
better valorize waste and biomass to energy, fuels and other added and methane cracking take place leading to coke deposition. Steam
value and specialty products, new concepts are developed during these reforming is found to be efficient for the conversion of biogas into
last decades including thermo-conversion route and biological route syngas, with low catalytic deactivation rate. The presence of vapor al-
(Supporting information 1). Pyrolysis/gasification of biomass and waste lows gasifying coke deposition and so limiting catalytic deactivation.
is intensively studied during these last decades [1–4]. The highest However, steam reforming is an energy-intensive process because of its
challenge of this valorization route is the syngas cleaning. This last one high operational temperature and high water to hydrocarbon ratios
is required to remove fine particles, condensable molecules and various used (3–4 for industrial installations). Partial oxidation and auto-
gaseous pollutants (H2S, COS, HCl, NH3…), which depend on the nature thermal oxidation do not allow including carbon dioxide to the process.
of feedstock, gasifier, and downstream utilization [5]. Much effort is By these reasons, dry reforming of methane (DRM) has been intensively
still needed to make this route competitive and viable. investigated these last years as new promising solution for biogas re-
Methanisation is a biological process for the degradation of waste forming. Generally, DRM is studied with an equimolar ratio mixture of
and biomass. Biogas is the main gaseous product which mainly contains CH4 and CO2 (Eq. (1)). Thermodynamic analysis of this reaction showed
CH4 and CO2. This appears as a good solution for the management of that it is favored at high temperature (i.e. above 700 °C) and low
non-hazardous wastes with minimization of the initial investment cost pressure (i.e. around atmospheric pressure) [9,10]. The main products
compared to thermal routes (incineration or pyro-gasification). Biogas of this reaction are CO and H2, but coke deposition is inevitable below
can be upgraded to produce biomethane or transformed into syngas by 900 °C at atmospheric pressure [10]. Water was usually reported as
reforming processes [6–8]. another by-product in the literature, and was recently quantified by

⁎
Corresponding author.
E-mail addresses: [email protected], [email protected] (D. Pham Minh).

http://dx.doi.org/10.1016/j.apcatb.2017.10.063
Received 22 July 2017; Received in revised form 16 October 2017; Accepted 26 October 2017
Available online 27 October 2017
0926-3373/ © 2017 Elsevier B.V. All rights reserved.
T.S. Phan et al. Applied Catalysis B: Environmental 224 (2018) 310–321

Rêgo de Vasconcelos et al. [11]. nickel-cobalt bimetallic catalysts in DRM process. Nickel and cobalt
were chosen for their high activity and their relative low cost compared
CH4 + CO2 → 2CO + 2H2 (1)
to other metals while HAP appears as a new promising catalytic support
The main challenge of DRM is related to the catalytic deactivation, as mentioned above.
together with side reactions such as reserve water-gas-shift reaction
(RWGS). The deactivation is mostly due to coke deposition and catalyst 2. Materials and methods
modification (active phase and/or support) at high temperature
[12–15]. Thus, much work was devoted to the development of new 2.1. Catalyst preparation
performing catalysts to prevent catalytic deactivation. The minimiza-
tion of the size of nickel particles as active phase was frequently at- Commercial HAP support (60 m2/g, fine powder) provided by
tempted [13]. In fact, coke formation can be inhibited by using highly- PRAYON S.A. (Belgium) was used as catalytic support without further
dispersed nickel particles [16–18]. Catalyst support plays also im- modification. Nickel nitrate (Ni(NO3)2·6H2O, Fisher Scientific, > 98 wt
portant role. Supports having high basicity and strong metal-support %) and cobalt nitrate (Co(NO3)2·6H2O, Acros Organics, > 98 wt%).
interaction are researched [19,20]. High basicity favors CO2 adsorption Distilled water was also used for catalyst preparation.
and limits coke formation while strong metal-support interaction limits Hydroxyapatite supported bimetallic nickel and cobalt catalysts
metal particles sintering [21–23]. were prepared by successive incipient wetness impregnation (SIWI) or
Conventional catalytic supports including Al2O3, MgO, TiO2, ZrO2, incipient wetness co-impregnation (COI). For the catalysts prepared by
SiC, zeolites, and nanostructured carbons were frequently reported in SIWI method, HAP support was firstly impregnated with an aqueous
the literature for DRM [24–28]. The combination of several metal solution of the first active metal. The volume of the solution and the
oxides allowed improving catalytic performance [27,29,30]. However, concentration of this metal were calculated to reach the desired metal
up-to-date and to the best of our knowledge, there is not application of content in the final catalyst. After drying at 105 °C, the solid was cal-
DRM at large industrial scale yet. A highly-performing catalytic system cined at 500 °C under air atmosphere. This procedure was repeated for
is still to be developed and it is important to enlarge research area on the deposition of the second active metal. For the catalysts prepared by
other types of catalyst. For this reason, our current research is focused COI method, HAP support was impregnated with an aqueous solution of
on synthetic calcium hydroxyapatite (Ca10(PO4)6(OH)2, HAP)-based both active metals precursors. Table 1 summaries the catalysts pre-
catalysts. pared. The theoretical metals content was 2.85 wt.% for each metal in
HAP has all the criteria required for a catalytic support: high spe- each catalyst.
cific surface area, with or without mesopores depending on the synth-
esis conditions, very low water solubility, and high thermal stability 2.2. Catalyst characterization
[11,13,31–33]. In addition, it contains both acid and basic sites and the
density of these sites can be controlled by varying the molar ratio of Ca Elemental analysis was carried out using inductive coupled plasma
to P. At high temperature, partial dehydration can take place but this atomic emission spectroscopy (ICP-AES) with a HORIBA Jobin Yvon
phenomenon is reversible under the presence of water vapor [34,35]. Ultima 2 apparatus. Prior to the analysis, solid catalysts were dissolved
Thus HAP becomes less sensitive to the presence of water, which is in a strong acid mixture of HNO3 and HCl. X-ray diffraction (XRD) data
usually formed during DRM process. All these properties make HAP as were collected using a Phillips Panalytical X’pert Pro MPD dif-
new potential support for heterogeneous catalytic processes. Boukha fractometer with a Cu Kα (1.543 Å) radiation source and a nickel filter
et al. [36] studied DRM over nickel loaded HAP in the temperature to suppress the CuKβ ray. The specific surface area was measured by
range of 600–800 °C. Encouraging results were obtained with high in- nitrogen adsorption following standard vacuum drying at 105 °C, using
itial conversion of methane and carbon dioxide during 4 h of time-on- the BET method (MICROMETRICS Gemini Vacprep 061). Scanning
stream. However, the catalytic stability was not investigated by these electron microscopy coupled with energy dispersive spectroscopy
authors. Recently, we reported our last results on the catalytic perfor- (SEM-EDX) measurement was performed on a Philips XL30 ESEM ap-
mance of ruthenium and platinum supported HAP in DRM process. At paratus (FEI Company). Transmission electron microscopy coupled
low Pt loading of 0.73 wt.%, the catalyst Pt/HAP prepared by the with energy dispersive spectroscopy (TEM-EDX) was done with a FEG
simple incipient wetness impregnation (IWI) showed interesting cata- JEOL JEM 2100F equipped with a HAADF detector. XRD, SEM and TEM
lytic activity and stability during 50 h of time-on-stream (at 700 °C and analyses were done with fresh catalyst after calcination at 500 °C or
atmospheric pressure) [11]. with spent catalysts recovered after catalytic tests. From TEM image,
Although noble metals catalysts are known to have good catalytic metals particle size was evaluated with up to 300 particles.
performance, their high cost hinders their use at large scale. So, many
researchers have focused on the use of transition metals such as nickel, 2.3. Catalytic evaluation
cobalt, iron etc. as active phases. Despite showing high activity, these
catalysts suffer from rapid deactivation mostly due to carbon deposition Catalytic test was carried out with a tubular fixed-bed ceramic re-
and metal sintering. In order to improve their stability, several ap- actor (internal diameter of 8 mm, length of 25 cm), which was sur-
proaches have been proposed such as the modification of methods for rounded by an Inconel625 tube to protect against mechanical impacts.
catalyst preparation or the addition of promoters. One of the most in- The details are described elsewhere [11]. Briefly, the catalytic bed was
vestigated approaches is the use of a second metal to enhance catalyst set at the center of the reactor and was fixed by fine powder of inert
stability in DRM process. Takanabe et al. [37] showed that combining support (α-alumina). The reaction temperature was controlled by a
Ni and Co could enhance the catalyst activity and also suppress the
carbon deposition during DRM. Zhang et al. [38] arrived at similar Table 1
Catalysts prepared in this work.
conclusions. They demonstrated that combining Ni and Co increased
metal dispersion and generated stronger metal-support interaction Catalyst Preparation method Preparation procedure
when compared to the Ni and Co monometallic catalysts. Recent work
of Wang et al. [39] highlighted again the beneficial effect of bimetallic Co-Ni/HAP_SIWI SIWI Cobalt deposition, followed by nickel
deposition
Ni-Co catalysts compared to monometallic Ni or Co catalysts in DRM
Ni-Co/HAP_SIWI SIWI Nickel deposition, followed by cobalt
reaction. deposition
This work investigated the catalytic performance of HAP supported Ni-Co/HAP_COI COI Co-impregnation of cobalt and nickel

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thermocouple set at the center of the catalyst bed. The reactor was Table 2
heated by an electrical furnace. The reaction pressure was observed Elemental analysis and specific surface area of the prepared catalysts.
around 1.6 bar which was slightly higher than the atmospheric pres-
Catalyst Co (wt.%) Ni (wt.%) Ca/P SBET(m2/g)
sure. This was due to the pressure drop inside the reactor tube provoked
by fine powders of inert support and catalyst. For a given catalytic test, Ni-Co/HAP_SIWI 2.4 2.4 1.7 46
340 mg of catalyst, diluted two times with SiC, both under fine powder Co-Ni/HAP_SIWI 2.6 2.8 49
Ni-Co/HAP_COI 2.8 2.6 48
form, were used. Prior to the test, the catalyst was heated under N2
HAP support 0 0 60
atmosphere (70 NmL/min) to 700 °C and reduced in-situ at this tem-
perature by 4vol.%H2/N2 stream (70 NmL/min) for 2 h. Then, the re-
actor system was set at the working temperature under N2 atmosphere. Table 3
At the working temperature, the reactor was fed with a gas mixture of Deactivation rates of the hydroxyapatite-based catalysts.
CH4 (20 vol.%) and CO2 (20 vol.%) diluted in N2 (total gas flow rate of
Catalyst Deactivation rate (% h−1) at Deactivation rate (% h−1) at
90 Nml/min). This high dilution was applied due to security measures
TOS = 6h TOS = 50h
required in our laboratory, despite being far from the real biogas
mixtures. The inlet gas composition and flow rate were controlled by Ni-Co/HAP_SIWI 2.13 0.23
mass flow controls (MFC). At the outlet of the reactor, a water trap was Co-Ni/HAP_SIWI 1.15 0.32
used to quantify periodically water formed during the reaction. Outlet Ni-Co/HAP_COI 1.45 0.23

gas composition was measured by a μ-GC (MyGC, Agilent). A gas

counter was also used to measure the total outlet gas flow rate, which 4
was used for the calculation of reaction conversion and selectivity. MFC
2
The main products of the reaction were CO and H2. Water and coke MFC
were identified as by product. The quantification of CO, H2 and H2O N2 Security disk
could be done during the reaction while it was not possible for coke. MFC
Thus, the reaction conversion and the selectivity in CO, H2, H2O, and
solid carbon, as well as the molar ratio of H2/CO were calculated by the
following formula.
Q̇ (CH4)in − Q̇ (CH4)out
CH 4 conversion(%) = x100 Vertical
Q̇ (CH4)in (2) Furnace Catalyst
Q̇ (CO2)in − Q̇ (CO2)out
CO2 conversion(%) = x100
Q̇ (CO2)in (3)

Q̇O(CO produced)
CO selectivity(%) = x100
Q̇O(CO2consummed) (4)

Q̇H(H2produced) Thermocouple
H2 selectivity(%) = x100
Q̇H(CH4consumed) (5)
Water trap
Q̇O(H2O produced)
H2 O selectivity(%) = x100
Q̇O(CO2consummed) (6) µ-GC
analysis
Q̇Cs(out)
C(s) selectivity(%) = x100 Fig. 1. Illustration of the fixed-bed reactor used in this work.
(Q̇C(CH4consumed) + Q̇C(CO2consumed) ) (7)

%H2 catalysts were also close to the theoretical value of 2.85 wt.%. The
H2/ CO =
%CO (8) difference must be due to metals deposition on the flask walls during
where Q̇ (CH4)in and Q̇ (CH4)out : methane molar flow rate (mmol h−1) at the the preparation. Metals deposition led to a small decrease of the specific
reactor inlet and outlet; Q̇ (CO2)in and Q̇ (CO2)out : carbon dioxide molar flow surface area of the support.
rate (mmol h−1) at the reactor inlet and outlet; Q̇O(H2O produced) and XRD patterns of HAP support and HAP supported metals catalysts
Q̇O(CO2consummed) : atomic oxygen flow rate (mmol h−1) at the reactor are presented in Fig. 2. The initial support had only hydroxyapatite as
inlet (under H2O form) and outlet (under CO2 form); Q̇O(CO produced) : crystalline phase with the main diffraction peaks at 2θ of 25.9, 31.8,
atomic oxygen flow rate (mmol h−1) at the reactor outlet (under CO 32.2, 32.9, 46.8 and 49.7°. NiO crystalline phase, which has the main
form); Q̇H(H2produced) and Q̇H(CH4consumed) : atomic hydrogen flow rate diffraction peaks at 37.2 and 43.2°, was detected for Co-Ni/HAP_COI,
(mmol h−1) at the reactor inlet (under H2 form) and outlet (under CH4 which was prepared by co-impregnation method. The average crystal-
form); QO(H2O produced) : atomic oxygen flow rate (mmol h−1) at the re- lite size of NiO of this catalyst was estimated at 11 nm. CaO crystalline
actor outlet (under H2O form). phase (with the main peak at 37.0°) was also observed for this co-im-
pregnated catalyst. Co3O4 crystalline phase (with the main diffraction
3. Results peaks at 36.7°) appeared in all three catalysts. The estimation of the
average crystallite size of CaO and Co3O4 of the prepared catalysts is
3.1. Catalyst characterization difficult because their main diffraction peaks were very close to each
other, and were also close to the second diffraction peak of NiO. Finally,
Table 2 shows ICP-AES and specific surface area results. The initial all three catalysts contained also new crystalline phase of cobalt ex-
HAP support used in this work had the molar ratio of Ca to P of 1.7, changed hydroxyapatite (Ca10-xCox(PO4)6(OH)2) and nickel exchanged
which is close to the stoichiometry of calcium hydroxyapatite (Ca/ hydroxyapatite (Ca10-xNix(PO4)6(OH)2).
P = 10/6 or 1.67). The contents of nickel and cobalt in the final The formation of CaO, Ca10-xCox(PO4)6(OH)2, and Ca10-

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Fig. 2. XRD patterns of the prepared catalysts; ♦: HAP, *: cobalt and nickel
Ƈ** exchanged hydroxyapatites, ◊: NiO, □: Co3O4, Δ: CaO.
ƇƇ*
Ƈ* Ƈ* ප Ƈ Ƈ* Ƈ*
Co-Ni/HAP_SIWI
ѕ
Co-Ni/HAP_COI
ප
ǻ ѕ
Ni-Co/HAP_SIWI
ප
Support HAP

10 20 30 40 50 60

Fig. 3. SEM images of: (a) Co-Ni/HAP_SIWI; (b) Ni-

Co/HAP_SIWI; (c) Ni-Co/HAP_COI; and (d) support
HAP.

xNix(PO4)6(OH)2 could be explained by the cationic exchange capacity The formation of CaO was only detected by XRD for the catalysts
of HAP. In fact, HAP is well known for its capacity to replace Ca2+ prepared by co-impregnation method. The aqueous solution containing
cations in its apatitic structure by other divalent cations such as Pb2+, both nickel and cobalt nitrates used for co-impregnation could be more
Ni2+, Co2+, Cd2+…in an aqueous suspension [40,41]. The cationic acidic than those containing only nickel or cobalt nitrate used for
exchanges with Ni2+ and Co2+ can be illustrated by the following successive impregnation. High acidity could lead to a local surface
equations: dissolution of HAP layers, thus favor the cationic exchange between
Ca2+ and Ni2+ and Co2+. However, CaO could be possibly formed for
Ca10(PO4)6(OH)2 + xNi(NO3)2 → Ca10-xNix(PO4)6(OH)2 + xCa(NO3)2
the two catalysts prepared by successive impregnation but its content
(9)
was not enough for XRD detection.
Ca10(PO4)6(OH)2 + xCo(NO3)2 → Ca10-xCox(PO4)6(OH)2 + xCa(NO3)2 SEM images of the fresh catalysts (after calcination) are presented in
(10) Fig. 3. For the catalyst prepared by cobalt deposition followed by nickel
deposition (Fig. 3(a)), SEM allowed identifying metal-based particles
Probably during the incipient wetness impregnation, the cationic (oxides) with particle size of dozens nm. These particles seemed to be
exchange took place leading to the formation of cobalt and nickel ex- well distributed on the surface of the HAP support. Similar results were
change hydroxyapatites, as well as the liberation of Ca(NO3)2 (Eqs. observed with the catalyst prepared by nickel deposition followed by
(9) & (10)). Ca(NO3)2 decomposed during calcination to form CaO (Eq. cobalt deposition (Fig. 3(b)). For the catalyst prepared by co-impreg-
(11)). nation method, it seemed that metal-based particles of larger size were
2Ca(NO3)2 → 2CaO + 4NO2 + O2 (11) formed (Fig. 3(c)). In all case, metal deposition did not affect the
morphology of HAP support.

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Fig. 4. TEM images of: (a, b) Co-Ni/HAP_SIWI; (c, d)

Ni-Co/HAP_SIWI; and (e, f) Ni-Co/HAP_COI.

To evaluate the distribution of Ni- and Co-based particles on the particles demonstrated the presence of both Ni and Co (i.e. spots 001
support surface, TEM-EDX coupling was performed on the fresh cata- and 002). This demonstrates the formation of “bi-metallic particles” with
lysts. Fig. 4 shows TEM images of all three catalysts which confirmed the simultaneous presence of the two active metals under oxides form.
SEM results presented above. From TEM images, particle size dis- On dark particles (surface support), no trace of Ni or Co was observed
tribution was also evaluated using Image J software and the results are (i.e. spot 003).
later shown in Fig. 11. Metal oxides particles of dozens nm were ob- Fig. 6 shows an example of cartography of the main elements pre-
served for all the prepared fresh catalysts which were similar to each sent in the catalyst Ni-Co/HAP_SIWI. As expected, Ca, P and O were
other. They were also well distributed on the surface of the support. observed as the three main elements of the HAP support. Most of Ni-
To identify the distribution of each active metal on the support and Co-based particles detected by EDX analysis were found to be su-
surface of the fresh catalysts, imaging of the main elements was per- perimposed to each other. This suggests the formation of bimetallic Ni-
formed with an EDX analyzer. Fig. 5 shows an example of EDX spot Co particles (yellow arrows in Fig. 6(e) and (f)). This catalyst was
analysis on the catalyst prepared by nickel deposition followed by co- prepared by the successive impregnation method. Since nickel and
balt deposition and calcination. All spot analyses on bright metal-based cobalt have similar physico-chemical properties, nickel particles formed

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Fig. 5. Example of EDX analysis of Ni-Co/HAP_SIWI.

from the first deposition could promote and orientate the deposition impregnated catalyst (Fig. 2). It is well known that metallic Co and Ni
and formation of cobalt particles during the second deposition. The were active for reforming reactions. On the other hand, exchanged Ni2+
superimposition of Ni and Co was also observed with the two other and Co2+ in the rigid apatitic strucure (Ca10-xNix(PO4)6(OH)2 and Ca10-
catalysts (Supporting information 2 and 3). Thus, the deposition order xCox(PO4)6(OH)2) were not active in DRM reaction as confirmed by
did not influence the formation of bimetallic Ni-Co particles. additional catalytic tests (results not shown). Thus, Ni-Co/HAP_COI
catalyst prepared by co-impregnation was less active than two other
catalysts prepared by successive impregnation.
3.2. Catalytic performance The catalytic performance of the prepared bimetallic Co-Ni catalysts
in this work was roughly comparable with that of the hydroxyapatite
Fig. 7 compares the catalytic activity of three catalysts under the supported monometallic nickel catalyst reported by Rêgo de
same reaction conditions. The two catalysts prepared by SIWI method Vasconcelos et al. under the similar experimental conditions [42].
had the similar catalytic behavior with the comparable CH4 and CO2 Table 3 shows the deactivation rates of each catalyst for 6 h and
conversions along the reaction. Both catalysts showed high initial cat- 50 h of time-on-stream (TOS). As expected, the deactivation rates of all
alytic activity (around 73–78%). Then, a deactivation was observed three catalysts was relatively low during 50 h of TOS (0.23-0.32% h−1),
within the first ten hours of reaction. Finally, the reactivity seemed to which emphasizes the high performance of the bimetallic hydro-
be relatively stable at around 60% for CH4 conversion and 68% for CO2 xyapatite catalysts. The deactivation of these catalysts was higher
conversion. For the catalyst prepared by co-impregnation method, the within the first 6 h of TOS (1.15-2.13% h−1), especially for the Ni-Co/
initial conversion of CH4 and CO2 were lower (around 60%) compared HAP_SIWI catalyst (2.13% h−1). The deactivation of the catalysts might
to those of the two other catalysts (around 73–78%). Then, the catalytic be related to different aspects such as coke deposition and sintering.
activity of this catalyst also became stable at around 47% for CH4 These aspects will be addressed later in the manuscript.
conversion and 50% for CO2 conversion. XRD results presented above Fig. 8 shows the selectivity of the reaction into H2, CO, H2O, and the
showed diffraction peaks of CaO which resulted from the partial ca- molar ratio of H2 to CO. In all cases, the selectiviy was roughly stable in
tionic exchange between Ca2+ and Ni2+ and Co2+ for the co-

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T.S. Phan et al. Applied Catalysis B: Environmental 224 (2018) 310–321

Fig. 6. Imaging of the main elements present in the

catalyst Ni-Co/HAP_SIWI; (a): TEM image of the
cartography zone; (b), (c), (d), (e), (f): imaging of O,
Ca, P, Co, Ni, respectively.

the range of 80–90% for H2 and CO, and 10–20% for H2O. In the lit- beneficial effects on the selectivity of the reaction. Previous work of
erature [43,44], Ni- and Co-based catalysts usually had high selectivity Bellido et al. [45] showed that the addition of CaO to Ni/ZrO2 catalysts
into H2 and CO as found in this work. For both H2 and CO selectivity, allowed decreasing the implication of CO2 in RWGS reaction, as well as
the catalyst prepared by the co-impregnation method was more selec- limiting coke deposition from Boudouard reaction or methane cracking.
tive (around 90%) than the catalysts prepared by the successive im- This improves H2 and CO selectivity. The beneficial effect of CaO ad-
pregnation method (around 83–86%). These high H2 and CO selectivity dition on H2 and CO selectivity in DRM reaction was also highlighted in
of Ni-Co/HAP_COI catalyst must be due to its physico-chemical and other works using nickel as active metal [46,47].
structural properties. As mentioned above, Ni-Co/HAP_COI prepared by About the H2 to CO morar ratio, its evolution was similar for all
co-impregnation was different from two other catalysts prepared by three catalysts. This ratio decreased within the first 20 h of reaction
successive impregnation, mostly with the presence of diffraction peaks from roughly 100% to appromaxively 90% and was then stable at this
of calcium oxide, resulting from the cationic exchange between Ca2+ value. The initial decrease in the H2/CO ratio might be related to the
and Ni2+ and Co2+. The presence of calcium oxide might have some occurrence of Boudouard reaction (Eq. (12)) and of RWGS (Eq. (13)).

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T.S. Phan et al. Applied Catalysis B: Environmental 224 (2018) 310–321

Fig. 7. Reaction conversions at 700 °C obtained with

90 different catalysts; gas flow rate of CH4, CO2 and Ar:
90
80 80 20, 20 and 50 NmL/min, respectively; 340 mg of

CO2 conversion (%)

70 70 catalyst.
60 60
50 50
40 40
30 Co-Ni/HAP_SIWI 30 Co-Ni/HAP_SIWI
20 Ni-Co/HAP_SIWI 20 Ni-Co/HAP_SIWI
10 Ni-Co/HAP_COI 10 Ni-Co/HAP_COI
0 0
0 10 20 30 40 50 60

Fig. 8. Reaction selectivity at 700 °C obtained with

different catalysts; gas flow rate of CH4, CO2 and Ar:
90 90 20, 20 and 50 NmL/min, respectively; 340 mg of
CO selectivity (%) catalyst.
80 80

70 Co-Ni/HAP_SIWI 70
Co-Ni/HAP_SIWI
Ni-Co/HAP_SIWI Ni-Co/HAP_SIWI
60 60
2

Ni-Co/HAP_COI Ni-Co/HAP_COI
50 50
0 10 20 30 40 50 60
Reaction time, h Reaction time, h

1.2 50
Ni-Co/HAP_SIWI
H2O selectivity (%)

40
1.0 Co-Ni/HAP_SIWI
30 Ni-Co/HAP_COI
2

0.8
20
Co-Ni/HAP_SIWI
0.6 Ni-Co/HAP_SIWI 10
Ni-Co/HAP_COI
0.4 0
0 10 20 30 40 50 60

selectivity was roughly similar for all three catalysts and was stable
Ni-Co/HAP_COI around 15% within the last 30 h of reaction. This high amount of water
40
Ni-Co/HAP_SIW indicated the omnipresence of RWGS for these catalytic systems. This
30 Co-Ni/HAP_SIW
explains also the higher CO2 conversion compared to CH4 conversion
for each catalyst (Fig. 7) and the molar ratio of H2 to CO smaller than 1
20 (Fig. 8). In the literature, Ni- and Co-based catalysts were well reported
as efficient catalysts for RWGS [50,51].
10
The solid carbon (C(s)) formed during the reaction could be deduced
0 from the mass balance. The results are shown in Fig. 9. Selectivity to
solid carbon was relatively low (< 13%) for all three catalysts in-
vestigated. Both catalysts prepared by SIWI method showed carbon
selectivity around 13% during 50 h of TOS. However, the catalyst
Fig. 9. Solid carbon selectivity at 700 °C obtained with different catalysts; gas flow rate of
prepared by the co-impregnation method (Ni-Co/HAP_COI) showed
CH4, CO2 and N2: 20, 20 and 50 NmL/min, respectively; 340 mg of catalyst.
initial carbon selectivity around 8%, which decreased to 4% during the
last 25 h of TOS. The decrease in the carbon selectivity is simultaneous
2CO → CO2 + C (12) to the increase in CO selectivity, which suggests the occurrence of the
reverse Boudouard reaction, in which the solid carbon reacts with CO2
CO2 + H2 → CO + H2O (13) to form CO. These results also emphasize the high performance of the
bimetallic hydroxyapatite catalysts. Indeed, there are several reports in
Despite numerous papers on DRM reaction in the literature, no
the literature concerning the benefits of bimetallic Ni-Co catalysts. The
study reported the experimental quantification of water as a by-pro-
formation of a Ni-Co alloy would enhance not only the catalytic activity
duct. Water formation was only deduced from the quantification of H2,
but also the supression of carbon deposits during the reaction
CO, CO2 and CH4 at the reactor outlet [44,48]. The reactor setup used
[37,52,53].
in this work (Fig. 1) allowed measuring water content formed along the
TEM analysis of the used catalysts was also carried out. TEM results
catalytic reaction, as shown in Fig. 8. Under the experimental condi-
are illustrated in Fig. 10. In all cases, the used catalysts contained only
tions used in this work, water formation from RWGS (Eq. (13)) is in-
few carbonaceous species on their surface. The growth of carbon
evitable as predicted by thermodynamic calculation [13,49]. The water

317
T.S. Phan et al. Applied Catalysis B: Environmental 224 (2018) 310–321

Fig. 10. TEM images the used catalysts recovered

after DRM reaction at 700 °C: (a, b) Co-Ni/
HAP_SIWI; (c, d) Ni-Co/HAP_SIWI; and (e, f) Ni-Co/
HAP_COI.

nanotubes (CNTs) was observed at low frequency compared to the re- for the used catalysts, TEM analysis showed the particle sizes of metallic
sults reported in the literature for DRM reaction [25,26,54]. In some particles, which could be partially oxidized in free contact with air after
cases, we can see the embedding of metals particles inside CNTs, DRM reaction. Co-Ni/HAP_SIWI (Fig. 11A) and Ni-Co/HAP_COI
causing the partial loss of the catalytic activity. Particularly, other kinds (Fig. 11B) fresh catalysts showed a d50 of 10–20 nm. However, after
of carbon (i.e. core-shell carbon, amorphous carbon) leading to the 50 h of TOS, the percentage of particles of more than 30 nm was rela-
embedding of metals particles and so the catalytic deactivation during tively higher, which indicates that sintering/agglomeration of the ac-
DRM reaction [25,55,56], was rarely observed. This explained the tive phase took place during the reaction. This decreased particles
catalytic stability of these catalysts. dispersion and, along with the carbon deposition, led to the initial
Fig. 11 compares metals particle size of the prepared catalysts be- deactivation of the catalysts in the first hours of TOS. On the other
fore and after catalytic tests at 700 °C. We particularly note that for the hand, Ni-Co/HAP_SIWI fresh catalyst showed higher percentage of
fresh catalysts which were pre-treated by air calcination, TEM analysis particles around 20–30 nm and its distribution did not significantly
showed the particle sizes of cobalt and nickel oxides. On the other hand, changed after 50 h of TOS (Fig. 11C). This might also explain the very

318
T.S. Phan et al. Applied Catalysis B: Environmental 224 (2018) 310–321

50 (A) Before test 80

70
40 After test
60
30 50 CH4

20 40
30 CO2
10
20 (A)
0 10
0-5 5-10 10-20 20-30 30-40 40-50 50-60
0
Particle size, nm 0 20 40 60 80 100 120 140 160
Reaction time (h)
50
(B) Before test
50
40 45 (B)
After test 40
30 35

2
30
20
25
10 20
15
0 10
0-5 5-10 10-20 20-30 30-40 40-50 50-60 5
Particle size (nm) 0
0 20 40 60 80 100 120 140 160
60 Reaction time (h)
(C) Before test
50 100
40 After test 90
80
30 70
20 60
50 H2
10 40
0 30 CO (C)
0-5 5-10 10-20 20-30 30-40 40-50 50-60 20
10
0
Fig. 11. Comparison of metals particle size distribution before and after catalytic test at
700 °C; (A): Co-Ni/HAP_ SIWI; (B) Ni-Co/HAP_ SIWI; and (C) Ni-Co/HAP_COI. Reaction time (h)

1.0
low C(s) selectivity presented by this catalyst. Indeed, it has been widely 0.9
reported in the literature that small metal particles are less prone to 0.8
carbon deposition [57,58] and thus favors the catalyst stability. In all 0.7
2

cases, the size of Ni-Co particles only slightly increased, which in- 0.6
dicated that sintering of metal particles took place in a low extent. This 0.5
explains also the overall catalytic stability observed during DRM reac- 0.4
(D)
tion. 0.3
The high performance of the catalysts is related to its physical- 0.2
chemical properties. The hydroxyapatite support gives thermal stability 0.1
to the catalyst and its well-known basic properties helps coke removal 0.0
through Boudouard reaction (Eq. (12)) [32,33,36,38]. Moreover, using
an active phase composed of Ni and Co probably enhanced the catalyst
activity and the suppression of carbon deposits. In fact, it has been Fig. 12. Catalytic results obtained with Ni-Co/HAP_SIWI at 750 °C; gas flow rate of CH4,
widely reported in the literature that combining Co and Ni results in CO2 and Ar: 20, 20 and 50 NmL/min, respectively; 340 mg of catalyst.
better metal dispersion and strong metal-support interaction, which
enhances the coke resistance of the catalysts [38,59]. Further char-
increasing the reaction temperature favors also the sintering of active
acterizations such as acido-basic titration, TPO, TPD and TG-MS cou-
metallic nanoparticles. It is needed to keep a compromise between the
pling seem to be necessary to understand why bimetallic Ni-Co/HAP
temperature effect on the thermodynamic and on the sintering of na-
allowed limiting the formation of amorphous carbon during DRM re-
noparticles as well as the operational cost. Thus, another catalytic test
action. Surface properties of HAP support such as its interaction with
was done at 750 °C with Ni-Co/HAP_SIWI. Despite not showing the
metals particles, its acido-basic properties need to be highlighted.
better catalytic performance among the three catalysts investigated at
700 °C, Ni-Co/HAP_SIWI catalyst suffered of sintering of metals parti-
3.3. DRM at 750 °C cles in a very low extent, which resulted in very low solid carbon se-
lectivity. Thus, this catalyst was chosen for the investigation of the
Previous study on the thermodynamic of DRM reaction showed that influence of temperature. The results are presented in Fig. 12. As ex-
high reaction temperature favors the conversion of CH4 and CO2 and pected, increasing the reaction temperature from 700 to 750 °C allowed
limits the deposition of carbonaceous species [13,49,60]. However,

319
T.S. Phan et al. Applied Catalysis B: Environmental 224 (2018) 310–321

Table 4
Examples of the catalytic performance of Ni- and Co-based catalysts at 700–750 °C in DRM.

Metal and its content Support Catalyst weight, Inlet gas composition, Gas feeding T (°C)/P CH4 conv., CO2 conv., Time-on- Ref.
(wt.%) mg vol.% (bar) % % stream, h

5.1%Ni Ce0.15Zr0.85O2 50 50%CO2, 50%CH4 60,000a 750/1 ≈85 ≈85 70 [61]

5.9%Ni Y2O3-ZrO2 50 4%CO2, 4%CH4, 92%He 120,000a 750/1 ≈93 ≈90 25 [61]
14.6%Ni Al2O3 50 4%CO2, 4%CH4, 92%He 120,000a 750/1 ≈10 ≈20 5 [61]
10%Ni Al2O3 100 40%CO2, 40%CH4, 20% 100b 750/1 48 48 100 [62]
N2
10%Ni Phosphate-modified 100 40%CO2, 40%CH4, 20% 100b 750/1 58 57 100 [62]
Al2O3 N2
10%Ni-3%Co Al2O3-ZrO2 100 50%CO2, 50%CH4 40b 750/1 ≈80 ≈90 n.r. [63]
2%Ni-1%Co CeZrO2/β-SiC 500 50%CO2, 50%CH4 100b 750/1.2 ≈65 ≈75 100–550 [64]
2.8%Ni-2.8%Co HAP 340 20%CO2, 20%CH4, 60% 90b 750/1.6 73 79 160 This
N2 work
10%Ni SiO2 200 50%CO2, 50%CH4 40b 700/1 ≈50 ≈62 5 [65]
10%Co SiO2 200 50%CO2, 50%CH4 40b 700/1 ≈21 ≈35 5 [65]
2.8%Ni-2.8%Co HAP 340 20%CO2, 20%CH4, 60% 90b 700/1.6 60 68 160 This
N2 work

a
Space velocity, cm3 h−1 g−1.
b
Ncm3/min; n.r.: not reported.

increasing the conversion of both CH4 and CO2 from around 60 and Ni2+ and Co2+.
68% (Fig. 7) to around 73 and 79% (Fig. 12A), respectively. An initial DRM reaction was carried out at 700 and 750 °C and 1.6 bar with an
catalytic deactivation was also observed at the beginning of the reac- equimolar mixture of CO2 and CH4 diluted in N2 (60%vol.). All the
tion. Then the catalytic activity was kept stable for a long reaction time prepared catalysts showed high catalytic activity and stability. For each
of 160 h. catalytic test, an initial catalytic deactivation took place within the first
Water was also formed as a by-product of the reaction and its se- 10 h of time-on-stream (TOS). Then the catalytic activity was stable up
lectivity was stable around 12%. This was slightly lower than the values to 50 or 160 h of TOS. CO and H2 were the main products of the re-
observed at 700 °C (Fig. 8). Thermodynamic prediction shows that both action and their selectivity reached about 80–90%. Reverse WGS also
water and carbon deposition decrease with the increase of the reaction occurred, which led to the formation of water as by-product, to the
temperature [13,49]. This could be resulted from the reaction between higher conversion of CO2 compared to that of CH4, and to the H2/CO
coke and water vapor (Eq. (14)). molar ratio close to 90%.
All the prepared catalysts showed good catalytic stability during
C + H2O → 2CO (14)
DRM reaction. This was explained by the formation of carbonaceous
Fig. 12C shows the selectivity into H2 and CO. The results were si- species under CNTs form at low content. Other kinds of carbon such as
milar to those obtained at 700 °C. After an initial deactivation during amorphous carbon or core-shell carbon, which mainly causes the cat-
the first 20 h of reaction, the selectivity into both H2 and CO was stable alytic deactivation in DRM reaction, were not observed.
around 75 and 85%, respectively. The H2 selectivity was lower than the
CO selectivity which was explained by RWGS reaction. Also, C(s) se- Acknowledgments
lectivity was very low (≈10%) during the 160 h of TOS (result not
shown here). Finally, the H2 to CO molar ratio was close to 90%, as The authors gratefully thank ADEME (Agence de l'environnement et
already observed at 700 °C. de la maîtrise de l'énergie, France, for the financial support of the
As conclusion, the increase of the reaction temperature from 700 to VABHYOGAZ3 project) and PRAYON for their supports. The authors
750 °C allowed significantly increasing the conversion of both CH4 and also thank our colleagues at the RAPSODEE center (CNRS UMR 5302)
CO2 with the similar catalytic selectivity and stability of Ni-Co/ for technical help.
HAP_SIWI catalyst.
Table 4 compares the performance of hydroxyapatite-based cata- Appendix A. Supplementary data
lysts to those of catalysts prepared with conventional supports for DRM
reaction under similar experimental conditions. For both the tempera- Supplementary data associated with this article can be found, in the
ture of 700 and 750 °C, hydroxyapatite supported bimetallic Ni-Co online version, at http://dx.doi.org/10.1016/j.apcatb.2017.10.063.
catalysts prepared in this work were found to be competitive versus
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