Renewable Energy 201 (2022) 314–322

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Renewable Energy
journal homepage: www.elsevier.com/locate/renene

Green hydrogen production from sorption-enhanced steam reforming of

biogas over a Pd/Ni–CaO-mayenite multifunctional catalyst
Chengxiong Dang a, Huanhuan Xia a, Shuting Yuan a, Xingchuan Wei a, *, Weiquan Cai a, b, **
a
School of Chemistry and Chemical Engineering, Guangzhou University, Guangzhou, 510006, China
b
School of Materials Science and Engineering, Zhengzhou University, Zhengzhou, 450002, China

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

Keywords: The carbon-neutral application of biogas to produce “green hydrogen” appears to be an attractive solution to
Biogas ensure the sustainability of energy production. However, the high and variable CO2 content in biogas has limited
Hydrogen production the development of biogas utilization. Herein, we report that sorption-enhanced steam reforming of biogas
Multifunctional catalyst
(SESRB) provides an efficient way to obtain high-purity hydrogen from biogas with the in-situ removal of CO2.
CO2 capture
The effect of temperature and CO2 content on CH4 conversion and H2 purity is studied. The results indicate that
the content of CO2 does not affect the CH4 conversion and H2 purity in the pre-breakthrough stage of SESRB
process. Meanwhile, the performance of long-term stability shows that 98.0 vol% H2 with ⁓97.8% conversion of
CH4 in the pre-breakthrough stage is stably obtained over the Pd/Ni–CaO-mayenite-2.8 multifunctional catalyst
for 30 SESRB-calcination cycles. The small amount of coke (0.8 wt%) formed during the SESRB reaction can be
effectively eliminated by carbon gasification during calcination treatment. The results point out that SESRB is a
promising technology for the efficient utilization of biogas to produce high-purity hydrogen.

1. Introduction transition [6]. The composition of the raw biogas largely depends on the
type of substrate. Biogas essentially consists of 15–55 vol % CO2 and
Hydrogen as an ideal clean fuel is prospective to decarbonize the 35–70 vol % CH4 [7,8], along with a small amount of other gases: H2O,
global energy supply to confront the soaring CO2 emission. Meanwhile, N2, H2, and traces of H2S, O2, NH3, siloxanes, and so on [9]. Up to now,
hydrogen is one of the most demanded feedstocks in the petroleum biogas is mainly used for power generation, but it is not the preferred
refining and chemical industries, and the global demand for H2 is energy source for power generation due to the serious environmental
continuously increasing [1,2]. Currently, the most commonly used emissions and low electrical conversion (18–25%) [9]. After the sepa­
method of hydrogen production is steam reforming of methane (SRM) ration of unwanted substances [10], biogas can provide bio-methane as
from natural gas. However, the SRM process provides the grey hydrogen a natural gas substitute for producing value-added chemicals or directly
with intrinsically significant CO2 emissions. In this context, the utiliza­ connecting to the conventional gas pipeline infrastructures [11,12].
tion of renewable raw materials, especially those from biomass, to However, the removal of high CO2 content through the physical sepa­
produce green hydrogen is an efficient, more sustainable, and environ­ ration technology reduced the energy efficiency of the plant by 5–15%
mentally friendly method, because the generated CO2 is recycled back [13].
into biomass to realize a carbon-neutral process [3,4]. 1
As an indispensable biomass resource, biogas is commercially pro­ H2O(g) + CH4(g) → 3H2(g) + CO(g) △Hr, 25◦ C = 206.2 kJ mol− (eq. 1)
duced in large quantities in landfills by anaerobic digestion or fermen­ CO2(g) + CH4(g) → 2H2(g) + 2CO(g) △Hr, 25◦ C = 247.0 kJ mol − 1
(eq. 2)
tation of any bio-wastes such as industrial wastewater, animal waste,
and agricultural waste [5]. From 1990 to 2018, the global supply of H2O(g) + CO(g) → H2(g) + CO2(g) △Hr, 25◦ C = − 41.2 kJ mol− 1
(eq. 3)
biogas increased markedly with an average annual growth of 11.5%,
Recently, hydrogen production from biogas as an effective process to
which makes it play an increasingly important role in the energy
produce “green hydrogen” has attracted more and more attention [4].

* Corresponding author.
** Corresponding author. School of Chemistry and Chemical Engineering, Guangzhou University, Guangzhou, 510006, China.
E-mail addresses: [email protected] (X. Wei), [email protected] (W. Cai).

https://doi.org/10.1016/j.renene.2022.10.106
Received 1 September 2022; Received in revised form 20 October 2022; Accepted 23 October 2022
Available online 31 October 2022
0960-1481/© 2022 Elsevier Ltd. All rights reserved.
C. Dang et al. Renewable Energy 201 (2022) 314–322

Table 1
Summary of literatures about the performance of the BSR reaction.
Catalyst S/Ca CH4/ Tc XCH4d XCO2e RH2/cof refs
CO2b (oC) (%) (%) (%)

Ni/CeZrO2 1.0 1.5 700 90.0 38.0 2.3 [16]

Ni–Cr 2.0 1.7 700 87.0 0.0 ~2.6 [15]
600 53.0 − 40.0 ~1.9
Pd–Rh/Ce 1.5 1.5 750 93.9 5.0 3.3 [17]
ZrO2–Al2O3
Rh/NiCrAl- 1.0 1.5 800 58.0 21.0 2.1 [22]
foam
Rh/La–Al2O3 2.6 1.0 650 93.0 10.5 ~2.5 [23]
Ni0.26Ce0.87O2 ~0.7 3.0 700 ~84.0 ~28.0 ~6.0 [19]
a
The molar ratio of H2O to CH4.
b
The molar ratio of CH4 to CO2 in the simulated biogas.
c
Reaction temperature.
d
The conversion of CH4.
e
The conversion of CO2 conversion.
f
The molar ratio of H2 to CO in the gaseous products.

Fig. 2. Effect of (A) temperature and (B) composition on the SESRB reaction
over the Ni–CaO-mayenite-2.8 catalyst.
Fig. 1. SESRB performance for the first SESRB reaction over the Ni–CaO-
mayenite-2.8 catalyst. (Thermodynamic values of H2 and CO2 for the conven­ reaction achieves a process intensification of traditional SR (eq. (1)),
tional BSR: black dash dot (-‧-‧-) for H2 and magenta dash dot dot (-‧‧-‧‧-) WGS (eq. (3)), and CO2 removal (eq. (4)) [24,25]. The regeneration step
for CO2). (eq. (6)) is then performed to decarbonize the sorbent for continuous
operation. In-situ CO2 sorption pushes WGS and SR equilibrium towards
Steam reforming (SR) reaction has been proved to be an effective products, increasing H2 production and purity [26]. Hydrogen with a
method for hydrogen production from biogas [14–16]. Table 1 shows purity of 95 vol%~99 vol% (dry and inert-free gas basis) can be readily
that high temperature, e.g. above 700 ◦ C, is usually required for biogas obtained from the SESR of various hydrocarbon feedstocks [27–29]. On
steam reforming (BSR, eq. (1)) to realize high conversion of CH4 due to the other hand, the exothermic nature of the CO2 capture (eq. (4))
the stable nature of CH4. However, the high temperature leads to process allows SESR to operate at a lower temperature than the tradi­
competition between dry reforming (eq. (2)) and BSR, especially under tional SR process. More importantly, SESR of biogas (SESRB) process
the condition of high CO2 content in biogas [15,17]. The severe carbon provides an effective solution to the problem of high CO2 content in
deposition caused by dry reforming leads to rapid deactivation of the biogas by in-situ CO2 capture (eq. (4)). Therefore, SESRB is a good
catalyst [18], which seriously affects the efficiency of the BSR reaction. alternative route to extract the potential energy from biogas.
Kim et al. showed that coke formation (above 10 wt%) for BSR was
CO2(g) + CaO(s) → CaCO3(s) △Hr, = − 178.8 kJ mol− 1
(eq. 4)
observed over Pd–Rh/CeZrO2–Al2O3 catalyst at 750 ◦ C [17]. The initial 25◦ C

activity of 84.6% was lost after 24 h of BSR reaction at 700 ◦ C over the 2H2O(g) + CH4(g) + CaO(s) → 4H2(g) + CaCO3(g) △Hr, 25◦ C = − 13.8 kJ
Ni0.1Ce0.95O2 catalyst [19]. Moreover, the H2 content produced by BSR mol− 1 (eq. 5)
hardly exceeds 70 vol% (dry and inert-free gas basis), especially in the
presence of competition of dry reforming [19]. To produce high-purity CaCO3(s) → CO2(g) + CaO(s) △Hr, 25◦ C = 178.8 kJ mol− 1
(eq. 6)
hydrogen, the formed CO and unconverted CH4 and CO2 must be
The present work reports the feasibility of producing high-purity
separated from the reaction system [20]. Two temperature-staged water
hydrogen from biogas by SESRB over the Pd/Ni–CaO-mayenite-2.8
gas shift (WGS, eq. (3)) reactors and different separation units are
multifunctional catalyst. The Pd/Ni–CaO-mayenite-2.8 is a combined
required for hydrogen purification, which inevitably increases the cost
catalyst-sorbent material with Pd-promoted Ni as catalytic active phase,
and complexity of the operation process [21]. In the context of high
CaO as CO2 sorbent, and mayenite (Ca12Al14O33) as support and spacer.
content CO2, a more effective method is preferred to directly convert
The effects of temperature (550–625 ◦ C) and biogas composition (CO2
biogas to high-purity hydrogen with the in-situ capture of CO2.
contents of 0–60 vol%) on the SESRB performance have been explored.
Sorption-enhanced steam reforming (SESR) technology provides a
Meanwhile, a total of 30 reaction cycles were tested to evaluate the
promising option for producing high-purity H2 from biogas. The SESR
stability of Pd/Ni–CaO-mayenite-2.8 multifunctional catalyst for SESRB.
reaction (eq. (5)) proposes that the addition of solid sorbents to the SR

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Fig. 3. (A) SESRB performance for the first SESRB reaction over the Pd/Ni–CaO-mayenite-2.8 catalyst, (B) Multiple SESRB-desorption cycles, (C) CH4 conversion, (D)
gaseous products and (E) CH4 conversion and pre-breakthrough duration over the Pd/Ni–CaO-mayenite-2.8 catalyst during cyclic tests.

Thermogravimetric analysis (TGA), Raman spectroscopy, and N2 tem­ 2.2. Characterization techniques
perature programmed desorption (N2-TPD) were employed to study the
coking properties of the spent multifunctional catalyst during the cyclic X-ray diffraction (XRD) patterns of the samples were recorded using
operation. a PANalytical X’pert Powder diffractometer with Cu-Kα radiation at 45
kV and 40 mA, and the scanned 2θ angle was varied from 10◦ to 80◦ .
2. Experimental section Inductively Coupled Plasma Optical Emission Spectrometer (ICP-OES)
was conducted using Agilent 5110, and the sample was dissolved in aqua
2.1. Synthesis of multifunctional catalysts regia before the analysis. Nitrogen physisorption was measured using a
Micromeritics ASAP 2460 apparatus. Before the analysis, the sample was
The Ni–CaO-mayenite was prepared by a homogeneous coprecipi­ degassed at a temperature of 300 ◦ C under vacuum overnight. The
tation method as detailed in the literature [27]. Firstly, the mixed metal morphology and microstructure of the sample were characterized by
nitrates (Ca, Al, and Ni) with the designed Ni content (10 wt%) and scanning electron microscopy (SEM, Hitachi SU8220) and transmission
Ca/Al molar ratio (1.8, 2.8, and 3.8) were dissolved in 200 mL deionized electron microscopy (TEM, FEI Talos F200S). The Raman patterns were
water under the protection of N2. Then NaOH solution (0.5 mol/L) was recorded on a Raman spectrometer (HORIBA LabRAM HR Evolution).
added to the mixed solution under agitating. After the pH of the solution Thermogravimetric analysis (TGA) was conducted by using a NETZSCH
reached 10, the obtained suspension was further stirred for 1 h. The STA 2500 instrument. The sample (⁓5 mg) was heated from room
suspension was then filtered, and the resulting precipitates were washed temperature to 800 ◦ C under an air atmosphere at a heating rate of
to neutral with deionized water. Finally, the sample was dried overnight 10 ◦ C/min.
in vacuum at 80 ◦ C and calcined in the air at 800 ◦ C for 2 h to obtain H2 temperature programmed reduction (H2-TPR) test was under­
Ni–CaO-mayenite-x catalyst, where x stands for the mole ratio of Ca to taken on Xianquan TP-5080 adsorption apparatus [27]. The catalyst (50
Al. The Pd was loaded by incipient wetness impregnation method [30]. mg) was first pretreated at 400 ◦ C under N2 (30 NmL/min) for 60 min to
The as-prepared Ni–CaO-mayenite-2.8 sample was added to the solution remove the adsorbed substances, and followed by cooling to room
containing desired amount of Pd (1 wt%). After stirring for 5 h, the temperature, then 10 vol% H2/N2 mixture gases (30 NmL/min) was
sample was dried at 110 ◦ C and then calcined at 800 ◦ C for 1 h to pro­ introduced. Data collection was performed when the temperature rose
duce Pd/Ni–CaO-mayenite-2.8 catalyst. The catalyst after SESRB reac­ from room temperature to 800 ◦ C at a rate of 10 ◦ C/min. To understand
tion was labeled as n-R and the regenerated catalyst as n-D, where n the effect of the desorption process on carbon deposition, temperature
represents the number of cycles. For example, programmed desorption in N2 atmosphere (N2-TPD) was carried out. 50
Pd/Ni–CaO-mayenite-2.8-10-R represents the Pd/Ni–CaO-mayenite-2.8 mg of the used sample was heated from 30 to 800 ◦ C with a heating rate
after 10 SESRB-calcination cycles. of 5 C/min in a 30 Nml min− 1 N2 flow. The outlet gas was measured
◦

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Fig. 4. (a) XRD pattern, (b) N2 physisorption isotherm, (c) pore size distribution of the reduced Pd/Ni–CaO-mayenite-2.8 catalyst, and (d) H2-TPR of the calcined Pd/
Ni–CaO-mayenite-2.8 catalyst.

(dry and inert-free gas basis).

Table 2
Physical properties of the Pd/Ni–CaO-mayenite-2.8 during the cycles. FCH4,in − FCH4,out
CH4 conversion (%) = × 100 (1)
Catalysts Nia CaOb SBETc Pore Average pore FCH4,in
(nm) (nm) (m2/g) volumed sizee (nm)
(cm3/g) Fi,out
Ci (%) = × 100 (2)
Pd/Ni–CaO- 14.8 22.9 16.5 0.086 17.5
FH2,out + FCO2,out + FCH4,out + FCO,out
mayenite-2.8-
fresh where Fin and Fout are the flow rates of each species i fed in and
Pd/Ni–CaO- 16.1 28.5 10.8 0.038 17.1 produced.
mayenite-2.8-
10-D
Pd/Ni–CaO- 19.2 42.9 7.3 0.025 20.3
3. Results and discussions
mayenite-2.8-
30-D 3.1. Performance of catalysts
a
Determined by Scherrer’s equation based on the (1 1 1) peak of Ni.
b
Determined by Scherrer’s equation based on the (2 0 0) peak of CaO. Fig. S1 shows that the Ni–CaO-mayenite-2.8 has the best stability
c
Specific surface area. with the highest sorption capacity during the 10 cyclic tests (see the
d
Total pore volume. detailed discussion in Supporting Materials), which suggests that the
e
Average pore size. optimized multifunctional catalyst is ultimately a compromise between
the CaO content and the structural stability. The evolution of product
every 25 ◦ C by Gas chromatography (GC, Fuli 9790II). components with time during the SESRB reaction for the Ni–CaO-
mayenite-2.8 catalyst is presented in Fig. 1. Three typical reaction stages
of the SESR process, namely pre-breakthrough, breakthrough, and post-
2.3. Experimental procedure
breakthrough stages, have been identified over the Ni–CaO-mayenite-
2.8 catalyst [28], as is related to the variation of CO2 capture behavior.
All SESRB experiments were performed in a fixed bed quartz tube
Rapid in-situ removal of CO2 in the initial stage provides a high H2
reactor (300 mm length with I.D. of 10 mm) with a loading of 1.0 g of
concentration (~94.5 vol%), obviously higher than the thermodynamic
catalyst. To carry out the experiments, the sample was reduced with 30
value of the conventional BSR, suggesting that the in-situ capture of CO2
NmL/min H2 at 750 ◦ C for 60 min. Once the operating temperature was
greatly improves the hydrogen concentration. Meanwhile, the low
reached, the simulated biogas containing CO2 and CH4 (total flow rate of
concentration of CO2 (~1.0 vol%) indicates that the SESRB process can
5 NmL/min, WHSVCH4 of 0.09–0.22 h− 1), together with steam (H2O/
effectively treat the high content of CO2 in the simulated syngas. With
CH4 molar ratio of 4) as well as 20 NmL/min N2 (as internal standard
the progress of the SESRB reaction, CaO is gradually transformed into
and diluent gas) were supplied to the reactor. The SESRB reaction was
CaCO3, resulting in the weakening of the sorption-enhanced effect,
carried out for 30min, and the regeneration process was conducted in 30
which is featured by the decrease of H2 purity and the increase of CO2
NmL/min N2 at 800 ◦ C for 30 min. The nitrogen-free gas composition
concentration. Finally, the purity of hydrogen is reduced to 60.1 vol%,
was analyzed by two GC with a measurement every 2 min. The SESRB
and the reaction behaves like the conventional BSR. On the other hand,
performance was evaluated based on the CH4 conversion and H2 purity

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Fig. 5. SEM images of (a) the reduced and (b) the used Pd/Ni–CaO-mayenite-2.8 catalyst; (A) HAADF, (B–G) EDS mapping, and (H) an EDS line scan of Ni and Pd of
the reduced Pd/Ni–CaO-mayenite-2.8 catalyst.

SESRB technology has improved CH4 conversion from 63.8% in the final presented in Fig. 3(A). 98.1 vol% hydrogen purity and 98.3% CH4
stage to 95.9% in the initial stage. The obvious difference in H2 purity conversion are achieved on the Pd/Ni–CaO-mayenite-2.8 catalyst due to
(94.5 vol% vs 60.1 vol%), CO2 concentration (1.0 vol% vs 16.2 vol%), the high activity for CH4, which is supported by the higher conversion of
and CH4 conversion (95.9% vs 63.8%) between the pre-breakthrough CH4 (83.6%) in the 30 min. Compared to the Ni–CaO-mayenite-2.8,
stage and post-breakthrough stage strongly suggest that SESRB reac­ ⁓3.5% improvement of H2 concentration over Pd/Ni–CaO-mayen­
tion is a prospective option for high purity H2 production from biogas. ite-2.8 is substantial, since the downstream purification through selec­
We have selected H2 purity and CH4 conversion at the 4th min and tive oxidation or PSA can be greatly simplified to produce industrial
30th min as indicators to explore the effect of operating temperature grade H2 (99.95 vol%) [34]. Fig. 3(B) presents the cyclic
(Fig. 2(A)) and the composition of biogas (Fig. 2(B)) on the SESRB SESRB-regeneration performance of the Pd/Ni–CaO-mayenite-2.8 cata­
performance. Fig. 2(A) shows that CH4 conversion at the 30th min in­ lyst. The sorption-enhanced effect throughout the 30 SESRB-desorption
creases as the reaction temperature increases, which is due to the cycles has been confirmed by the three characteristic stages of gaseous
endothermic nature of BSR [31]. The CH4 conversion at the 4th min is products (Fig. 3(B)) and the enhancement of methane conversion (Fig. 3
enhanced from 89.2% at 550 ◦ C to 95.6% at 600 ◦ C with H2 purity (C)). Fig. 3(D) shows that the reaction-regeneration cycles offer stable
increased from ⁓89.0 vol% to ⁓94.5 vol%. However, when the tem­ SESRB performance for 30 cycles, with H2 purity and CO2 concentration
perature further rises to 625 ◦ C, the CH4 conversion hardly changes, and at the 4th min maintaining at ⁓98.0 vol% and ⁓0.7 vol%, respectively.
the purity of hydrogen decreases, due to the unfavorable thermody­ Meanwhile, CH4 and CO concentrations also do not show significant
namics of CaO carbonation reaction at high temperature [32]. This in­ changes. The stability of SESRB also ensures the high conversion of CH4
dicates that the optimum temperature is a compromise between BSR and (⁓97.8%, Fig. 3(E)) in the cyclic tests. However, the H2 purity in the
CaO carbonation reaction. The effect of biogas composition on the pre-breakthrough stage for the Ni–CaO-mayenite-2.8 sample (Fig. S2)
SESRB performance was studied at 600 ◦ C. Fig. 2(B) shows that the H2 decreases slightly from 94.5 vol% to 93.0 vol%, which is related to the
purity at the 4th min slightly increases with the increase of CO2 content decrease in methane conversion (Fig. S2(D)). Obviously, high H2 purity
in biogas. Meanwhile, the CH4 conversion at the 4th min does not and CH4 conversion can be obtained only at the first stage, so the
change significantly under the studied conditions. These results indicate duration of the first stage (defined as the pre-breakthrough stage) is
that the biogas composition has little effect on the SESRB performance, often adopted as another key indicator to evaluate the cyclic stability of
which should be ascribed to the effective occurrence of CO2 removal by the SESR process [35] It can be seen that the pre-breakthrough duration
CaO [33]. The adaptability of SESRB reaction to biogas components decreases from ⁓22 min in the 1st cycle to ~15 min in 7th cycle, and
makes it a prospective technology for the efficient utilization of biogas. then remains almost constant till the 30th cycle.
Different from aqueous phase oxygenates derived from biomass
sources, high conversion of CH4 is necessary to obtain high-purity
3.2. Characterization of the fresh catalyst
hydrogen from biogas due to the presence of CH4 in the product gas.
We have performed SESRB over the multifunctional catalyst with the
Fig. 4(a) displays the XRD pattern of the reduced Pd/Ni–CaO-
modification of Pd (Pd/Ni–CaO-mayenite-2.8) [18,33], and the result is
mayenite-2.8 catalyst upon reduction at 700 ◦ C. The characteristic peaks

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Fig. 6. (a) Evolutions of XRD patterns of the Pd/Ni–CaO-mayenite-2.8 during the SESRB-calcination cycles; (A) HAADF, (B–G) EDS mapping of the Pd/Ni–CaO-
mayenite-2.8-30-D catalyst.

of metallic Ni species and CaO are observed, unambiguously suggesting The physical morphology of the Pd/Ni–CaO-mayenite-2.8 catalyst
the formation of Ni–CaO multi-compounds [36]. The absence of typical was investigated by SEM and TEM, and the results are shown in Fig. 5.
diffraction peaks of Pd species is due to its low actual content of 0.94 wt As observed in the SEM image (Fig. 5(a)), the Pd/Ni–CaO-mayenite-2.8
% measured by the ICP-OES. Meanwhile, the alloying of Pd with Ni may catalyst has a block structure composed of a large number of stacked
also lead to Pd species not being detected. The characteristic diffraction sheets, agreeing well with the results of physisorption isotherm in Fig. 4
peaks belonging to two calcium aluminate phases (Ca3Al2(OH)12 and (b). It can be clearly observed that a dense structure similar to a Voronoi
Ca12Al14O33) are observed, which is usually observed in the Al2O3-­ pattern is formed after the SESRB reaction [43]. This is due to the vol­
supported CaO-based materials [27,37]. Generally, Ca(OH)2 in the ume expansion caused by the conversion of CaO to CaCO3 [44,45].
Pd/Ni–CaO-mayenite-2.8 catalyst can be ascribed to the high reactivity Moreover, the surface of the used Pd/Ni–CaO-mayenite-2.8 catalyst
between atmospheric moisture and CaO [38]. According to the IUPAC appears to be clean, implying that the sample does not have obvious
(International Union of Pure and Applied Chemistry) classification [39], coking after the SESRB reaction. HAADF image and STEM-EDS mapping
Pd/Ni–CaO-mayenite-2.8 catalyst (Fig. 4(b)) possesses a type II for the catalyst are depicted in Fig. 5(A-H). Notably,
adsorption-desorption curve with an H3 type hysteresis loop, which is Pd/Ni–CaO-mayenite-2.8 catalyst shows uniform dispersion of Ni
due to the presence of non-rigid aggregates of plate-like structure with nanoparticles (NPs), as ⁓71% of the Ni NPs are concentrated in the
slit-shaped pores [40]. The SBET of Pd/Ni–CaO-mayenite-2.8 is 16.5 range of 12–18 nm and the average size of 16 nm (Fig. 5(A)). And the Pd
m2/g, as listed in Table 2. The low SBET is also found in other multi­ is well dispersed on Pd/Ni–CaO-mayenite-2.8 catalyst surface in the
functional catalysts [2,36,41]. Three distinct peaks are clearly seen in form of nanoclusters (Fig. 5(C)). Fig. 5(D) further shows that the Pd is
the H2-TPR profile of Pd/Ni–CaO-mayenite-2.8 (Fig. 4(d)), due to the overlapped with Ni due to the presence of Pd–Ni solid solutions [46],
reduction of nickel oxides in different chemical environments [42]. The which is supported by a similar pattern of Pd and Ni signals in the EDS
reduction peak at around 460 ◦ C is attributed to bulk-phase NiO with line-scan analysis (Fig. 5(H)). The distribution of Ca element (Fig. 5(E))
stronger reducibility, and the peak at 570 ◦ C is related to nickel oxides basically coincides with that of Al element (Fig. 5(F)), implying that Ca
with strong interaction with support and/or CaO [36,42]. The small species are well separated by Al species, which are critical to the for­
reduction peak at about 720 ◦ C is generally due to the reduction of Ni2+ mation of uniformly dispersed CaO component. The intimate contact
in NiAl2O4. The results of H2-TPR indicated that nickel oxide species can between Ni and Ca element (Fig. 5(G)) suggests that there is sufficient
be completely reduced below 750 ◦ C, which is supported by the XRD contact between the catalytic active components and the sorbents,
results in Fig. 4(a). which is conducive to giving full play to the advantages of dual

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functions.

3.3. Characterization of the used catalyst

To understand the influence of cyclic process on the catalyst, the

micro-structural evolution of Pd/Ni–CaO-mayenite-2.8 was investigated
by XRD and N2 physisorption. As revealed by the XRD patterns in Fig. 6
(a), CaCO3 and CaO phases appear alternately during the cycle due to
the reversible carbonation reactions (eq. (4) and eq. (6)) in the calcium
looping process [47]. Mayenite phase as spacer exists in all samples due
to its high thermal stability (Melting point of 1390–1400 ◦ C). The sin­
tering of Ni species is observed, supported by the stronger peak and
smaller half-peak width of Ni in the XRD patterns. To be specific, as
listed in Table 2, Ni crystallite size increases from the initial of 14.8
nm–19.2 nm after 30 SESRB-desorption cycles. Meanwhile, a decrease in
SBET, i.e. from 16.5 to 7.3 m2/g after 30 cyclic tests, is also shown,
implying the deterioration of microstructure induced by the
high-temperature process, which causes the loss of sorption-enhanced
effect in Fig. 3(E). To further investigate the structure of the catalyst
after the cycle test, HAADF image and STEM-EDS mapping of
Pd/Ni–CaO-mayenite-2.8-30-D catalyst were taken (Fig. 6(A-H)). Fig. 6
(A-D) show that Ni particles are still uniformly distributed on the
mayenite. However, the sizes of Ni particles are obviously increased, and
the average size of Ni NPs is 36.7 nm. Meanwhile, the overlap of Ni and
Pd signals is also observed in Fig. 6(D), indicating that the Ni–Pd solid
solution still exists. Although Ca (Fig. 6(E)) and Al (Fig. 6(F)) elements
show similar distribution, the enrichment of Ca element highlighted by
the white rectangle is observed, which indicates the presence of CaO
phase. The sintering of Ca species is proved by the increasing CaO
crystallite size with the number of cycles (Table 2), which is further
supported by the decrease of the pre-breakthrough duration in Fig. 3(E).
Interestingly, even if the Ni species have obvious sintering during the
cycles, there is still no filamentous carbon or carbon nanotube found on
the surface of Pd/Ni–CaO-mayenite-2.8-30-D, suggesting that the
multifunctional catalyst has no carbon deposits or can effectively elim­
inate the carbon deposits during the cycle tests.
Carbon deposition usually occurs in the reforming reaction at high
temperatures, leading to the loss of catalytic active sites for reforming
reaction. To study the coking properties of Pd/Ni–CaO-mayenite-2.8
during the reaction, the sample was analyzed by TGA. Fig. 7(A) shows a
slight weight gain stage in the temperature range of 250–360 ◦ C in the
TGA curve of Pd/Ni–CaO-mayenite-2.8-10-R, which is caused by the re-
oxidation of the metallic Ni [42,48]. Meanwhile, the tiny mass gain in
the range of 400–550 ◦ C is likely caused by the oxidation of Ni strongly
combined with the dense CaCO3 layer [49]. Three regions of mass loss
are also identified. The mass loss occurring between 360 and 450 ◦ C is
due to the decomposition of Ca(OH)2 [50,51]. The subsequent weight
loss between 550 and 630 ◦ C is associated with the oxidation of carbo­
naceous species [49,52], and the amount of carbon deposited is calcu­
lated to be 0.8 wt% based on the TGA analysis. The negligible weight
loss indicates that almost no carbon deposition is formed on
Pd/Ni–CaO-mayenite-2.8 catalyst during the SESRB reaction, due to the
positive effect of sorbent on decreasing coke formation [49,53,54]. The
large peak observed at 700 ◦ C is assigned to the decomposition of
CaCO3. The initial peak that appears below 310 ◦ C for
Pd/Ni–CaO-mayenite-2.8-10-D is ascribed to the loss of
surface-adsorbed water and/or the dehydroxylation of the sample [55].
Interestingly, the Pd/Ni–CaO-mayenite-2.8-10-D does not show the
carbon-related peak, due to carbon gasification by CO2 generated from
Fig. 7. Evolutions of (A) TGA and (B) Raman patterns of the Pd/Ni–CaO- CaCO3 decomposition [18,52]. Therefore, there is little carbon accu­
mayenite-2.8 during the SESRB-calcination cycles; (C) N2-TPD profiles of the mulation during the cycle test due to the in-situ carbon removal, sup­
Pd/Ni–CaO-mayenite-2.8-10-R catalyst. ported by the absence of carbon-related peaks on the
Pd/Ni–CaO-mayenite-2.8-30-D sample.
Raman spectra of the spent samples were collected, and the result is
presented in Fig. 7(B). The two peaks assigned as D band (1345 cm− 1)
and G band (1586 cm− 1) can be identified on Pd/Ni–CaO-mayenite-2.8-

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10-R sample, implying the existence of the deposited carbon after the Appendix A. Supplementary data
SESRB reaction [52,56]. It should be noted that all the peaks are very
weak, probably related to the low crystallinity of carbon deposition, Supplementary data to this article can be found online at https://doi.
which can be easily eliminated by oxidation [56]. No D and G bands are org/10.1016/j.renene.2022.10.106.
observed in the same region for Pd/Ni–CaO-mayenite-2.8-10-D sample,
indicating that carbon deposition has been eliminated after calcination References
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