Fuel 257 (2019) 116032

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Fuel
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Full Length Article

Roles of alkali/alkaline earth metals in steam reforming of biomass tar for T

hydrogen production over perovskite supported Ni catalysts
Zhonghui Zhanga, Zhiliang Oua, Changlei Qina, , Jingyu Rana, Chunfei Wub
⁎

a
Key Laboratory of Low-grade Energy Utilization Technologies and Systems of Ministry of Education, School of Energy and Power Engineering, Chongqing University,
Chongqing 400044, China
b
School of Chemistry and Chemical Engineering, Queen's University Belfast, Belfast BT7 1NN, UK

ARTICLE INFO ABSTRACT

Keywords: Biomass steam gasification has a large potential to produce high-purity hydrogen, and perovskites are good
Biomass to hydrogen candidates to act as catalyst supports in eliminating the biomass tar produced during reforming. However,
Alkali and alkaline earth metals various alkali and alkaline earth metals are contained in actual biomass, which would be released during re-
Perovskite support actions and could affect the catalytic performance of perovskite-supported catalysts. To explore potential roles of
Biomass tar
alkali and alkaline earth metals in the catalysis process, in this work, typical K, Ca and Mg were added into Ni/
La0.7Sr0.3AlO3−x catalysts, and their performance in steam reforming of toluene as a model of biomass tar for
hydrogen production were investigated comprehensively. Catalytic performance shows that the presence of K,
Ca, and Mg leads to a better resistance to coking (a reduction of over 60%) and sintering of the Ni/perovskite
catalysts utilized, and this trend becomes more pronounced as the decrease of reaction temperature.
Furthermore, a series of catalyst characterizations, including XRF, XRD, SEM, TPR, TPD, and XPS were con-
ducted to understand the action mechanism. And results reveal that the presence of K, Ca, and Mg in catalysts
promotes the absorption ability of surface oxygen, which could oxidize reaction intermediates or the carbon
deposited, thus enabling good reforming properties of the perovskite-supported Ni catalysts in the reforming of
biomass tar.

1. Introduction
With increasing concerns on the lack of fossil fuels and severe en-
vironmental pollution, hydrogen has been considered as a kind of clean
and sustainable energy, which could even possibly replace traditional
energy carriers in the near future. To develop hydrogen energy, it is
necessary to produce hydrogen from sustainable feedstock with af-
fordable cost. Nowadays, over 96% hydrogen is obtained from steam
reforming of fossil fuel [1–3], especially CH4, which could cause a
massive emission of CO2, and what’s more, fossil fuels are not renew-
able. In contrast, biomass is a kind of sustainable material and its
conversion to hydrogen could not only reduce the presence of solid
waste [4], but also have no carbon emission over the whole life cycle of
energy system. Therefore, hydrogen production from the gasification of
biomass with steam [5–7] is a promising and sustainable technology.
Biomass steam gasification is usually operated at a temperature over
550 °C and has a very complicated composition of products, which is
determined by reaction conditions and the type of biomass sources
[8–12]. Generally, the gas phase composition is mainly H2, O2, CO, CO2
and CH4 [13,14]. Though with great advantages, the commercialization
of biomass steam gasification still faces several problems. It is known
that tar is generally formed in the accompanied complex thermo-
chemical reactions during biomass gasification [7,15–17], such as
polymerization and cycloaddition. The presence of tar not only inhibits
the proceeding of reactions, but also causes pipeline blockage and
equipment contamination [18], which could further largely decrease
the efficiency of hydrogen production. Due to the complexity of tar
components, including benzene, toluene, naphthalene, phenol, gly-
cerol, PAH etc., most researchers use toluene [19] as tar model, which
is also adopted in this work.
Catalysts play key roles in the process of tar steam reforming for the
directed, fast, and enormous production of specific valuable gases.
Among various catalysts (including Pt, Pd, Ru, Ni, Fe, Co, Mo etc.) re-
ported, Ni-based catalysts [20,21] are widely studied in hydrocarbon
reforming, for its low cost and high activity in cleaving the C–C and
C–H bond [22]. Additionally, suitable supports should be included to
synthesize high-efficiency catalysts [23], as catalyst supports could not
only disperse the active metal, but also participate in secondary

⁎
Corresponding author.
E-mail address: c.qin@cqu.edu.cn (C. Qin).

https://doi.org/10.1016/j.fuel.2019.116032
Received 20 May 2019; Received in revised form 9 July 2019; Accepted 15 August 2019
0016-2361/ © 2019 Elsevier Ltd. All rights reserved.
Z. Zhang, et al.
reactions, thus that influence reaction activity and carbon deposition.
Al2O3, ZrO2, CeO2, MgO, TiO2, SiO2, and dolomite [24–31] are among
the most commonly studied catalyst supports in the literature, and
exhibited good abilities to inhibit the rapid deactivation of Ni compo-
nent. Interestingly, Ni/CeO2 (75%)-ZrO2 (25%) [32] catalyst is reported
to have a superior performance in toluene steam reforming, owing to
not only its great surface area, but also the high oxygen mobility and
oxygen storage capacity of the support utilized. It was demonstrated
that the capacity of oxygen storage of catalyst support is very important
for hydrogen production from catalytic tar reduction.
Perovskite is a kind of octahedrons ceramic oxide with a molecular
formula of ABO3. Its A-site ion is generally occupied by an alkaline
earth or lanthanide metal with a large ionic radius to stabilize the
whole structure, and B-site ion is generally a transition metal element,
such as Mn, Co, Fe. Compared with the common metal oxides, per-
ovskite structure could let some elements exist in abnormal valance
state, thus the oxygen is able to present with non-stoichiometric ratio.
This feature makes perovskite possess a special ability in oxygen mo-
bility and storage, which is specifically suitable to be used as the sup-
port of catalysts. Sekine et al. [33–36] reported a superior activity of
La0.7Sr0.3AlO3−x, adapting from LaAlO3 with a partial replacement of
La by Sr, in toluene steam reforming with much less carbon deposition.
And the promotion is attributed to the migration of lattice oxygen and
its following participation in the oxidization of hydrocarbons, which is
experimentally verified by the isotope-labelling method, where the
embedded 18O in support appears in CO2 and CO during toluene steam
reforming. The work of Oemar et al. [37] revealed that the doping of
strontium in A-site could lower the activation energy of lattice oxygen
migration and improve the adsorption ability of oxygen, thus benefits to
the production of oxygen vacancies on catalyst surface. Marinho et al.
[38] observed that LaNiO3/CeSiO2 support could promote Ni dispersion
and inhibit carbon accumulation in ethanol steam reforming. Ad-
ditionally, Chen et al. [39] reported a high activity and good stability of
NiO/LaFexNi1−xO3 in ethanol steam reforming, for the anti-sintering
characteristics due to the interaction between Ni and perovskite sup-
port.
Although great efforts have been devoted to investigate perovskite-
type materials as Ni-catalyst supports, little consideration has been
given to the inclusion of alkali and alkaline earth metals [40,41] existed
in the actual biomass. In some studies, the addition of alkali and al-
kaline earth metals has been reported to improve the coking resistance
of catalysts in the steam reforming of hydrocarbon. Some adverse
phenomena, such as the decrease of catalyst activity [42] were also
observed, and the role of alkali and alkaline earth metal presented in
catalysts has many different explanations [43,44]. To the best of our
knowledge, there is no systematic work yet reporting on the effect of
alkali and alkaline earth metals on perovskite-supported catalysts in
toluene steam reforming for hydrogen production. To get to the target,
in this work, low-concentration alkali and alkaline earth metals (K, Ca,
Mg) were presented in Ni/La0.7Sr0.3AlO3−x catalysts, and the influence
of reaction temperature, types of alkali and alkaline earth metals and
their loading amount were tested in a fixed bed system equipped with
an online gas analyzer. Techniques of SEM, TPR, TG, XRD, XRF and XPS
were also used to characterize the catalysts and to understand the re-
action mechanism.
2. Experimental
2.1. Catalyst preparation
Perovskite supports were prepared via a sol-gel method using pre-
cursors including La(NO3)3·6H2O, Al(NO3)3·9H2O and Sr(NO3)2 and
citric acid. Then, Ni(NO3)2·6H2O was loaded on the support by an in-
cipient-wetness impregnation method. To understand the effect of al-
kali and alkaline earth metals, a small amount of KNO3, Ca
(NO3)2·4H2O, or Mg(NO3)2·6H2O was also introduced on the catalyst.
2
Fuel 257 (2019) 116032
All chemicals used in the work have a purity higher than 99%
(Analytical Reagent, from Aladdin chemicals and Chron chemicals).
The preparation procedures of supports and catalysts are as follows.
Synthesis of perovskite support: La(NO3)3·6H2O, Sr(NO3)2 and Al
(NO3)3·9H2O were dissolved in distilled water at a stoichiometric ratio
of 1:0:1 (LaAlO3) or 0.7:0.3:1 (La0.7Sr0.3AlO3−x) and mixed at 80 °C for
30 min. Then a specific amount (molar ratio of citric acid to metal ions
is 1.5:1) of citric acid was added into the solution dropwise, and kept
stirring until gel was formed. After the gel was dried in an electric
drying oven at 110 °C overnight, the solid formed was grinded into
powder and calcined at 800 °C in a muffle furnace for 6 h.
Nickle and alkali/alkaline earth metal impregnation: First 2.434 mol/L
Ni(NO3)2·6H2O solution with/without a fixed amount of KNO3, Ca
(NO3)2·4H2O, Mg(NO3)2·6H2O was prepared, and it was added ade-
quately to the solid support dropwise with a Ni/support mass ratio of
1:10 and a fraction of 1 wt% alkali/alkaline earth metal. After that, the
materials were dried in an electric vacuum oven at 110 °C overnight,
and samples were finally obtained after a calcination at 500 °C for
240 min in a muffle furnace.
For simplicity, we abbreviate the two perovskites of LaAlO3 and
La0.7Sr0.3AlO3−x as LAO and LSAO, respectively. Other samples were
named as follows: the symbol and number before ‘/’ referring the
dipped elements and their mass fractions. The symbol after ‘/’ referring
the type of perovskite. For example, 1K9Ni/LSAO means 1 wt% po-
tassium and 9 wt% nickel were supported on the perovskite of
La0.7Sr0.3AlO3−x.
2.2. Fixed-bed reactor tests
Catalytic activity tests were conducted in a lab-scale fixed-bed re-
actor system, and the apparatus is as shown in Fig. 1. A quartz tube
reactor with a length of 670 mm and an inner diameter of 20 mm was
used and it was heated by a 3-stage vertical furnace (temperature of
each stage can be controlled separately). To support catalysts, a quartz
disk was set in the middle of the quartz tube. In the apparatus, feeding
gases were accurately controlled by mass flow controllers, and feeding
liquids were controlled by injection pumps. Gases and liquids were first
mixed in a preheated furnace before going into the reactor loading with
a fixed amount of catalysts. At outlet of the reactor, the off gas passed a
circulating water condenser and was then continuously monitored by
an online gas analyzer (NOVA 970P) equipped with infrared detectors
for CO, CO2, and CH4, and a thermal conductivity H2 detector. The
measuring range of the machine is 0–10 vol% for both CO and CH4, and
it is 0–15 vol% for CO2 and 0–40 vol% for H2. Additionally, they all
have an accuracy of 1% of full scales.
In each experiment, 2 g catalyst was loaded in the reactor and he-
ated to 650 °C in N2 with a flow rate of 400 ml/min. Then H2 with a
flow rate of 120 ml/min was switched on for 1 h in order to reduce Ni
components. Subsequently, H2 flow was switched off, and the reactor
was adjusted to the targeted temperature (550–700 °C) at 10 °C/min.
After the gas analyzer readings were stable, two injection pumps were
used to feed H2O at a flow rate of 5.478 ml/h and toluene at a flow rate
of 2.309 ml/h (S/C = 2), respectively. In order to achieve the optimum
response time of the gas analyzer, N2 with a flow rate of 300 ml/min
was added before outlet gases entering the condenser. Generally, the
catalytic reforming was kept for 120 min followed by a 15 min purging
in pure N2 flow. To determine the amount of carbon deposition pro-
duced, each test was ended with a complete oxidation in a mixed flow
of O2/N2 (80 ml/min O2 and 400 ml/min N2) at 650 °C for 10 min, and
the amount of carbon produced can be calculated by the numerical
integration of CO and CO2 concentration monitored in real time.
The conversion of toluene, gas selectivity, and H2 yield were defined
using the following equations:
Z. Zhang, et al. Fuel 257 (2019) 116032

Fig. 1. Schematic diagram of the fixed-bed reactor system with an online gas analyzer.

rCH4 + rCO2 + rCO a themogravimetric analyzer (NETZSH TG209F3). 20 mg sample was

Toluene conversion = × 100% (r = molar quantity )
7 × rC7 H8 placed in a ceramic crucible, which was loaded in the TGA sample
(1) room, and the test was carried out starting from 25 °C to 950 °C at
20 °C/min followed by an isothermal calcination for 5 min under ni-
rx
Gas selectivity = × 100% (x = reaction product ) trogen atmosphere.
rCH4 + rCO2 + rCO + rH2
(2)
3. Results and discussion
rH2
Hydrogen yield = × 100%
18 × rC7 H8 (3) 3.1. Characterization of various samples

2.3. Materials characterization The mass fraction of various elements in the prepared catalysts
(without reduction) determined by XRF is shown in Table 1. It is in-
Composition of the prepared catalysts was detected using a dicated that all samples have a very similar Ni distribution with a mass
Shimadzu Lab Center XRF-1800. After background corrections and in- fraction of around 9%. And when alkali/alkaline earth metal is in-
terelement corrections, elements heavier than or equal to oxygen cluded, their mass fraction varies in a narrow range of 1–1.2% as ex-
(Z = 8) were quantified. Crystal structures of catalysts were in- pected. These characteristics indicate that the proportions of various
vestigated on a Bruker D8 Advance powder diffractometer using cobalt elements accorded with the nomenclature of catalysts.
X-ray radiation. The working voltage was 35 kV and the current was X-ray powder diffraction patterns are shown in Fig. 2, including two
40 mA. The intensity data of all samples were collected at 25 °C in a 2θ perovskites of LAO and LSAO, and the catalyst of 9Ni/LSAO after re-
range from 10° to 90° with a scan rate of 6°/min. duction in H2 atmosphere at 650 °C for 45 min. All the X-ray powder
Surface morphology and the nature of carbon deposition were in- diffraction curves are identified basing on the ICDD database. The
vestigated using a Hitachi SU8230 high-resolution scanning electron diffraction angles (2θ) are 27.2°, 38.9°, 48.2°, 56.2°, 63.6°, 70.5°, 83.6°
microscope (SEM). Sample powders were dispersed on a conductive for LaAlO3 and La0.7Sr0.3AlO3−x, and 52.2°, 61.0° for Ni. It is clear that
adhesive tab, and all SEM images were acquired from secondary elec- there are no significant differences between La0.7Sr0.3AlO3−x and
trons with an accelerating voltage of 3 kV. LaAlO3, which agrees well with the results in the literature [37,45].
Temperature programmed reduction of H2 (H2-TPR) was performed Fig. 2 also proves that the crystalline phases of perovskite support do
in a PX100A chemisorption analyzer. Typically, 200 mg dry sample was
Table 1
loaded in a U-shaped quartz tube reactor and the catalyst was tested in
Composition of prepared catalysts (wt%).
a constant flow of H2 (5 ml/min) and N2 (45 ml/min) with a uniform
temperature rise from 30 °C to 900 °C at 10 °C/min. Element 9Ni/LAO 9Ni/LSAO 1K9Ni/LSAO 1Ca9Ni/LSAO 1Mg9Ni/LSAO
Valence distribution of surface elements was detected by a Thermo
Ni 9.27 9.08 9.03 8.85 8.99
scientific EscaLab 250Xi X-ray photoelectron spectroscopy (XPS), using La 45.72 34.45 33.90 33.40 33.59
Al Kα X-ray source with 1486.71 eV photons. Survey and narrow scan Sr – 11.83 12.29 12.10 12.10
spectra were recorded with a pass energy of 160 eV and 25 eV, re- Al 15.09 14.98 14.24 13.80 14.16
spectively. Before analysis, all samples were reduced at 650 °C in H2 O 29.72 29.49 28.97 30.44 29.87
K – – 1.08 – –
atmosphere for 45 min. Binding energies were calibrated by setting the
Ca – – – 1.28 –
C–C bond at 284.7 eV. Mg – – – – 1.14
Temperature programmed desorption (TPD) of O2 was evaluated by

3
Z. Zhang, et al. Fuel 257 (2019) 116032

Actural Generated Peak 1 Peak 2 Peak 3

A: LaAlO3/LaxSr1-xAlO3-y
Peak 4 Peak 5
A B: Ni
9Ni/LAO
236.4 331.2 393.2 731.3
A
A
A A
A A
LAO 9Ni/LSAO
263.5 350.3 449.7 712.1 766.52
A

A A 1K9Ni/LSAO
A A 309.4 327.1 452.2 719.4 760.6
A A
LSAO

A 1Ca9Ni/LSAO
280.8 394.6 456.8 728.8 768.7

A A A
A
B B A A 1Mg9Ni/LSAO
9Ni/LSAO 720.6 770.6
284.0 400.6 509.2

0 100 200 300 400 500 600 700 800 900

0 20 40 60 80 100 Temperature (°C)
2-theta degree
Fig. 4. H2-TPR profiles of the various prepared catalysts.
Fig. 2. XRD patterns of (a) LAO, (b) LSAO and (c) 9Ni/LSAO in the reduced
state.
Table 2
XPS elemental surface concentrations for the prepared catalysts.
not transform after loading Ni. Additionally, no patterns of strontium
Catalyst Peak Concentration
oxides and aluminum oxides are observed, indicating these phases have (wt%)
a very low content and will not affect the catalytic performance in
experiments. 9Ni/LAO O1s A 57.64
Surface morphology of the 9Ni/LSAO catalyst was obtained by SEM, O1s B 42.36
9Ni/LSAO O1s A 63.21
and the results are presented in Fig. 3. It is seen that the catalyst is
O1s B 36.79
composed of a great amount of spherical grains around 200–300 nm, 1K9Ni/LSAO O1s A 74.90
and a well-distributed microporous structure is formed, implying a O1s B 25.10
good uniformity of the catalyst prepared. 1Ca9Ni/LSAO O1s A 66.64
O1s B 33.36
Fig. 4 shows H2-TPR spectrums of the prepared Ni/Perovskite cat-
1Mg9Ni/LSAO O1s A 70.7
alysts. For the 9Ni/LAO catalyst, a small peak at 236.4 °C is assigned to O1s B 29.3
the reduction of free NiO species. The maximum H2 consumption ap-
pears at 331.2 °C and a shoulder peak exists at around 393.2 °C. The
first zone is related to bulk NiO with negligible interaction with sup- free NiO species almost forms a single peak, indicating the decrease of
port, and the second one is assigned to smaller NiO particles interacting bulk NiO. On the contrary, in catalysts with Ca and Mg, the peak rise
with support [44]. At 731.3 °C, there is a slight reduction peak, which is significantly to around 400 °C. In addition, comparing with initial 9Ni/
related to the strong interaction between NiO and the support. Com- LSAO sample, the presence of alkali and alkaline earth metal leads to a
paring with 9Ni/LAO, TPR profiles of 9Ni/LSAO changes with the po- further rise of the position of all peaks, implying a stronger interaction
sition of all peaks raising by 20–50 °C, and the peaks above 700 °C between Ni and the support. Similar effects have also been reported in
become much more evident. It is well known that the lower tempera- the literature [29,46,47].
ture peaks are related to the reduction of free NiO species, and the X-ray photoelectron spectra of O1s in all samples is summarized in
higher one is caused by the reduction of complex NiO [46]. These re- Table 2 and Fig. 5. Double peaks are observed on all samples. The peak
sults show that the substitution of La3+ by Sr2+ partly enhances the with the higher binding energy (531.5 eV) is marked as surface ab-
interaction between NiO and the perovskite support, and reduces the sorbed oxygen, and the peak at the lower binding energy (529.3 ev) is
fraction of free NiO species. assigned to lattice oxygen. Comparing with LAO support, the partial
When K, Ca, or Mg is presented, a further change of H2-TPR profiles substitution of La3+ by Sr2+ increases oxygen vacancies presented in
is observed on all catalysts. In the sample containing K, it is seen that

Fig. 3. SEM images of fresh 9Ni/LSAO catalyst in oxidation state.

4
Z. Zhang, et al. Fuel 257 (2019) 116032

Actrual O1S A O1S B Background Generated there is a very low concentration of methane detected (under 1% se-
lectivity) during the reforming using both catalysts. In addition, more
9Ni/LAO
toluene is observed to be converted to CO2 rather than CO when 9Ni/
LSAO is adopted.
After the completion of reforming experiment (totally 2 g toluene
9Ni/LSAO
was fed), the reactor was purged by a flow containing 80 ml/min O2
Count (s)

and 400 ml/min N2 at 650 °C to obtain the amount of carbon deposited

1K9Ni/LSAO
1Ca9Ni/LSAO
1Mg9Ni/LSAO
525 530 535 540
Binding Energy (eV)
Fig. 5. XPS O1s spectra for the various catalysts.
the catalyst, thereby enhancing the mobility of lattice oxygen and
promoting its transformation to surface oxygen. It is also clear that the
presence of alkali and alkaline earth metal further enhances this trend.
3.2. Catalytic performance of perovskite supported Ni
The performance of the LAO and LSAO supported Ni catalysts in
toluene steam reforming was shown in Fig. 6. Apparently, reaction
activity of both Ni-based catalysts is stable within 120 min. Comparing
with 9Ni/LAO, 9Ni/LSAO shows a little higher carbon conversion
(92.55% vs. 89.61%) and hydrogen yield (78.18% vs. 76.76%). Though
on the surface of catalyst. The results are summarized in Fig. 7(a). The
amount of carbon deposition on the 9Ni/LAO catalyst is 80 mg/g·ca-
talyst, while for 9Ni/LSAO, it is only 30 mg/g·catalyst. As evident from
the result, La0.7Sr0.3AlO3−x is more appropriate to be used as the sup-
port in Ni catalyst for toluene steam reforming, and this phenomenon
agrees well with literature [34–36]. In these papers, O16 in catalysts
support were partially replaced by O18, and the result shown that
comparing with LAO support, a great quantity of syngas containing O18
545 appeared in the LSAO sample. It is proposed that the substitution of A
or B site in perovskite-type materials with different valence cations
could affect the mobility of lattice oxygen, [48] and lattice oxygens
stored in perovskite can reduce the carbon deposited on Ni surface,
which is also verified in our experiments.
To inspect the oxygen desorption capacity of these two perovskite
supports, an additional experiment was carried out using TGA.
Temperature programmed desorption curves of LAO and LSAO samples
under pure nitrogen atmosphere are presented in Fig. 7(b). It is seen
that the mass of LAO is maintained during the whole test. In contrast,
there is a continuous mass decline of LSAO starting after 200 °C and the
most obvious mass drop appears at around 750–900 °C. These results
indicate that LSAO has a very good oxygen releasing ability (about
37.9 mg/g·catalyst) in nitrogen atmosphere, which is consistent with
the previous work [37].

120
14 (a) (b) Average conversion 89.61%
100
12
Gas composition (%)

10 80
Percentage (%)

H2
8 CO
60 Average H2 yield 76.76%
CO2
6 CH4
40
4
20
2 Carbon Conversion
H2 yield
0 0

0 20 40 60 80 100 120 0 20 40 60 80 100 120

120
14 (c) (d) Average conversion 92.55%
100
12
Gas composition (%)

10 80
Percentage (%)

H2
8 CO 60 Average H2 yield 78.18%
CO2
6 CH4
40
4
20 Carbon Conversion
2 H2 yield

0 0

0 20 40 60 80 100 120 0 20 40 60 80 100 120

Time (min) Time (min)
Fig. 6. Real-time gas composition, carbon conversion and hydrogen yield of (a, b) 9Ni/LAO and (c, d) 9Ni/LSAO in toluene steam reforming at S/C = 2.0 under
650 °C, balanced with a total N2 flow of 700 ml/min.

5
Z. Zhang, et al. Fuel 257 (2019) 116032

100 (a) Toluene conversion

(a) 100
9Ni/LAO 100 H2 yield
9Ni/LSAO
Carbon deposition (mg/g·cat)

80

Carbon deposition (ml/min)

80 80
60

Percentage (%)
40

60 60
20

40 40
0 2 4 6 8
Time (min)

20
20
0
9Ni 1K9Ni 1Ca9Ni 1Mg9Ni
0 /LSAO /LSAO /LSAO /LSAO
9Ni/LAO 9Ni/LSAO
120
115 (b) CH4 CO2 CO H2
LAO LSAO
1000 (b) 100 0% 0% 1% 1%
10%
110 15% 13% 12%

Gas selectivity (%)

800 80 19% 19% 20%
16%
Temperature (°C)

105 TG (wt%)
600 60
100
400 40
68% 68% 67% 69%
95
200 20
90
0
0 9Ni 1K9Ni 1Ca9Ni 1Mg9Ni
85 /LSAO /LSAO /LSAO /LSAO
0 20 40 60 80 100
Time (min) (c)
Carbon deposition (mg/g·catalyst)

Fig. 7. (a) Carbon deposition on 9Ni/LAO and 9Ni/LSAO, and (b) oxygen re-
leasing of LAO and LSAO under the atmosphere of N2.

3.3. Effect of the presence of alkali/alkaline earth metals

To evaluate impacts of the presence of alkali and alkaline earth

metals on catalyst activities, the common alkali and alkaline earth
metals (K, Ca, Mg) in the conventional biomass were selected and re-
sults are depicted in Fig. 8(a, b). It is demonstrated that all samples
maintain a stable catalytic activity in toluene steam reforming. There is
only a slight lower toluene conversion with the presence of Ca and Mg,
and H2 yield becomes a little lower in 1K9Ni/LSAO and 1Ca9Ni/LSAO. 9Ni 1K9Ni 1Ca9Ni 1Mg9Ni
For the selectivity of product gases, it could be observed that the pre- /LSAO /LSAO /LSAO /LSAO
sence of alkali or alkaline earth metals increases the production of CO Fig. 8. (a) Carbon conversion and hydrogen yield, (b) gas selectivity and (c)
(Mg > Ca = K > initial) while the amount of CO2 produced is ob- carbon deposition of different catalysts in toluene steam reforming at S/C = 2.0
served to decrease in the order of initial > K > Ca > Mg. According under 650 °C lasting for 120 min.
to the thermodynamic equilibrium calculation by Silva [13], the in-
crease of CO selectivity is approximate to chemical equilibrium. These there is a uniform distribution of 200–300 nm grains in diameter for the
experiments confirmed that the presence of alkali and alkaline earth fresh 9Ni/LSAO, the presence of 1 wt% K leads to an obvious growth of
metals promotes the reaction toward chemical equilibrium. these grains to around 300–500 nm with some kind of aggregation
In addition, the presence of alkali or alkaline earth metal is observed appeared. After reaction, severe sintering is observed for 9Ni/LSAO,
to have a huge impact on the amount of carbon deposition. As shown in which however is less serious in the used 1K9Ni/LSAO catalyst. Another
Fig. 8(c), with only 1 wt% alkali or alkaline earth metal presented, there observation is that the amount of carbon deposited on the catalyst is
is a great decline of the amount of carbon deposited. It is 30 mg/g·ca- very different. For the 9Ni/LSAO catalyst, there are many rod-type
talyst for the 9Ni/LSAO catalyst after 120 min. However, the amount of carbons on catalyst surface, indicating a fast accumulation of carbon
carbon deposited decreases to 15.38 mg/g·catalyst, 14.33 mg/g·catalyst, deposition in the reaction process. For the used 1K9Ni/LSAO catalyst,
and 11.76 mg/g·catalyst for 1Mg9Ni/LSAO, 1Ca9Ni/LSAO, and 1K9Ni/ much less and shorter rod-like carbons are found. Therefore, the pre-
LSAO, respectively. The maintenance in toluene conversion with a great sence of a small amount of alkali or alkaline earth metals could largely
reduced amount of carbon deposition in experiments also indicates that prohibit the production of carbon in steam reforming of biomass tar,
alkali and alkaline earth metals (especially K) could act as a promoter of which is in accordance with the previous work [49,50].
coking inhibition in toluene steam reforming. Basing on aforementioned results in experiments and material char-
Fig. 9 shows SEM images of the fresh and the used catalysts. While acterizations, mechanism is proposed to explain the promotion effect of

6
Z. Zhang, et al.
Fig. 9. SEM images of (a) fresh 9Ni/LSAO, (b) fresh 1K9Ni/LSAO, (c) used 9Ni/LSAO and (d) used 1K9Ni/LSAO.
Fig. 10. Principle of carbon deposition inhibition by lattice oxygen and alkali and alkaline earth metals.
alkali and alkaline earth metals on perovskite-supported catalysts, and it is
depicted in Fig. 10. Here, it is suggested that the presence of alkali and
alkaline earth metals enhances the interaction between Ni particles and
the support, and suppresses the sintering of Ni, which could be observed in
SEM images. More importantly, the introduction of K, Ca or Mg leads to
more oxygen absorbed on catalyst surface, which has a strong oxidizability
and could react with reaction intermediates or carbon, avoiding the de-
position of carbon on catalysts. As surface absorbed oxygen and lattice
oxygen could transform to each other, in this case, when surface absorbed
oxygen is consumed in the oxidation of coke, the –OH dissociated from
vapor could continuously supply lattice oxygen and sustain the above
promotion effect in the catalysis process.
3.4. Effect of temperature on toluene steam reforming
Reaction temperature is one of the most important factors affecting
product-gas composition, thus its effects with the presence of alkali and
7
Fuel 257 (2019) 116032
alkaline earth metals need to be well understood. Here, influences of
temperature ranging from 550 °C to 700 °C on toluene steam reforming
were studied, and results are shown in Fig. 11. It is seen in Fig. 11(a)
that as reaction temperature increasing, all samples show an increase in
toluene conversion and hydrogen yield. While there are decreases in the
selectivities of CH4, H2 and CO2 at a higher temperature, the selectivity
of CO shows an variation in inverse, which is consistent with thermo-
dynamic equilibrium estimation [13].
Results of toluene conversion and H2 yield as a function of reaction
temperature are depicted in Fig. 11(b) and (c). Apparently, there is
almost no difference in toluene conversion and H2 yield between initial
catalyst and those with the presence of alkali or alkaline earth metals
when temperature goes above 600 °C, and the toluene conversion
reaches 100% around 700 °C. However, when temperature decreases to
550 °C, catalyst 1Mg9Ni/LSAO shows the maximum toluene conversion
of 78.47%, while the value for catalyst 9Ni/LSAO is only 65.11%. This
kind of increase in toluene conversion also appears in catalysts with
Z. Zhang, et al. Fuel 257 (2019) 116032

120
(a) CH4 CO2 CO H2 (b) 9Ni/LSAO 1K9Ni/LSAO
1Mg9Ni/LSAO 1Ca9Ni/LSAO 1Mg9Ni/LSAO
700 1Ca9Ni/LSAO 100
1K9Ni/LSAO

Toluene conversion (%)

9Ni/LSAO
Temperature (K)

1Mg9Ni/LSAO
80
1Ca9Ni/LSAO
650 1K9Ni/LSAO
9Ni/LSAO 60
1Mg9Ni/LSAO
1Ca9Ni/LSAO
600 1K9Ni/LSAO
40
9Ni/LSAO

1Mg9Ni/LSAO 20
1Ca9Ni/LSAO
550 1K9Ni/LSAO
9Ni/LSAO
0
0 20 40 60 80 100 550 600 650 700
Gas selectivity (%) °C
100
(c) 9Ni/LSAO 1K9Ni/LSAO 400 (d) 9Ni/LSAO
1Ca9Ni/LSAO 1Mg9Ni/LSAO
1K9Ni/LSAO

Carbon deposition (mg/g cat)

80 1Ca9Ni/LSAO
1Mg9Ni/LSAO
300
H2 yield (%)

60

200
40

100
20

0 0
550 600 650 700 550 600 650 700
°C °C
Fig. 11. (a) Gas selectivity, (b) toluene conversion, (c) hydrogen yield, and (d) carbon deposition using different catalysts in toluene steaming reforming as a function
of temperature at S/C = 2.0, reaction time = 120 min.

other alkali and alkaline earth metals presented. Furthermore, the
maximum hydrogen yield of 69.35% appears in catalyst 1K9Ni/LSAO,
but it is only 60.19% for 9Ni/LSAO without any alkali and alkaline
earth metals presented. All these results indicate that the presence of
alkali and alkaline earth metals could only hold positive effect in to-
luene steam reforming under slight lower temperature (550 °C).
In addition, the relationship between carbon deposition and reac-
tion temperature is summarized and shown in Fig. 11(d). When there is
almost no carbon deposition detected for all catalysts at 700 °C, a
growth trend of carbon deposition becomes very obvious under lower
temperature. It is seen that at 550 °C, there is over 370 mg/g·catalyst on
9Ni/LSAO after the reforming lasting for 120 min. However, the
amount of carbon deposited decreases largely to be around 100 mg/
g·catalyst for the three catalysts with 1 wt% K, Ca, or Mg presented.
These results fully demonstrate that the presence of alkali and alkaline
earth metals has a great potential to inhibit carbon deposition espe-
cially under low temperature conditions.
3.5. Effect of the loading amount of alkali/alkaline earth metals
To further understand impacts of the concentration of alkali and
alkaline earth metals (K, Ca, or Mg) on the performance of perovskite-
supported catalysts in toluene steam reforming, samples loading with
the alkali or alkaline earth metal (ranging from 0.1 wt% to 3 wt%) were
tested, and these results are depicted in Fig. 12. It is seen that with the
increase of K loading, toluene conversion decreases from 99.58% to
89.56%, and hydrogen yield shows a slight decrease from 77.88% to
75.93%. The presence of Mg shows the similar trend in toluene
conversion, which decreases from 94.28% to 87.85%, however the
hydrogen selectivity is maintained at the original level. For catalysts
with Ca presented, the maximum toluene conversion (99.1%) and hy-
drogen selectivity (78.94%), and the minimum carbon deposition
(1.05 mg/g·catalyst) all appear when its loading amount is 0.3 wt%.
Fig. 12(d) summaries the variation of carbon deposition on catalysts
with the increase of alkali or alkaline earth metal loaded. Apparently,
catalysts’ ability in resisting carbon deposition shows the same ten-
dency with the presence of alkali and alkaline earth metals. A small
amount (< 0.3 wt%) of alkali or alkaline earth metal has a better role in
increasing catalytic reactivity and decreasing carbon deposition in to-
luene steam reforming. With the amount of alkali or alkaline earth
metals increasing in the range below 1 wt%, there is a slight decrease of
the observed positive effect, and a little more carbon deposition is
shown. According to our observation and the work in the literature
[51,52], it is possibly that alkali or alkaline earth metals would accu-
mulate on the surface of catalysts, decline the surface area of catalysts
and inhibit the contact of Ni with reactants, resulting a reduction in the
conversion. However, the aforementioned condition appears only in the
case where the content of alkali metal and alkaline earth metal is re-
latively low. With the addition of relatively large amounts of alkali or
alkaline earth metals, some carbonates will be formed, which may af-
fect the reaction equilibrium and inhibit carbon deposition.
4. Conclusions
In this work, the common alkali and alkaline earth metals (K, Ca,
Mg) in actual biomass were loaded on the catalyst of Ni/

8
Z. Zhang, et al. Fuel 257 (2019) 116032

100 (a) 100 (b)

80 80
Percentage (%)

Percentage (%)
60 Toluene conversion 60 Toluene conversion
H2 yield H2 yield
H2 selectivity H2 selectivity
40 CO selectivity 40 CO selectivity
CO2 selectivity CO2 selectivity
CH4 selectivity CH4 selectivity
20 20

0 0
0.1 0.3 1 3 0.1 0.3 1 3
K Loading (wt%) Ca Loading (wt%)
100
(c) 16 (d) K

Carbon deposition (mg/g·catalyst)

Ca
Mg
80
12
Percentage (%)

60 Toluene conversion
H2 yield
H2 selectivity 8
40 CO selectivity
CO2 selectivity
CH4 selectivity
4
20

0 0
0.1 0.3 1 3 0.1 0.3 1 3
Mg Loading (wt%) Alkali metal loading (wt%)

Fig. 12. Gas selectivity, toluene conversion, and hydrogen yield using catalysts loaded with various concentrations of (a) K, (b) Ca, (c) Mg and their (d) carbon
deposition at S/C = 2.0, reaction time = 120 min.

La0.7Sr0.3AlO3−x and their potential effects on the catalytic activity in References

toluene steam reforming were investigated systematically. Results show
that the presence of K, Ca, Mg in Ni/perovskite catalysts leads to a
better catalytic performance, especially on the anti-sintering char-
acteristic and the resistance to carbon deposition. With the help of
characterization techniques of TPR, XPS etc., the promotion effect is
attributed to the strong interaction between nickel and alkali/alkaline
earth metals, which not only improves the reducibility of Ni particles,
and suppresses the sintering of Ni, but also increases the oxygen ad-
sorbed on catalysts surface, thus inhibiting the production of coking.
Additionally, the effects of reaction temperature and loading amount of
alkali/alkaline earth metals were investigated. Although all samples
show a higher carbon deposition at low temperature, comparing with
the initial 9Ni/LSAO catalyst, the presence of alkali/alkaline earth
metal improves the ability of carbon deposition resistance more evi-
dently. Additionally, low-concentration (0.3 wt%) alkali and alkaline
earth metals is found to possess the best carbon deposition resistance,
and their further increase would lead to a decrease of catalytic activity.
Acknowledgements
The authors are grateful for financial support from the National
Natural Science Foundation of China, China (No. 51606018),
Chongqing Basic Science and Advanced Technology Research Program
(No. cstc2017jcyjAX0324), the Venture & Innovation Support Program
for Chongqing Overseas Returnees (No. cx2017021), Fundamental
Research Funds for the Central Universities (No. 2018CDJDDL0005)
and Key industrial generic technology innovation project of Chongqing
(No. cstc2016zdcy-ztzx20006).
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