Research Article

Cite This: ACS Sustainable Chem. Eng. 2017, 5, 10248-10257 pubs.acs.org/journal/ascecg

Dry Reforming of Model Biogas on a Ni/SiO2 Catalyst: Overall

Performance and Mechanisms of Sulfur Poisoning and Regeneration
Xuejing Chen,†,‡ Jianguo Jiang,*,†,§,∥ Feng Yan,† Kaimin Li,† Sicong Tian,† Yuchen Gao,†
and Hui Zhou‡
†
School of Environment, Tsinghua University, Beijing 100084, China
‡
Department of Earth and Environmental Engineering, Columbia University, New York, New York 10027, United States
§
Key Laboratory for Solid Waste Management and Environment Safety, Ministry of Education of China, Beijing 100084, China
∥
Collaborative Innovation Center for Regional Environmental Quality, Beijing 100084, China
*
S Supporting Information

ABSTRACT: Carbon-neutral application of renewable biogas

to valuable chemical raw materials has received much attention
in sustainable areas, while sulfur poisoning remains a big
problem in biogas dry reforming process. In this work, sulfur
deactivation and regeneration performance of a Ni/SiO2
catalyst in model biogas dry reforming and related mechanisms
were studied. The effects of H2S content (50 and 100 ppm)
and reaction temperature (700−800 °C) on biogas dry
reforming were investigated. Three regeneration methods
(H2S feeding cessation, temperature-programmed calcination
(TPC), and O2 activation) were applied. The results showed that the presence of H2S caused server deactivation in catalytic
activity, and higher H2S content led to faster deactivation. The deactivation was not reversed simply by stopping H2S feeding and
TPC, but O2 activation could totally recover deactivated catalysts. The formation of Ni7S6, detected for the first time in biogas
conditioning catalytic processes, confirmed by X-ray diffraction and X-ray photoelectron spectroscopy, led to sulfur poisoning, as
well as catalyst sintering and carbon deposition. This work revealed that sulfur poisoning and regeneration mechanism is the
formation and elimination of Ni7S6, and concluded that oxygen activation was the most effective method for reviving the catalytic
activity, preventing sintering, and reducing carbon deposition. These findings will contribute to the industrial application of
syngas production from biogas dry reforming.
KEYWORDS: Biogas, Dry reforming, Sulfur poisoning, Regeneration, Nickel sulfide (Ni−S)

■ INTRODUCTION
Biogas, an important renewable source of green energy, is
consumption of H2 and production of CO, thus decreasing the
H2/CO ratio.10,11
produced from the anaerobic digestion of biomass, including CH4 + CO2 → 2CO + 2H 2 ; ΔH298K = 247 kJ mol−1
landfill, food waste, and municipal sludge. With increasing (1)
concerns over climate change caused by anthropogenic CO2
emissions, the carbon-neutral application of biogas to valuable CH4 → CS + 2H 2 ; ΔH298K = 75 kJ mol−1 (2)
chemical raw materials has received much attention. Biogas dry
reforming can convert the two main greenhouse gases (GHGs) 2CO → CS + CO2 ; ΔH298K = − 172 kJ mol−1 (3)
to syngas (H2 and CO), which are valuable energy-related
chemicals (eq 1). This process has both environmental and CO2 + H 2 → CO + H 2O; ΔH298K = 41 kJ mol−1
commercial benefits.1−4 A typical biogas from municipal solid (4)
waste contains 50−75% CH4, 25−50% CO2, 0−10% N2, and The sulfur poisoning effect of nickel-based catalysts was first
0−3% H2S.5 The H2S impurities in biogas may poison catalysts, studied in the catalytic process of biomass/coal gasification12,13
especially when nonprecious metals (mainly Ni) are used, and steam reforming.5,14−16 Recently, sulfur poisoning in the
which is a major concern in biogas dry reforming.6,7 Catalyst dry reforming process has also been investigated1,6 because
deactivation can also be caused by carbon deposition, which is sulfur impurities are inevitably produced during the process of
mainly caused by CH4 decomposition (eq 2) and CO
disproportionation (eq 3).3,8,9 In addition, an important side Received: July 6, 2017
reaction, the reverse water gas shift (RWGS, eq 4), usually Revised: August 4, 2017
occurs simultaneously with dry reforming, leading to additional Published: September 25, 2017

© 2017 American Chemical Society 10248 DOI: 10.1021/acssuschemeng.7b02251

ACS Sustainable Chem. Eng. 2017, 5, 10248−10257
ACS Sustainable Chemistry & Engineering
biogas production, and the presence of even low sulfur levels
after desulfurization may lead to the deactivation of nickel
catalysts.17,18 It has been accepted for decades that catalysts can
be deactivated by sulfur via the chemisorption of sulfur with
active metal to form metal sulfides (eq 5), which occupy the
surface active sites, deactivating the catalyst.17,19−21 However,
the detailed sulfur poisoning performance and mechanism in a
biogas dry reforming process with regard to the formation and
elimination of Ni−S species still remains unclear.
H 2S + Ni ⇄ Ni−S + H 2 (5)
14
According to Ashraf et al., a high H2S/H2 ratio is
responsible for the formation of bulk sulfide, and only surface
nickel sulfide (Ni−S) is formed at a low H2S/H2 ratio. The
Ni−S species that are formed have been mostly represented as
Ni3S2 in the literature;20,22 however, the formation of Ni−S
species is influenced by reaction temperature, gas-phase
composition, and reactor parameters. Furthermore, the Ni−S
species formed may undergo phase transportation and may be
oxidized during handling, which makes the identification of
Ni−S species more difficult.20 It is therefore important to
determine the formation and elimination of Ni−S species
during the deactivation and regeneration of a Ni/SiO2 catalyst
in biogas dry reforming.
Because the chemisorption process is theoretically reversible
and exothermal, surface Ni−S can be reduced by stopping H2S
feeding or by temperature enhancement. Appari et al.5 applied
H2S removal, temperature enhancement, and a vapor treatment
method to regenerate deactivated Ni/γ-Al2O3 in a methane
steam reforming process. Ashraf et al.14 studied three
regeneration methods, and found that a temperature increase
was more effective than removing sulfur from the feed gas or an
oxidative treatment in Ni/Al2O3 in a biogas steam. Choudhary
et al.23 conducted sulfur regeneration of a NiCoMgCeOx
catalyst in an oxy−methane reforming process by air treatment,
and reported that it was very effective. To the certainty of our
knowledge, a comparison study on the reversibility of sulfur
poisoning in a Ni/SiO2 catalyst in a biogas dry reforming
process has not been undertaken. The effect of sulfur poisoning
on a nickel catalyst in a typical biogas dry reforming process
and the poisoning mechanism remain unknown; an effective
regeneration method needs to be developed.
The aim of this study was to evaluate the deactivation and
regeneration performance of a Ni/SiO2 catalyst under various
operating conditions and different regeneration methods during
a biogas dry reforming process. Catalytic activity and selectivity
under different temperatures and H2S concentrations were
tested, and three regeneration methods (stopping H2S feeding,
temperature-programmed calcination (TPC), and O2 activa-
tion) were applied to compare the effects on reversibility.
Furthermore, physical adsorption, X-ray diffraction (XRD), X-
ray photoelectron spectroscopy (XPS), and thermal gravimetric
analysis (TGA) were conducted to characterize the sulfur
poisoning and carbon deposition of freshly reduced, original
deactivated, and regenerated catalysts by different regeneration
methods to further determine the sulfur deactivation
mechanism.
■
EXPERIMENTAL METHODS
Preparation of Support and Catalyst. A SiO2 support was
prepared by vapor-phase hydrolysis of SiCl4 at 150 °C, as previously
described by the authors.24 A degas procedure in a vacuum oven at 70
°C for 4 h and a calcination process in a muffle furnace at 800 °C for 4
10249
Research Article
h were applied for support pretreatment. A SiO2 supported catalyst
with a Ni loading of 10 wt %, was synthesized by wet impregnation. A
5 g amount of calcined SiO2 was dispersed into 50 mL of ethanol
under ultrasonic oscillation, and Ni(NO3)2·6H2O (99%, Sigma-
Aldrich, St Louis, MO, USA) was dissolved into 50 mL of ethanol
to obtain the active metal precursor. Then, the two solutions were
mixed together using a magnetic stirrer at 70 °C at a rotation rate of
650 rpm for ∼12 h to evaporate the ethanol. The supported catalyst
powders were further dried at 60 °C in a vacuum oven for 2 h,
followed by a TPC procedure to 800 °C in an air flow of 30 mL min−1.
Finally, catalyst powders were tableted and screened to obtain particles
of 0.42−0.84 mm for catalytic testing.
Dry Reforming Experiments. The biogas dry reforming
experiments were conducted in a fixed-bed quartz reactor (inner
diameter, 6 mm; outer diameter, 8 mm; length, 520 mm) heated by an
electric furnace. Catalyst particles (0.42−0.84 mm, 100 mg) were
loaded into the center of the reactor beside a K-type thermocouple to
detect temperatures. Four flows of gas feeding, including reducing gas
(10 vol % H2 in N2 balance), model biogas mixture (CH4/CO2/N2 =
0.4:0.4:0.2), model H2S mixture (200 ppmv H2S in N2 balance), and
standard air, were controlled by four separate mass flow controllers
(MFC). The outlet gas mixture underwent a cooling water circulation
process before being analyzed by an online micro-GC apparatus
(Micro 490, Agilent), which is equipped with two independent
channels installed with a molecular sieve 5A PLOT column and a
PoraPLOT U column, respectively, coupling with two thermal
conductivity detectors (TCD). N2 was used as the internal standard
gas for calibration. Figure S1 (Supporting Information) shows the
experimental setup of the fixed-bed reactor for the biogas reforming
process.
Before each test, the catalyst samples were reduced in situ using a 10
vol % H2 in N2 balance of 30 mL min−1 by heating from room
temperature (RT) to 800 °C at a rate of 10 °C min−1, followed by a
steady state at 800 °C for 60 min. After the reduction, the temperature
was lowered to the initial activity test temperature. For H2S tolerance
tests, three temperatures (700, 750, and 800 °C) and two H2S
concentrations (50 and 100 ppmv) were used. First, model biogas
without H2S was introduced for about 30 min to obtain the original
activity. Different H2S contents were then introduced, and the
deactivation of catalysts was observed. The H2S feeding was stopped
when the conversion of CH4 and CO2 dropped to ∼5%. The biogas
dry reforming process was then continued to determine whether the
activity could be regenerated by stopping in situ H2S feeding. Table S1
(Supporting Information) shows the gas components of biogas with
different H2S concentrations. During biogas dry reforming process, the
flow rates of CH4 and CO2 were always kept at 40 mL min−1, which
made the gas hourly space velocity (GHSV) stable at 24,000 mL g−1
h−1.
In addition to stopping the in situ H2S feeding, two other methods
were also applied to study the regeneration of deactivated catalysts.
One was the TPC method, during which the deactivated catalysts were
calcined from RT to 800 °C with a temperature ramp of 10 °C min−1,
followed by an isothermal step at 800 °C for 30 min. The overall TPC
process was conducted under a N2 stream of 30 mL min−1. The
activity was then tested under related temperatures. Oxygen activation
was also applied, in which the deactivated catalysts were calcined in
standard air (50 mL min−1) from RT to 800 °C by a temperature ramp
of 10 °C min−1 and kept in an isothermal state for 30 min; then, the
catalysts were reduced using a reducing gas (50 mL min−1) at 800 °C
for 1 h. After regeneration, the catalytic activity tests were kept on
stream for 70 min. The conversion (X) of CH4 and CO2 and the H2/
CO ratio were calculated by eqs 6−8:
[CH4]in − [CH4]out
XCH4 /% = × 100
[CH4]in (6)
[CO2 ]in − [CO2 ]out
XCO2 /% = × 100
[CO2 ]in (7)
DOI: 10.1021/acssuschemeng.7b02251
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ACS Sustainable Chemistry & Engineering Research Article

H2 [H 2]out
ratio =
CO [CO]out (8)

where [CH4], [CO2], [H2], and [CO] refer to the molar flow rates of
the gas species, mol min−1.
Catalyst Characterization. Catalysts that were freshly reduced,
originally deactivated, and regenerated by the different regeneration
methods were characterized by physical adsorption, XRD, TGA, and
XPS methods. Physical adsorption was carried out by a surface area
and porosity analyzer (ASAP2020 HD88, Micromeritics, GA, USA) to
obtain the specific surface area (SSA), pore volume, and pore size of
different samples. The SSA was calculated by the Brunauer−Emmett−
Teller (BET) model, and the average pore diameter was calculated by
the Barrett−Joyner−Halenda (BJH) model. XRD patterns were
obtained through high-resolution XRD (D8 Advance, Siemens,
Munich, Germany) using Cu Kα radiation (λ = 0.154 nm) with a
scanning rate of 2 deg min−1 and 2θ range of 10−90°. A
thermogravimetric analyzer (TGA/DSC 2, Mettler Toledo, Columbus,
OH, USA) was applied to detect carbon deposition. Samples (∼15
mg) were placed in an alumina crucible of 150 μL and then treated
from RT to 900 °C at a temperature ramp of 10 °C min−1 under an air
stream of 60 mL min−1 with a protective argon gas stream of 20 mL
min−1. XPS measurements were conducted using an ESCALAB 250XI
instrument (Thermo Fisher Scientific, Waltham, MA, USA) with
monochromatized Al Kα X-rays (1486.6 eV). The binding energies
were corrected using the C 1s peak observed at 284.8 eV.

■ RESULTS AND DISCUSSION

Catalytic Activity under Different H2S Concentrations.
Catalytic activity was observed under the different H2S
concentrations. Figure 1 shows the effect of H2S concentration
on biogas dry reforming at 700 °C. The conversion profiles can
be divided into three regimes: before H2S introduction, with
H2S exposure, and after stopping H2S feeding. In the first 30
min, biogas reformed in the absence of H2S, and it was clear
that both CH4 and CO2 conversion decreased slightly at 700
°C, even when no H 2 S impurities were present; CH 4
conversion dropped from 53.4% to 50.5%, and CO2 conversion
dropped from 63.8% to 61.5%. When H2S was introduced at a
concentration of 100 ppm, the conversion of CH4 and CO2
decreased rapidly, dropping to ∼2.5% after 140 min. The use of
a lower H2S concentration of 50 ppm also caused an obvious
decrease in CH4 and CO 2 conversion; however, the
deactivation rate was slower than at the higher H2S
concentration. By 200 min after the H2S was introduced,
CH4 conversion dropped to 7.9% and CO2 conversion fell to
8.5%. The deactivation rates of conversions were calculated by
the conversion drop over time on H2S stream, and results were
listed in Table S2. The deactivation rate of CH4 conversion was
22.9% with 50 ppm H2S and increased to 36% when H2S
content was 100 ppm, indicating that a higher H2 S
concentration will lead to a faster sulfur deactivation. This
situation also went well with CO2 conversion.
Conversion profiles were also recorded after H2S feeding was
stopped. At the very moment that H2S feeding was stopped,
both CH4 and CO2 conversion were revived slightly, but they
then resumed the decline. During the tests with the two
different H2S concentrations, CH4 conversion was always lower
than CO2 conversion at 700 °C, which can be explained by the
RWGS side reaction, which consumed more CO2 and H2 to
produce CO and water vapor, resulting in a H2/CO ratio lower
than 1.25 Figure 1b shows the related variation in the H2/CO
ratio. Before the introduction of H2S, the H2/CO ratio was
∼0.8, but the value dropped with the introduction of H2S,
displaying a trend similar to that of the CH4 and CO2
10250
Figure 1. Influence of the H2S concentration on biogas dry reforming
at 700 °C: (a) CH4 and CO2 conversion and (b) H2/CO ratio. Gas
hourly space velocity (GHSV) = 24,000 mL g−1 h−1; P = 1 atm.
conversion profiles and indicating that H2S in the biogas
inhibited the production of H2 more than that of CO. A similar
conclusion has also been reported for H2 selectivity, which was
observed to decrease to a greater degree than that of CO during
a deactivation process.26
When the biogas dry reforming temperature was increased to
750 °C, the influence of the H2S content on CH4 and CO2
conversion and the H2/CO ratio are shown in Figure 2. The
conversion and selectivity profiles were divided into the three
same regimes. There was a notable difference, with the
conversion of CH4 and CO2 remaining stable before the
introduction of H2S, and the difference between CH4 and CO2
conversion being small at 83% for CH4 conversion and 85% for
CO2 conversion. The related H2/CO ratio was ∼0.92, which
was much closer to 1 than the value at 700 °C. A higher
temperature can achieve a higher conversion of reactants and
help retain the catalytic stability.27 After exposure to a H2S
impurity of 100 pm, CH4 conversion dropped to 5.5%, and
CO2 conversion fell to 7.9% in 180 min, whereas at a H2S
concentration of 50 ppm, CH4 conversion fell to 6.5% and CO2
conversion fell to 7.5% in 200 min. When H2S feeding was
stopped, the conversions continued to drop slowly. This was
the same trend as that for the H2/CO ratio.
Figure 3 shows the influence of the H2S concentration on
biogas dry reforming at 800 °C. It is clear that both CH4 and
CO2 conversion increased as the temperature increased, with
DOI: 10.1021/acssuschemeng.7b02251
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ACS Sustainable Chemistry & Engineering
Figure 2. Influence of the H2S concentration on biogas dry reforming
at 750 °C: (a) CH4 and CO2 conversion and (b) H2/CO ratio. GHSV
= 24,000 mL g−1 h−1; P = 1 atm.
the conversion reaching ∼88% at 800 °C, and the H2/CO ratio
was 0.94 before H2S exposure. When the H2S concentration
was 100 ppm, CH4 conversion and CO2 conversion fell to 5.1%
and 7.9% in 130 min, respectively. It took 150 min for the
conversions to drop to a similar level when the H2S
concentration was 50 ppm. After stopping H2S feeding, both
the CH4 and CO2 conversions were slowly revived. After 200
min, the conversions were still below 20%. The H2/CO ratio
followed the same trend as that of the CH4 and CO2
conversions.
From the results of the tests with H2S, it was apparent that,
before H2S feeding, the catalytic activity of dry reforming was
stable at high temperatures (750 and 800 °C); at 700 °C, there
was a slight deactivation even in the absence of H2S feeding.
After the introduction of H2S, catalysts displayed obvious
deactivation at all of the temperatures investigated, and higher
H2S concentration led to faster deactivation, which was
considered reasonable because a higher H2S/H2 ratio has
been shown to benefit the chemisorption of H2S on active
metal and the formation of Ni−S species.20 This shows that the
deactivation of H2S poisoning is not reversible simply by
stopping the H2S feeding. The activity continued to drop at 700
and 750 °C; a high temperature of 800 °C led to a slight
recovery in catalytic activity, but the original activity could not
be attained. Although in theory, it is possible to regenerate the
deactivated catalyst by stopping H2S feeding (i.e., by reversing
the chemisorption of H2S on Ni), the relatively low driving
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Research Article
Figure 3. Influence of H2S concentration on biogas dry reforming at
800 °C: (a) CH4 and CO2 conversion and (b) H2/CO ratio. GHSV =
24,000 mL g−1 h−1; P = 1 atm.
force and diffusion limit in real experiments leads to a low
degree of regeneration of deactivated catalysts.14 Both reaction
temperature and H2S concentration can influence the degree of
catalyst recovery, and full regeneration could not be achieved in
these tests, which agrees with previous findings.5,14
Regeneration of Catalysts. Because a higher temperature
is favorable for catalyst recovery, a TPC method to 800 °C was
also applied to compare the reversibility of the regeneration
method. Figure 4 shows the conversion and selectivity results of
deactivated catalysts regenerated by the TPC method. After
calcination, the deactivated catalysts showed some recovery of
activity, and then the conversions declined during the initial 30
min and remained stable at a lower level. The H2/CO ratio had
a trend similar to that of the conversions. Table 1 shows the
detailed changes in conversions. Compared to the original
activity without the introduction of H2S at 800 °C, the CH4
conversion initially recovered to 66%, and then it slowly
dropped to 44%, followed by a period of stability. The CO2
conversion initially recovered to 75%, and then it slowly
dropped to 60%, followed by a period of stability. This
phenomenon was similar to the situation at 700 and 750 °C,
where the conversion of both CH4 and CO2 was revived
slightly at first and then fell to a lower level, where it remained
stable. It seems that, after regeneration by the TPC method, the
activity could be partly revived, but there was still an obvious
deactivation process, indicating that the absorbed sulfur was not
fully removed by calcination.
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ACS Sustainable Chemistry & Engineering Research Article

Figure 4. Conversions and selectivity of deactivated catalysts Figure 5. Conversions and selectivity of deactivated catalysts
regenerated by temperature-programmed calcination (TPC): (a) regenerated by O2 activation: (a) CH4 and CO2 conversion and (b)
CH4 and CO2 conversion and (b) H2/CO ratio. H2/CO ratio.

Figure 5 shows the conversions and H2/CO ratios of
deactivated catalysts regenerated by the O2 activation method.
Both the CH4 and CO2 conversions and the H2/CO ratio were
stable after O2 activation at all the temperatures tested. At a
high temperature of 800 °C, the activities revived to the original
level, i.e., ∼88% conversion of CH4 and CO2 and a H2/CO
ratio of 0.94. When the temperature was 750 °C, the
conversion of CH4 and CO2 was 68% and 76%, respectively,
which is a little lower than the original conversion at the same
temperature. For the results at 700 °C, the conversion of CH4
and CO2 was 49% and 59%, respectively, also slightly lower
than the fresh catalysts. The exact conversion data obtained
from the O2 activation method, as well as the conversions of
fresh and regenerated catalysts achieved by stopping H2S
feeding, are listed in Table 1 for comparison. After O2
activation, the deactivated catalyst displayed stable activity,
which was recovered to exactly the level of fresh catalysts at a
high temperature of 800 °C. Previously, Blanchard et al.28
concluded similarly that catalyst activity can be completely
recovered by calcining in air at 900 °C.
Analysis of the Mechanism of H2S Poisoning and
Regeneration. The characterizations of catalyst support,
freshly reduced catalyst, original deactivated catalyst, and
regenerated catalysts by different methods were conducted to
analyze the mechanism of H2S poisoning and regeneration.
Table 2 shows the SSAs, pore volumes, and average pore sizes
of different samples. After wet-impregnation and reduction
process, the SSA and pore volume was reduced by 42.0% and
34.3%, respectively, and the average pore size decreased slightly
by 2.5%; this was caused by pore blocking during the wet-

Table 1. Summary of the Conversion of Fresh Catalysts and Regenerated Catalysts under Different Temperatures

original stopping H2S feeding TPC O2 activation

temp (°C) XCH4 XCO2 XCH4 XCO2 XCH4 XCO2 XCH4 XCO2
700 52 63 drop to ∼0 drop to ∼0 37→9 51→20 49 59
750 82 84 drop to ∼0 drop to ∼0 47→17 65→29 68 76
800 88 88 rise to 9 rise to 16 66→44 75→60 88 88

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Table 2. Textural Properties of Different Catalysts patterns of freshly reduced, originally deactivated, and
regenerated catalysts by stopping H2S feeding, TPC, and O2
BJH av av cryst
SSA PV pore size sizea activation. All of the catalysts had diffraction peaks of Ni° (PDF
no. sample (m2 g−1) (cm3 g−1) (nm) (nm) 04-0850), while the peak intensity of the original deactivation
1 support 337.0 1.28 15.20 for Ni° was weak. The broad peak at ∼22° in all samples was
2 reduced 195.7 0.84 14.82 5.64 attributed to the diffraction of the amorphous SiO2 support.24 It
3 original deactivation 180.9 0.89 12.00 9.54 is also important to note that only the original deactivated
4 stop H2S feeding 98.5 0.72 29.25 7.54 catalyst had a new crystal phase of Ni7S6 (PDF 14-0364),35
5 TPC 117.3 0.78 18.09 6.53 which was caused by the reaction of H2S in biogas with the
6 O2 activation 147.5 0.82 13.21 6.09 active nickel of the catalysts to form Ni−S. The existence of
a
Average crystal size was obtained through Scherrer’s equation from Ni7S6 species in the original deactivated catalyst is further proof
the diffraction of the Ni(200) plane. that the sulfur poisoning mechanism (i.e., the formation of Ni−
S blocks the active sites) leads to severe deactivation of
impregnation process29−31 and the thermal contraction and/or catalysts. The Ni7S6 species has been detected in the sulfur
condensation by dehydration and dehydroxylation of catalyst poisoning process for the first time.
support during the high-temperature reduction process.32,33 The crystal sizes of nickel were calculated using Scherrer’s
After catalyst was deactivated under H2S tolerance for about equation, and the results are listed in Table 2. The freshly
150 min, the SSA of original deactivated catalyst was 180.9 m2 reduced catalyst had an average Ni° crystal size of 5.64 nm,
g−1, there was no obvious change in pore volume and average whereas the size of the crystal deactivated by H2S poisoning
pore size compared with freshly reduced catalyst. After was 9.54 nm, indicating obvious sintering. Although the peak
regeneration through different methods, all the regenerated intensity of Ni7S6 is small, we can use it to calculate the crystal
catalysts have a decrease in SSA and pore volume and an size of the Ni7S6 phase through the Scherrer equation. The
increase in average pore size. However, the loss in SSA and diameter result was calculated to be ∼42 nm, which is much
pore volume for catalyst regenerated by stopping H2S feeding bigger than the 9.5 nm of Ni. The formation of Ni7S6 in large
was most obvious. While catalysts regenerated by TPC and O2 particle size may change the surface energy of the nickel particle
activation have less decrease in SSA and pore volume. The and lead to catalyst sintering.
degree of SSA and pore volume loss by different regenerated After various regeneration methods, the average nickel crystal
catalysts decreased by stop H2S feeding > TPC > O2 activation. size changed to differing degrees. The diameter of the Ni°
Considering that catalyst poisoned by H2S was related to the crystal size decreased in the order of original deactivation >
chemical sorption with active metal species, and changes in SSA stopping H2S feeding > TPC > O2 activation > freshly reduced
and pore volume were caused by the change of the textural catalyst, indicating that sulfur poisoning may also enhance
structure of the catalyst support,5,34 so the reaction time of catalyst sintering and that O2 activation is the most effective
regenerated catalysts played an important role in affecting the regeneration method for retarding catalyst sintering. This is in
SSA and pore volume of the catalysts. The reaction time of accordance with the conclusion of Yuan et al., who reported
catalyst regenerated by stopping H2S feeding, which was 200
that the adsorption of sulfur might block the active sites and
min, was responsible for the most obvious loss in SSA and pore
accelerate sintering as well.36
volume. When the reaction time of catalyst regenerated by TPC
XPS analysis was used to determine the surface composition
and O2 activation was the same, the SSA of catalyst regenerated
and chemical state of the nickel and sulfur species of the
by O2 activation was higher, indicating that O2 activation was
deactivated and regenerated catalysts. Figure 7 shows the Ni 2p
more effective.
XRD analysis was used to characterize the change in the 3/2 and S 2p XPS spectra of the original deactivated catalyst
crystal phase in different catalysts. Figure 6 shows the XRD and regenerated catalysts using different regeneration methods.
The strong peaks at 852.6 eV of Ni 2p in three regenerated
catalysts indicate the existence of Ni°,37 whereas the peaks at
856.1 eV and ∼861.5 eV refer to the main and satellite peaks of
Ni2O3,36 indicating that slight oxidation occurred during the
biogas dry reforming process. The Ni° peak of the original
deactivated catalyst shifted to a higher value (853.4 eV) than
the regenerated catalyst, probably due to a different chemical
environment of Ni° caused by the existence of Ni7S6. When the
original deactivated catalyst was regenerated by different
methods, the peak area of Ni° at 852.6 eV increased in the
order of the original deactivation < stopping H2S feeding <
TPC < O2 activation, and the peak of Ni2O3 at 856.1 eV
decreased in the same order, which implied that sulfur
poisoning had an oxidative effect on the nickel catalyst36 and
the oxidative composition of nickel decreased to a different
extent after regeneration by different methods. The S 2p
spectrum in Figure 7b exhibited an obvious noise signal, as the
formation of bulk Ni−S was unstable;17 however, a broad peak
at 160.5−163.0 eV was still noticeable in the original
Figure 6. X-ray diffraction (XRD) patterns of fresh, deactivated, and deactivated catalysts, which could be attributed to a S2− species
regenerated catalysts using different regeneration methods. according to Struis et al.38 The results also confirmed the
10253 DOI: 10.1021/acssuschemeng.7b02251
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ACS Sustainable Chemistry & Engineering Research Article

Figure 7. XPS spectra of original deactivated catalysts and regenerated catalysts using different regeneration methods: (a) Ni 2p and (b) S 2p.

formation of Ni−S in the original deactivated catalyst, which
agreed with the XRD results.
The Ni−S species were only detected in the original
deactivated catalysts, implying that the regeneration methods
also helped to eliminate Ni−S, at least to a level making it
undetectable by XRD and XPS.
Figure 8 shows the TGA profiles of the original deactivated
and regenerated catalysts using different regeneration methods.
Figure 8. Thermal gravimetric analysis (TGA) profiles of the original
deactivated catalysts and regenerated catalysts using different
regeneration methods (60 mL min−1 air stream).
At temperatures below 200 °C, all four samples experienced a
slight weight loss of ∼0.5%, which was attributed to the loss of
adsorbed gas and surface water. From 200 to 400 °C, the three
regenerated catalysts exhibited an obvious weight increase of
∼2%, which was due to the oxidation of Ni° to NiO.39,40 When
the temperature increased above 400 °C, the three regenerated
catalysts started to lose weight in the air stream, which was
ascribed to the oxidation of deposited carbon.41 The carbon
deposition rate is calculated by the amount of carbon deposited
over time on stream, and the results were listed in Table 3. The
regenerated catalysts experienced a slight carbon deposition
amount of ∼1%. The original deactivated catalyst had a TGA
profile that was distinguishable from the three regenerated ones
above 200 °C. The weight increase process occurred from 200
to ∼530 °C, with the increase being 2.73%, which was much
larger than that of the regenerated catalysts. Because the same
catalyst was applied here, the difference in weight increase was
attributed to the oxidation of Ni−S, which was shown to exist
by XRD and XPS analyses. During O2 activation by an air
stream, Ni−S can be oxidized to nickel sulfate and decomposed
to nickel oxide under an air stream42,43 (eqs 9 and 10). A
reduction process was then applied to reduce NiO to metal Ni,
thus reviving the catalytic activity.43,44 Ashrafi et al. reported
that H2S poisoning was not reversible by air treatment,14
probably because of the absence of a reduction process after air
treatment.
Ni−S + O2 → NiSO4 (9)
NiSO4 → NiO + SO2 (10)
Assuming that the four samples would have the same weight
increase due to nickel oxidation, the actual amount of carbon
deposited on the original deactivation catalyst would be the
weight loss at 530 °C minus the difference during the weight

Table 3. Calculation of Carbon Deposition Amount of Catalyst Regenerated by Different Methods

catalyst freshly reduced original deactivation stopping H2S feeding TPC O2 activation
av cryst size (nm) 5.64 9.54 7.54 6.53 6.09
wt increase (%) 2.73 2.10 1.95 2.08
wt loss (%) 3.97 1.10 0.94 0.86
carbon deposition amount (%) 3.28 1.10 0.94 0.86
carbon deposition rate (mmol h−1) 0.86 0.29 0.25 0.22

10254 DOI: 10.1021/acssuschemeng.7b02251

ACS Sustainable Chem. Eng. 2017, 5, 10248−10257
ACS Sustainable Chemistry & Engineering
increase process of nickel and nickel sulfide oxidation. The
carbon deposition rate on the original deactivated catalyst was
calculated to be 0.86 mmol h−1, which was much more than
that on the regenerated catalyst. The amount of carbon formed
followed the order of the original deactivation > stopping H2S
feeding > TPC > O2 activation, implying that sulfur poisoning
blocked the active metal and inhibited carbon gasification.45,46
However, if sulfur concentration was precisely controlled, the
existence of trace sulfur can inhibit carbon formation due to the
ensemble of Ni atoms where carbon growth is not active,
although the reaction rate would decrease.47
Since the catalytic activity was related to the number of active
nickel sites, with the increase of time on stream (TOS), the
number of active nickel sites will decrease, and the coverage of
nickel sulfide (Ni−S/Nitotal) was lower than 1. For the original
deactivated catalyst, the CH4 and CO2 conversions almost
dropped to 0, which means the total loss of active nickel sites.
However, the XRD and XPS results proved that metal Ni°
dominates in the original deactivated catalyst. One probable
explanation is that the residual active Ni was blocked by
deposited carbon. Usually, carbon deposition is prohibited at
high conversions since the main dry reforming reaction
dominated this process, while when conversions are low, side
reactions to form coke are more favorable. Thus, conversion
loss was be caused by a combined and sequential poisoning
effect of sulfur and carbon deposition.2,48 All three of the
regeneration methods could effectively remove Ni−S and
reduce carbon formation; however, the O2 activation method
was the most effective for reviving catalytic activity, preventing
sintering, and reducing carbon deposition.
■
CONCLUSIONS
To better understand the deactivation and regeneration
performance and mechanism of sulfur poisoning in a biogas
dry reforming process, an evaluation of the deactivation and
regeneration of a Ni/SiO2 catalyst under various operating
conditions was conducted. Three regeneration methods,
stopping H2S feeding, TPC, and O2 activation, were applied
to compare their reversibility. The testing of catalytic activity
and selectivity under different temperatures and H 2 S
concentrations showed that H2S exposure in biogas feeding
could cause severe catalyst deactivation, and a higher H2S
concentration led to a faster deactivation.
The deactivation of H2S poisoning was not reversible by
simply stopping the H2S feeding. Only at a high temperature of
800 °C was a slight catalytic activity recovery evident, but the
original activity could not be attained due to the diffusion limit.
After being regenerated by the TPC method, the activity could
be partly revived, but there was still obvious deactivation due to
the incomplete removal of Ni−S. Oxygen activation stabilized
catalytic activity at a certain level and was the most effective
way to regenerate the deactivated catalyst.
Furthermore, XRD, XPS, and TGA were applied to
characterize the mechanism of sulfur poisoning and carbon
deposition in freshly reduced, originally deactivated, and
regenerated catalysts using different regeneration methods.
The formation of Ni7S6 was detected for the first time through
XRD in a sulfur poisoning process. The XPS spectrum also
revealed the existence of Ni−S species, which blocked the
active sites and led to catalyst sintering and carbon deposition.
The reversibility of different regeneration methods was
dependent on the degree of elimination of Ni−S. This work
provides that the key factor for sulfur deactivation and
10255
Research Article
regeneration on nickel catalyst is the formation and removal
of Ni7S6, and O2 activation method is the most effective for
reviving catalytic activity, preventing sintering, and reducing
carbon deposition.
■
*
ASSOCIATED CONTENT
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acssusche-
meng.7b02251.
Scheme of the experimental setup, table of gas
components of biogas with different H2S concentrations,
and calculation of H2S deactivation rate under various
conditions (PDF)
■
AUTHOR INFORMATION
Corresponding Author
*E-mailjianguoj@mail.tsinghua.edu.cn.
ORCID
Xuejing Chen: 0000-0002-6692-3727
Jianguo Jiang: 0000-0002-0074-040X
Hui Zhou: 0000-0003-1410-4794
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
This work was financially supported by the Major Science and
Technology Program for Water Pollution Control and
Treatment (Grant 2017ZX07202005), the National Natural
Science Foundation of China (Grant 21576156), and Tsinghua
University Initiative Scientific Research Program (Grant
2014z22075). The English in this document has been checked
by at least two professional editors; both are native English
speakers. For a certificate, please see http://www.textcheck.
com/certificate/1H0Ldp.
■
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10257 DOI: 10.1021/acssuschemeng.7b02251

ACS Sustainable Chem. Eng. 2017, 5, 10248−10257