Article

Cite This: Ind. Eng. Chem. Res. XXXX, XXX, XXX−XXX pubs.acs.org/IECR

Low-Temperature H2S Removal from Gas Streams over γ‑FeOOH,

γ‑Fe2O3, and α‑Fe2O3: Effects of the Hydroxyl Group, Defect, and
Specific Surface Area
Yanning Cao,† Xiaohai Zheng,† Zhongjie Du,† Lijuan Shen,† Ying Zheng,*,‡ Chaktong Au,†
and Lilong Jiang*,†
†
National Engineering Research Center of Chemical Fertilizer Catalyst, Fuzhou University, Fuzhou, Fujian 350002, P. R. China
‡
Department of Chemical and Biochemical Engineering, Western University, 1151 Richmond Street, London, Ontario N6A 3K7,
Canada
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ABSTRACT: Samples of γ-FeOOH, γ-Fe2O3, and α-Fe2O3

were prepared by calcining a γ-FeOOH precursor at selected
Downloaded via LMU MUENCHEN on October 20, 2019 at 07:35:26 (UTC).

temperatures and tested for low-temperature H2S removal.

The prepared materials were characterized by powder X-ray
diffraction, N2 adsorption−desorption measurement, trans-
mission electron microscopy, and in situ Fourier transform
infrared spectroscopy of pyridine adsorption. The results
suggested that the oxygen vacancies, specific surface areas, and
surface hydroxyl groups of the iron oxides have significant
influence on the desulfurization performance at room
temperature. In H2S adsorption experiments, the sample
calcined at 250 °C (FE-250) showed the highest performance, reaching 53% of the maximum sulfur capacity, and
desulfurization precision at 25 °C.

1. INTRODUCTION Gong et al.25 prepared α-FeOOH and γ-FeOOH by adding

Hydrogen sulfide (H2S) is predominantly released from
agricultural sewage, coal gasification, and natural gas refineries.
It is harmful to the environment and is difficult to get rid of
because it is poisonous to most catalysts.1−4 It is of great
importance to develop efficient technologies for the removal of
H2S, not only for environment protection but also for the
efficacy of a large number of catalytic processes. Various
methods including condensation, adsorption, and oxidation
have been developed for H2S removal.5−9 The use of sorbents
is popular because it is reliable, environmentally benign, and
workable in a wide range of temperatures.10−13 Over the past
decade, metal-oxide-based materials have been investigated for
H2S adsorption, but the results were not satisfactory.14,15 For
example, zinc-based materials were prepared as desulfurization
sorbents because of their high sulfur capacity and favorable
sulfidation thermodynamics.16−19 However, efficient desulfur-
ization can only be achieved at high temperatures (∼300 °C).
The previously published works indicated that the sorbents
based on transition-metal oxides became effective for H2S
removal only at high temperatures, none of which can perform
well at low temperatures due to the limitation of active sites
and low diffusion rates of sulfur species.20−22 Nonetheless,
increasing attention has been devoted to iron-based materials
for low-temperature desulfurization because the materials are
inexpensive and can easily be regenerated.23,24 Iron-based
sorbents mainly include iron oxides (e.g., α-Fe2O3, γ-Fe2O3,
etc.) and iron oxyhydroxides (e.g., α-FeOOH, γ-FeOOH, etc.).
ammonium bicarbonate and sodium carbonates as precipitants,
respectively. With larger specific surface area, the former
showed higher desulfurization activity than the latter. Huang et
al.26 reported that the presence of oxygen vacancies is an
important factor in H2S removal by γ-Fe2O3 because the
vacancies facilitate the diffusion of ions in the lattice and thus
promote the sulfur capture ability. In general, the desulfuriza-
tion performance of sorbents can be affected by many factors.
Our earlier works demonstrated that the high desulfurization
activities of FeOOH can be attributed to its large specific
surface area, as well as the ample presence of surface oxygen
vacancies and OH groups.27−29 The work reported herein aims
to investigate the combined effects of the factors mentioned
above.
In the present study, we prepared γ-FeOOH, γ-Fe2O3, and
α-Fe2O3 using γ-FeOOH as precursor. Through the control of
calcination temperature, we regulated the specific surface area,
amount of oxygen vacancies, and surface OH groups. The
physicochemical properties of the as-prepared sorbent
materials were characterized using various techniques, and
the desulfurization experiments were carried out at room
temperature. We investigated the effects of oxygen vacancies,
Received: June 26, 2019
Revised: August 26, 2019
Accepted: October 1, 2019
Published: October 1, 2019

© XXXX American Chemical Society A DOI: 10.1021/acs.iecr.9b03430

Ind. Eng. Chem. Res. XXXX, XXX, XXX−XXX
Industrial & Engineering Chemistry Research
specific surface areas, and surface OH groups on H2S removal
in detail. The findings of the present study provide new
insights that are beneficial for the design of iron-based
adsorbents for efficient H2S removal at low temperatures.
2. EXPERIMENTAL SECTION
2.1. Preparation of Sorbent Materials. γ-FeOOH was
prepared by a modified precipitation method. In a typical
procedure, an aqueous solution of FeSO4·7H2O (0.1 M) was
premade in a flask. Then, an aqueous solution of ethyl-
enediaminetetraacetic acid (EDTA) (0.1 mol L−1) at a Fe2+/
EDTA molar ratio of 1:0.03 was added. Subsequently, a NH3·
H2O solution (6.0 M) was added at a constant rate into the
FeSO4 solution with vigorous stirring under the condition of
air isolation until pH = 8. After precipitation, the suspension
was exposed to air and allowed to crystallize at 30 °C for 3 h
with stirring at this pH value. The obtained precipitate was
washed with deionized water to remove sulfate and impurity
ions and dried at 90 °C for 24 h. The resulting precursor was
divided into four equal portions, which were sequentially
placed in a vacuum furnace and calcined at 150, 250, 350, and
450 °C for 5 h. The calcined samples are herein denoted as FE-
150, FE-250, FE-350, and FE-450, respectively.
2.2. Characterization. The X-ray diffraction (XRD)
measurements of the adsorbents were performed on a
PANalytical diffractometer (X’PertPro) with a Co Kα radiation
source (λ = 0.17902 nm) at 40 mA and 40 kV. N2 adsorption−
desorption experiments were carried out on a Micromeritics
ASAP 2020 instrument. The samples were outgassed at 120 °C
for 2 h before N2 adsorption at −196 °C to measure the
Brunauer−Emmett−Teller (BET) surface area and Barett−
Joyner−Halenda pore size distribution. Preliminary thermog-
ravimetry−differential scanning calorimetry (TG−DSC) anal-
ysis of the γ-FeOOH precursor was conducted to follow the
phase transition process. The measurement was carried out
using a simultaneous thermal analyzer (Setsys Evolution). The
sample (20 mg) was first dried at 90 °C in an oven for 2 h and
then heated at a linear rate (10 °C min−1) from 50 to 500 °C
in a N2 flow (20 mL min−1). Transmission electron
microscopy (TEM) and high-resolution TEM (HR-TEM)
images were taken using a high-resolution transmission
electron microscope (Tecnai G2 F20, operating at 200 kV).
In situ Fourier transform infrared spectroscopy (FT-IR) of
pyridine adsorption were collected at 4 cm−1 resolution and
128 scans over a Nicolet 6700 spectrometer (Thermo Fisher
Scientific) equipped with an MCT detector. The sample (25
mg) was heated in a He flow at 150, 250, 350, or 450 °C for 5
h and then cooled to 25 °C. Subsequently, pyridine was
introduced into the system until adsorption saturation. After
purged with He, DRIFTS spectra were acquired at elevated
temperatures.
2.3. Desulfurization Performance Test. The evaluation
of H2S breakthrough capacity for the samples was performed in
a fixed-bed reactor at 25 °C. The sorbent sample (0.5 g) was
secured in a quartz tube of 5 mm internal diameter, and a 4%
H2S/N2 gas stream (20 mL min−1) was fed into the reactor at a
weight hourly space velocity (WHSV) of 2400 mL·g−1·h−1.
The actual value of gas volume was measured by a wet-gas
flowmeter. Simultaneously, the H2S concentration at the outlet
was regularly recorded using a high-precision H2S detection
tube. The test was stopped when the H2S concentration
reached the breakthrough point (330 ppm at the outlet). The
amount of sulfur captured per gram of adsorbent was defined
B DOI: 10.1021/acs.iecr.9b03430
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as the H2S breakthrough capacity (X), which was calculated by
the equation28
32 × V × C
X= × 100%
(22.4 × G)(1‐C)
In the equation, 32 (g mol−1) is the molar mass of sulfur, 22.4
(L mol−1) is the gas molar volume at the standard state, V (L)
stands for the stream volume and is measured by a wet-gas
flowmeter located at the exit of the reactor, G (g) is the weight
of the adsorbent, and C (%) is the H2S concentration in the
gas stream.
Unlike the test for H2S breakthrough capacity, the evaluation
of desulfurization precision was conducted using a standard gas
of 0.5% H2S and 99.5% N2. Meanwhile, the H2S concentration
was directly detected with a high-accuracy H2S detection tube
at the outlet. The curve of desulfurization was plotted
according to the detected H2S concentration.
3. RESULTS AND DISCUSSION
3.1. TG−DSC Analysis. A simultaneous thermal analysis
technique was applied to study the phase transformation of the
as-prepared γ-FeOOH precursor. As can be seen from Figure
1, the precursor exhibits an endothermic peak at 108 °C, which
Figure 1. TG−DSC curves of the γ-FeOOH precursor.
is ascribed to the release of physically adsorbed water. A large
endothermic peak with a sharp weight loss is detected at 225
°C, which is associated with dehydration (chemically adsorbed
water) and dehydroxylation.30 In addition, there is a weak
exothermic peak at 470 °C with almost no weight loss
corresponding to phase transformation of γ-Fe2O3 to α-
Fe2O3.3132
A previous study32 suggested that for the γ-Fe2O3 derived
from phase transition of γ-FeOOH there is existence of surface
hydroxyl groups. It is noted that there are exothermic and
endothermic processes, though indistinguishable, accompanied
by a slight weight loss in the temperature range of 350−450
°C. These phenomena may be attributed to factors such as the
removal of residual hydroxyl groups, rearrangement of ions
within the structure, crystallization of amorphous γ-Fe2O3 as
well as phase transition of γ-Fe2O3 to α-Fe2O3.33 Therefore, we
calcined the divided γ-FeOOH portions separately at different
temperatures to obtained γ-FeOOH, γ-Fe2O3, and α-Fe2O3
according to the TG−DSC results.
3.2. Desulfurization Performance. Figures 2 and 3
illustrate the desulfurization precision and H2S breakthrough
capacity of the FE-150, FE-250, FE-350, and FE-450
Ind. Eng. Chem. Res. XXXX, XXX, XXX−XXX
Industrial & Engineering Chemistry Research Article

Figure 2. (A) Desulphurization precision and (B) standard deviation (error bar) indicated for the FE-150, FE-250, and FE-350 samples. All data
are average of at least four measures (feed gas composition: 0.5% H2S and 99.5% N2).

was performed 4 times and the standard deviation presented in

Figure 3. H2S breakthrough capacity of the FE-150, FE-250, FE-350,
and FE-450 samples (feed gas: 4% H2S/N2).
adsorbents, respectively. As shown in Figure 2, the samples
calcined at different temperatures are different in desulfuriza-
tion precision. The desulfurization performance of FE-450 is
the worst, showing a H2S concentration of 3580 ppm in the
outlet at the start of recording. The FE-250 sample displays the
best desulfurization precision, showing an outlet H2S
concentration of only 130 ppm after a reaction of 400 min.
In addition, the test of desulfurization precision for all samples
Figure 2B shows that the tests are well reproducible. Overall,
the samples show a descending order of FE-250 > FE-150 >
FE-350 > FE-450 both for desulfurization precision (Figure 2)
and H 2 S breakthrough capacity (Figure 3). Table 1
summarizes the performance of various adsorbents for the
removal hydrogen sulfide at room temperature. It can be found
that the adsorption capacity of γ-FeOOH and γ-Fe2O3 is
higher than most of the listed adsorbents. The H2S
breakthrough capacity of FE-250 is 53%, while that of FE-
450 is close to 0%. It is clear that the calcination temperature
adopted for the preparation of sorbents has a significant effect
on desulfurization performance. The reason may be related to
certain key factors of sorbent generated at different calcination
temperatures, such as crystal phase, specific surface area, lattice
defect, and surface hydroxyl group, which will be discussed in
detail in the later section.
3.3. Structural Studies. The structures of FE-150, FE-250,
FE-350, and FE-450 samples were characterized by XRD, and
the results are presented in Figure 4A. The diffraction patterns
of the samples are obviously different. The sample calcined at
150 °C shows peaks that can be ascribed to γ-FeOOH (PDF
no. 00-044-1415). After calcination at 250 and 350 °C, the
diffraction peaks of FE-250 and FE-350 match those of γ-
Fe2O3 (PDF no. 01-089-5892), while weak signals of γ-
FeOOH are still recognizable over the FE-250 sample. It is

Table 1. Summary of Metal Oxide and Hydroxide for H2S Removal at Room Temperature

support material
metal material formula adsorption capacity (%) SBET (m2/g) pore volume (cm3/g) average pore size (nm) refs
iron none γ-FeOOH (FE-150) 46.9 79 0.19 9.80 this work
γ-Fe2O3 (FE-250) 53.0 137 0.23 6.80
γ-Fe2O3 (FE-350) 39.6 68 0.18 11.0
α-Fe2O3 (FE-450) 0 17 0.10 22.6
iron none γ-Fe2O3/SiO2 40.61 113 8.21 8.1 26
γ-Fe2O3 10.58 82 9.75 11.6
α-Fe2O3 0 36 2.44 54.2
iron none Fe2O3 10 110 NA NA 34
iron none α-FeOOH 6.5 188 0.579 12.3 35
activated carbon α-FeOOH 17.1 500 0.449 3.6
iron none Fe3O4 1.54 73 0.313 17 36
graphene oxide Fe3O4 1.37 176 0.253 5.7
zinc none ZnO 0.89 NA NA NA 17
carbon nanotube ZnO 2.99 NA NA NA
cobalt none CoOOH 6.91 203 0.679 NA 37
graphene oxide CoOOH 6.62 191 0.417 NA

C DOI: 10.1021/acs.iecr.9b03430
Ind. Eng. Chem. Res. XXXX, XXX, XXX−XXX
Industrial & Engineering Chemistry Research
Figure 4. (A) XRD pattern of the samples calcined at different temperatures and (B) crystal structure of γ-FeOOH.
noted that compared with FE-350, FE-250 is poorer in
crystallinity and smaller in grain size as indicated by the
relatively weak signals and large full width at half-maximum
values.38 As for the sample calcined at 450 °C, the crystal
phase is α-Fe2O3 (PDF no. 01-086-2368) and the strong and
sharp peaks suggest high crystallinity and large particle size.39
γ-FeOOH (lepidocrocite) is an isomorphic boehmite with a
layered structure, which consists of arrays of cubic close-
packed (ccp) anions (O2−/OH−) stacked along the [150]
direction with Fe3+ occupying the octahedral interstices. This
structure consists of double chains of Fe(O,OH)6 octahedral
running parallel to the c-axis. The double chains share edges
with adjacent double chains, forming corrugated sheets of
octahedral, which are held together by hydrogen bonds (Figure
4B).
According to the results of TG−DSC and XRD analyses, the
processes of hydroxylation and phase transition of γ-FeOOH
could be illustrated as follows: At around 190 °C, there is the
desorption of weakly adsorbed water as well as partial removal
of hydroxyl groups. At 250 °C, the sample would have lost
most of the hydroxyl groups and there is phase transformation
from γ-FeOOH to γ-Fe2O3. At 350 °C, there is structural
rearrangement and grain growth as well as formation of defect
sites. In the process of phase transformation, the collapse of γ-
FeOOH structure is relatively rapid at the beginning and there
is ample presence of γ-Fe2O3 crystal nuclei. However, in the
later stage, the rearrangement process gradually slows down
and the growth of γ-Fe2O3 grains becomes lagging,40 as
reflected in the weak and broad XRD peaks of the FE-250 and
FE-350 samples. At 450 °C, there is the complete conversion
of γ-Fe2O3 to α-Fe2O3.
3.4. Texture Analysis. Nitrogen adsorption−desorption
measurements were conducted to investigate the texture of the
samples (Table 1). After calcination at 150 °C, the γ-FeOOH
has low BET surface area, pore volume, and average pore size.
When the calcination temperature was 250 °C, the resulted
FE-250 sample, which is mainly γ-Fe2O3, has significantly
larger BET surface area and pore volume but smaller average
pore size. A further rise of calcination temperature to 350 and
450 °C would result in a gradual decrease of BET surface area
and pore volume but in an increase of average pore size. This
may be because the removal of hydroxyl groups at 150 °C
would result in pores of a small size.30 Previous studies by
Sudakar and Giovanoli showed that the discharge of adsorbed
water during the initial stage of γ-FeOOH dehydroxylation
could create a large number of micropores.30,40 Therefore, the
BET surface area of FE-250 (137 m2 g−1) is higher than that of
FE-150 (79 m2 g−1). When calcined at 450 °C, a number of
D DOI: 10.1021/acs.iecr.9b03430
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larger pores are formed due to the merging of smaller pores
caused by structural rearrangement and phase transformation
to α-Fe2O3. Therefore, the BET surface area and pore volume
of the samples calcined at 350 and 450 °C decrease, while the
pore diameter increases.41,42 In general, being larger in the
BET surface area and pore volume is beneficial for
desulfurization. However, the FE-250 and FE-150 samples
are somewhat similar in desulphurization precision and H2S
breakthrough capacity despite the specific surface area of the
former being nearly twice that of the latter. Therefore, in
addition to the specific surface area, there may be other factors
affecting the desulfurization performance of the samples.
3.5. TEM Images. The TEM images of the FE-150, FE-
250, and FE-450 samples are shown in Figure 5. As can be seen
from Figure 5A, FE-150 is composed of platelets that are 200−
400 nm in length and 40−60 nm in width. The HR-TEM
image (Figure 5B) shows that FE-250 is dominated by (210)
crystal facets of γ-FeOOH, showing a lattice spacing of 0.329
nm. The FE-250 sample retains the nanosheet structure of FE-
150 (Figure 5C,D). There are slit pores on the lamellar
structure, which may be due to the cleavage of nanosheet
(about 3.2 nm in thickness) in γ-FeOOH caused by the
removal of hydroxyl and water during thermal treatment. The
drastic dehydroxylation and dehydration cause the collapse of
the γ-FeOOH structure and result in the formation of γ-Fe2O3.
However, we cannot obtain clear HR-TEM images of FE-250
due to the strong magnetism of γ-Fe2O3. As for the FE-450
sample, the nanoparticles are dense and irregular in size
(Figure 5E). The HR-TEM image of FE-450 in Figure 5F
reveals that the nanoparticles are enclosed by (104) facets with
an interplanar spacing of 0.270 nm, which confirms that the
crystalline phase of FE-450 is α-Fe2O3.43
The above TEM images intuitively show the change of
morphology and crystal phase with the calcination temper-
ature, which is consistent with the XRD and BET results.
Based on this information, it is deduced that there is variation
in the number of hydroxyl groups across the sorbents.
Meanwhile, with the rearrangement of iron and oxygen ions,
there is generation of defects in the iron−oxygen matrices.44
With the idea that hydroxyl groups and defects could get
involved in the low-temperature removal of hydrogen sulfide
by ferric oxide, we proceeded to characterize these species by
FT-IR and in situ DRIFTS of pyridine adsorption.
3.6. In Situ DRIFTS of Pyridine Adsorption. Due to
dehydroxylation during heat treatment, there is ready
formation of a large amount of oxygen vacancies on the
FeOOH surface. Meanwhile, corresponding to the defect sites,
there is the presence of electron-receptive Fe3+ ions of
Ind. Eng. Chem. Res. XXXX, XXX, XXX−XXX
Industrial & Engineering Chemistry Research
Figure 5. TEM images (left) and corresponding HR-TEM images
(right) of samples: (A, B) FE-150, (C, D) FE-250, and (E, F) FE-450.
unsaturated coordination. In the reaction of H2S removal, both
H2S and SH− groups readily bond to the electrophilic oxygen
vacancies on the surface of ferric oxide. Therefore, the
concentration of surface oxygen vacancies on ferric oxide has
a significant impact on its desulfurization performance.26 In
view of the electrophilic properties of oxygen vacancies on the
surface of ferric oxide, we characterized and measured the
Lewis acid sites of the catalyst.45
In view that pyridine is the most used basic probe to study
surface acidity, we used in situ DRIFTS of pyridine adsorption
to characterize the surface acid sites of the γ-FeOOH sample
(Figure 6). The sample exposed to pyridine at room
temperature shows absorption bands at 1400−1700 cm−1.
The bands at ca. 1448 and 1489 cm−1 can be ascribed to the
ν19b and ν19a modes of pyridine adsorbed on Lewis acid sites,
respectively.46 The bands at 1576 cm−1 are assigned to the
physically adsorbed pyridine.47 The bands at 1593 cm−1 are
related to hydrogen-bonded pyridine, having the nitrogen atom
weakly interacting with surface hydroxyl groups through
hydrogen bonding.48 When the temperature increases to 150
°C, the absorption bands assigned to hydrogen-bonded and
physically adsorbed pyridine disappear completely, indicating
that both of them are weakly adsorbed and relatively easy to
remove. As for the absorption bands at ca. 1448, 1489 and
1605 cm−1, they can still be detected when the temperature is
raised to 250 °C, suggesting the presence of Lewis acid sites. In
addition, there is no detection of bands that could be related to
Brønsted acid sites, which indicates that the −OH in FeOOH
E DOI: 10.1021/acs.iecr.9b03430
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Figure 6. In situ DRIFTS spectra of pyridine on γ-FeOOH recorded
at different temperatures. (RT-Py represents pyridine adsorption at
room temperature.)
is a basic hydroxyl group and can directly adsorb the H2S
molecules.
To avoid the interference of physically adsorbed and
hydrogen-bonded pyridine, we treated the FE-150, FE-250,
FE-350, and FE-450 samples at 150 °C under vacuum before
pyridine adsorption. As shown in Figure 7, the peak intensity
Figure 7. Pyridine absorption curves of FE-150, FE-250, FE-350, and
FE-450 samples with pyridine adsorbed at 150 °C.
of pyridine increases with the rise of calcination temperature,
which indicates that the number of Lewis acid sites increases
with the rise of calcination temperature. In this temperature
range, most of the OH groups of the samples have been
removed and there is a change of Fe3+ chemical environment
and the generation of a large number of Lewis acid sites. As for
FE-450, the intensity of the bands suffers a decrease because of
the formation of α-Fe2O3 (Figure 4A) as well as the reduction
of the BET surface area (Table 1). Consequently, there is a
significant decrease in the number of Lewis acid sites. Taking
that oxygen vacancies act as Lewis acid sites on the iron-based
materials, the number of oxygen vacancies across the samples
decreases in the order of FE-350 > FE-450 > FE-250 > FE-150.
As can be seen, there is a certain correspondence between the
oxygen vacancies and desulfurization performance such as in
the cases of FE-250 and FE-150 (Figure 3). However, although
FE-350 has the highest number of oxygen vacancies, it is not
the best in desulfurization performance, while having the least
number of oxygen vacancies, FE-150 shows desulfurization
performance better than that of FE-350. The results indicate
Ind. Eng. Chem. Res. XXXX, XXX, XXX−XXX
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that the number of oxygen vacancies is not a dominating factor
that governs desulfurization performance.
3.7. FT-IR Analysis. We hence turned our attention to the
role of surface hydroxyl groups in the iron oxides. The FT-IR
spectra of FE-150, FE-250, FE-350, and FE-450 samples were
recorded to investigate the relationship between surface
hydroxyl groups and desulfurization performance. As shown
in Figure 8, the IR spectrum of sample FE-150 shows typical γ-
Figure 8. FT-IR spectra of FE-150, FE-250, FE-350, and FE-450
samples.
FeOOH bands at 1153 and 1022 cm−1, which can be assigned
to in-plane Fe−OH bending vibrations.49,50 In addition, there
is no detection of bands related to H2O bending vibration near
1636 cm−1, indicating the complete removal of physically
adsorbed H2O. The sample has a strong and wide band at
2990−3700 cm−1, which can be assigned to the OH stretching
vibration of Fe−OH groups and chemisorbed H2O.51 During
dehydroxylation, the bands at 1550, 1434, and 1336 cm−1 can
be attributed to a small amount of residual carboxylate ligand,
carbonate, and/or NH4+ species. The band of OH stretching
vibration is still detectable over FE-250, indicating that there is
still ample presence of hydroxyl groups. The OH bands
become extremely weak over FE-350 and almost undetectable
over FE-450, indicating the gradual and final removal of
hydroxyl groups. Overall, the number of hydroxyl groups
decrease in the order of FE-150 > FE-250 > FE-350 > FE-450.
It is worth pointing out that the bands at 1153 and 1022 cm−1
of FE-150 become broadened and weakened with the rise of
calcination temperature, indicating the occurrence of phase
transition and atom rearrangement.
Generally, with adsorbed H2O on the FeOOH surface, H2S
molecules diffuse into the surface basic water film formed by
hydroxyl groups and dissociate into S2− and SH− species that
displace the OH− and O2− on the FeOOH surface, leading to
the formation of FeSx species. To the H2S molecules, the
surface hydroxyl groups play a “capture” role, blocking the H2S
molecules from penetrating into the bulk of adsorbent and
increasing the contact time between H2S molecules and iron
oxides. Therefore, the existence of surface hydroxyl groups
improves the sulfur capacity and desulfurization precision.
Perhaps this might explain why in test of desulfurization
performance over FE-350 at H2S concentration of 0.5% there
is high desulfurization precision but low H2S breakthrough
capacity. Thus, in addition to the specific surface area and the
F DOI: 10.1021/acs.iecr.9b03430
Article
number of Lewis acid sites, the effect of surface hydroxyl
groups and defects should not be ignored.
3.8. Normalization Analysis of the Three Factors.
Previous studies52,53 have demonstrated that the interaction
between adsorbed H2S molecules and metal oxides involves
lattice diffusion, which is the migration or diffusion of ions in
the oxide lattice. It is well conceived that the presence of defect
sites (e.g., oxygen vacancies) not only promotes lattice
diffusion but also reduces the activation energy for ion
exchange, enhancing the interaction of ions with surface iron
atoms as a consequence.54 Nonetheless, it is envisaged that
lattice diffusion at low temperatures is difficult and
desulfurization at room temperature is not controlled by the
rate of lattice diffusion. Although the mechanism of ion
diffusion in the lattice at low temperatures is not well
understood, the conducive effect of surface hydroxyl groups
on the dissociation of H2S molecules into S2− and SH− is
known.55
Based on the above analyses, it is deduced that there is a
correlation between the three factors (viz., the number of
hydroxyl groups, oxygen vacancies, and specific surface area)
and desulfurization performance. We conducted a normal-
ization analysis to explore the degree of influence of the three
factors on H2S breakthrough capacity and desulfurization
precision (Figure 9). FE-250 and FE-150, which have a high
Figure 9. Normalization analysis of the three factors (i.e., the number
of hydroxyl groups, density of oxygen vacancies, and specific surface
area) on (a) desulfurization precision and (b) H2S breakthrough
capacity.
specific surface area and a large number of hydroxyl groups,
respectively, have high H2S breakthrough capacity and
desulfurization precision. Although FE-350 has the highest
number of oxygen vacancies, its performance is below that of
FE-250 and FE-150 due to the decrease of the specific surface
area and surface hydroxyl groups. Despite medium in the
number of oxygen vacancies, FE-450 has the lowest
desulfurization performance because it has the lowest specific
surface area and number of hydroxyl groups. It is hence
deduced that the specific surface area and the number of
hydroxyl groups have stronger influence than the number of
oxygen vacancies on desulfurization. To optimize the perform-
ance of iron oxides for H2S removal at room temperature, the
FeOOH precursor has to be treated in a way to achieve high
specific surface area and abundant presence of surface hydroxyl
groups. At low temperatures, the effect of Lewis acid sites
(oxygen vacancies) is less significant due to the poor diffusion
of ions in the lattice. Such an understanding can serve as a
Ind. Eng. Chem. Res. XXXX, XXX, XXX−XXX
Industrial & Engineering Chemistry Research
guideline for the design of solid adsorbents for desulfurization
at low temperatures.
4. CONCLUSIONS
Samples of γ-FeOOH, γ-Fe2O3, and α-Fe2O3 were fabricated
by calcining γ-FeOOH at selected temperatures and evaluated
for H2S removal. Both specific surface area and surface
hydroxyl groups have great influence on desulfurization
performance. Among the prepared sorbents, the FE-250
calcined at 250 °C exhibited the highest H2S breakthrough
capacity (53%) and desulfurization precision at 25 °C. The
results of the present work elucidate the factors that govern the
desulfurization performance of iron oxides at room temper-
ature, and such an understanding is beneficial for the design of
desulfurizers.
■
AUTHOR INFORMATION
Corresponding Authors
*E-mail: ying.zheng@uwo.ca (Y.Z.).
*E-mail: jll@fzu.edu.cn (L.J.).
ORCID
Xiaohai Zheng: 0000-0002-3652-2236
Lilong Jiang: 0000-0002-0081-0367
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
This work was financially supported by the National Natural
Science Foundation of China (21878052), Natural Science
Foundation of Fujian Province (2018J01693), and Young and
Middle-aged Teacher Education and Science Research
Foundation of Fujian Province, China (JAT160047).
■
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H DOI: 10.1021/acs.iecr.9b03430
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