Fuel 107 (2013) 539546

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Fuel
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Manganese-based regenerable sorbents for high temperature H2S removal

Ju Wang a,b, Bin Liang a,, Richard Parnas a,c
a

College of Chemical Engineering, Sichuan University, No. 24 South Section 1, Yihuan Road, Chengdu 610065, China
Department of Materials and Environmental Protection, Chengdu Textile College, No. 186 Taishan South Street, Xipu, Chengdu 611731, China
c
Chemical Engineering Department, University of Connecticut, 2131 Hillside Road, Unit 3088 Storrs, CT 06269-3088, USA
b

h i g h l i g h t s
" Co-precipitation method was used to prepare Mn/Al sorbents for 850 C H2S removal.
" Regeneration of sulded sorbents with diluted air, SO2 or steam was studied.
" Elemental S can be obtained as a regeneration product with diluted air.
" A two step regeneration with 50% SO2 followed with 3% O2 at 850 C can provide elemental sulfur and complete regeneration.
" Steam was another way for complete regeneration.

a r t i c l e

i n f o

Article history:
Received 22 August 2012
Received in revised form 11 October 2012
Accepted 30 October 2012
Available online 23 November 2012
Keywords:
H2S removal
Co-precipitation
Manganese-based regenerable sorbent

a b s t r a c t
A series of sorbents with different manganese contents have been prepared by co-precipitation method
for 850 C regenerative H2S removal. The sulfur capacity increased linearly with the increase of manganese content. The performance of sorbents prepared by co-precipitation of Mn nitrate and Al nitrate
appears to be stable over ve suldationregeneration cycles. Al2O3 plays an important role in the performance of sorbents and the recovery of elemental sulfur in O2 regeneration. With increasing Mn content in the sorbent, increasing O2 concentration in the regeneration gas or increasing total regeneration
gas ow rate, the recovery of elemental sulfur decreased. Elemental sulfur is the only product with SO2
regeneration. The sorbents cannot be completely regenerated with SO2 under the conditions used. The
sorbents, however, can be completely regenerated by steam. The main product for steam regeneration
is H2S. Steam regeneration results in less sintering than O2 regeneration.
2012 Elsevier Ltd. All rights reserved.

1. Introduction
Hot removal of H2S from coal gases at high temperatures up to
850 C is required in many processes. In the production of directly
reduced iron (DRI), coal is gasied at 11001300 C. Then, the coal
gas containing about 0.11.5% of H2S is puried and used to reduce
the iron ore at 850 C [1]. For reasons of thermal efciency, a high
temperature sulfur removal process (higher than 850 C) is a most
preferable choice. Integrated Gasication Combined Cycle (IGCC) is
a clean and efcient electricity production method, in which the
high temperature desulfurization is a key step for overall thermal
efciency.
Because of the high temperature operation, traditional commercial desulfurization is not suitable. A solid acceptor of sulfur is the
only choice for the high temperature desulfurization process. For
Corresponding author. Address: College of Chemical Engineering, Sichuan
University, No. 24 South Section 1, Yihuan Road, Chengdu 610065, China. Tel.:
+86 28 85460556/85990278; fax: +86 28 85460557.
E-mail address: liangbin@scu.edu.cn (B. Liang).
0016-2361/$ - see front matter 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.fuel.2012.10.076

sulfur contents of 0.11.5%, the sulfur acceptor must be regenerated in order to convert the sulfur to useful product.
Some metal oxides can be used as acceptors to remove H2S from
hot coal gas. Zinc ferrite [29], zinc titanate [1014] and copper
based sorbents [1517] were reported to be used as the sorbents
of hot coal gas under high temperature. These metal oxides are,
however, unstable because they are easily reduced to their metallic
state, or form corresponding metal carbides in the hot coal gas.
These changes inuence the mechanical strength and the sulfur
capacity of the sorbent.
Manganese-based sorbents are promising acceptors of H2S for
hot coal gases. Pure manganese oxide can react with H2S and remove sulfur from coal gas. However, the manganese sulde cannot
be simply regenerated at the same temperature with steam. Wakker [1820] impregnated manganese acetate solution onto c-Al2O3
support and obtained sulfur acceptors with 8% Mn content. The
acceptor was regenerated at 600 C. The highest sulfur capacity
of their acceptors was 46%. Their acceptors deactivated quickly
under higher temperatures in the recycle operations. They suggested that the surface spinel MnAlO species were active sites

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J. Wang et al. / Fuel 107 (2013) 539546

and regenerated in the suldationregeneration operation. The

reactions of suldation and regeneration are:

were analyzed with N2 adsorption on a SSA-3000 surface area

analyzer.

MnOx =Al2 O3 H2 S ! MnSx =Al2 O3 H2 O

2.3. Suldationregeneration tests

MnSx =Al2 O3 H2 O ! MnOx =Al2 O3 H2 S

Thermodynamic calculations [21] showed that high temperature was benecial for the S/O exchange rate of the manganesebased acceptor and the sulfur capacity was proportional to the
manganese content at elevated temperatures. In order to increase
of the manganese content of the acceptor, Liang et al. [22,23] prepared the Mn/c-Al2O3 acceptors by repeated impregnation and obtained a high manganese content of 34 wt%. The high Mn-content
acceptor achieved a sulfur capacity of about 22 wt% S at 850 C.
Their results showed that the sulfur capacity linearly increased
with the manganese content of the acceptor. Bakker et al. [24] also
reported a regenerative high capacity MnAl sorbent made by repeated impregnation for high temperature desulfurization. Its sulfur capacity was 20 wt% S when the manganese content was
36 wt%. The acceptor was stable during 110 sulding and regeneration cycles at 850 C.
Co-precipitation can achieve a more even distribution of the
sorbent components and provide a higher manganese content
compared to previously used formulation methods. In addition,
co-precipitation is easier and more energy efcient than repeated
impregnation of manganese-based sorbents. A series of sorbents
with different manganese contents were prepared and tested during successive suldationregeneration cycles. X-ray diffraction
(XRD), scanning electron microscope (SEM) and surface area measurement are used to characterize the acceptors. The inuence of
the regeneration gas atmospheres and operation conditions on
the chemical stability of the sorbents and the products during
regeneration were investigated.
2. Experimental

Acceptors were tested in suldationregeneration cycles. The

experimental setup was equipped with a gas feeding unit, a suldationregeneration reaction unit and a detecting unit. Gases were
controlled by mass ow controllers and then owed through a vertically oriented quartz tube reactor. The inner diameter of the reaction tube was 4 mm. In each case, 0.2765 g of acceptor was
packed in the tube reactor to a height of roughly 3 cm. A typical
experiment repeated several cycles, and each cycle consisted of
four steps: suldation, ushing, regeneration, and ushing again.
In earlier work [24], suldation tests with simulated coal gas
showed similar results to these tests with feed gas containing H2,
H2S and inert gas. No coke formation was observed. In this work,
a mixture of H2 containing 1% (15.179 g/m3) H2S was used and
the ow rate was maintained at 50 ml min1 (STP) during the sulfidation. For each suldation the temperature was maintained at
850 C. And the suldation conditions were kept constant in this
work. In the regeneration step, diluted air, SO2 or H2O was used
to regenerate the sulded acceptor. The products evolved during
regeneration with diluted air were SO2 and elemental sulfur. The
elemental sulfur was condensed after the reactor. The main products of both SO2 and steam regeneration were S2 and H2S respectively. The regeneration step was nished when the measured
concentration of SO2 or H2S was close to the detection limit (diluted air or steam regeneration) or reached the content of feed
gas (SO2 regeneration). The regenerated acceptor was directly used
for suldation test in the next cycle. H2S or SO2 in the exit gas is
measured by a SC2000 gas chromatograph (GC), equipped with a
thermal conductivity detector (TCD) and a ame photometric
detector (FPD) for low concentrations of H2S or SO2 with sensitivity
lower than 5 ppm or 50 ppm, respectively.

2.1. Preparation of acceptors

A series of sorbents with different manganese contents were
prepared by co-precipitation method. 1.27 mol/L Mn(NO3)2 and
1 mol/L Al(NO3)3 solutions were separately prepared from 50 wt%
manganous nitrate solution (AR) and aluminum nitrate anhydrate
(AR). The solutions were mixed with different ratios and then neutralized with 10% NH3H2O. Pure manganese oxide was prepared as
a reference with Mn(NO3)2 and NH3H2O.
During the precipitation, the nitrate solution and the NH3H2O
were simultaneously pumped into the reactor, which already contained a small amount of water, and the pH value was kept in the
range of 910 by regulating the ow rates of both base and salt
solutions. And the temperature was kept at 50 C during the neutralization. The co-precipitation slurry was aged for 2 h at 50 C,
and then ltered. The ltration cake was washed with distilled
water and dried overnight in air at 7090 C. The dried cake was
crushed and sieved to the size of 80200 mesh, and then calcined
at 850 C in air for 6 h.
2.2. Analysis and characterization of the acceptors
The manganese content of the acceptors was analyzed by
ammonium iron || sulfate titrimetric method (GB1506-2002-T).
The crystal structure of the acceptors was detected by XRD. A
DX-1000 CSC Goniometer was used to scan the acceptor samples.
The scan angle (2h) was varied from 20 to 80. A JSM-5900LV
scanning electron microscope (SEM) was used to follow the surface
morphology of selected samples. The surface areas of acceptors

3. Results and discussion

3.1. Preparation of sorbents by co-precipitation method
By changing the Mn/Al molar ratio in the precipitation solution,
ve sorbents with different manganese contents were obtained
(see Table 1). Samples 1, 2, 3 and 4 were prepared by mixed nitrate
solutions of Mn(NO3)2 and Al(NO3)3. For sample 5, only Mn(NO3)2
solution was neutralized in precipitation.
The sorbents with different manganese contents were characterized by XRD and the XRD proles are illustrated in Fig. 1. For
the sample with low manganese content (13.7%), both Al2O3 and
Mn3O4 phases were detected, in which the peaks of Mn3O4 were
signicantly broadened. It means that manganese oxide was dispersed over alumina. Compared with the samples of high manganese content, the Mn2O3 crystal phase gradually increased with
the manganese content. From the XRD peaks, the degree of crystallinity of the Mn2O3 increased. The crystal structures of the sorbents
prepared by co-precipitation method agree with those prepared by
repeated impregnation. Mn3O4, a crystal phase with a similar
structure as the spinel, was observed in samples with low Mn content. When the Mn content increased to a value higher than 16.2%,
the manganese oxide tends to form the Mn2O3 cystal phase because of the weaker interaction between manganese and alumina
[23].
The calculated manganese content from mole ratios of precipitation solution were in good agreement with the results measured
by ammonium iron || sulfate titrimetric method. It indicated that

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J. Wang et al. / Fuel 107 (2013) 539546

Table 1
Recipes of the precipitation solutions.
Sample

1
2
3
4
5

Mixed nitrate solution

Precipitator

1.27 mol/L Mn(NO3)2 solution/ml

1 mol/L Al(NO3)3 solution/ml

10%NH3H2O/ml

45
100
140
200
300

330
300
260
200

375
400
400
400
300

Calculated Mn-content (wt%)

Measured Mn-content (wt%)

14.8
27.6
35.8
46.2
69.6

13.7
26.9
35.4
46.5
69.8

Fig. 1. XRD proles for samples with different manganese content.

both manganese and alumina ions precipitated completely in the

preparation process.
3.2. Suldationregeneration tests
3.2.1. Suldation performance during successive cycles
Suldation tests were performed with each of the samples with
different Mn-content. The H2S breakthrough curves for the rst
suldation cycle are presented in Fig. 2.

Fig. 2. The rst suldation breakthrough curves for samples with different
Mn-content.

In the initial period, no H2S is detected at the exit of the reactor

and the removal ratios of H2S of all acceptors were essentially
100%. As the Mn content increased, H2S breakthrough occurred later. The breakthrough curves of samples with Mn content from
13.7% to 46.5%, prepared by Mn/Al co-precipitation, are sharp.
For the sample with Mn content of 69.6%, pure Mn2O3, the curve
has a signicant tail in the breakthrough period. This behavior
most likely indicates that the sulfur adsorption rate was reduced
in pure manganese oxide because of diffusion limitations. Co-precipitation achieved a good dispersion of MnAl in bulk phase of
acceptor, which decreased the diffusion limitation. When the sorbents were saturated by H2S, the S/Mn molar ratios of all the samples were between 0.88 and 0.96.
For the high temperature desulfurization, the sorbent should be
regenerable and its activity should be stable during suldation
regeneration cycles. In this work, the ve samples were all repeatedly sulded and regenerated for 5 cycles to investigate the stability of the sorbents. Diluted air with 3% O2 was used as the
regeneration medium. The gas ow during regeneration was maintained at 50 ml/min and the temperature was 850 C.
The sulfur capacities for the ve samples during each cycle were
measured and are illustrated in Fig. 3. In the rst cycle, the sulfur
capacity increased linearly with increasing manganese content.
For the Mn/Al sorbents prepared by co-precipitation, no signicant
capacity drop was observed during 5 cycles. Only sample ve, the
pure Mn2O3, showed a signicant reduction of sulfur capacity during the cycles.
It was shown previously [22] that alumina supported manganese oxide, prepared by repeated impregnation, could be regenerated due to a cooperative effect of MnAl. A good dispersion of
manganese oxide on the alumina carrier is required to form the

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J. Wang et al. / Fuel 107 (2013) 539546

reaction of Mn3O4 with H2S is about 109 at 1100 K and the value
for reaction of MnAl2O4 with H2S is about 10 [24]. During sulding
MnAl2O4 captures the bulk of the H2S while manganese oxide captures efciently the remainder. The existence of Mn3O4 can remove
H2S to a few ppm.

Fig. 3. Sulfur capacities for samples with different Mn content.

uniform MnAlO spinel phase, which led to the regenerative active sites. Repeated impregnation only guaranteed a dispersion of
manganese oxide near the surface of the sorbent [2123]. Co-precipitation can achieve a good dispersion of manganese oxide
throughout the entire volume of the acceptor. According to the
XRD results, the particle size of manganese oxides in the Mn/Al
sorbents is estimated to be between 20 and 30 nm, which is lower
than the pure Mn2O3 which is about 40 nm. It indicated that the
Mn2O3 crystal clusters cannot be regenerated completely with diluted air and the Mn/Al sorbents prepared by co-precipitation were
stable under the reaction conditions.
3.2.2. Crystal structure change of sorbents during suldation
regeneration cycles
The crystal structures of the sorbents before suldization and
regeneration were measured by XRD method. The results of the
sorbent with Mn content of 35.4% are shown in Fig. 4, including
the fresh calcined, the sulded and the regenerated patterns. The
fresh sorbent exhibits the diffraction patterns of both Mn2O3 and
Al2O3. The XRD patterns of the sulded sample include the peaks
of MnS and Al2O3, and the regenerated sample is composed of
mainly MnAl2O4 phase and some Mn3O4 and Al2O3 phases. The
combination of manganese oxide and MnAl2O4 ensures a good
capacity and desulfurization depth. The equilibrium constant for

Fig. 4. XRD patterns for a fresh sorbent (1), a sulded sorbent (2) and a regenerated
sorbent (3).

3.2.3. SEM images and specic surface area

The scanning electron micrographs of the sorbents with Mn
content of 35.4% are shown in Fig. 5. The fresh, sulded and regenerated samples are denoted A, B and C.
The surface of the fresh sorbent was loose and porous. Compact
particulates were observed on the surface of the sulded sample.
The deposit on the surface might have been caused by the suldation. After regeneration, the particulates disappeared and the porous structure was restored.
The BET area of the fresh sample was 32.74 m2/g. The area for
the sample after suldation and regeneration was 12.84 m2/g and
20.14 m2/g, respectively. It indicates that the sulded product is
more compact which results in signicant decrease in the surface
area. The surface area of the regenerated sample was increased
but remained lower than the fresh ones. The porous structure
was partially restored after regeneration.
3.3. Regeneration with diluted air
The regeneration of sulded sorbents depends on the regeneration gas atmosphere and operating conditions. Regenerating the
sorbent is very important for the desulfurization of coal gas. It
can convert the sulfur into useful products. Elemental sulfur is
the most preferable regeneration product that is easy to be stored
and transported. Diluted air was used as the regeneration medium.
The inuence of regeneration conditions such as temperature, O2
concentration and ow on the regeneration of sorbent activity
was investigated. Furthermore, the sulfur yield was measured.
3.3.1. Yield of elemental sulfur in the regeneration of different sorbents
According to the results of suldation, the initial sulfur capacity
linearly depends on the manganese content. The corresponding
sorbents were regenerated after suldation with diluted air of 3%
O2 at 850 C. The gas ow during regeneration was maintained at
50 ml/min. The concentration of SO2 in the regeneration product
gas is shown in Fig. 6 as a function of reaction time. The theoretical
maximum SO2 concentration in the product gas is shown in Fig. 6
as a horizontal dashed line. This value corresponds to regeneration
with 3% O2 and complete consumption of the oxygen, and is calculated based on the stoichiometry of the overall regeneration of MnS
to MnO. The SO2 concentrations for all the samples are lower than
the theoretical value. For the sorbents with high Mn-content and
high sulfur capacity, it took longer for complete regeneration.
In regeneration experiments, bright yellow elemental sulfur
was observed at the exit of the reactor and along the connecting
tube. However, the accurate collection of solid S was difcult in
the experimental process. We therefore assumed all of the sulfur
was released as either the S form or SO2 form, and estimated the
S amount by subtracting the SO2 form sulfur from the total adsorbed sulfur. The elemental sulfur recovery rate was calculated
by dividing the total S absorbed in suldation. The results showed
that S recovery decreased with the increase of Mn content in sorbents (see Table 2). Same rule was observed in the other regeneration cycles. For the pure Mn2O3, the sulfur liberated during
regeneration was all in the form of SO2. No elemental sulfur was
observed.
The most important regeneration reactions that take place are
given below:

MnS 1:5O2 ! MnO SO2

J. Wang et al. / Fuel 107 (2013) 539546

543

Fig. 5. SEM of the fresh sorbent (A), the sulded sample (B) and the regenerated sample (C).

Fig. 6. Regeneration curves of sulded sorbents with different Mn contents.

Table 2
S recovery in regeneration of sulded sorbents with different Mn contents.
Sample

Measured Mn-content (wt%)

S recovery (wt%)

1
2
3
4

13.7
26.9
35.4
46.5

59.3
43.7
38.6
20.4

MnS=Al2 O3 0:5SO2 ! MnAl2 O4 1:5S

In previous work it was shown that regeneration of sulded

manganese oxides is difcult with SO2. The thermodynamic equilibrium Keq constant of the reaction of MnS to MnO with O2 at
1100 K is about 1017, but is about 102 with SO2. The Keq of MnS/
Al2O3 to MnAl2O4 with SO2 is about 101 [24]. This indicates that
regeneration of MnS dispersed in Al2O3 with SO2 is more favorable
than the regeneration of pure MnS, which produced elemental sulfur. With the increase of Mn content, the effect of Al2O3 weakened,
and the elemental sulfur recovery decreased.
3.3.2. The effect of O2 concentration on the regeneration reactions
The oxidation of MnS to MnO and SO2 is highly exothermic
(DH1100K = 530 kJ/mol). A low O2 concentration is required in order to control the regeneration temperature. Uncontrolled oxidation of sulde sorbents may result in sintering and activity
reduction of the sorbent due to the high temperature rise. The effect of O2 concentration on the regeneration reaction was investigated at a temperature of 850 C and a total ow rate of 50 ml/min.
Table 3 lists the sulfur capacities of the sorbent with Mn content
of 35.4% in 5 cycles using different O2 concentrations in the regener-

ation gas. When the O2 concentration increased from 3% to 21%, the

sulfur capacities did not change signicantly. BET surface areas were
measured after 5 cycles and the results showed that all the surface
areas signicantly decreased compared with the fresh ones. The surface area decreased about 30% when the O2 content increased from
3% to 21%. However, the drop in BET area did not inuence the sulfur
capacity. In previous work [24], solid state diffusion in Mn/Al2O3 sorbents was described as an activated process at 850 C. The activated
transport process may be more important than the total surface area
and explain the insensitivity of the results to the measured surface
areas. The activated diffusion process was also shown by Liang
[25] using temperature programmed suldation.
The rst regeneration curves are shown in Fig. 7. It was observed that the time required for complete regeneration shortened
at higher O2 concentrations. The maximum SO2 concentration in
the product gas is proportional to the O2 content in the feed gas,
and is much lower than the theoretical maximum SO2 concentration corresponding to the complete consumption of oxygen. Thermodynamic calculations indicate that regeneration of MnS/Al2O3 is
more favorable with O2 than SO2. With the increase of oxygen concentration, more S was released in the form of SO2 and the S recovery rate decreased (see Table 3).
3.3.3. Gas ow
The effect of gas ow on the regeneration reaction was investigated for the sorbent with Mn content of 35.4% regenerated at
850 C and with 3% O2. As gas ow rate increased, the regeneration
became quicker. The time for complete regeneration is about
70 min with 50 ml/min regeneration gas ow rate, about 40 min
with 100 ml/min, and roughly 25 min with 200 ml/min. Comparing
the SO2 concentrations at the outlet during the regeneration, we
found the maximum concentrations remained nearly constant.
The residence time inside the catalyst bed was less than 0.1 s at
200 ml (STP)/min. Complete regeneration was still achieved which
means that the oxidation reaction of MnS is quite rapid. The short
residence time did not inuence the reaction. The sulfur capacities
in the rst cycle and the second cycle with different regeneration
ow rates were maintained between 18 g S/100 g sorbent and
19 g S/100 g sorbent. They changed very little in the regeneration
gas ow range of 50200 ml/min. The sulded sorbents completely
regenerated in high gas ow rate.
However, with the increase of regeneration gas ow rate, the
elemental sulfur recovery decreased (see Table 4). Under high
gas ow rate, the contact time of SO2 and MnS is short, which
has an obvious inuence on reaction (2).
3.3.4. Regeneration temperature
Under the regeneration conditions of 50 ml(STP)/min and
3 vol% O2, the effects of regeneration temperature were investigated. The regenerations were conducted at 850 C, 450 C and
350 C, respectively. The results showed that the regeneration of

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J. Wang et al. / Fuel 107 (2013) 539546

Table 3
Variation of sulfur capacities, surface areas and S recovery with O2 content in regeneration gas.
O2 content (vol%)

Sulfur capacity (g S/100 g sorbent)

1st cycle

2nd cycle

3rd cycle

4th cycle

5th cycle

3
10
14
21

19
18
18
19

19
18
17
18

20
18
18
18

19
17
17
17

19
18
17
18

Fig. 7. Regeneration curves with different O2 content.

Table 4
Effect of feed gas rate on S recovery.
Feed gas rate (ml(STP)/min)

S recovery (wt%)

50
100
200

38.6
31.3
11.0

the sulded acceptor was not complete at 350 C, the breakthrough

time during the second suldation was short and it was about 42%
of the time over the fresh sample. The sulfur capacity dropped from
18 g/100 g-sorbent to 12 g/100 g-sorbent. In contrast, the sample
regenerated at 850 C and 450 C did not show any reduction in
the sulfur capacity during the second cycle. It appears that the
acceptor can be completely regenerated at 450850 C. However,
the regeneration rate was slower and the product SO2 concentration was lower at 450 C. The reaction rate constant for the oxidation of MnS improved with the increase of temperature, which
induced shorter regeneration time and higher SO2 concentration.
The elemental sulfur recovery rate at 450 C was about 36.8%,
which is close to the value at 850 C.
The regenerated samples after the second cycles were measured
with XRD. From Fig. 8, MnS residue can be found in the 350 C
regenerated sample, which means that the oxidation of MnS was
not complete during the regeneration at 350 C. The MnS phase
was not detected in the sample regenerated at 450 C. It indicates
the complete conversion of MnS during the regeneration at 450 C.
And all of the MnS was converted to the form of MnO, MnO2 and
Mn3O4. No sulfate formation was observed by XRD at the temperatures mentioned above.
3.4. SO2 regeneration
Using SO2 as a regeneration medium, the adsorbed S can be converted into elementary S by the Clause reaction. It is extremely

Surface areas after 5 cycles (m2/g)

S recovery (wt%)

9.64
8.03
8.95
6.80

38.6
29.1
16.4
6.9

Fig. 8. XRD patterns for samples regenerated under different temperatures.

attractive that 100% selectivity for elemental sulfur and 100%

recovery of S is reached, as shown below.
Fig. 9 shows the suldation breakthrough curves of fresh and
regenerated acceptors, in which the regeneration was conducted
with SO2. From the breakthrough curves, a signicant drop of the
sulfur capacity can be observed after the acceptor was regenerated
by SO2-containing gas. Compared with the O2 regeneration, the SO2
regeneration is not complete. By increasing SO2 concentration and
raising temperature, breakthrough time in the next suldation cycle is delayed. Therefore, the regeneration degree increased with
increases in SO2 concentration and temperature. Previous experiments showed that O2 regenerated sorbents can reduce the H2S
concentration to below the sensitivity of FPD (<5 ppm) before the
breakthrough point. In contrast, the SO2 regenerated sorbents only
reduce the exit H2S concentration in ue gas to about 0.060.1 g/
m3 (4066 ppm) before breakthrough occurs (see Fig. 9).
The XRD proles of sorbents regenerated with SO2 are shown in
Fig. 10. When regenerated with 50% SO2 at 850 C, the sample
shows diffraction patterns of MnAl2O4 and MnS. When the regeneration condition was 950 C and 90% SO2, the XRD shows mainly
MnAl2O4 and the diffraction intensity of MnS is greatly decreased.
This difference explains why the sulfur capacity in the second cycle
is increased when regeneration is done at higher SO2 concentration
and higher temperature. Compared with O2 regeneration, we did
not detect any manganese oxide phase in the SO2 regenerated sample. Based on thermodynamic analysis [24], regeneration of sulded manganese oxides with SO2 is relatively difcult. The formation
of manganese oxide is thermodynamically unfavorable. Manganese oxides absorb H2S more easily than MnAl2O4. Therefore, the
suldation efciency of the sample regenerated with O2 is higher
than those with SO2. However, the MnS remaining after regeneration with SO2 can be completely removed with diluted O2. The sulded sample regenerated with 3% O2 after regeneration with 50%
SO2 at 850 C did not show any reduction in the sulfur capacity
during the second cycle. Thus, a two stage regeneration, with SO2

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J. Wang et al. / Fuel 107 (2013) 539546

Fig. 9. Effect of SO2 regeneration conditions on the sorbent activity.

Fig. 10. XRD patterns for samples regenerated with SO2.

followed by 3% O2, can provide elemental sulfur and complete

regeneration.
3.5. Steam regeneration
Steam was also used as regeneration gas. In regeneration, steam
reacts with sulded sorbent by the reverse reaction of suldation.
Regeneration with H2O is successful at temperatures above 550 C.
The main product during regeneration is H2S. Above 850 C, besides H2S, some SO2 and S2 is also formed. This has been observed

Fig. 11. Breakthrough curves in 5 cycles test.

during experiments and has been predicted by thermodynamic

calculations [26]. The time for complete regeneration depended
on the regeneration temperature. For sample 3, the time for complete regeneration is about 15 min with 81% H2O at 850 C, about
100 min at 650 C, and roughly 295 min at 550 C.
The stability of the acceptor regenerated with steam was also
tested. The sample with Mn content of 35.4% was sulded and
regenerated for 5 cycles. The regeneration temperature was
maintained at 650 C and 81% H2O was used. The breakthrough
curves of suldation during a 5 cycles test are shown in Fig. 11.

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J. Wang et al. / Fuel 107 (2013) 539546

No deactivation was observed after 5 cycles. The sulfur capacity

was maintained between 18 g S/100 g sorbent and 19 g S/100 g
sorbent.
XRD patterns of the sample with Mn content of 35.4% after ve
suldationregeneration cycles revealed that the main phase is
MnAl2O4, which is essential to the regenerability of sorbent. BET
results revealed that the surface area of sample 3 after 5 cycles is
about 17.70 m2/g, which is larger than when regenerated with
O2. The reaction heat of regeneration with steam is about
10.19 kJ/mol at 1100 K, which is less exothermic than regeneration with O2. Thus, steam regeneration results in less sintering.
4. Conclusions
The co-precipitation method can be used to prepare high temperature H2S sorbents, in which the manganese content can be easily controlled. It is an energy efcient and simple process compared
with the repeated impregnation method. The results showed that
sulfur capacity of the sorbents linearly increased with the manganese content. During ve successive suldationregeneration cycles, the sorbents so prepared showed stable capacities.
In the tests with O2 regeneration, the existence of Al2O3 made
the sorbents more stable. The results showed that elemental S
can be obtained as a regeneration product with the Mn/Al sorbents.
With an increase of Mn content in the sorbent, an increase in the
O2 concentration in the regeneration gas or the total regeneration
gas ow rate, the recovery of elemental sulfur decreased. In the
test with SO2 regeneration, elemental sulfur is the only product,
but the sorbents are not completely regenerated below 850 C.
So, a two step regeneration with 50% SO2 followed with 3% O2
regeneration at 850 C was suggested to maximize S recovery.
The sorbent can also be regenerated completely with steam. The
main product of steam regeneration is H2S. Steam regeneration results in less sintering than O2 regeneration.
Acknowledgement
This work was jointly supported by the National Natural Science Foundation of China (No. 50876121) and Baosteel Group.
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