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Energy Procedia 9 (2011) 15 – 24

9th Eco-Energy and Materials Science and Engineering Symposium

Comparative Study of Hydrogen Sulfide Adsorption by using

Alkaline Impregnated Activated Carbons for Hot Fuel
Gas Purification
Russamee Sitthikhankaewa, Somrudee Predapitakkunb, Ratanawan (Wibulswas)
Kiattikomolb, Sudhibhumi Pumhiranb, Suttichai Assabumrungratc and
Navadol Laosiripojanaa,*
a
The Joint Graduate School of Energy and Environment, CHE Center for Energy Technology and Environment, King Mongkut's
University of Technology Thonburi, 126 Prachauthit Rd, Bangkok 10140, Thailand
b
Process Technology Research Department, PTT Research and Technology Institute, Phahonyothin Rd, Ayuthaya 13170, Thailand
C
Faculty of Engineering, Chulalongkorn University, 254 Payathai Rd, Bangkok 10330, Thailand

Abstract

Biogas, natural gas, and synthesis gas from coal gasification contain hydrogen sulfide (H2S) that is highly toxic for
human and corrosive for machine. H2S must be removed from fuel gases prior utilization. The objective of this
research was to compare the adsorption of H2S by using commercial and alkaline impregnated activated carbons. The
commercial and alkaline impregnated activated carbons were tested by the temperature program adsorption of H 2S at
30 ºC and 550 ºC. At high temperature of adsorption, alkaline activated carbons adsorbed H2S significantly higher
than commercial activated carbon (in the range of 3-29 times higher depending on modification method).
Furthermore, the concentration of H2S came out at the outlet gas after treated by the KOH and Na2CO3 impregnated
activated carbons was less than 30 ppmv, which was safe for utilizing in mechanical and power engine.
© 2011 Published by Elsevier Ltd. Open access under CC BY-NC-ND license.
Selection and/or peer-review under responsibility of CEO of Sustainable Energy System,
Rajamangala University of Technology Thanyaburi (RMUTT).
Keywords: Activated carbon; Adsorption; Alkaline impregnation; Gas purification; Hydrogen sulfide.

* Corresponding author.
E-mail address: [email protected], [email protected].

1876-6102 © 2011 Published by Elsevier Ltd. Selection and/or peer-review under responsibility of CEO of Sustainable Energy System, Rajamangala
University of Technology Thanyaburi (RMUTT). Open access under CC BY-NC-ND license.
doi:10.1016/j.egypro.2011.09.003
16 Russamee Sitthikhankaew et al. / Energy Procedia 9 (2011) 15 – 24

1. Introduction

Biogas that produced from anaerobic digestion of biodegradable materials can be utilized for
generation of electrical power and heat production. Generally, biogas (as well as natural gas and synthesis
gas from coal gasification) contained hydrogen sulfide (H2S) that was highly toxic for human body and
corrosive for machine. The content of H2S in biogas was about 0-1% and H2S must be removed from fuel
gases prior utilization [1].
Activated carbon that is a highly porous material was used for removal of impurities from gases and
liquids including gas separation and purification, vehicle exhaust emission control, and environmental
technology [2]. For low concentration H2S removal, the adsorption by activated carbon was known as an
efficient process [3-4]. Moreover, activated carbon has a high activity and long-lasting. In Thailand, it is
inexpensive adsorbent as compared to inorganic adsorbents such as alumina, zeolite and metal oxide. It
was produced from agricultural waste such as coconut shell, palm shell, and corncob.
The adsorption capacity of activated carbons was determined by their physical or surface property, but
also influenced by their chemical property. Typically, the surface properties of activated carbon such as
surface area, pore volume, and pore size affect on the adsorption capacity.
Activated carbon that was impregnated with alkaline material such as sodium hydroxide (NaOH) and
potassium hydroxide (KOH) was used for the H2S removal at ambient temperature [5-6]. At surface of the
impregnated activated carbon, acid-base reaction occurs. The advantages of impregnated activated carbon
in the removal of H2S are high efficiency and fast kinetically reaction. However, the adsorption of H2S on
alkaline impregnated activated carbon under the adsorption temperature program has not been
investigated. Therefore, this research focuses on the effect of temperature toward H2S adsorption
characteristic and capacity. Commercial and four types of alkaline impregnated activated carbons were
studied. In addition, the reaction of H2S on the commercial and alkaline impregnated activated carbon at
room and high temperature were proposed.

2. Experimental

2.1. Materials

Materials in this experiment were commercial and modified activated carbons. The granular
commercial activated carbon (A) made from coconut shell. The parameters of surface properties for
commercial activated carbon are shown in Table 1.
The commercial activated carbon was impregnated with alkaline compound such as KOH, NaOH,
sodium carbonate (Na2CO3), and potassium iodide (KI) according to the following procedure. First, the A
was soaked with this alkaline solution (10% w/v) for 30 minutes. Then, the sample was heated at 100 ºC
to evaporate water. Finally, the sample was dried at 110 ºC for 24 h. Activated carbon which was
impregnated with KOH, NaOH, Na2CO3, and KI was referred to A_100-KOH, A_100-NaOH, A_100-
Na2CO3, and A_100-KI, respectively.
 Russamee Sitthikhankaew et al. / Energy Procedia 9 (2011) 15 – 24 17

Table 1. Surface properties of the commercial activated carbon.

Parameters Value
2
Surface area (m /g) 1343
3
Pore volume (m /g) 0.45
Pore size (nm) 0.67

2.2. Adsorption test apparatus

Schematic diagram of adsorption system as shown in Figure 1 consisted of gas supply unit, a fixed-
bed reactor in the horizontal furnace, and gas monitor system. The mixture of He and H2S gas that was
controlled by mass flow controllers was pass through the fixed-bed reactor. The reactor (12.0 mm of
internal diameter and 70 cm of length) was filled with adsorbent bed. The amount of activated carbon in
the reactor was 1.0 g. The H2S continuous monitor system used QRAE model PGM-50Q to measure
concentration of H2S from the outlet of reactor.

2.3. Temperature program adsorption of hydrogen sulfide

In Figure 1, the condition of H2S adsorption was H2S inlet concentration as 3000 part per million by
volume (ppmv). The flow rate of inlet gas was 100 ml/min. The A, A_100-KOH, A_100-NaOH, A_100-
Na2CO3, and A_100-KI were tested by the H2S adsorption temperature program. The temperature
program had 2 parts. The first part was processed at 30 ºC that H 2S gas was fed into the reactor and the
concentration of H2S was recorded until the concentration at the outlet reached to 3000 ppmv. The
condition of the second part was the same as the first, but the temperature was programmed to increase
from 30 to 550 ºC at a rate of 10 ºC/min. Then reactor temperature was held constant at 550 ºC. When the
H2S outlet concentration was 300 and 3000 ppmv, the breakthrough time and total adsorption time were
recorded. The adsorption capacity of activated carbon was calculated using the integrated area above the
adsorption curve; the difference between the inlet concentration and the outlet concentration curves, the
flow rate, and the mass of activated carbon.

Fig. 1. Schematic diagram of adsorption system.

18 Russamee Sitthikhankaew et al. / Energy Procedia 9 (2011) 15 – 24

2.4. Sulfur analysis

The content of sulfur in fresh and exhausted activated carbons was analyzed with sulfur analyzer
(TruSpec CHNSO, LECO). Samples were analyzed in triplicate.

3. Results and discussion

3.1. H2S adsorption test at 30 ºC

Performances of the commercial and alkaline impregnated activated carbons in H 2S adsorption process
at 30 ºC were shown in Table 2. Adsorption curve of H2S by NaOH impregnated activated carbon at 30
ºC was shown in Figure 2. At an initial time of adsorption, the concentration of outlet H2S decreased
suddenly from 3000 ppmv to about 10 ppmv. Then the concentration of H2S increased continuously when
the time was increased until the concentration at the outlet reached to 300 ppmv. At this point, the ratio of
concentration of outlet H2S per concentration of inlet H2S was 0.1 so that this point indicates the
breakthrough time. The breakthrough time of A_100-NaOH was 4 minutes. After that, the concentration
of H2S at the outlet increased continuously until the concentration of H2S reached to 3000 ppmv. At this
point, the outlet concentration is equal to the inlet concentration so that this point indicates the total
adsorption time. The total adsorption time was 24 minutes (Table 2). The adsorption capacity of A_100-
NaOH was 0.4 mg of H2S per one gram of activated carbon.

Fig. 2. Adsorption curve of H2S at 30 ºC by NaOH impregnated activated carbon.

For the adsorption of H2S by the commercial activated carbon, the concentration of H2S came out at
the outlet gas was almost 0 ppmv for 4 minutes. Then the concentration of H2S increased continuously
when the time was increased until the concentration at the outlet reached to 3000 ppmv. The breakthrough
time and total adsorption time were 15 and 67 minutes, respectively. Adsorption capacity of the A was
higher than that of the A_100-NaOH (4 times higher). From the result, NaOH might occupy a portion of
the carbon pore volume and surface area, so physical adsorption of H2S was limited.
The reactions of H2S on the commercial and alkaline impregnated activated carbon at room
temperature could be proposed as physical adsorption. For physical adsorption, a conceptual reaction of
 Russamee Sitthikhankaew et al. / Energy Procedia 9 (2011) 15 – 24 19

H2S adsorption was proposed. First, the H2S transferred from the bulk stream into the pore or surface of
the activated carbon. Then H2S adsorbed on activated carbon (equation 1).

H2S (g) ė H2S (ads) (1)

H2S (g) and H2S (ads) correspond to H2S in gas and adsorbed phases.

Table 2. Adsorption time and adsorption capacities of activated carbons at 30 ºC.

Sample Adsorption time (min) Adsorption capacity (mg of H2S/

g of activated carbon)
A 67 1.67
A_100-NaOH 24 0.4
A_100-KOH 151 1.58
A_100-KI 145 1.56
A_100-Na2CO3 109 1.58

For the adsorption of H2S by the A_100-Na2CO3, A_100-KOH, and A_100-KI, the concentration of
H2S came out at the outlet gas after treatment was less than 10 ppmv for 1-3 minutes. The breakthrough
times of alkaline impregnated activated carbons were less than that of the commercial one. In detail, the
breakthrough time of A_100-Na2CO3, A_100-KOH, and A_100-KI were 10, 2, and 2 minutes,
respectively. However, the total adsorption times of alkaline impregnated activated carbons were
significantly higher than that of the commercial one (2 times higher). Therefore, the adsorption capacities
of alkaline impregnated activated carbons were slightly less than that of the commercial one (Table 2).

3.2. H2S adsorption test at high temperature

Performances of commercial and alkaline impregnated activated carbons in H2S adsorption process at
high temperature are shown in Tab. 3 and Figures 3-5.

Table 3. Adsorption time and adsorption capacities of activated carbons at high temperature.

Sample Adsorption time (min) Adsorption capacity (mg of H2S/

g of activated carbon)
A 472 1.41
A_100-NaOH 475 10.02
A_100-KOH 1530 40.46
A_100-KI 1174 4.45
A_100-Na2CO3 2554 29.5

Figure 3 shows adsorption curve of H2S under temperature program by using the commercial activated
carbon as an adsorbent. The temperature increased from 30 to 550 ºC at a rate of 10 ºC per minute. At
temperature in the range of 30 - 150 ºC, the concentration of H2S came out at the outlet gas was increased
from 3000 to about 6610 ppmv, this result indicated that adsorbed H2S on activated carbon was desorbed.
At temperature between 150 - 550 ºC, the outlet concentration of H2S was decreased from 6610 to about
20 Russamee Sitthikhankaew et al. / Energy Procedia 9 (2011) 15 – 24

187 ppmv. This phenomenon showed that H2S was adsorbed on activated carbon. The adsorption capacity
of the A was 1.41 mg of H2S per gram of activated carbon.
For the A_100-NaOH, the concentration of H2S came out at the outlet gas was decreased from 3000 to
about 40 ppmv in the heating step (Figure 4). At 550 ºC, the outlet concentration of H2S was about 10
ppmv for 170 minute. The breakthrough time and total adsorption time were 252 and 475 minutes,
respectively. The adsorption capacity of activated carbon was increased more than seven times after
impregnation with 100% weight of NaOH.

Fig. 3. Adsorption curve of H2S at high temperature by commercial activated carbon.

Fig. 4. Adsorption curve of H2S at high temperature by NaOH impregnated activated carbon.

For the A_100-KOH, A_100-Na2CO3, and A_100-KI, the adsorbed H2S on activated carbon was
desorbed at temperature in the range of 30 - 140 ºC. After that, the outlet concentration of H2S was
decreased that indicated that H2S was adsorbed on activated carbon (Figure 5-7). Chemical adsorption of
H2S on activated carbon was mainly occurred but physical adsorption was partly.
The breakthrough time of A_100-KOH, A_100-Na2CO3, and A_100-KI were 617, 182, and 71
minutes, respectively. The adsorption capacity of A_100-KOH and A_100-Na2CO3 was greater than the
 Russamee Sitthikhankaew et al. / Energy Procedia 9 (2011) 15 – 24 21

A. The adsorption capacity increased more than 29 and 21 times after impregnation with 100% weight of
KOH and Na2CO3, respectively (Table 3). The adsorption capacity of activated carbon was increased
more than three times after impregnation with 100% weight of KI. The results clearly indicated that the
breakthrough was delayed by alkaline impregnation.

Fig. 5. Adsorption curves of H2S at high temperature by KOH impregnated activated carbon.

Fig. 6. Adsorption curves of H2S at high temperature by KI impregnated activated carbon.

22 Russamee Sitthikhankaew et al. / Energy Procedia 9 (2011) 15 – 24

Fig. 7. Adsorption curves of H2S at high temperature by Na2CO3 impregnated activated carbon.

The reactions of H2S on alkaline impregnated activated carbon at high temperature could be chemical
adsorption as the main reaction and physical adsorption. For chemical adsorption, H2S reacts with alkali
at carbon surface. The reactions of H2S and four kinds of alkaline are as follows:

1. KOH or NaOH

H2S (g) + AOH(q)-C → AHS (q) + H2O (2)

H2S (g) + 2AOH(q)-C → A2S (q) + 2H2O (3)

A was indicated as K or Na
AOH(q)-C is the KOH or NaOH impregnated on the activated carbon covered by the water film which
was generated by the produced water from equation 2 and 3.

2. Na2CO3

H2S (g) + Na2CO3(q)-C → NaHS (q) + NaHCO3 (q) (4)

H2S (g) + Na2CO3(q)-C → Na2S (q) + H2CO3 (liq) (5)

Na2CO3(q)-C is the Na2CO3 impregnated on the activated carbon.

3. KI

H2S (g) + KI(q)-C → KHS (q) + HI (g) (6)

H2S (g) + 2KI(q)-C → K2S (q) + 2HI (g) (7)
 Russamee Sitthikhankaew et al. / Energy Procedia 9 (2011) 15 – 24 23

KI(q)-C is the KI impregnated on the activated carbon. The chemical adsorption was the endothermic
reaction. Therefore, the chemical adsorption effected to increase adsorption capacity with increasing
temperature in the reactor into high temperature.
Furthermore, the outlet concentration of H2S after treated by the KOH and Na2CO3 impregnated
activated carbons at temperature as 550 ºC was less than 30 ppmv, which is safe for utilizing in
mechanical and power engine. The outlet concentration of H2S after treated by the KI impregnated
activated carbons at temperature as 550 ºC was less than 90 ppmv. Therefore, the KOH and Na2CO3
impregnated activated carbons are applicable for hot fuel gas purification.

3.3. Sulfur analysis

The contents of sulfur in the commercial and alkaline impregnated activated carbons before and after
H2S adsorption test were measured with a sulfur analyzer. The results were shown in Table 4. The
contents of sulfur in fresh activated carbons were in the range of 0.30 - 0.60 %. After H2S adsorption test,
the content of sulfur in commercial activated carbon was increased to 3.80 %. The contents of sulfur in
exhausted KOH and Na2CO3 impregnated activated carbons are significantly higher than that of the
exhaust commercial activated carbon (2-6 times higher). The content of sulfur could be originate from
H2S that was adsorbed on surface of activated carbon and sulfur compound that was produced from
chemical adsorption such as KHS, K2S, NaHS, and Na2S. This result was consistent with the adsorption
capacities of KOH and Na2CO3 impregnated activated carbons that are high performance when using for
H2S removal at high temperature. It is indicated that chemical reaction between H2S and KOH or Na2CO3
was mainly occurred at high temperature.

Table 4. Content of sulfur in fresh and exhausted activated carbons.

Sample Sulfur in fresh Sulfur in exhausted

sample (%) sample (%)
A 0.60 3.80
A_100-NaOH 0.32 6.04
A_100-KOH 0.39 9.31
A_100-KI 0.30 20.97
A_100-Na2CO3 0.34 2.15

4. Conclusion

The commercial and alkaline impregnated activated carbons were tested by the temperature program
adsorption of H2S at 30 ºC and 550 ºC. At 30 ºC, the adsorption capacities of alkaline impregnated
activated carbons were slightly less than the commercial one. Alkaline solid might occupy a portion of the
carbon pore volume and surface area, so physical adsorption of H2S was limited. The reactions of H2S on
the commercial and alkaline impregnated activated carbon at room temperature could be proposed as
physical adsorption.
At high temperature of adsorption, alkaline activated carbons adsorbed H2S significantly higher than
commercial activated carbon (in the range of 3-29 times higher depend on modification method). In
detail, 1 gram of activated carbon that was modified by KOH, Na2CO3, NaOH, and KI impregnation can
24 Russamee Sitthikhankaew et al. / Energy Procedia 9 (2011) 15 – 24

adsorb H2S as 40.46, 29.50, 10.02, and 4.45 mg, respectively. The results clearly indicated that the
breakthrough was delayed by alkaline impregnation.
The reactions of H2S on the alkaline impregnated activated carbon at high temperature could be
proposed as chemical adsorption that was the main reaction and physical adsorption that partly occurred.
The chemical adsorption effected to increase adsorption capacity with increasing temperature in the
reactor into high temperature. Furthermore, the concentration of H2S came out at the outlet gas after
treated by the KOH and Na2CO3 impregnated activated carbons was less than 30 ppmv, which was safe
for utilizing in mechanical and power engine. Therefore, the KOH and Na2CO3 impregnated activated
carbons were applied for hot fuel gas purification.

Acknowledgements

This research was supported by The Joint Graduate School of Energy and Environment, CHE
Center for Energy Technology and Environment, PTT Research and Technology Institute, and PTT
Public Company Limited. Financial support from The Thailand Research Fund through The Royal
Golden Jubilee Ph.D. Program (Grant No. PHD/0162/2550) and National Science and Technology
Development Agency (Grant No. P-10-11166) are acknowledged.

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