International Conference on Agricultural, Environmental and Biological Sciences (AEBS-2014) April 24-25, 2014 Phuket (Thailand)

Removal of Hydrogen Sulfide from Biogas

using Dry Desulfurization Systems
Antonio-Abdu Sami M. Magomnang , and Prof. Eliseo P. Villanueva, Ph.D.

carbon dioxide-rich, hydrogen sulfide off gas stream. A basic

Abstract—Raw biogas has produced many applications. flow diagram of biogas purification is given in Figure 1.
However, its hydrogen sulfide content must be eliminated to avoid
possible damages to equipment and hazards to users and the
environment. Among the various set-ups available for removal of
hydrogen sulfide from biogas is a fixed-bed of steel wool.
This study investigated the effectiveness of iron steel wool in
eliminating hydrogen sulfide in a biogas, its efficacy and the amount
of H2S removed. A three-stage removal system was installed for the
removal of Hydrogen Sulfide. The raw gas was produced by a
continuous flow type Biogas Digester.
Testing the steel wool as an adsorbent indicates that it has
potential as an effective and economical adsorbent for H2S removal.
Polyvinyl-chloride (PVC) columns were constructed and a biogas
mixture passed through the columns containing the steel wool. The
most significant results indicate the intake H2S concentrations
averaging 170 ppm – 150 ppm and 0 ppm – 0.1 ppm output, as Fig. 1 Basic flow diagram of biogas purification
measured by a portable hydrogen sulfide gas analyzer.
Removal efficiencies over 95% were observed for a majority of the The raw biogas basically is split into two gas streams during
run time. Elimination capacities recorded were between 3-4 Standard biogas purification: the methane-rich bio-methane stream and
liters per minute (SLPM). Temperature in the system varied from 26-
27°C and the relative humidity in the spent column was above 90%. the carbon-dioxide-rich, Hydrogen sulfide off gas stream. As
The removal of Hydrogen Sulfide in a biogas demonstrated good no separation technology is perfect, this waste-gas stream still
performance throughout the testing phase. Based on the field contains a certain amount of methane depending on the
measurements, the system required only a few days for startup. The methane recovery of the applied technology. Whether this gas
desulfurization systems, under normal operating conditions, had stream is legally permitted to be vented to the atmosphere or
reduced 170 ppm of H2S to 0 ppm with accuracy of ± 0.1ppm. has to be further treated is depending on the methane content
on the methane slip of the purification plant (amount of
Keywords—Biogas, Digestion, Hydrogen Sulfide (H2S), Steel
methane in the off gas related to the amount of methane in the
Wool
raw biogas) and on the emission regulations at the plant site.
I. INTRODUCTION Systems damage begins exhibiting itself when hydrogen
sulfide in biogas exceed 100 ppm [1]. Oil and gas industries

B IOGAS purification technologies for the production of

biomethane in various applications is technically and
economically feasible and are already commercially available.
are faced with the severe corrosion effects of hydrogen sulfide
in piping especially in wells operating in acidic conditions. To
decrease costs in the transportation of oil and gas to refineries
However, there is still a need to optimize and further develop and utilities, removal of hydrogen sulfide and/or carbon
these technologies in every biogas purification situation in the dioxide is essential to create a low corrosion environment.
production of bio-methane stream of sufficient quality. A mechanistic model which would predict H2S corrosion of
Biogas purification is a gas separation process that splits mild steel over time at pH 5.0–5.5 was reported [2]. The study
raw biogas into a methane-rich bio-methane gas stream and a observed that the corrosion rate increased with an increase in
H2S gas concentration but the magnitude of the corrosion rate
is lower after 24 hours compared to 1 hour because of the
build-up of a protective iron sulfide film. It also studied the
Antonio-Abdu Sami M. Magomnang is with the Mechanical Engineering
Department, Mindanao State University – Iligan Institute of Technology, effect of H2S gas concentration at room temperature and had
Iligan City, Lanao del Norte, 9200, Philippines (e- reported an increase in corrosion rate with increasing gas
mail:[email protected]). concentration.
Prof. Eliseo P. Villanueva, Ph.D is also with the Mechanical Engineering
Department, Mindanao State University – Iligan Institute of Technology, Efficient reduction of sulfide in biogas depends on the use
Iligan City, Lanao del Norte, 9200, Philippines (e- of appropriate technology. Choosing the appropriate
mail:[email protected]).

http://dx.doi.org/10.15242/IICBE.C414016 65
 International Conference on Agricultural, Environmental and Biological Sciences (AEBS-2014) April 24-25, 2014 Phuket (Thailand)

technology for purification depends on factors such as quality certain properties to be an effective adsorbent. Materials that
and quantity of the raw biogas to be upgraded, the desired bio- have high surface area per unit weight ratio are effective
methane quality and the final utilization of the gas, the adsorbents. Some materials have extremely high surface area
operation of the anaerobic digestion plant and the types and per unit weight ratios due to the surface area of the internal
continuity of the used substrates as well as the local pores of the solid. Adsorbate particle diameter can range from
circumstances at the plant site [1]. about 1.3cm to less than 200μm. If the pore diameter is larger
Having better methods for reducing biogas corrosion is than the molecular diameter of the adsorbate, the pores will be
likely to become more important in the coming years, readily available for adsorption.
especially in systems that use metals such as copper, zinc,
C. Hydrogen Sulfide Specific Removal Process
nickel, tin, platinum, and their alloys since the supply of ore
for these metals are limited. The goal of this study is to present Hydrogen specific removal processes can be grouped
a low cost effective technology for removing hydrogen sulfide together as sulfur scavenging processes. Sulfur scavenging
from biogas. process systems in general operate as a batch process either as
wet or dry systems. Wet systems are generally not used in
II. THEORY biogas systems due to their smaller size. The most common
dry systems use either iron or zinc oxide:
A. Standards for Hydrogen Sulfide Removal in a Biogas
2Fe2O3 + 6 H 2 S → 2Fe2S3 + 6 H 2O (1)
The biogas systems are an alternative energy source with
limited waste and many realistic applications. However, 2Fe2S3 + 3O2 → 2Fe2O3 + 6 S (2)
environmental pollution is associated with the formation of Equation (1) describes the reaction of iron oxide with
sulfur dioxide in the burning of hydrogen sulfide in biogas. hydrogen sulfide to form iron sulfide and (2) of zinc oxide to
Therefore, to protect devices and adhere to safety standards for form zinc sulfide. The latter however, is treated as non-
biogas technology systems operations, removal of hydrogen regenerable system.
sulfide is critical. The standards of H2S component in biogas Hence, iron oxide in the form of iron sponge is the most
depend on the intended use, described in Table 1. [1], [3] – typical form of a dry sulfur scavenging system as iron oxide
[6]. can be regenerated several times before the material loses its
TABLE I
activity due to the build up of elemental sulfur.
H2S CONCENTRATION STANDARDS
ZnO + H 2 S → ZnS + H 2O (3)
Application H2S Concentration Standards
Heating (Boiler) 1,000 ppm, P=0.8-2.5 kPa The dry iron oxide sulfur scavenging system typically
Internal Combustion Engines 100 ppm, P = 0.8 – 2.5 kPa consists of a series of vessels loaded with iron ores containiang
Turbines 70,000 ppm, P= 520 kPa
Phosphoric Acid Fuel Cells 20 ppm high levels of iron oxide or iron oxide on a supported media
Molten Carbonate Fuel Cells 10 ppm called the iron sponge.
Solid Oxide Fuel Cells 1 ppm
Stirring Engines 1,000 ppm, P = 1-14 kPa D.Removal of Hydrogen Sulfide
Upgrade to the natural gas 4 ppm, P > 3000 kPa Hydrogen sulfide is corrosive and toxic. Burning biogas
with hydrogen sulfide produces the environmentally hazardous
B. Adsorption
sulfur dioxide. It has been observed that corrosiveness of
Adsorption is a process to remove undesirable compounds hydrogen sulfide increases with increasing concentration,
(adsorbate) in gas or liquid streams by passing through a temperature and pressure, and is enhances by the presence of
media bed composed of a solid material (adsorbent). The water [8]. This study used dry oxidation methods to remove
adsorbate penetrates into the pores of the adsorbent but not hydrogen sulfide from gas streams.
into the lattice itself [7]. In dry oxidation processes, the sulfur is removed from
Adsorption mechanism can either be physical or chemical. hydrogen sulfide with the use of iron oxide. Iron oxide used is
In physical adsorption, gas molecules attract and adhere to the in the form of iron fillings, iron pellets, iron sponge or steel
surface of the adsorbent by intermolecular forces. An wool [9], [10]. The sulfur removal capacities of iron oxide
adsorption process is always exothermic. Heat released is range from 0.20 – 0.716 kg of hydrogen sulfide for every one
usually between 2 and 20 kJ/g-mol and depends on the kg of iron oxide [1], [12]. Also given as 3.7 kg of sulfur per
magnitude of the attractive force. It is usually reversible bushel (0.0352m3) of iron oxide [1].
allowing regeneration and reuse of spent adsorbent. Reversal
process involves either lowering the pressure of the adsorbate Fe2 O 3(s) + 3H 2 S ( g ) → Fe2S3( s ) + 3H 2O(l ) (4)
in the gas stream or raising the temperature.
Adsorption system design should consider the properties of Apart from the reaction of iron oxide as shown above,
both the adsorbent and the adsorbate and the composition of several other reactions do occur during scrubbing of biogas
the gas stream. The adsorption capacity is directly proportional with iron oxide, including [13]:
to the surface area of the adsorbent. A material must have

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 International Conference on Agricultural, Environmental and Biological Sciences (AEBS-2014) April 24-25, 2014 Phuket (Thailand)

Fe3O 4(s) + 4 H 2 S( g ) → 3FeS( s ) + 4 H 2O(l ) + S (5)

Fe3O 4(s) + 6 H 2 S( g ) → 3FeS2 ( s ) + 4 H 2O(l ) + 2 H 2 ( g ) (6)
FeS(s) + S ( g ) → FeS2 ( s ) (7)

E. Implemented Design
As shown in Fig. 1, the biogas from the gas holder/tank
passes through the inlet section on which mass flow,
temperature, humidity and initial concentration of the
hydrogen sulfide from the biogas is being measured. It passes
through the 1st stage purifying chamber and passed through
another until it reaches the last chamber, upon exiting the
respective chambers the concentration of the hydrogen sulfide
is measured until it reaches the 3rd stage chamber. The
completed test rig for removal hydrogen sulfide is shown
Fig. 2 Graph on the H2S Inter-stage Concentration versus volume
below.
flow

IV. CONCLUSION
Based on the results of the experiment as shown on Fig.
1&2, the following conclusions are derived.
1. The steel wool as an adsorbent for removing hydrogen
sulfide from the biogas is effective, During the first stage
outlet, recorded H2S concentration of around zero (0)
ppm is achieved.
2. For a given bed to diameter ratio of 6-7, flow rate of
untreated biogas of around 3-4 liters per minute and mass
of steel wool as an absorbent of about 1.9 kg, one (1)
chamber or stage for removal of hydrogen sulfide in the
system suffice from inlet H2S concentration of higher
than 150 ppm to an outlet H2S concentration of zero (0)
ppm with ± 0.1 ppm accuracy.
Fig. 1 Biogas Desulphurization system test rig 3. The preliminary experimental results show that the
reduction of H2S to almost zero parts per million is
III. RESULTS AND DISCUSSIONS
maintained even after 17 kg of gas passed through the
The desulfurization system using steel wool as an adsorbent system.
was designed to remove H2S from the digester gas using three
stages removal systems and produce a purified gas with H2S V. RECOMMENDATIONS
concentration of less than 1 ppm. The desulfurization system This study showed that various parameters are needed in
performance is illustrated in Fig. 2. The hand-held gas order to understand more the removal of hydrogen sulfide
monitoring kit could measure H2S levels above 100 ppm. from biogas. The following are recommended for further
As shown in Fig. 2, the H2S desulfurization system removed studies:
H2S effectively. The results confirmed that the H2S levels in 1. More experiments shall be conducted in the
the outlet biogas were maintained below 1 ppm regardless of determination of the deterioration rate of the steel wool
the high H2S concentrations in the inlet biogas. as an adsorbent.
The graph confirms that the removal of hydrogen sulfide 2. More experiments should be conducted in determining
was very effective and efficient. the performance of the regenerated steel wool.
3. Investigation on the surface area to weight ratio and
particle size of the adsorbent using Scanning Electron
Microscope (SEM) and X-Ray Diffraction (XRD)
analysis and also with regard to the adsorption of steel
wool.

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 International Conference on Agricultural, Environmental and Biological Sciences (AEBS-2014) April 24-25, 2014 Phuket (Thailand)

ACKNOWLEDGMENT
The authors would like to thank Engineering Research and
Development for Technology (ERDT) under the Science
Education Institute (SEI) of Department of Science and
Technology in the Philippines and the College of Engineering,
MSU-IIT for their financial support to this project.

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Antonio-Abdu Sami M. Magomnang was born on April 10, 1989 in

Cagayan de Oro City Philippines, an Engineering Research and Development
for Technology (ERDT) grantee for his Master of Science in Mechanical
Engineering in Mindanao State University – Iligan Institute of Technology,
Iligan City, Philippines, in April 2014. He completed his Bachelor of Science
in Mechanical Engineering in Mindanao University of Science and
Technology, Cagayan de Oro City, Philippines in 2011. This author became a
Member of Philippine Society of Mechanical Engineers, PSME in 2011.

Prof. Eliseo P. Villanueva was born on July 8, 1953 in Davao City

Philippines, a Doctor of Philosophy in Mechanical Engineering Graduate in
University of New South Wales, Sydney, Australia in year 1999. He
completed his Master of Science in Nuclear Engineering in the University of
the Philippines, Diliman, Quezon City, Philippines in year 1984. And also
completed his Bachelor of Science in Mechanical Engineering in Mindanao
State University – Marawi Campus, Marawi City, Philippines in year 1976.
He holds the rank of Professor VI at the Department of Mechanical
Engineering in the Mindanao State University – Iligan Institute of
Technology, Iligan City, Philippines. He practice as Professional Mechanical
Engineer. This author became a lifetime Member of the Philippine Society of
Mechanical Engineers, PSME in 1985.

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