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a r t i c l e i n f o
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Article history:
Received 13 October 2009
Received in revised form
5 April 2010
Accepted 7 April 2010
Available online 10 May 2010
Biogas from anaerobic digestion of biological wastes is a renewable energy resource. It has been used to
provide heat, shaft power and electricity. Typical biogas contains 50e65% methane (CH4), 30e45%
carbon dioxide (CO2), moisture and traces of hydrogen sulphide (H2S). Presence of CO2 and H2S in biogas
affects engine performance adversely. Reducing CO2 and H2S content will signicantly improve quality of
biogas. In this work, a method for biogas scrubbing and CH4 enrichment is presented. Chemical
absorption of CO2 and H2S by aqueous solutions in a packed column was experimentally investigated.
The aqueous solutions employed were sodium hydroxide (NaOH), calcium hydroxide (Ca(OH)2) and
mono-ethanolamine (MEA). Liquid solvents were circulated through the column, contacting the biogas in
countercurrent ow. Absorption characteristics were examined. Test results revealed that the aqueous
solutions used were effective in reacting with CO2 in biogas (over 90% removal efciency), creating CH4
enriched fuel. H2S was removed to below the detection limit. Absorption capability was transient in
nature. Saturation was reached in about 50 min for Ca(OH)2, and 100 min for NaOH and MEA, respectively. With regular replacement or regeneration of used solutions, upgraded biogas can be maintained.
This technique proved to be promising in upgrading biogas quality.
2010 Elsevier Ltd. All rights reserved.
Keywords:
Biogas
Chemical absorption
Fuel upgrade
Gas scrubbing
Renewable energy
1. Introduction
Renewable energy deriving from biomass sources has great
potential for growth to meet our future energy demands. Biogas is
a very important source of renewable methane. It is produced from
anaerobic biodegradation of biomass in the absence of oxygen and
the presence of anaerobic microorganisms. Anaerobic digestion is
the consequence of a series of metabolic interactions among
various groups of microorganisms. The process is carried out in
digesters that are maintained at temperatures ranging from 30 to
65 C. Biogas is rich in CH4 with typical range between 40 and 70%,
and its lower heating value is between 15 and 30 MJ/Nm3. In
Thailand, biogas resources are from industrial wastewater and live
stock manure, which have potential of 7800 and 13,000 TJ/year,
respectively [1]. Conversion of chemical energy in biogas to heat or
electricity is possible via combustion. Apart from direct combustion
in burners or boiler units, gas engines are usually employed as
prime movers in utilization of biogas [2e4]. There is even greater
potential for biogas if it can be made viable as a transport vehicle
* Corresponding author.
E-mail address: n.tippayawong@yahoo.com (N. Tippayawong).
0360-5442/$ e see front matter 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.energy.2010.04.014
fuel. Biogas may be made transportable via pipelines, or by compressing in gas cylinders. This is possible only after removing CO2,
H2S and water vapour. In all cases, quality of biogas is crucial in both
its CH4 content and purity. CO2 is present in large quantities in
biogas and is inert in terms of combustion. Its presence therefore
decreases the energetic content of biogas. The CH4 content in
biogas will be increased if CO2 is removed. The most common
contaminant in biogas is H2S and other S-containing compounds
that come from S-bearing organic matters [5]. Depending on the
composition of the organic matter, the H2S content in biogas can
vary from 100 to 10,000 ppm. This contaminant is highly undesirable in combustion systems due to its conversion to highly corrosive and environmentally hazardous compounds. Its removal is
essential before any eventual utilization of biogas.
Reducing CO2 and H2S content will signicantly improve the
quality of biogas. Various technologies have been developed for
separation of CO2 from gas streams in the past. These include
absorption by chemical solvents, physical absorption, cryogenic
separation, membrane separation and CO2 xation by biological or
chemical methods [5e7]. There are also a number of techniques to
remove H2S. Examples are chemical absorption in aqueous solutions, physical absorption on solid adsorbents and conversion to
base S or low solubility metal sulphides [8,9]. These techniques are
4532
Nomenclature
A
A0
C
Ci
k
t
(4)
A 1
C
Ci
(5)
dA
kA 1 A
dt
(6)
A 1 A0
ln
ks t
A0 1 A
After rearrangement, we get:
1
C
s
ln
k
Ci C
e
CO2 CO2e
3 H2O / 2HCO3
(2)
e
CO2 R-NH2 H2O / R-NH
3 HCO3
(3)
(8)
2. Theory
(7)
3. Experimental
The semi-batch experimental apparatus is shown in Fig. 1, with
(1) gas inlet measurement point, (2) ow meter, (3) ow distributor, (4) packed column, (5) packing material, (6) outlet measurement point, (7) are, (8) solvent container, (9) drainage, (10) pH
meter, (11) pump, (12) ow meter, (13) pressure gauge, (14)
injector. The apparatus consists of a Pyrex glass cylinder of 70 mm
in diameter and 1.0 m high. The absorption column was randomly
packed with a packing material (commonly known by the trade
name plastic bioball, having an overall spherical shape, with
uniform and structured spikes around the body and high surface
area to volume ratio of 1895 m2/m3, as shown in Fig. 2) to a height
of 700 mm, to facilitate gas/liquid interaction. These bioballs are
normally used in anaerobic lter reactors for biogas production.
The packed bed was found to have a void fraction of 0.916. NaOH,
CaO and MEA were employed in the present investigation. They
were obtained from Fisher Scientic. Biogas was obtained from
a local chicken farm. At the beginning of a typical run, 10 l of the
liquid solvent was placed in the vessel. The biogas purication
process took place in the packed column reactor where the gas was
continuously fed from the bottom of the column, and the liquid
solvent was sprayed from the top, creating counter current ow.
The solvent was circulated between the column and a liquid vessel
by means of a peristaltic pump. The liquid ow rate was controlled
to maintain a smooth liquid lm. Gas ow rates were regulated
using a gas ow meter. The pressure was slightly above atmospheric level. The CO2 and H2S concentrations in the biogas
entering and exiting the column were constantly monitored by an
IR gas analyzer. The pH of the liquid solvent was measured using
a pH meter. All measurements were repeated at least three times.
Table 1
Compositions of biogas immediately after the treatment with different solvents.
CH4
CO2
H2S
(%)
(%)
(ppm)
Inlet
NaOH
Ca(OH)2
MEA
53.1
46.8
2150
95.5
3.2
0
95.0
4.0
0
98.0
1.3
0
proceeded with time, the CO2 and H2S were continuously accumulated in the solvents. Due to its much higher concentration in
comparison with H2S, the CO2 started to evolve in the outlet stream
after a certain time. The end of each run was determined when the
liquid solvent became completely saturated or neutralized (pH
7e8). The corresponding breakthrough curves obtained are presented in Fig. 3, showing variation of the dimensionless CO2
concentration and changes in pH level with time. It was found that
NaOH, Ca(OH)2 and MEA showed similar patterns. NaOH and MEA
were found to become saturated in about 100 min. However, rate of
Ca(OH)2 saturation appeared to be much faster than for the other
two. This was observed after around 50 min, compared with about
100 min observed for NaOH and MEA. It should be noted that MEA
possessed lower basicity than NaOH and Ca(OH)2 but its rate of
change in pH level was also slower. The relatively fast saturation
time realised in this investigation may be attributed to the fact that
biogas used here contained very high concentration (47%) of CO2. It
should be noted that each data presented was an average value.
1.0
0.8
0.6
C/C0
4533
0.4
NaOH
Ca(OH)2
MEA
0.2
0.0
20
40
60
80
100
120
Time (min)
13.0
12.0
NaOH
Ca(OH)2
11.0
MEA
pH
10.0
9.0
8.0
7.0
6.0
20
40
60
80
100
120
Time (min)
Fig. 3. Variations of normalized outlet CO2 concentration and pH of the solutions with
time; solvent concentration of 0.1 M, gas to solvent ow ratio of 1.0, 47% inlet CO2
concentration and temperature of 30 C.
4534
Time (min)
120
100
NaOH
Ca(OH)2
80
MEA
NaOH
Ca(OH)2
60
MEA
40
20
0
-2.0
-1.0
0.0
1.0
2.0
3.0
ln[C/(Ci-C)]
Fig. 4. Kinetics of CO2 absorption by different solvents: solvent concentration of 0.1 M,
gas to solvent ow ratio of 1.0, 47% inlet CO2 concentration and temperature of 30 C.
Table 3
Comparison of absorption performance reported in literature.
References
Gas composition
Aqueous solvents
Capacity
(mol/mol)
This work
[14]
[15]
0.10 M NaOH
0.10 M Ca(OH)2
0.10 M MEA
0.10e0.25 M NaOH
10% wt MEA
10% wt MDEA
10% wt MEA
10% wt MDEA
10% wt MEA
10% wt MDEA
7e14% wt NH3
3 M MEA
0.20
0.32
0.25
0.05e0.12
0.44
0.37
0.51
0.44
0.50
0.46
0.04e0.06
0.25e0.55
Table 2
Kinetic parameters for CO2 absorption by different solvents.
1
solvents
k (min
NaOH
Ca(OH)2
MEA
23.74
13.00
26.71
8% CO2, 92% N2
s (min)
42
29
36
0.962
0.975
0.844
4535
Fig. 6. Comparison of CH4 concentration proles in the treated biogas (i) with and (ii)
without fresh solvent addition.
used may be operated in such a way that purity of greater than 80%
CH4 enriched biogas could be obtained over a period of time. In
terms of practical applications, these chemicals proved to be
potentially suitable absorbents. However, it should be pointed out
that although high concentrations of CH4 were obtained after
a short time (as shown in Table 1), these high concentrations were
found to decrease rapidly. To maintain high absorption rate,
a substantial fraction of original volume of the solution needed to
be replaced or regenerated. Frequent replacement would lead to
a uctuation in concentrations, as observed in Fig. 6. One of the
limitations of biogas upgrading lies in economics of the bulk
separation of CO2. The main disadvantage of using alkaline solvents
was that they are very difcult or impossible to regenerate for
reuse. Even though they are relatively low cost materials, large
amount of chemicals would be required to satisfy purity requirements of CH4 enriched gas. Use of MEA has the advantage of being
able to be regenerated. However, for a small scale biogas production
as considered in this study, initial investment cost for constructing
the set up, as well as energy requirement may be excessive and
outweigh the benet of using high purity biogas. Further work may
thus be required.
5. Conclusions
Removal of CO2 and H2S from biogas by aqueous solutions in
a packed column was investigated. NaOH, Ca(OH)2 and MEA were
employed in the present study and their absorption characteristics
were examined. A simple empirical model was also adopted for CO2
absorption rate prediction. Test results indicated similar absorption
patterns between the chemical solvents used. Chemical absorption
by solvents in a packed column was an effective technique for
removing CO2 and H2S over a short operation time, but their
absorption capability declined rapidly with time. Ca(OH)2 appeared
to become saturated more rapidly than the other solvents. The CO2
loading ranged between 0.18 and 0.22 kg CO2 per kg chemicals