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Energy xxx (2010) 1e5

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Energy
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Biogas quality upgrade by simultaneous removal of CO2 and H2S in a packed column reactor
N. Tippayawong*, P. Thanompongchart
Department of Mechanical Engineering, Faculty of Engineering, Chiang Mai University, Chiang Mai 50200, Thailand

a r t i c l e i n f o
Article history: Received 13 October 2009 Received in revised form 5 April 2010 Accepted 7 April 2010 Available online xxx Keywords: Biogas Chemical absorption Fuel upgrade Gas scrubbing Renewable energy

a b s t r a c t
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.

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

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Nomenclature A A0 C Ci k t fraction of specic gas absorbed or removed from the gas mixture after time t (e) fraction of specic gas absorbed or removed from the gas mixture after t s (e) outlet CO2 concentration (% v/v) inlet CO2 concentration (% v/v) absorption constant (e) absorption time (s) characteristic absorption time (s)

CO2 RR0 -NH / RR0 -NCOOe H

(4)

In the aqueous solution, the dissolved CO2 reacts with alkaline or amine following a complex reaction mechanism. This depended strongly on the pH, CO2 concentration and other factors. In this work, the temperature, pressure and ionic strength of solutions were assumed to be constant. The packed column reactor was considered as a continuously stirred tank reactor and the rate of CO2 absorption can then be obtained through a material balance for a complete mixing reactor. Correlation may be developed for empirical modeling of absorption process. The fraction of CO2 in the gas mixture that is absorbed or removed by the solution in the packed column at time t was denoted as;

of signicant industrial importance, generally applied during natural gas sweetening as well as in the removal of CO2 from ue gases of power plants. Apart from the use of gas permeation membranes [10], applications of such technologies to biogas have been quite rare. To the authors knowledge, there were relatively few reports on biogas purication and upgrading, especially in small-scale applications. The majority of previous studies were carried out on water scrubbing systems [11,12], which is the simplest and cheapest method involving the use of pressurised water as an absorbent. The process performance is dependent on factors such as the dimensions of the scrubbing tower, gas pressure, composition of raw biogas, water ow rates and purity of water used. It is possible to produce high quality CH4 enriched gas from biogas by chemical absorption where a packed bed column and bubble column are normally used to provide liquid/gas contact [13]. However, there remain several drawbacks of using liquid solutions for CO2 and H2S removal. These include high energy requirement for regeneration, stability and selectivity of chemicals used, environmental impact from waste liquids, requirement for large equipment sizing and high equipment corrosion rate. Even though this conventional method is complex and expensive, it may be adopted and modied for employment in small-scale biogas production. There is a paucity of literature available on small scale sizing of biogas upgrading systems. This work is among the rst attempt to investigate the technical feasibility of this concept and its application to a small farm. The objective of this work was therefore to determine technical feasibility of a chemical absorption system designed for small-scale biogas production. In this work, absorption by chemical solvents was used to capture CO2 and H2S in biogas. A laboratory scale, packed column reactor was used to investigate absorption performance by NaOH, Ca(OH)2 and MEA solutions at different gas-to-liquid ow rates. The main objective was to evaluate chemical absorption technology for biogas purication, and to generate data for scale-up calculation and techno-economic analysis of the process. 2. Theory Chemical absorption is an efcient technology for the removal of CO2 and H2S from gas mixture. In an absorption column, the pollutant is transferred from the gas to the gas/liquid interface, and then to the bulk of the liquid phase, where reactions take place. Alkaline and alkanolamines are among the popular reagents for practical applications. In the case of CO2 absorption, the following reactions take place [14]:
e CO2 2OHe / CO2 3 H2O e e CO2 CO2 3 H2O / 2HCO3 e CO2 R-NH2 H2O / R-NH 3 HCO3

A 1

C Ci

(5)

where Ci and C are, respectively, the inlet CO2 concentration and CO2 concentration in the gas exiting the column after time t. The removal rate is a transient effect for this particular setup. Rate of declining CO2 absorption was assumed to be proportional to the CO2 fraction that was absorbed in the packed column, and the CO2 fraction that passed through. It can then be expressed as [15];

dA kA 1 A dt
Integration of the above equation yields:

(6)

  A 1 A0 ln ks t A0 1 A
After rearrangement, we get:

(7)

  1 C s ln k Ci C

(8)

where k is an absorption constant and s is the characteristic absorption time when 50% absorption of CO2 occurs. This implies that the solutions in the packed column should be completely saturated after elapsed time of 2s.

(1) (2) (3)

Fig. 1. Experimental apparatus.

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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. 4. Results and discussion Aqueous solutions of NaOH, Ca(OH)2, and MEA were used as chemical solvents to demonstrate the experimental apparatus function and ability to absorb CO2 and H2S. Table 1 shows composition of biogas downstream of the experimental setup after about three minutes of operation. The packed column reactor was observed to simultaneously remove high proportion of CO2 and H2S (over 90% removal efciency), resulting in CH4 enriched biogas. However, this was a time dependent process. These gaseous concentrations were found to decrease with time. This effect will be discussed later in the section. Initially, the liquid solvents reacted rapidly with, and almost completely absorbed CO2 and H2S. Their concentrations at the outlet stream were practically very small compared to their original values. As the absorption process

Table 1 Compositions of biogas immediately after the treatment with different solvents. Inlet CH4 CO2 H2S (%) (%) (ppm) 53.1 46.8 2150 NaOH 95.5 3.2 0 Ca(OH)2 95.0 4.0 0 MEA 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 0.4 0.2 0.0 NaOH Ca(OH)2 MEA 0 20 40 60 Time (min) 80 100 120

13.0 12.0 11.0 10.0 pH 9.0 8.0 7.0 6.0 0 20 40 60 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.

NaOH Ca(OH)2 MEA

80

100

120

Fig. 2. Plastic bioball as packing material.

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120 100 80 60 40 20 0 -2.0

Fig. 5. Total CO2 absorption and loading by different chemicals used.

NaOH Ca(OH)2 MEA NaOH Ca(OH)2 MEA

Time (min)

-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.

Their coefcient of variations, dened as a ratio between standard deviation and mean value were found to be within about 10%. Plots of absorption time against dimensionless biogas concentration for CO2 absorption by NaOH, Ca(OH)2 and MEA are shown in Fig. 4. These curves may be approximated by straight lines, as shown by Eq. (6). These linear relationships were obtained within a different range of operation times for different solutions used. The ranges were 100, 50, and 110 min for NaOH, Ca(OH)2 and MEA, respectively. Table 2 lists model parameters for these aqueous solutions, as well as correlation coefcient R2 of each linear approximation. For NaOH and Ca(OH)2, R2 values of greater than 0.96 were obtained, showing good linear relationships. However, an R2 value of only 0.84 was obtained for MEA. It appeared that the MEA curve was not exactly linear. A single linear relationship may not be sufcient to describe the behaviour of MEA. This observation was in line with the previous reported work [15] on absorption with primary and tertiary amines, where two line sections were proposed. The reasons for the observed characteristics of MEA as well as for the difference from NaOH and Ca(OH)2 are not yet known. From the reaction kinetic parameters of NaOH and linearly approximated MEA, they were found to be similar. The saturation time of the solutions in the packed column was predicted to be 2s. While saturation time for Ca(OH)2 observed from the experiment was closely predicted by the theoretical model, signicant theoretical underestimations of saturation time were observed for NaOH and MEA. With respect to absorption capacity of the solvents, Fig. 5 depicts the total amount of CO2 absorbed by these solutions in kg CO2 per kg chemicals used. Error bars show standard deviations of each case. It was observed that the total amounts of CO2 absorbed were in the range between 0.18 and 0.22 kg/kg, with highest loadings occurring for NaOH solution. The better loading for NaOH over MEA did not imply that NaOH was a better absorbent for CO2 removal. Other properties such as cost, ability to regenerate, chemical stability, etc. must be taken into account. For a packed bed

column reactor technology, comparison of CO2 absorption capacity with data from various references are summarised in Table 3. It can be seen that most studies were undertaken at relatively low CO2 concentrations of about 15% or less, compared to that found in typical biogas (>40%). Various chemicals used include NaOH, NH3, MEA and MDEA (methyl-diethanolamine). Results obtained from this work appeared to be in similar range to those in the literature. With respect to MEA, our results were observed to be lower than those from Lin and Shyu [15] and Aroonwilas et al. [17] results. This may be attributable to the fact that they used higher MEA concentrations, 0.1 M in our case compared to 1.8 M and 3 M for Lin and Shyu [15] and Aroomwilas et al. [17] cases, respectively. Published data for NaOH and Ca(OH)2 was rather scarce. However, with regards to NaOH, we obtained higher absorption than that reported by Georgiou et al. [14]. Attempts were made to generate high quality CH4 enriched gas for a prolonged period. This was conducted by replacing used NaOH and Ca(OH)2 solutions with fresh ones at about 20% of total volume to maintain basicity level above pH 11.9. However, preliminary testing revealed that the addition had to be done in the rst 15 min. And after 30 min, addition of fresh solutions was not able to produce greater than 80% purity of CH4 enriched gas. Therefore, sole spent solutions had to be replaced in a 30-min interval. For MEA, a similar procedure was also performed. Replacement of a 20% volume fraction of used MEA solution with clean solution was carried out at regular intervals of 15 min. This was done to mimic partial regeneration of the spent MEA solution. Within the operation time considered, the basicity level of recirculated MEA was found to reduce only slightly from its original value prior to when the rst mixing commenced. Fig. 6 shows CH4 concentration proles obtained, and comparison with the case where the absorbents were employed until saturated. It was clear that all solutions

Table 3 Comparison of absorption performance reported in literature. References This work Gas composition 47% CO2, 53% CH4 Aqueous solvents 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 Capacity (mol/mol) 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

[14] [15] Table 2 Kinetic parameters for CO2 absorption by different solvents. solvents NaOH Ca(OH)2 MEA k (min 23.74 13.00 26.71
1

10% CO2, 90% N2 5% CO2, 95% N2 8% CO2, 92% N2

s (min)
42 29 36

15% CO2, 85% N2 [16] [17] 15% CO2, 85% N2 15% CO2, 85% Air

0.962 0.975 0.844

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used. Chemical absorption by alkali aqueous solutions did not appear to be promising for biogas quality upgrade due to the nonregenerable nature, requirement of large liquid solvents volume and the environmental impact. However, amine solutions may be worth exploring further, due to the regeneration capability. Additional experimental results are required to provide the basis for system selection and design, as well as subsequent up-scaling. The next phase of experimental work will involve setting up a regeneration system for amine absorbent, evaluating its long term performance, and undertaking cost analysis of the system, as well as a possible scale up study and eld test in a biogas farm. Acknowledgements Support from the Commission on Higher Education, Ministry of Education, and the Fund for Energy Conservation Promotion, Energy Policy and Planning Ofce, Ministry of Energy are highly appreciated. The authors wish to thank Drs P. Polchan and M. O. T. Cole for their valuable technical discussions, and staff at the Energy Research and Development Institute, Chiang Mai University for technical and laboratory assistance. References
[1] Prasertsan S, Sajjakulnukit B. Biomass and biogas energy in Thailand: potential, opportunity and barriers. Renewable Energy 2006;31:599e610. [2] Borjesson P, Mattiasson B. Biogas as a resource-efcient vehicle fuel. Trends Biotechnol 2007;26:7e13. [3] Tippayawong N, Promwungkwa A, Rerkkriangkrai P. Long-term operation of a small biogas/diesel dual-fuel engine for on-farm electricity generation. Biosyst Eng 2007;98:26e32. [4] Tippayawong N, Promwungkwa A, Rerkkriangkrai P. Durability of a small agricultural engine on biogas/diesel dual fuel operation. Iran J Sci Technol Trans B Eng 2010;34(B2):167e77. [5] Abatzoglou N, Boivin S. A review of biogas purication processes. Biofuels Bioprod Bioren 2009;3:42e71. [6] Yang H, Xu Z, Fan M, Gupta R, Slimane RB, Bland AE, et al. Progress in carbon dioxide separation and capture: a review. J Environ Sci 2008;20:14e27. [7] Granite EJ, OBrien T. Review of novel methods for carbon dioxide separation from ue and fuel gases. Fuel Process Technol 2005;86:1423e34. [8] Horikawa MS, Rossi F, Gimenes ML, Costa CMM, da Silva MJC. Chemical absorption of H2S for biogas purication. Brazil J Chem Eng 2004;21:415e22. [9] Osorio J, Torres JC. Biogas purication from anaerobic digestion in a wastewater treatment plant for biofuel production. Renewable Energy 2009;34:2164e71. [10] Favre E, Bounaceur R, Roizard D. Biogas, membranes, and carbon dioxide capture. J Membr Sci 2009;328:11e4. [11] Kapdi SS, Vijay VK, Rajesh SK, Prasad R. Biogas scrubbing, compression and storage: perspective and prospectus in Indian context. Renewable Energy 2005;30:1195e202. [12] Rasi S, Lantela J, Veijanen A, Rintala J. Landll gas upgrading with countercurrent water wash. Waste Manage 2008;28:1528e34. [13] Krumdieck S, Wallace J, Curnow O. Compact low energy CO2 management using amine solution in a packed bubble column. Chem Eng J 2008;135:3e9. [14] Georgiou D, Petrolekas PD, Hatzixanthis S, Aivasidis A. Absorption of carbon dioxide by raw and treated dye-bath efuents. J Hazardous Mater 2007;144:369e76. [15] Lin SH, Shyu CT. Performance characteristics and modeling of carbon dioxide absorption by amines in a packed column. Waste Manage 1999;19:255e62. [16] Yeh JT, Resnik KP, Rygle K, Pennline HW. Semi-batch absorption and regeneration studies for CO2 capture by aqueous ammonia. Fuel Process Technol 2005;86:1533e46. [17] Aroonwilas A, Tontiwachwuthikul P, Chakma A. Effects of operating and design parameters on CO2 absorption in columns with structured packings. Separ Purif Technol 2001;24:403e11.

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

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