Muhammad Rashed
Al Mamun
a,
Shuichi
Torii
b,
Mohammed M.
Rahman
c and
Mohammad Razaul
Karim
*d
aDepartment of Farm Power and Machinery, Faculty of Agricultural Engineering and Technology, Sylhet Agricultural University, Sylhet-3100, Bangladesh
bDepartment of Advanced Mechanical System Engineering, Graduate School of Science and Technology, Kumamoto University, 2-39-1 Kurokami, Kumamoto 860-8555, Japan
cCenter of Excellence for Advanced Materials Research (CEAMR) & Chemistry Department, King Abdulaziz University, P. O. Box 80203, Jeddah 21589, Saudi Arabia
dDepartment of Chemistry, School of Physical Sciences, Shahjalal University of Science and Technology, Sylhet-3114, Bangladesh. E-mail: krazaul@yahoo.com
First published on 19th November 2018
Biomethane, the principal component of biogas, is one of the major alternatives to fossil fuel. Reducing the amount of carbon dioxide (CO2), hydrogen sulfide (H2S) and water (H2O) content from their mixture with methane (CH4) in biogas is necessary for ensuring their practical applications as fuels and the minimum methane (CH4) content is stipulated to be 95%. Herein, a facile process for the combined removal of CO2, H2S and H2O by using two different sets of purifying mixtures including calcium hydroxide (Ca(OH)2) + activated carbon + silica gel for experiment T1 and Ca(OH)2 + zero-valent iron (Fe0) + sodium sulphate (Na2SO4) for experiment T2 is presented. The CO2 concentration was reduced from 33% in raw biogas to 2.65 and 4.8% in biogas treated in T1 and T2, respectively. The corresponding H2S concentration falls from 365 ppm to 14 and 29 ppm, while H2O content decreased from 5% to 0.03 and 0.87%. As a result of this physico-chemical minimization of the unwanted gas fraction, the overall biomethane concentration increased from 62% in raw biogas to 97.55 and 95.02% in the purified gas after the accomplishment of the purification process by experiments T1 and T2, respectively. We propose that this purification method can be applied in a small farmland or rural area to obtain purified biomethane.
Besides methane (40–75%), the major components of biogas produced from the nonaerobic process contain 15–60% carbon dioxide. It also contains minor amounts of water (5–10%), hydrogen sulphide (0.005–2%) and traces of siloxanes (0–0.02%), halogenous volatile organic compounds (VOCs, <0.6%), ammonia (NH3, <1%), oxygen (O2, 0–1%), carbon monoxide (CO, <0.6%) and nitrogen (N2, 0–2%). The composition of the components varies depending on the type of biomass raw material and production methods.12–16 The fuel value of biogas is proportional to the CH4 concentration. For use as a fuel in internal combustion engines, the CH4 content in biogas must be higher than 90%.17
The unwanted gases have some harmful effect on the machinery. For example, the high CO2 content (∼40%) in raw biogas reduces the engine efficiency and power output by increasing the carbon monoxide and hydrocarbon emissions. Thus, the use of biogas in power plants or internal combustion engines is hindered.4,18,19 The presence of H2S causes corrosion in the engine or piping system by forming metal sulfides through chemical reactions with metallic parts. Therefore, removal of contaminated gases from raw biogas is necessary not only to increase the caloric value, but also to use the gas safely without facing any corrosion risks.20 The corrosion mechanism of sulfur is initiated in the presence of an H2S concentration higher than 50 ppm.21 The valve systems, bronze gears and the exhaust system are attacked by H2S and the deterioration of engines becomes significant. In general, the presence of H2S in biogas reduces the lifetime of the engine by 10 to 15%.11 Water also functions as corrosive materials when react with H2S as well as reduce the caloric value. Water forms acids with H2S and CO2, which react with the compressors, gas storage tanks etc. By means of condensation and freezing the water fraction reduces the lifetime of pipelines.22 Therefore, it is necessary to reduce the CO2, H2S and H2O content from raw biogas.
There exist a number of methods for the biomethane upgradation process and removal of the unwanted gas fraction from biogas mixtures. All the processes are associated with their own advantages and disadvantages, which were discussed in some previous studies.22–32 In short, the processes include physical adsorption, chemical treatment, reverse flow of gas through various scrubbing towers and separation of the harmful component using a number of polymeric molecular filters. However, in small-scale plants and rural farmhouses, it is quite feasible to employ physico-chemical adsorption and precipitation methods, as these are associated with simple and affordable techniques with a low cost set up. Based on this necessity, herein, we report a combined process for the removal of CO2, H2S and H2O through a single stage operation. We used two different sets of purifying agents in the form of their solid phase adsorbent mixtures: calcium oxide (CaO), activated carbon and silica gel, and CaO, zero-valent iron (Fe0) and sodium sulfate (Na2SO4), for experiments T1 and T2, respectively. The successful elimination of CO2, H2S and H2O content from raw biogas along with the increment in the CH4 percentage indicates the potential of these processes for using biogas in rural areas and small-scale plants.
Test | Purifying agents in the mixture | Amount of uploaded water (L) | Amount (g) | Gas flow rate (L min−1) | Time per exp. (min) | Pressure (bar) |
---|---|---|---|---|---|---|
T1 | CaO | 1 | 1–10 | 1.5 | 120 | 8 |
Activated carbon | — | |||||
Silica gel | — | |||||
T2 | CaO | 1 | 1–10 | 1.5 | 120 | 8 |
Fe0 | — | |||||
Na2SO4 | — |
Fig. 2 Changes in CO2 content in the biogas during purification by Ca(OH)2 solution of varied concentrations. |
Fig. 3 presents the concentration profile of H2S in raw biogas and the biogas treated with a varied amount of activated carbon or Fe0 in experiments T1 and T2, respectively. The average concentration of H2S in raw biogas is 400 ppm. In T1, after treatment, the H2S content decreases significantly with increase in the mass of activated carbon. The H2S content becomes 219.3, 135.4, 65.8, 31.8 and 14.7 ppm on treating the raw biogas with 2, 4, 6, 8 and 10 g activated carbon, respectively. This is well below the maximum concentration of H2S acceptable for running in internal combustion engines.36 It seems that the removal efficiency reaches saturation on using a higher amount of activated carbon. Almost a similar trend for the concentration change of H2S is observed for treating the raw biogas with Fe0 in experiment T2. Here the H2S content in treated biogas becomes 210.3, 135.6, 74.2, 45.9 and 29.4 ppm on treating the raw biogas with 2, 4, 6, 8 and 10 g Fe0, respectively. A state of saturation for the adsorption of H2S is noticeable here also on using a higher amount of adsorbent and we continued the experiment until 10 g of Fe0 was used.
Fig. 3 Changes in H2S content in the biogas purified by treating the raw biogas with varied amounts of activated carbon (for experiment T1) and Fe0 (for experiment T2). |
Fig. 4 presents the change in H2O-content in raw biogas and biogas purified after treating with varied amounts of silica gel and Na2SO4 in experiments T1 and T2, respectively. The average concentration of H2O in raw biogas is around 5%. On treating with 1.0 g of silica gel, the H2O content becomes 2.65% and is decreased gradually on treating with a higher amount of silica gel. The H2O content reaches 1.92, 1.88, 1.06, 0.16 and 0.03% on treating the raw biogas with 2, 4, 6, 8 and 10 g silica gel. H2O is also eliminated gradually on treating the raw biogas with Na2SO4. On using 1, 2, 4, 6, 8 and 10 g Na2SO4, the H2O concentration is changed to 3.6, 3.54, 2.1, 1.45, 0.99 and 0.87% respectively. In both cases (T1 and T2) the extent of removal seems to be optimized when around 10 g of the adsorbent phase is used.
Fig. 4 H2O content in raw and purified biogas with respect to the mass of silica gel or Na2SO4 used during the purification. |
The CO2, H2S and H2O removal efficiencies are 32.12, 30.96 and 33.33% when 1 g each of Ca(OH)2, activated carbon and silica gel, respectively, is used. The removal efficiencies increase gradually with increase in the mass of removing agents and reached the highest value of 92.09, 96.05 and 97.97%, respectively when 10 g of the respective removal agents was used. Similarly, in experiment T2 the CO2, H2S and H2O removal efficiencies increase from 22.35, 29.55 and 29.67% when 1 g of Ca(OH)2, Fe0 and Na2SO4 was used to 86.58, 89.15 and 84.19% when 10 g of the respective removing agents was used.
Fig. 5 represents the removal efficiencies of CO2, H2S and H2O with respect to the amount (concentration/masses) of removing agents for experiments T1 and T2. The results showed that the most efficient performance in T1 was investigated to compare with T2. The operation of the system in T1 was observed better results than T2 with respect to CO2 removal efficiency although same material used. A possible reason for this was that in T1 was contained activated carbon, which extremely porous and thus to have a very large surface area for adsorption of H2S simultaneously CO2.
Fig. 5 CO2, H2S and H2O removal efficiencies with respect to the amount of purifying agents used in experiments T1 and T2. |
The CH4 enrichment profile is presented in Fig. 6. Here the y-axis represents the CH4 percentage in the purified biogas, while the values along the x-axis represent the amount of each of the adsorbents used in experiments T1 and T2. The CH4 content in raw biogas is around 62%. In experiment T1, the CH4 content increased to 76.2% on treating the raw biogas with 1 g each of CaO, activated carbon and silica gel. The percentage of CH4 increases gradually with increase in the mass of the purifying agents. When 2, 4, 6, 8 and 10 g each of CaO, activated carbon and silica gel are used, the CH4 content becomes 78.65, 82.54, 86.57, 92.5 and 97.55%, respectively. Similarly, in experiment T2 after treating with 1, 2, 4, 6, 8 and 10 g each of CaO, activated carbon and silica gel, the CH4 content reaches 71.2, 74.6, 79.86, 84.56, 90.24 and 95.02%, respectively. The mirror X-axis in Fig. 6 represents the concentration of CH4 with respect to the production date. It shows that the CH4 concentration is almost the same over a duration of 20 days of gas collection.
Fig. 6 CH4 content in raw biogas and in purified biogas after treating with various amounts of purifying agents. The mirror face of X-axis represents the date of gas production. |
Being an acidic gas, CO2 reacts with CaO to produce a colloidal suspension of CaCO3, which ultimately precipitated out from the system after undergoing coagulation in the basic medium. This acid–base neutralization method can be presented by two consecutive chemical reactions as:
CO2(g) + H2O(l) → H2CO3(aq.) | (1) |
Ca(OH)2(aq.) + H2CO3(aq.) → CaCO3(s) + H2O(l) | (2) |
The overall chemical process is highly exothermic and a well-known spontaneous reaction. Hence the removal process takes place under ambient conditions. The removal of CO2 by CaO, therefore, is clearly a chemical elimination process, the efficiency of which is influenced partly by agitation, turbulence, the extent of interaction between the gaseous and liquid phase reactants and the concentration of Ca(OH)2 solution.33 The activated carbon and Fe0 in their commercial form possess nanometer range dimensions with high surface areas. Therefore, the exposure of these materials to H2S gas might result in the maximum adsorption or chemical elimination process for the optimized surface of contact.34–36 The removal mechanism of H2S by activated carbon is the adsorption of H2S within the carbon phase by means of the micropore filling theory, which in fact is a phenomenon of enhanced physisorption by adsorbent atoms closely surrounding the adsorbate due to the small pore size. Sometimes the presence of oxygenous functional groups on the carbon phase accelerates the physical adsorption method. There also exists the possibility of chemisorption if the carbon phase pore size is extraordinarily low. Such a phenomenon can be confirmed only if the heat of adsorption is very high. However, in the present case, such a thorough study is beyond our scope of this paper. The removal mechanism of H2S by Fe0 is associated with chemical transformation of the gas into solid sulphide by a two-step method as follows:
Fe0 + 2H2O → Fe2+ + H2(g) + OH− | (3) |
Fe2+ + H2S → FeS + 2H+ | (4) |
At first, Fe0 reacts with moisture to form Fe2+ ion. The generated Fe2+ ion possesses high chemical affinity toward sulphide. The H2S thus transformed into FeS after a rapid chemical reaction. The reaction is accompanied by an increase in H+ ion or a decrease in system pH. The process thus seems to be pH sensitive. Our next study includes a detailed investigation of this issue. Both in the experiments T1 and T2, the H2S content in biogas after treating with 10 g purifying agent (activated carbon or Fe0) lies below the maximum concentration of H2S acceptable for running internal combustion engines.12 However, the results showed that the H2S removal capability of activated carbon is higher than that of Fe0. This variation needs further scientific reasoning. Fe0 removes gaseous H2S by forming metallic sulphide through the reaction H2S(g) + Fe0(s) → FeS(s). The reaction stoichiometry suggests the formation of sulphide at the surface of iron nanoparticles in a 1:1 ratio. The extent of removal is therefore limited by the surface area of Fe0. Here, rather than a perfect solid phase–gas phase interaction, the chemical reaction is supported by the water molecules present in the biogas mixture. In contrast, the H2S adsorption process on the surface of activated carbon is supported by van der Waals type of interactions.11 It is not clear whether the adsorption process is in the single layer form or in the BET type multilayer form. However, it is expected that for a multilayer deposition, the removal efficiency will exceed the extent displayed by Fe0.
The removal mechanism of H2O by sodium sulphate and silica gel is simply adsorption. The blue silica gel turns pink gradually by adsorbing water molecules. The silica gel can be reactivated after saturation by removing the water molecules from its pink form by heating for 3 hours at 150 °C. The removal of water vapour from biogas is significant as it reduces the risk of formation of sulphuric and carbonic acids (H2SO4 and H2CO3) from the possible reactions between the water molecules and H2S and CO2, respectively.37,38 The acids are responsible for corrosion in piping and engines.
Even the composition of biogas varies due to the nature of raw materials and operational conditions; this report represents a composite phenomenon to purify the raw biogas of any source. We propose that the biogas purification method is highly fascinating, as it could eliminate the unwanted components by desirable amounts from the raw biogas. In fact, we primarily used 12 g of all the purifying agents. But, on using beyond 10 g of the purifier no substantial changes in the concentration of gas component were observed. For this reason, we conducted the experiment three times for each of the unit tests and the results from the average of the 3 tests using 10 g of the purifier are presented. Even it seems that using 10 g Ca(OH)2 solution, the methane content slightly increased, while carrying out the experiment with the higher amount of Ca(OH)2 didn't show any significant variation in the result. The purifying materials used are cheap, inexpensive and non-hazardous in nature. Besides, the technology employed is simple and affordable. The CO2 is removed by a simple chemical transformation. Fe0 and activated carbon could remove H2S simply by adsorption. The water vapour is removed by physical adsorption only. The experimental results revealed that the biomethane content could be enriched to >95% using the proposed combined chemical and physical removal process. Between experiments T1 and T2, the maximum methane concentration after treatment was achieved in T1.
This journal is © The Royal Society of Chemistry 2019 |