The most valuable component of biogas is methane (CH4) which typically makes up 60%, with the balance being carbon dioxide (CO2) and small percentages of other gases. However, biogas also contain significant amount of hydrogen sulfide (H2S) gas which needs to be stripped off due to its highly corrosive nature. Hydrogen sulfide is oxidized into sulfur dioxide which dissolves as sulfuric acid. Sulphuric acid, even in trace amounts, can make a solution extremely acidic. Extremely acidic electrolytes dissolve metals rapidly and speed up the corrosion process.
The corrosive nature of H2S has the potential to destroy expensive biogas processing equipment. Even if there is no oxygen present, biogas can corrode metal. Hydrogen sulphide can become its own electrolyte and absorb directly onto the metal to form corrosion. If the hydrogen sulphide concentration is very low, the corrosion will be slow but will still occur due to the presence of carbon dioxide.
The obvious solution is the use of a biogas cleanup process whereby contaminants in the raw biogas stream are absorbed or scrubbed. Desulphurization of biogas can be performed by biological as well as chemical methods. Biological treatment of hydrogen sulphide typically involves passing the biogas through biologically active media. These treatments may include open bed soil filters, biofilters, fixed film bioscrubbers, suspended growth bioscrubbers and fluidized bed bioreactors.
The simplest method of desulphurization is the addition of oxygen or air directly into the digester or in a storage tank serving at the same time as gas holder. Thiobacilli are ubiquitous and thus systems do not require inoculation. They grow on the surface of the digestate, which offers the necessary micro-aerophilic surface and at the same time the necessary nutrients. They form yellow clusters of sulphur. Depending on the temperature, the reaction time, the amount and place of the air added the hydrogen sulphide concentration can be reduced by 95 % to less than 50 ppm.
Most of the sulphide oxidising micro-organisms belong to the family of Thiobacillus. For the microbiological oxidation of sulphide it is essential to add stoichiometric amounts of oxygen to the biogas. Depending on the concentration of hydrogen sulphide this corresponds to 2 to 6 % air in biogas. Measures of safety have to be taken to avoid overdosing of air in case of pump failures.
Biofiltration is one of the most promising clean technologies for reducing emissions of malodorous gases and other pollutants into the atmosphere. In a biofiltration system, the gas stream is passed through a packed bed on which pollutant-degrading microbes are immobilized as biofilm. A biological filter combines water scrubbing and biological desulfurization.
Biogas and the separated digestate meet in a counter-current flow in a filter bed. The biogas is mixed with 4% to 6% air before entry into the filter bed. The filter media offer the required surface area for scrubbing, as well as for the attachment of the desulphurizing microorganisms. Microorganisms in the biofilm convert the absorbed H2S into elemental sulphur by metabolic activity. Oxygen is the key parameter that controls the level of oxidation.
The capital costs for biological treatment of biogas are moderate and operational costs are low. This technology is widely available worldwide. However, it may be noted that the biological system is capable to remove even very high amounts of hydrogen sulphide from the biogas but its adaptability to fluctuating hydrogen sulphide contents is not yet proven.
Biofuel commercialization has proved to be costly and lingering than expected due to its high production cost and modification to flexibility in engines. Drop-in fuels are alternatives to existing liquid fuels without any significant modification in engines and infrastructures. According to IEA, “Drop-in biofuels are liquid bio-hydrocarbons that are functionally equivalent to petroleum fuels and are fully compatible with existing petroleum infrastructure”.
What are Drop-in Biofuels
Drop-in biofuels are can be produced from oilseeds via trans-esterification, lignocellulosic biomass via thermochemical process, sugars and alcohol via biochemical conversion or by hybrids of the above methods. Drop-in fuels encompass high hydrogen to carbon ratio with no/low sulfur and oxygen content, low water solubility and high carbon bond saturation. In short drop-in fuel is a modified fuel with close functional resemblance to fossil fuel.
Existing biofuels – bioethanol and biodiesel – have wide variation from fossil fuels in their blend wall properties – high oxygen content, hydrophilicity, energy density and mainly compatibility in existing engines and infrastructures. Oxygenated groups in biofuel have a domino effect such as reduction in the energy density, production of impurities which are highly undesirable to transportation components, instability during storage etc.
Major advantages of drop-in fuels over existing fuels are as follows:
Reduced sulphur oxide emissions by ultra low sulphur content.
Reduced ignition delay by high cetane value
Reduced hydrocarbons and nitrogen oxides emissions
Low aromatic content
Low olefin content, presence of olefin compounds undergo auto-oxidation leading to surface depositions.
High saturates, therefore leaving minimum residues
Low particulate emissions
No oxygenates therefore has high stability.
Potential Biomass Feedstock
Drop-in biofuels can be produced from various biomass sources- lipids (vegetable oils, animal fats, greases, and algae) and lignocellulosic material (such as crop residues, woody biomass, and dedicated energy crops). The prominent technologies for biomass conversion to drop-in fuel are the thermochemical and the biochemical process.
The major factor playing role in selection of biomass for thermochemical methods is the energy content or heating value of the material, which is correlated with ash content. Wood, wood chips accounts for less than 1% ash content, which is favorable thermal processing than biochemical process, whereas straws, husks, and majority of the other biomass have ash content ranging up to 25% of dry mass.
Free sugar generating plants such as sugarcane and sweet sorghum, are desirable feedstock for Acetone-Butanol-Ethanol fermentation and have been widely implemented. Presently there is a focus to exploit lignocellulosic residues, rich in hydrocarbon, for fuel production. However, this biomass requires harsh pretreatment to remove lignin and to transform holocellulose (cellulose & hemicelluloses) into fermentable products.
The lignocellulose transformation technology must be circumspectly chosen by its life cycle assessment, as it resists any changes in their structural integrity owing to its complexity. Lignocellulosic biomass, when deoxygenated, has better flexibility to turn to drop-in fuels. This is because, in its native state of the feedstock, each oxygen atom consumes two hydrogen atoms during combustion which in turn reduces effective H: C ratio. Biomass feedstock is characterized with oxygen up to 40%, and higher the oxygen content higher it has to be deoxygenated.
Thermochemical methods adopted for biomass are pyrolysis and gasification, on thermolysis of biomass produce intermediate gas (syngas) and liquid (bio crude) serving as precursors for drop-in fuel. Biomass when exposed to temperature of 500oC-600oC in absence of oxygen (pyrolysis) produce bio-oil, which constitutes a considerable percentage of oxygen. After down streaming by hydroprocessing (hydrotreating and hydrocracking) the rich hydrocarbon tar (bio-oil) can be converted to an efficient precursor for drop-in fuel.
At a higher temperature, above 700, under controlled oxygen, biomass can be converted to liquid fuel via gas phase by the process, gasification. Syngas produced is converted to liquid fuel by Fischer-Tropsch with the help of ‘water gas shift’ for hydroprocessing. Hydroprocessing after the thermochemical method is however costly and complex process in case of pyrolysis and inefficient biomass to fuel yield with gasification process.
The advanced biocatalytic processes can divert the conventional sugar-ethanol pathway and convert sugars to fatty acids. Modified microbial strain with engineered cellular machineries, can reroute the pathway to free fatty acid that can be transformed into butanol or drop-in fuel with necessary processing.
Schematic for the preparation of jet fuel from biomass
Biological processing requires operation under the stressful conditions on the organisms to reroute the pathways, in additional to lowering NADPH (hydrogen) consumption. Other value added products like carboxylic acid, polyols, and alcohol in the same biological routes with lower operational requirements have higher market demands and commercial success. Therefore little attention is given by chemical manufacturers to the biological pathways for drop-in fuel production.
The mechanisms of utilization of lignocellulosic biomass to fuel by biological pathway rely heavily on the availability of monomeric C5 and C6 sugars during fermentation. Ethanol is perhaps the best-known and commercially successful alcohol from ABE fermentation. However, butanol has various significant advantages over ethanol- in the perception of energy content, feasibility to existing infrastructures, zero blend wall, safety and clean aspects. Although butanol is a closer drop-in replacement, existing biofuel ethanol, is a major commercial competitor. Low yield from fermentation due to the toxicity of butanol and complexity in down streaming are the vital reasons that hamper successful large scale butanol production.
Challenges to Overcome
Zero oxygen and sulphur content mark major challenges for production of drop-in fuels from conventional biomass. This demands high hydrogen input on the conventional biomass, with H: C ratio below 0.5, like sugar, starch, cellulose, lignocellulose to meet the effective hydrogen to carbon ratio of 2 as in drop-in fuel. This characterizes most of the existing biomass feedstock as a low-quality input for drop-in fuels. However oleochemicals like fats, oils, and lipids have closer H: C ratio to diesel, gasoline and drop-in fuels, thus easier to conversion. Oleochemical feedstock has been commercially successful, but to prolong in the platform will be a major challenge. Lipid feedstock is generally availed from crop-based vegetable oil, which is used in food sectors. Therefore availability, food security concerns, and economics are the major constraints to sustaining the raw material. Consequently switching to lignocellulosic biomass feedstock for drop-in holds on.
Despite the hurdles on biomass characteristics and process technology for drop-in fuel, it is a vital requirement to switch to better replacement fuel for fossil fuel, considering environmental and economic benefits. Understanding its concepts and features, drop-in fuel, can solve existing greenhouse emission debate on current biofuels. Through crucial ambiguities existing on future of alternative fuels, drop-in fuel has a substantial potential to repute itself as an efficient sustainable eco-friendly fuel in the naear future.
Neal K Van Alfen: ENCYCLOPEDIA OF AGRICULTURE AND FOOD SYSTEMS, Elsevier, Academic Press.
Pablo Domínguez de María John: INDUSTRIAL BIORENEWABLES:A Practical Viewpoint: Wiley & Sons.
Ram Sarup Singh, Ashok Pandey, Edgard Gnansounou: BIOFUELS- PRODUCTION AND FUTURE PERSPECTIVES, CRC Press.
Satinder Kaur Brar, Saurabh Jyoti Sarma, Kannan Pakshirajan : PLATFORM CHEMICAL BIOREFINERY-FUTURE GREEN CHEMISTRY, Elsevier.
Sergios Karatzos, James D. McMillan, Jack N. Saddle: Summary of IEA BIOENERGY TASK 39 REPORT-THE POTENTIAL AND CHALLENGES OF DROP-IN BIOFUELS, IEA Bioenergy.
Vijai Kumar Gupta, Monika Schmoll, Minna Maki, Maria Tuohy, Marcio Antonio Mazutti: APPLICATIONS OF MICROBIAL ENGINEERING, CRC Press.
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