Biochemical Conversion of Biomass

Biochemical conversion of biomass involves use of bacteria, microorganisms and enzymes to breakdown biomass into gaseous or liquid fuels, such as biogas or bioethanol. The most popular biochemical technologies are anaerobic digestion (or biomethanation) and fermentation. Anaerobic digestion is a series of chemical reactions during which organic material is decomposed through the metabolic pathways of naturally occurring microorganisms in an oxygen depleted environment. Biomass wastes can also yield liquid fuels, such as cellulosic ethanol, which can be used to replace petroleum-based fuels.

Anaerobic Digestion

Anaerobic digestion is the natural biological process which stabilizes organic waste in the absence of air and transforms it into biofertilizer and biogas. Anaerobic digestion is a reliable technology for the treatment of wet, organic waste.  Organic waste from various sources is biochemically degraded in highly controlled, oxygen-free conditions circumstances resulting in the production of biogas which can be used to produce both electricity and heat. Almost any organic material can be processed with anaerobic digestion. This includes biodegradable waste materials such as municipal solid waste, animal manure, poultry litter, food wastes, sewage and industrial wastes.

An anaerobic digestion plant produces two outputs, biogas and digestate, both can be further processed or utilized to produce secondary outputs. Biogas can be used for producing electricity and heat, as a natural gas substitute and also a transportation fuel. A combined heat and power plant system (CHP) not only generates power but also produces heat for in-house requirements to maintain desired temperature level in the digester during cold season. In Sweden, the compressed biogas is used as a transportation fuel for cars and buses. Biogas can also be upgraded and used in gas supply networks.

Working of Anaerobic Digestion Process

Digestate can be further processed to produce liquor and a fibrous material. The fiber, which can be processed into compost, is a bulky material with low levels of nutrients and can be used as a soil conditioner or a low level fertilizer. A high proportion of the nutrients remain in the liquor, which can be used as a liquid fertilizer.

Biofuel Production

A variety of fuels can be produced from waste resources including liquid fuels, such as ethanol, methanol, biodiesel, Fischer-Tropsch diesel, and gaseous fuels, such as hydrogen and methane. The resource base for biofuel production is composed of a wide variety of forestry and agricultural resources, industrial processing residues, and municipal solid and urban wood residues. Globally, biofuels are most commonly used to power vehicles, heat homes, and for cooking.

The largest potential feedstock for ethanol is lignocellulosic biomass wastes, which includes materials such as agricultural residues (corn stover, crop straws and bagasse), herbaceous crops (alfalfa, switchgrass), short rotation woody crops, forestry residues, waste paper and other wastes (municipal and industrial). Bioethanol production from these feedstocks could be an attractive alternative for disposal of these residues. Importantly, lignocellulosic feedstocks do not interfere with food security.

Ethanol from lignocellulosic biomass is produced mainly via biochemical routes. The three major steps involved are pretreatment, enzymatic hydrolysis, and fermentation. Biomass is pretreated to improve the accessibility of enzymes. After pretreatment, biomass undergoes enzymatic hydrolysis for conversion of polysaccharides into monomer sugars, such as glucose and xylose. Subsequently, sugars are fermented to ethanol by the use of different microorganisms.

A Glance at Drop-in Biofuels

drop-in-biofuelsBiofuel 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 Route

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.

Biochemical Pathway

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

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.

Conclusions

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.

References

  • 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.

Bioethanol: Challenges in India

bioethanol-indiaGlobal demand for fuel efficiency, environmental quality and energy security have elicited global attention towards liquid biofuels, such as bioethanol and biodiesel. Around the world, governments have introduced various policy measurements, mandatory fuel blending programmes, incentives for flex-fuel vehicles and agricultural subsidies for the farmers. In India, the government launched Ethanol Blended Petrol (EBP) programme in January 2013 for 5% ethanol blended petrol. The policy had significant focus on India’s opportunity to agricultural and industrial sectors with motive of boosting biofuel (bioethanol and biodiesel) usage and reducing the existing dependency on fossil fuel.

The Government of India initiated significant investments in improving storage and blending infrastructure. The National Policy on Biofuels has set a target of 20% blending of biofuel by 2017. However, India has managed to achieve only 5% by September 2016 due to certain technical, market and regulatory hurdles.

In India, sugarcane molasses is the major resource for bioethanol production and inconsistency of raw material supply holds the major liability for sluggish response to blending targets.  Technically speaking, blend wall and transportation-storage are the major challenges towards the biofuel targets. Blending wall is the maximum percent of ethanol that can be blended to fuel without decreasing the fuel efficiency.

Various vehicles are adaptable to various blending ratio based on the flexibility of engines. The technology for the engine modification for flex fuel is not new but making the engines available in India along with the supply chain and calibrating the engine for Indian conditions is the halting phase. The commonly used motor vehicles in the country are not effectual with flex fuel.

Sugarcane molasses is the most common feedstock for bioethanol production in India

Sugarcane molasses is the most common feedstock for bioethanol production in India

Ethanol being a highly flammable liquid marks obligatory safety and risk assessment measures during all phases of production, storage and transportation. The non-uniform distribution of raw material throughout the country, demands a compulsory transportation and storage, especially inter-state movement, encountering diverse climatic and topographic conditions.

Major ethanol consumers in India are potable liquor sector (45%), alcohol based chemical industry (40%), the rest for blending and other purposes. The yearly profit elevation in major sectors is a dare to an economical ethanol supply for Ethanol Blending Programme. Drastic fluctuation in pricing of sugar cane farming and sugar milling resulted to huge debt to farmers by mill owners. Gradually the farmers shifted from sugarcane cultivation other crops.

Regulatory and policy approaches on excise duty on storage and transportation of ethanol and pricing strategy of ethanol compared to crude oil are to be revised and implemented effectively. Diversifying the feedstocks (especially use of lignocellulosic biomass) and advanced technology for domestic ethanol production in blending sectors are to be fetched out from research laboratories to commercial scale. Above all the knowledge of economic and environmental benefits of biofuel like reduction in pollutants and import bills and more R&D into drop-in biofuels, need to be amplified for the common man.