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.

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.

Ethanol Production via Biochemical Route

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.

Pretreated biomass can directly be converted to ethanol by using the process called simultaneous saccharification and cofermentation (SSCF). Pretreatment is a critical step which enhances the enzymatic hydrolysis of biomass. Basically, it alters the physical and chemical properties of biomass and improves the enzyme access and effectiveness which may also lead to a change in crystallinity and degree of polymerization of cellulose. The internal surface area and pore volume of pretreated biomass are increased which facilitates substantial improvement in accessibility of enzymes. The process also helps in enhancing the rate and yield of monomeric sugars during enzymatic hydrolysis steps.

Pretreatment methods can be broadly classified into four groups – physical, chemical, physio-chemical and biological. Physical pretreatment processes employ the mechanical comminution or irradiation processes to change only the physical characteristics of biomass. The physio-chemical process utilizes steam or steam and gases, like SO2 and CO2. The chemical processes employs acids (H2SO4, HCl, organic acids etc) or alkalis (NaOH, Na2CO3, Ca(OH)2, NH3 etc). The acid treatment typically shows the selectivity towards hydrolyzing the hemicelluloses components, whereas alkalis have better selectivity for the lignin. The fractionation of biomass components after such processes help in improving the enzymes accessibility which is also important to the efficient utilization of enzymes.

The pretreated biomass is subjected to enzymatic hydrolysis using cellulase enzymes to convert the cellulose to fermentable sugars. Cellulase refers to a class of enzymes produced chiefly by fungi and bacteria which catalyzes the hydrolysis of cellulose by attacking the glycosidic linkages. Cellulase is mixture of mainly three different functional protein groups: exo-glucanase (Exo-G), endo-glucanase(Endo-G) and ?-glucosidase (?-G). The functional proteins work synergistically in hydrolyzing the cellulose into the glucose. These sugars are further fermented using microorganism and are converted to ethanol. The microorganisms are selected based on their efficiency for ethanol productivity and higher product and inhibitors tolerance. Yeast Saccharomyces cerevisiae is used commercially to produce the ethanol from starch and sucrose.

Escherichia coli strain has also been developed recently for ethanol production by the first successful application of metabolic engineering. E. coli can consume variety of sugars and does not require the complex growth media but has very narrow operable range of pH. E. coli has higher optimal temperature than other known strains of bacteria.

Lower GHG emissions and empowerment of rural economy are major benefits associated with bioethanol

The major cost components in bioethanol production from lignocellulosic biomass are the pretreatment and the enzymatic hydrolysis steps. In fact, these two process are someway interrelated too where an efficient pretreatment strategy can save substantial enzyme consumption. Pretreatment step can also affect the cost of other operations such as size reduction prior to pretreatment. Therefore, optimization of these two important steps, which collectively contributes about 70% of the total processing cost, are the major challenges in the commercialization of bioethanol from 2nd generation feedstock.

Enzyme cost is the prime concern in full scale commercialization. The trend in enzyme cost is encouraging because of enormous research focus in this area and the cost is expected to go downward in future, which will make bioethanol an attractive option considering the benefits derived its lower greenhouse gas emissions and the empowerment of rural economy.

Ethanol from Lignocellulosic Biomass

Cellulosic ethanol technology is one of the most commonly discussed second-generation biofuel technologies worldwide. Cellulosic biofuels are derived from the cellulose in plants, some of which are being developed specifically as “energy” crops rather than for food production. These include perennial grasses and trees, such as switchgrass and Miscanthus. Crop residues, in the form of stems and leaves, represent another substantial source of cellulosic biomass.

The largest potential feedstock for ethanol is lignocellulosic biomass, which includes materials such as agricultural residues (corn stover, crop straws, husks 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. Lignocellulosic feedstocks do not interfere with food security and are important for both rural and urban areas in terms of energy security reason, environmental concern, employment opportunities, agricultural development, foreign exchange saving, socioeconomic issues etc.

Production of Ethanol

The production of ethanol from lignocellulosic biomass can be achieved through two different processing routes. They are:

  • Biochemical – in which enzymes and other micro-organisms are used to convert cellulose and hemicellulose components of the feedstocks to sugars prior to their fermentation to produce ethanol;
  • Thermochemical – where pyrolysis/gasification technologies produce a synthesis gas (CO + H2) from which a wide range of long carbon chain biofuels, such as synthetic diesel or aviation fuel, can be reformed.

Lignocellulosic biomass consists mainly of lignin and the polysaccharides cellulose and hemicellulose. Compared with the production of ethanol from first-generation feedstocks, the use of lignocellulosic biomass is more complicated because the polysaccharides are more stable and the pentose sugars are not readily fermentable by Saccharomyces cerevisiae. In order to convert lignocellulosic biomass to biofuels the polysaccharides must first be hydrolysed, or broken down, into simple sugars using either acid or enzymes. Several biotechnology-based approaches are being used to overcome such problems, including the development of strains of Saccharomyces cerevisiae that can ferment pentose sugars, the use of alternative yeast species that naturally ferment pentose sugars, and the engineering of enzymes that are able to break down cellulose and hemicellulose into simple sugars.

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.

Pretreated biomass can directly be converted to ethanol by using the process called simultaneous saccharification and cofermentation (SSCF).  Pretreatment is a critical step which enhances the enzymatic hydrolysis of biomass. Basically, it alters the physical and chemical properties of biomass and improves the enzyme access and effectiveness which may also lead to a change in crystallinity and degree of polymerization of cellulose. The internal surface area and pore volume of pretreated biomass are increased which facilitates substantial improvement in accessibility of enzymes. The process also helps in enhancing the rate and yield of monomeric sugars during enzymatic hydrolysis steps.

Pretreatment of Lignocellulosic Biomass

Pretreatment methods can be broadly classified into four groups – physical, chemical, physio-chemical and biological. Physical pretreatment processes employ the mechanical comminution or irradiation processes to change only the physical characteristics of biomass. The physio-chemical process utilizes steam or steam and gases, like SO2 and CO2. The chemical processes employs acids (H2SO4, HCl, organic acids etc) or alkalis (NaOH, Na2CO3, Ca(OH)2, NH3 etc). The acid treatment typically shows the selectivity towards hydrolyzing the hemicelluloses components, whereas alkalis have better selectivity for the lignin. The fractionation of biomass components after such processes help in improving the enzymes accessibility which is also important to the efficient utilization of enzymes.

Conclusions

The major cost components in bioethanol production from lignocellulosic biomass are the pretreatment and the enzymatic hydrolysis steps. In fact, these two process are someway interrelated too where an efficient pretreatment strategy can save substantial enzyme consumption. Pretreatment step can also affect the cost of other operations such as size reduction prior to pretreatment. Therefore, optimization of these two important steps, which collectively contributes about 70% of the total processing cost, are the major challenges in the commercialization of bioethanol from 2nd generation feedstock.

The Concept of Biorefinery

A biorefinery is a facility that integrates biomass conversion processes and equipment to produce fuels, power, and value-added chemicals from biomass. Biorefinery is analogous to today’s petroleum refinery, which produces multiple fuels and products from petroleum. By producing several products, a biorefinery takes advantage of the various components in biomass and their intermediates, therefore maximizing the value derived from the biomass feedstock.

A biorefinery could, for example, produce one or several low-volume, but high-value, chemical products and a low-value, but high-volume liquid transportation fuel such as biodiesel or bioethanol. At the same time, it can generate electricity and process heat, through CHP technology, for its own use and perhaps enough for sale of electricity to the local utility. The high value products increase profitability, the high-volume fuel helps meet energy needs, and the power production helps to lower energy costs and reduce GHG emissions from traditional power plant facilities.

Biorefinery Platforms

There are several platforms which can be employed in a biorefinery with the major ones being the sugar platform and the thermochemical platform (also known as syngas platform).

Sugar platform biorefineries breaks down biomass into different types of component sugars for fermentation or other biological processing into various fuels and chemicals. On the other hand, thermochemical biorefineries transform biomass into synthesis gas (hydrogen and carbon monoxide) or pyrolysis oil.

The thermochemical biomass conversion process is complex, and uses components, configurations, and operating conditions that are more typical of petroleum refining. Biomass is converted into syngas, and syngas is converted into an ethanol-rich mixture. However, syngas created from biomass contains contaminants such as tar and sulphur that interfere with the conversion of the syngas into products. These contaminants can be removed by tar-reforming catalysts and catalytic reforming processes. This not only cleans the syngas, it also creates more of it, improving process economics and ultimately cutting the cost of the resulting ethanol.

Plus Points

Biorefineries can help in utilizing the optimum energy potential of organic wastes and may also resolve the problems of waste management and GHGs emissions. Biomass wastes can be converted, through appropriate enzymatic/chemical treatment, into either gaseous or liquid fuels. The pre-treatment processes involved in biorefining generate products like paper-pulp, HFCS, solvents, acetate, resins, laminates, adhesives, flavour chemicals, activated carbon, fuel enhancers, undigested sugars etc. which generally remain untapped in the traditional processes. The suitability of this process is further enhanced from the fact that it can utilize a variety of biomass resources, whether plant-derived or animal-derived.

Future Perspectives

The concept of biorefinery is still in early stages at most places in the world. Problems like raw material availability, feasibility in product supply chain, scalability of the model are hampering its development at commercial-scales. The National Renewable Energy Laboratory (NREL) of USA is leading the front in biorefinery research with path-breaking discoveries and inventions. Although the technology is still in nascent stages, but it holds the key to the optimum utilization of wastes and natural resources that humans have always tried to achieve. The onus now lies on governments and corporate sector to incentivize or finance the research and development in this highly promising field.

Biobutanol as a Biofuel

The major techno-commercial limitations of existing biofuels has catalyzed the development of advanced biofuels such as cellulosic ethanol, biobutanol and mixed alcohols. Biobutanol is generating good deal of interest as a potential green alternative to petroleum fuels. It is increasingly being considered as a superior automobile fuel in comparison to bioethanol as its energy content is higher. The problem of demixing that is encountered with ethanol-petrol blends is considerably less serious with biobutanol-petrol blends. Besides, it reduces the harmful emissions substantially. It is less corrosive and can be blended in any concentration with petrol (gasoline). Several research studies suggest that butanol can be blended into either petrol or diesel to as much as 45 percent without engine modifications or severe performance degradation.

Production of Biobutanol

Biobutanol is produced by microbial fermentation, similar to bioethanol, and can be made from the same range of sugar, starch or cellulosic feedstocks. The most commonly used microorganisms are strains of Clostridium acetobutylicum and Clostridium beijerinckii. In addition to butanol, these organisms also produce acetone and ethanol, so the process is often referred to as the “ABE fermentation”.

The main concern with Clostridium acetobutylicum is that it easily gets poisoned at concentrations above 2% of biobutanol in the fermenting mixture. This hinders the production of bio-butanol in economically viable quantities. In recent years, there has been renewed interest in biobutanol due to increasing petroleum prices and search for clean energy resources. Researchers have made significant advances in designing new microorganisms capable of surviving in high butanol concentrations. The new genetically modified micro-organisms have the capacity to degrade even the cellulosic feedstocks.

Latest Trends

Biobutanol production is currently more expensive than bioethanol which has hampered its commercialization. However, biobutanol has several advantages over ethanol and is currently the focus of extensive research and development. There is now increasing interest in use of biobutanol as a transport fuel. As a fuel, it can be transported in existing infrastructure and does not require flex-fuel vehicle pipes and hoses. Fleet testing of biobutanol has begun in the United States and the European Union. A number of companies are now investigating novel alternatives to traditional ABE fermentation, which would enable biobutanol to be produced on an industrial scale.

A Primer on Waste-to-Energy

Waste-to-Energy is the use of modern combustion and biochemical technologies to recover energy, usually in the form of electricity and steam, from urban wastes. These new technologies can reduce the volume of the original waste by 90%, depending upon composition and use of outputs.

Energy is the driving force for development in all countries of the world. The increasing clamor for energy and satisfying it with a combination of conventional and renewable resources is a big challenge. Accompanying energy problems in different parts of the world, another problem that is assuming critical proportions is that of urban waste accumulation.

The quantity of waste produced all over the world amounted to more than 12 billion tonnes in 2006, with estimates of up to 13 billion tonnes in 2011. The rapid increase in population coupled with changing lifestyle and consumption patterns is expected to result in an exponential increase in waste generation of upto 18 billion tonnes by year 2020.

Waste generation rates are affected by socio-economic development, degree of industrialization, and climate. Generally, the greater the economic prosperity and the higher percentage of urban population, the greater the amount of solid waste produced. Reduction in the volume and mass of solid waste is a crucial issue especially in the light of limited availability of final disposal sites in many parts of the world. Millions of tonnes of household wastes are generated each year with the vast majority disposed of in open fields or burnt wantonly.

The main categories of waste-to-energy technologies are physical technologies, which process waste to make it more useful as fuel; thermal technologies, which can yield heat, fuel oil, or syngas from both organic and inorganic wastes; and biological technologies, in which bacterial fermentation is used to digest organic wastes to yield fuel.

The three principal methods of thermochemical conversion are combustion in excess air, gasification in reduced air, and pyrolysis in the absence of air. The most common technique for producing both heat and electrical energy from wastes is direct combustion. Combined heat and power (CHP) or cogeneration systems, ranging from small-scale technology to large grid-connected facilities, provide significantly higher efficiencies than systems that only generate electricity.

Biochemical processes, like anaerobic digestion, can also produce clean energy in the form of biogas which can be converted to power and heat using a gas engine. In addition, wastes can also yield liquid fuels, such as cellulosic ethanol, which can be used to replace petroleum-based fuels. Cellulosic ethanol can be produced from grasses, wood chips and agricultural residues by biochemical route using heat, pressure, chemicals and enzymes to unlock the sugars in biomass wastes.

Waste-to-energy plants offer two important benefits of environmentally safe waste management and disposal, as well as the generation of clean electric power.  The growing use of waste-to-energy as a method to dispose of solid and liquid wastes and generate power has greatly reduced environmental impacts of municipal solid waste management, including emissions of greenhouse gases.