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Biofuels

Fillmore is one of the characteristic characters of the film "Cars" (Disney Pixar). He is a 1960 Volkswagen bus, its liberal/environmental psychedelic symbols clearly present it as a hippie. Filmore is a fierce advocate of "natural" products and earns his living selling organic fuel. What are they? The term "biofuels" means liquid or gaseous fuel obtained from biomass, which can be used to power internal combustion engines. They are traditionally used for automotive use, replacing (or mixed with) fossil fuels, but their use is rapidly expanding and the scope of application of biofuels is shifting towards generating electricity and heat, in particular towards cogeneration1. The will and the need to find renewable fuels has increased significantly in recent decades due to the now recognisable environmental and climate impacts generated by fossil fuels and to ensure security of supply. The advantages deriving from the use of biofuels compared to fossil fuels are significant: sustainability, reduction of greenhouse gas emissions, opportunities for economic development at the regional level and an increase in employment and, last but not least, greater security of supply. Finally, let us not forget that the CO2, SO2 and Nox derivative emissions from the combustion of fossil resources are the main cause of air pollution. As for the general reduction in the reserves of fossil fuels expected in the more or less near future, suggested in 1956 by the American geophysicist Marion King Hubbert and recently revived by various scholars, it must be said that the approach of the production peak and subsequent descent are not as imminent as some scholars claim2. Table 1 summarises the historical and projected data of world primary energy demand, broken down by source, and Figure 1 shows the historical and projected scenario (in million tons of oil equivalent).

1 Cogeneration: simultaneous production, by an energy generation or conversion plant (a power plant, but also an engine, a motor vehicle, etc.) of mechanical energy and possibly electricity and thermal energy (which can be used for various purposes: agricultural, urban, etc.), with the aim of recovering the thermal energy otherwise lost. (http://www.treccani.it) 2 There is no doubt that this has happened or is happening for a large number of deposits and/or producing countries. Drawing the conclusion that this may be "imminent" for world production is, however, logically incorrect, not least because of the low level of knowledge of the subsoil of large parts of the planet, of the discovery of unconventional resources that have allowed countries like the United States to resume a pattern of increasing production and of improving recovery techniques that have led to significant revaluations of existing fields. Source: “L’Importanza e le Opportunità dell’Industria Petrolifera Italiana”, Ricerche Industriali ed Energetiche (RIE) per Assomineraria, 2012.

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Table 1

Figure 1: historical and projected world energy demand scenario (in million tons of oil equivalent), source International Energy Agency In the oil sector dedicated to the automotive segment, the economic and technological efforts of recent years have significantly improved the quality of petrol and diesel and were guided by two key objectives: reduction of consumption and continuous decrease of pollutant emissions3. With these aims, technological development in recent decades has been influenced by the gradual introduction of organic components in liquid fuels. In Europe, 1997 can be considered as the start date of this process, following the M/245 mandate of the European Commission, which entrusted CEN4 with the

4 The European Committee for Standardization, founded in 1961, is an institution that aims to harmonise and produce European technical standards (EN) in Europe in collaboration with national and supranational bodies, such as ISO. CEN works in accordance with the policies of the European Union and of EFTA to promote free trade, worker and consumer

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task of drawing up the standard for fatty acid methyl esters (biodiesel) for automotive use. In other words, the mandate requests the development of a standard that defines the quality specifications and the minimum characteristics necessary for the proper functioning of engines, to reduce pollutant emissions and for distribution safety. The Commission's objective was twofold: reduce the impact of emissions from combustion on anthropogenic climate change and diversify energy sources. In the current definition, biofuels are divided into two categories depending on the raw materials and the state of progress of production technologies. Biodiesel, pure vegetable oils, bioethanol produced from grain and from sugary raw materials, bio-ETBE (ethyl-tert-butyl-ether, produced by hydrolysis of bioethanol) and biogas are defined as first generation biofuels . Their production and applications have already started. Second generation biofuels are represented by bioethanol produced from lignocellulose raw materials, bio-DME, bio-MTBE, biobutanol and synthetic diesel obtained via the Fischer-Torpsch reaction. Other raw materials used for the production of second-generation biofuels are algae, industrial waste or grasses that can be grown on residual land such as miscanthus. In some cases, these are still experimental techniques and not yet in full-scale production, in others the products are already on sale5,6. Not all biofuels are the same. Their evolution Why have we switched to the so called second generation biofuels? The choice was dictated by the realisation, reached over time, than using edible raw materials for biofuel production was anything but sustainable. Although first generation biofuel has undeniable environmental benefits, especially in terms of net carbon footprint, on the other it has given way over time to intensive cultivation of sugar cane, rape-seed oil or corn, reserved exclusively for the fuel industry, subtracting land from growing food crops. In fact, food security aside, first generation biofuels are closely related to land grabbing, deforestation and the harmful effects of the change of use of the soil (ILUC – indirect land use change factor). In 2012 alone, the European Union dedicated 3% of its arable land to the production of raw materials for biofuels. In summary, the advantages are: biodegradability, reduction of greenhouse gas emissions, reduction of ozone levels in the lower layers of the atmosphere, reduction of VOC (volatile organic compound) emissions. But if alongside these advantages we consider the environmental disadvantages from deforestation and intensive agriculture, associated with the use of herbicides, fertilizers and pesticides and we add the water for crop irrigation and transport, the final outcome is not so viable. Other factors to be taken into consideration for assessing the environmental impact of biofuels:

• emissions for the production and transportation of the biomass; • irrigation and fertilizer use; • emissions for the production and transportation of the biofuel.

These activities require energy, thus producing CO2. If we consider the entire production cycle, from biomass to the fuel pump, not all biofuels are environmentally SUSTAINABLE! At our latitudes, vegetable oils for the production of first generation biofuels are derived from oily crops, consisting of rape, sunflower and, to a lesser extent, soy. The Italian surface area used for the production of oily crops shows significant numbers, shown in the table below (data in hectares, source: ISTAT).

CROP 2006 2007 2008 2009 Soy 171,000 130,000 110,000 135,000 Sunflower 144,000 126,500 115,000 125,000 Rape 3,500 7,000 12,500 23,000 Total 318,500 263,500 237,500 283,000

Table 2 In 2009 there were approximately 125,000 hectares of land for the cultivation of sunflower and over 20,000 hectares for rape, used for the production of pure vegetable oil and biodiesel. In addition to vegetable oils from dedicated crops, oils deriving from the preparation and preservation of food, from agro-food industries, from catering, but also from household use can be used. The same goes for animal fat residue from meat processing. These "residual" materials are however of inferior quality, mainly due to their high acidity. They therefore require preliminary "regeneration" before conversion into to biodiesel, mixed with vegetable oils obtained from oily crops7, rendering the entire process economically less advantageous. Therefore, the focus of the industry has shifted to the production of second generation biofuels, which do safety, environmental protection, etc. The standards produced by CEN, normally harmonised, are transposed by the individual national committees. (http://www.assil.it)      

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not require the exclusive use of fertile land but rather residual land, and the use of agricultural waste (lignocellulose raw materials). In this way, the biomass is already available!

Bioethanol: is it possible to replace fossil fuels? The use of ethanol as fuel for internal combustion engines is certainly not new, considering that the first engines designed (we are in the early 20th century) were suitable to be powered by pure alcohol (methanol or ethanol). The Dodge 1800 was the first prototype of a pure ethanol-powered engine. The use of petrol as a fuel, in fact, became widespread only in the period prior to the first world war. Ethanol has interesting characteristics to be used as fuel in petrol-engine cars: it has, for example, a high octane rating (it is in fact also used to increase the octane rating of petrols) and thus allows the compression ratio to be increased, improving engine efficiency. Already in the early 1970s, in the wake of the energy crisis, the Brazilian Government began to promote the National Alcohol Program, with plans to reduce oil imports and replace fossil fuel with its own and easy-to-be-found source. The main purpose was the partial replacement of diesel of oil origin with ethanol obtained from biomass, in particular from sugar cane. In 1979, the Brazilian Government signed an agreement with the automobile industry and prototypes were developed by several manufacturers (including Fiat) able to use 100% ethanol (Fig. 4). In 1984, 94% of the cars sold in Brazil were alcohol powered. In later years, after the oil crisis, the trend triggered in Brazil gradually declined, but with the increases in petrol prices in recent years, ethanol cars are again in vogue: in 2010, there were as many as 3 million ethanol-powered cars on the roads. The use of ethanol instead of petrol is, however, not without its problems. First of all, ethanol is very soluble in water and very hygroscopic, and when it absorbs a lot, when mixed with petrol, a phase separation can take place which can cause engine damage. It is corrosive and lacking in lubricant properties, so it is necessary to use new materials compared to those used for petroleum-based fuels in storage and distribution systems, as well as in certain mechanical components of the car, such as filters. It can,on the other hand, be used mixed with petrol up to 20-22% without making any changes to the engine of the car. For the reasons mentioned above, only so-called Flexible Fuel Vehicles (FFVs), developed since 2005 by car manufacturers, including FIAT, can be powered solely by ethanol.

How is second generation bioethanol produced? Second generation bioethanol is obtained from lignocellulosic biomass by enzymatic hydrolysis reaction and is the subject of research since the 1970s. The cellulose and hemicellulose are polysaccharides, which are the raw materials from which, by enzymatic hydrolysis, we obtain simple sugars, to be transformed into ethanol by fermentation. The enzymes selectively "cut" the polysaccharides (cellulose, hemicellulose or starch) allowing simpler glucose molecules to be obtained (Fig. 3).

Figure 2: waste from the cultivation of sugar cane provides lignocellulosic biomass useful for bioethanol production. Source: Ethanol as biofuel for transport applications, Isabella De Bari, ENEA-Renewable energy division, Unesco School, TRISAIA 2005.

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Figure 3: Schematic representation of the enzymatic hydrolysis of cellulose. Source: Ethanol as biofuel for transport applications, Isabella De Bari, ENEA-Renewable energy division, Unesco School, TRISAIA 2005.

Subsequently, the glucose is converted into ethanol by a fermentation process and Saccharomycescerevisiae(yeast) is the microrganism generally most used. The production of ethanol from cellulose, which as mentioned is not new, is considered particularly interesting and is the subject of investment by a number of major industrial players. Its use is particularly advantageous because the lignocellulosic biomass, coming for example from agricultural waste, is an abundant raw material and has no competition with food crop production. The availability of agricultural waste in a number of European countries and in Italy is shown in Figures 5 and 6.

Figure 4: Availability of agricultural waste in a number of countries of the European Union. Source: FAO.

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Figure 5: Availability of agricultural waste in Italy. Source: FAO.

Future developments At its meeting of 28 April 2015, the European Parliament adopted the directive on second generation biofuels, pushing to reduce the production of those derived from agricultural crops and starting the trend toward production of advanced biofuels8, derived from waste, residues and new sources such as algae. The use of the latter, as demonstrated by recent studies carried out by researchers at the Rice University (Houston, Texas, USA)9, would simultaneously solve two environmental problems: the treatment of civil waste water and biofuel production. In fact, the algae used in the experiment were grown using the civil wastewater of a treatment plant in Houston, literally "feeding them" with the phosphorus and nitrates they contain and thus obtaining a purifying effect of this water10. In practice, making the algae grow in reactors containing wastewater, producers need no longer resort to fertilizers and more sustainable biofuels can be obtained, together with the treatment of the wastewater used. But this is only one of the possible "solutions" investigated. Technological and biotechnological research in the field of sustainable production of second generation biofuels has in fact become a very vibrant frontier in recent decades and new scenarios emerge in front of the world audience. It is in fact essential that the production of biofuels takes place in a sustainable manner if we really want to totally or partially eliminate the harmful effects associated with the use of fossil fuels.

By Tiziana Perri

Bibliographical references

• Directive No. 2015/1513/EU of 9 September 2015, . • Ethanol as biofuel for transport applications, Isabella De Bari, ENEA-Renewable energy division, Unesco

School, TRISAIA 2005.

• I Biocarburanti. Le filiere produttive, le tecnologie, i vantaggi ambientali e le prospettive di diffusione. Various authors, coordination Roberto Jodice, Michela Pin, Centro di Ecologia Teorica e Applicata di Gorizia, 2007.

 

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• La normazione dei combustibili per autotrazione:oltre cento anni di storia”, curated by Davide Faedo Innovhub - Ente Federato all'UNI, U&C no. 6 June 2015 Divisione Stazione Sperimentale per i Combustibili - CT "Prodotti petroliferi e lubrificanti" UNICHIM.

• “L’Importanza e le Opportunità dell’Industria Petrolifera Italiana”, Ricerche Industriali ed Energetiche (RIE) per

Assomineraria, 2012. • �MeenakshiBhattacharjee and Evan Siemann, “Low algal diversity systems are a promising method for

biodiesel production in wastewater fed open reactors”, ALGAE, 30(1), 2015. • http://www.eniscuola.net/2015/04/03/alghe-dalle-acque-reflue-per-ridurre-linquinamento-produrre-biofuel/

• http://www.assil.it)

• http://www.ideegreen.it/biocarburanti-seconda-generazione • http://www.greenstyle.it/storie/biocarburanti • http://www.treccani.it • www.reteambiente.it