Brazil stands as the second largest producer of ethanol obtained from sugarcane in the international market, having similar energy potential and much lower cost vis-a-vis ethanol from corn of countries such as the USA, and regions such as the European Union (EU), from beet and starch. Table 1 presents the global ethanol production between 2007 and 2012.

In Table 1, it is observed that the USA, Brazil, and Europe account for over 90 % of global ethanol production. The first two countries had similar production scale at the beginning of the period mentioned, occurring an expressive shift in favor of the USA during the period. In turn, EU has doubled its production with­out, however, reducing the difference to the first two significantly.

Brazil is pointed out as a tropical country with continental dimensions, in which the supply of biomass has great potential for use in power generation by Castro and Dantas (2008). In 2007, biomass was the second source of energy used in Brazil, with 31.1 % of the energy matrix, preceded by oil and its derivatives. Considering the national supply, biomass, along with other sources of internal origin, accounted for 3.7 % of the offer, according to the National Energy Balance (NEB) (ANEEL 2008).

According to Tolmasquim (2012), a great part of the Brazilian territory is within the most thriving region of the planet for the production of biomass, not only due to the high degree of sunlight on its territory, but also for its environ­mental conditions. In bioenergy, sugarcane stands out owing to technological advances, both in the agricultural and industrial phases, making ethanol and bio­electricity competitive products internally and externally.

The technological advance was not only due to the energy offer. The flex-fuel vehi­cle, whose engines work on any proportion of ethanol or gasoline, has already been consolidated in the market. Such was the acceptance of the Brazilian consumer that only 9 months after its release in 2003, the fleet of flex-fuel vehicles accounted for 57 % of the national fleet of light vehicles, i. e., about 18 million units (UNICA 2013b).

According to the Center for Sugarcane Technology (CTC) (2005), the biomass of sugarcane may become more important in energetic, economic, and environ­mental terms, with the increasing search for improvements in the production sys­tems of the sugarcane industry.

According to Dias et al. (2009), this highlight is due to the relevance of etha­nol production, its by-products, bagasse (cogeneration of electricity), and straw, as well as most of the biomass residues obtained in the agricultural and industrial activities, which become raw material capable of producing energy.

Among the sources of biomass for electricity generation in the country, sug­arcane is an alternative with great potential through the use of bagasse and straw. The participation of the cane is not only important for the diversification of the electric matrix, but also because the harvest coincides with the dry season in the Southeast and Midwest regions, where the greatest capacity of hydropower in Brazil is concentrated (ANEEL 2008).

Table 2 presents the main secondary sources, being expressively featured the electricity, produced mainly from hydropower and biomass, which have the sus­tainable characteristics due to the low GHG generation.

1.1.1 The Sugarcane Biomass

Both in Brazil and in the international market, biomass has been considered one of the main alternatives for diversification of energy sources and reduction of the use of fossil fuels (ANEEL 2008).

According to UNICA (2013a), there are 64.7 millions of hectares fit to sugar­cane plantation, i. e., 7.5 % of Brazilian cultivable area. However, sugarcane plan­tation occupied only 1 % of cultivable area in 2012. The sugarcane productivity in 2011/2012 harvest was 58.25 ton/ha for an area of 9.6 millions of hectares. The sugarcane production for milling was of 559.2 millions of tons, of which 297 mil­lions of tons of sugarcane were earmarked for the production of ethanol and the rest were earmarked for the production of sugar. It was produced a total of 22.7 millions of m3 of ethanol (8.6 million m3 of anhydrous ethanol and 14.1 million m3 of hydrated ethanol), i. e., about 6.8 m3/ha (UNICA 2013b) (Fig. 1).

In Brazil, there are 327 mills and distilleries allowed to operate for sugar and ethanol production, in which average capacity is about 810 m3/day. These mills are distributed in most Brazilian states, but their concentration is in Middle-South region. The total quantity of workers in these mills and distilleries was 160,984 in 2011 (Portal da Cana 2013; RAIS 2012). According to Shikida (2013), ‘1 ton of sugarcane produces, simultaneously, 120-135 kg of sugar and 20-23 l of ethanol, or if only produce ethanol, the amount is 80-86 l of ethanol’ (oral information).

The Brazilian areas suitable for the cultivation of sugarcane are concentrated in the Central-South region of Brazil (Fig. 2).

The sugarcane production is not adequate to the biome of the Brazilian Amazon or Pantanal, not only because they are protected areas by environmental legisla­tion, but also because they do not have edaphoclimatic conditions for sugarcane cultivation. It is noted that most of the sugarcane units, i. e., mills and distilleries are located in the Central-South and the northeastern coast of the country.

Veiga Filho (2008:3) reinforces this statement saying:

Rodrigues, [coordinator of the Agribusiness Center of Getulio Vargas Foundation] and Marcos Jank, [former] president of UNICA [Sugarcane Industry Union], say that 75 % of the sugar cane expansion occurs in pasture areas, which disallows another aspect of the offensive mounted against Brazilian ethanol. They say that the cane does not represent a real threat to the environmentally critical areas, such as the Amazon.

Chagas (2012) points out that in Brazil, ethanol is used in three sectors of the economy: transport, the chemical industry, and beverage manufacturing. Regardless of its allocation, Brazilian ethanol is more competitive than that pro­duced in other countries due to the large scale, which provides low production cost and low GHG emission, among other factors.

Table 3 depicts the volume of primary sources of biomass used in Brazil in 2011, highlighting the by-products of cane, which represent for more than 78 % of the primary sources.

In Brazil, there is no importation and exportation of sugarcane by-products. These by-products are consumed in the same mills and distilleries which they are produced because their transportation is infeasible. The transport of sugarcane also is infeasible for distance about 50-80 km from the mills (Rangel et al. 2008).

The results of the production cost analysis for fuels are based on scenarios of crude oil prices of Euro 50, Euro 100, Euro 150 and Euro 200 per barrel and under consideration of the technical status for the years 2015 and 2020. Table 5 summa­rises these results.

1. Estimated biofuel production costs in 2015

Our modelling results (Fig. 4) show that in 2015 only biodiesel is able to reach competitive production costs and only at high crude oil prices. Biodiesel made from waste oil can compete with fossil fuels in the Euro 150/barrel and Euro 200/ barrel scenarios. Biodiesel from palm oil reaches competitiveness in the crude oil price scenario of Euro 200/barrel. Production costs for second-generation bioetha­nol are significantly higher than those of fossil fuels in all crude oil price scenar­ios. Furthermore, unlike for other biofuels, the simulation of different crude oil scenarios in Fig. 4 indicates that production costs for bioethanol from lignocel — lulosic waste is largely independent of the crude oil price levels. In addition, our simulation reveals that HVO and BTL are unlikely to be a reasonable alternative to other fuels as their production costs are significantly higher than the others.

2. Estimated biofuel production costs in 2020

At the crude oil price scenario of Euro 50/barrel, the production cost of all bio­fuel alternatives is too high to be competitive (Fig. 5), even when scale and learn­ing effects are considered for 2020. Again, biodiesel made from waste oil seems to be the most promising option. In the Euro 100/barrel scenario, waste oil bio­diesel production costs (Euro-Cent 55 per litre) are lower than those of fossil fuel (Euro-Cent 68 per litre), followed by the more expensive biodiesel made from palm oil (Euro-Cent 81 per litre) and second-generation bioethanol (Euro-Cent 86 per litre). At a market price of Euro 150/barrel, ethanol made from lignocellulosic waste becomes attractive. While production costs for fossil fuel stand at Euro-Cent 99 per litre, second-generation bioethanol can be produced for Euro-Cent 91 per

litre. In this crude oil price scenario, bioethanol is even cheaper to produce than biodiesel made from palm oil (Euro-Cent 98 per litre). However, biodiesel from waste oil (Euro-Cent 64 per litre) remains the most attractive option, cost-wise. The 150 Euro/barrel results are documented in Fig. 6.

First-generation biodiesel and first-generation bioethanol show an increase of overall production costs between 2015 and 2020 despite positive learning and scale effects. This is due to the influence of high raw material prices. One can note that all first-generation biofuels, except palm oil biodiesel, experience increasing production costs. In regard to palm oil biodiesel, advancements in production pro­cesses are capable of overcompensating the rise of feedstock prices.

There is a similar situation with HVO and especially BTL. The combination of relatively high raw material costs and high conversion costs make both types of biofuel uncompetitive. Although significant learning effects between 2015 and 2020 will lead to considerably lower conversion costs, HVO’s and BTL’s poten­tial as a substitute for fossil fuels is virtually non-existent. The related cost-sav­ing potentials are simply not sufficient to compensate the high raw material costs. Consequently, one cannot expect either of these two types of biofuel to be pro­duced at competitive costs, even though both have a higher energy density com­pared with other biofuels and, in particular, bioethanol.

When learning and scale effects are considered, second-generation biofuels seem to be the most promising alternatives to fossil fuels throughout all crude oil price scenarios until 2020. In detail, the most promising options in regard to production costs are biodiesel from waste oil and bioethanol made from ligno — cellulosic raw materials when produced at large scales.

Our results are in line with research from de Wit et al. (2010), who explain this order between those two types of biofuels by lower feedstock, capital and opera­tional costs. Compared to bioethanol of the first generation, the production of bio­diesel is associated with lower feedstock costs. In addition, capital and operational expenditures for the transesterification of oil to biodiesel are lower compared to the conversion process of first-generation bioethanol (hydrolysis and fermentation of sugar/starch crops). This initial advantage of biodiesel over bioethanol, how­ever, may impede the exploitation of positive effects associated with learning and a larger scope and, in consequence, may prevent the use of related cost-saving potentials for bioethanol.

Silvio Vaz Jr. and Jennifer R. Dodson

Abstract Analytical techniques are vital for the development of new added-value materials and products from biomass, such as liquid biofuels, by evaluating the quality and chemical composition of the raw materials and all materials and byprod­ucts in the production process. This also enables the evaluation and implementation of environmental laws and better understanding of the economics of new biomass processes. Different analytical techniques are applied to different biomass feed­stocks, such as sugarcane, soybean, corn, forests, pulp and paper, waste and agri­cultural residues, dependent on the final end biofuel product. This chapter highlights how the use of analytical chemistry can be used as a tool to ensure quality and sus­tainability of the biomass and liquid biofuels, with, some aspects of green analysis also considered.

1 Introduction

The technological development of modern society is increasingly resulting in the need for methods to control products and processes, to ensure that they fulfill quality standards, and to prevent negative impacts on the environment. The increasing demand from society for more sustainable and lower impact products has become important across all aspects of production, including in agricultural sector. The agri­cultural sector has proposed in recent years to reduce the generation of greenhouse

S. Vaz Jr. (*)

Brazilian Agricultural Research Corporation (EMBRAPA), Brasilia, DF, Brazil e-mail: silvio. vaz@embrapa. br

J. R. Dodson

Federal University of Rio de Janeiro (UFRJ), Rio de Janeiro, RJ, Brazil

A. Domingos Padula et al. (eds.), Liquid Biofuels: Emergence, Development and Prospects, Lecture Notes in Energy 27, DOI: 10.1007/978-1-4471-6482-1_9, © Springer-Verlag London 2014

gases through increased yields combined with the application of sustainable practices, e. g., lower tillage per area, a decrease in the use of agrochemicals, and a decrease in the water usage. One example of how agriculture could contribute to reductions in greenhouse gases worldwide is through the use of biomass for bio­energy applications, particularly the production of liquid fuels such as bioethanol and biodiesel from agricultural crops and waste products to replace petroleum feedstocks (Grafton et al. 2012; Norse 2012; Rathmann et al. 2010; Balat and Balat 2009; Goldemberg et al. 2008).

There are four main types of biomass which can be used to produce liquid bio­fuels: oleaginous, sugary, starchy, and cellulosic (International Energy Agency 2013). For instance, soybean (Glycine max) and oil palm (Elaeis guineensis) gen­erate oils for biodiesel production; sugar from sugarcane (Saccharum spp.) and sorghum (Sorghum bicolor (L.) Moench) and starch from corn (Zea mays) can be used to produce first-generation ethanol (1G ethanol); while bagasse, straw, and cellulosic wood are applicable for second-generation ethanol (2G ethanol). Each one has unique structural and chemical characteristics, which therefore require different analytical technologies and approaches to better understand the process­ing of the materials, the products formed and economic aspects. Analytical meth­ods are vital for enabling quality control of raw materials and products, providing accurate knowledge for the regularization of products and markets (Scarlat and Dallemond 2011; Orts et al. 2008). Analytical techniques can therefore support the development of new products and processes from biomass, helping to promote a bioeconomy (Gallezot 2012). Chemical analyses, either based on classical or instrumental techniques, play an important role in the exploitation of biomass as supporting technologies for all stages of biomass processing and for different bio­mass sources, including sugarcane, soybean, corn, forests, pulp and paper, waste and agricultural residues, among others (Feng and Buchman 2012; Sluiter et al. 2010; Orts et al. 2008).

Fundamentally, a liquid biofuel is defined as:

• Liquid state under normal conditions of temperature and pressure (25 °C and 1 atm, respectively);

• Lower vapor pressure and high energy content;

• Presence of oxygen in almost all biofuels;

• Obtained from a chemical synthesis process: biodiesel by transesterifica­tion (Meher et al. 2006); biokerosene by transesterification and esterification, followed by distillation (Llamas et al. 2012); and gasoline and diesel by Fischer-Tropsh (Balat and Balat 2009);

• Obtained from a fermentation process: ethanol by Saccharomyces cerevisiae strain (Balat and Balat 2009), and n-butanol by Clostridium acetobutylicum strain (Lu et at. 2012).

The practical application of analytical techniques for chemical analysis of feed­stocks and biofuels is discussed in this chapter in order to convey their potential use for technical or scientific applications. Alongside, some aspects of green anal­ysis, quality control, and technological trends are considered.

Fig. 1 Some chemical structures of fatty acids from oleaginous plants such as soybean. Author Silvio Vaz Jr