**1. Introduction**

284 Recent Trends for Enhancing the Diversity and Quality of Soybean Products

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Craighall, South Africa

Ithaca, NY, United States

New York, NY, United States

Pessoa, PB, Brazil.

3, Washington, DC, United States

06997-1, Washington, DC, United States

DID, CDD 631.850981, Brasília, DF, Brazil

ISSN 1983-4357, João Pessoa, PB, Brazil

Currently, fossil fuels represent over 80% of energy consumption in the world. However, due to environmental and geopolitical issues the development of new energy sources is mandatory. For example, only the Middle East holds 63% of global reserves, which directly influences in the final price of fuel.

In developed nations there is a growing trend towards employing modern technologies and efficient bioenergy conversion using a range of biofuels, which are becoming cost competitive with fossil fuels (Puhan et al., 2005). In Brazil, this work is focused on the production of bioethanol and biodiesel.

There are discussions around the world on the feasibility of using renewable fuels, which may cause a much smaller impact to global warming, because the balance of CO2 emissions decreases when using these fuels. (Demirbas, 2008)

In 1997 at a meeting in Kyoto, Japan, many of the developed nations agreed to limit their greenhouse gas emissions, relative to the levels emitted in 1990. In this occasion Brazil established social and environmental policies to collaborate with those global goals (Puhan et al., 2005). An example is the biodiesel program which in 2008 implemented the use of B2 (2% biodiesel into conventional diesel). In other countries, like Germany, it is possible to supply only with B100 biodiesel (100% biodiesel).

#### **1.1 Biodiesel**

Biodiesel, a renewable biofuel produced from biomass, is biodegradable and does not cause significant contamination with emissions containing sulfur or aromatics. Biodiesel, is an viable alternative for compression-ignition engines (Puhan et al., 2005), in total or partial substitution of fossil diesel (Chiang, 2007).

The use of biodiesel as fuel should occupy a prominent place in the world, with a market that is booming because of its enormous contribution to the environment, such as qualitative and quantitative reduction of environmental pollution (Ferrari et al., 2005). Furthermore, this fuel is a strategic source of renewable energy to replace petroleum products.

Biodiesel is fuel produced mainly by transesterification of vegetable oils, but can also be obtained by the reaction of animal fat (Pinto et al. 2005; Puhan et al., 2005; Chiang, 2007)

Chemical Conversion of Glycerol from

**1.3 Use of the glycerol** 

not exceed € 300 t-1, in 2010.

Polymerization

Esterification

glycerol.

lotion (Kimura, 1993).

applications. Some of these processes are listed in Table 1.

steam reforming T = 200-250°C; 1% cat.

Oxidation T = 50°C; Pd/C (5-8% of

Etherization T = 90°C; 1-7,5%

Oligomerization T = 260°C; 2% Mg25Al20

Table 1. Conversion of glycerol to different products.

T = 210-230°C; reduced pressure (~0,3atm); 0,5- 1,5% NaOH.

Níquel-Raney (Ni-Sn).

T = 200-240°C; 0,1-0,3% NaOH; t =0,5 h; 100% methanol.

amberlist 15; t = 2-3h.

(cat.); t = 8h.

Pyrolise T = 650°C. CO; acetaldehyde;

industry.

Biodiesel into Products for Environmental and Technological Applications 287

The investigation of new uses for glycerol is critical for the success of the biodiesel program, especially in relation to the crude glycerol, which has few direct uses and market value marginalized. Currently, the demand for purified glycerol PA for the pharmaceuticals, food additives, personal care (Puhan et al., 2005), industry is supplied by the petrochemical

The biodiesel production will produce a large increase in, the amount of glycerol in the market, causing a decrease in the prices significantly, in the world. In the European Union, for example, the price of glycerol, in 1995 was € 1500 t-1 and reduced to 330 € t-1 in 2006 (Puhan et al., 2005). In Brazil, in 2005 the price of glycerol reached € 1270 t-1, but already in 2007 the price dropped to 720 € t-1. And in regions close to the price of biodiesel plants did

Different routes have been investigated to transform this glycerol to new products and new

**Process Conditions Products Ref.** 

Table 1 can be summarized in Scheme 1, which shows some reactions that originate from

Oxidation products of glycerol, for example, can be used in cosmetics and pharmaceuticals intermediates (Davis et al., 2000; Pachauri & He, 2006; Krishna et al., 2007) and even suntan

The products of oligomerization of glycerol can be used as additives for cosmetics and foods, the raw material for resins and foams (Shenoy , 2006; Lemke, 2003; Werpy, 2004; Pagliaro & Rossi, 2008), lubricants (Pagliaro & Rossi, 2008), cement additives (retains moisture) and are synthetic intermediates and possible substitutes of polyols, e.g. polyvinyl alcohol, in some applications (Werpy, 2004; Pagliaro & Rossi, 2008; Medeiros et al., 2008).

Cyclic polymers. (Blytas & Frank,

acrolein. (Chiang, 2007)

50-70% H2; 30-40% CO; 2-11% of alkanes.

Carbohydrates and esters.

70% of 3-tert-butoxi-1,2-propanodiol (*mono ether*). 87% of mono ether.

65% of diglycerol; 20% of triglycerol and 15% of tetraglycerol.

Pd), t = 8h; pH = 5-11. Dihydroxyacetone. (Garcia et al.,

1993)

(Stein et al., 1983)

(Noureddini & Medikonduru, 1997)

1995)

(Klepácová et al., 2003, 2006)

(Barrault et al., 2004)

soybean (Costa Neto & Rossi, 2000), Cotton (Pinto et al., 2005; Puhan et al., 2005), castor bean (Pinto et al., 2005), canola (Pinto et al., 2005; Catharino et al., 2007; Kocak et al., 2007; Puhan et al., 2005), palm (Pinto et al., 2005; Catharino et al., 2007; Puhan et al., 2005), sunflower (Pinto et al., 2005; Catharino et al., 2007; Puhan et al., 2005; Costa Neto & Rossi, 2000), peanut and babassu.

 Synthesis of biodiesel can be accomplished by using acid, basic (Costa Neto & Rossi, 2000; Puhan et al., 2005; Chiang, 2007; Pinto et al., 2005) or enzymes (Talukder et al., 2007; Schuchardt, 1990) catalysts or even in supercritical methanol (Puhan et al., 2005).

#### **1.2 Biodiesel production**

Transesterification (Figure 1) is the reaction of triglycerides with an alcohol to form esters and glycerol (Chiang et al., 2007; Georgogianni et al., 2007; Krishna et al., 2007; Wu et al., 2007; Talukder et al., 2007; Aparício et al., 2007; Zuhair, 2005; Vicente et al., 2005; Medeiros et al., 2008; Stern & Hillion, 1990; Freedman et al., 1984; Encinar et al, 2002; Vicente et al., 2006; Bunyakiat et al., 2006; Karinen & Krause, 2006). This process decreases the viscosity of the oil and transforms the large, branched molecular structure of bio-oils into smaller molecules, of type required in regular diesel engines.

Fig. 1. Synthesis of biodiesel by transesterification of triglyceride.

In the transesterification for biodiesel production, a large amount of glycerol as a byproduct (about 10% compared to the mass of ester produced) (Puhan et al., 2005; Medeiros et al., 2010) is produced. The separation step of glycerol can be accomplished by decanting, in which the lower phase has the glycerol, the catalyst of the process (usually homogeneous and high polar character), alcohol and oil residue without reacting (crude glycerol, Figure 2, a). The biodiesel separates from the upper stage, almost pure.

The transesterification using methanol is the most used process around the world (Chiang, 2007) offering several advantages, such as: (i) small volume of alcohol recovery, (ii) lower cost of alcohol compared to ethanol (not in Brazil) and (iii) shorter reaction times (Pinto et al., 2005). The use of ethanol proves more advantageous, when considering its lower toxicity.

Fig. 2. (a) crude glycerol, (b) pre-purified glycerol, (c) glycerol purified.
