The industrial conversion of renewable resources has a quite long history, lasting since 6000 BC, in particular on the utilization of sugar cane (Demirbas, 2010; Kamm et al., 2006). However, proofs on the production of ethanol by distillation were found in China, in the form of dried residues of 9000 years old. Also, the ancient Egyptians used to produce alcohol by fermenta­tions from vegetal materials (Demirbas, 2010).

An analysis of biorefineries history should entail various aspects of wood saccharification, sugar produc­tion, synthesis of various bio-based products (furfural, lipids, lactic acid and many others), energy sources, and integrated processes (Kamm et al., 2006; Demirbas, 2010; de Jong and Marcotullio, 2010; Martin and Grossmann, 2012). Therefore, the topic branches of bio­refineries which process renewable materials became well known and applied worldwide. These develop­ments were more evident since the nineteenth and the beginning of the twentieth century, distinctively in the pulp and paper industry, where wood is the main raw material and the derived wastes gave rise to various so­lutions for the exploitation of valuable components they include (Rodsrud et al., 2012). Also, the food industry was a sector with high potential of waste valorization and recovery. Moreover, the increase in environmental concerns, especially related to the use of fossil fuels, has asked for sustainable solutions to limit the green­house gas effects and resources depletion. Table 14.1 provides a short outline of biorefinery evolution, based on data existent in various sources (Demirbas, 2010; Kamm et al., 2006; Rodsrud et al., 2012).

However, some voices claim that the concept of "bio­refinery" appeared in the 1990s as reaction to some trends of industry such as the need to use biomass re­sources in a more balanced way from both economic and environmental perspectives; an emergent concern in the promotion of low-quality lignocellulosic biomass to valuable products; an increased attention to the pro­duction of starch for energy applications; a need to develop extra high-value products and expand product combinations to face global competition; and to exploit an excess of biomass (especially in the pulp and paper industry) (Alakangas and Makinen, 2008; Berntsson et al., 2012).

BIOMASS FEEDSTOCK

Biorefineries process a bio-based feedstock input, analogous to the petroleum refineries, where a variety of different products may result, such as fuel, power, or chemicals (WEF, 2013). Although biorefineries use a large variety of different raw materials and conversion technologies, a clear alternative to fossil-based products does not exist still today (WEF, 2013). However, four classes of feedstocks are established (Demirbas, 2010):

• First generation which entails edible biomass (starch — rich, oily plants) to produce bioalcohols, vegetable oil, biodiesel, biosyngas, and biogas.

• Second generation which uses biomass in the form of nonfood sources and crops (residual nonfood parts of crops, solid waste, wheat straw, etc.) to produce bioalcohols, biooil, biohydrogen, bio-Fischer— Tropsch diesel.

• Third generation which includes algae to produce vegetable oil and biodiesel.

• Fourth generation which uses vegetable oil and biodiesel to produce biogasoline.

A more detailed presentation is done in Table 14.2. The option to choose one or more of the four different

Key Moment	Place and Actors	Innovations and Activities	References
9000 BC	China	— Discovery of the art of distillation, which increases the concentration of alcohol in fermented solutions	Demirbas, 2009
6000 BC	Asia	— Utilization of sugar cane	Demirbas, 2010
Fifteenth Century	American plantations	— Export of sugar cane	James et al., 1989
1748	Andreas Sigismund Margraff, German scientist	— Key initiator of the modern sugar industry — Research on the isolation of crystalline sugar from different roots and beet	Kamm et al., 2006, Burton and Cox, 1998
1780	Carl Wilhem Scheele	— Discovery of lactic acid	Benninga, 1990
1801	Cunern/Schlesien Poland	— The first sugar refinery based on sugar bet F. C. Achard	Paulik, 2011 Pennington and Baker, 1990
Early Nineteenth Century	Samule Morey	— First tested ethanol in internal combustion engine	Lee and Lavore, 2013
1806	Napoleon Bonaparte	— Economic continental blockade to limit overseas trade in cane sugar starch hydrolysis became of interest for the economy	Brown, 2009 Harris, 1919 Paulik, 2011
1811	G. S.C. Kirchoff German pharmacist	— Conversion of potato starch into "grape sugar" — The starting point of starch industry	Kamm et al., 2006, Paulik, 2011 van der Maarel et al., 2002
1812	Weimar, Germany J. W. DObereiner	— The first starch sugar plant was established	Jentoft, 2003 Kamm et al., 2006
1819	H. Braconnot, French plant chemist	— Treatment of wood with concentrated H2SO4 results in sugar (glucose)	Binder and Raines, 2010 Jeffries and Lindblad, 2009; Paulik, 2011
1831	Dobereiner	— First report on the production and separation of furfural by bran distillation with diluted acid	de Jong and Marcotullio, 2010 Yang et al., 2011
1835	J. J. Berzelius, Swedish Professor	— Development of enzymatic hydrolysis of starch to sugar ("catalysis")	Buchholz et al., 2005 Cheeptham and Lal, 2012
1839	A. Payen	— Cellulose was obtained by wood treatment with nitric acid and subsequent treatment with a sodium hydroxide solution ("les cellules")	Kamm et al., 2006 Paulik, 2011
1840	G. J. Mulder	— Synthesis of levulinic acid by heating fructose with hydrochloride	Kamm et al., 2006 Paulik, 2011
1845	G. Fowners	— Proposed the name of "furfurol" changed in "furfural" due to aldehyde function	Kamm et al., 2006
1854	M. A.C Mellier	— Disintegration of cellulose pulp from straw with caustic soda and steam	Hofmann, 1873 Jeffries and Lindblad, 2009 Kamm et al., 2006
1855	G. F. Melsens	— Wood conversion to sugar with dilute acid — Development of two approach on wood hydrolysis — Hydrolysis with concentrated acid at low temperature; hydrolysis with diluted acid at high temperature	Kamm et al., 2006 Kupiainen, 2012
1863	B. C. Tilghman	— The first patent for cellulose production by use of calcium bisulphite	Gao et al., 2013

		BIOMASS FEEDSTOCK	223
TABLE 14.1 Short History of Biorefineries and Bio-Based Products—cont’d
Key Moment	Place and Actors	Innovations and Activities	References
1866	B. C. Tilghman and brother (paper mill Harding and Sons)	— Start of the first industrial experiment for the production of pulp from wood and hydrogen sulphite	Antonsson, 2008; de Sa, 2004
1872	C. D. Ekman	— Production of cellulose sulfate using magnesium sulfate as cracking agent	Kamm et al., 2006
1874	W. Haarman F. Tiemann	— Vanillin synthesis from cambial juice of coniferous wood	Kamm et al., 2006 Paulik, 2011
1875	Company Haarman and Reimer	— Coniferin—the first precursor for the production of vanillin was isolated, oxidized to glucovanillin and cleaved into glucose and vanillin — Industrial vanillin production — The first industrial utilization of lignin	Kamm et al., 2006 Paulik, 2011 Wolfrom, 1970
1878	A. Mitscherlich	— Improved the sulfite pulp process by fermentation of sugar from waste liquor to ethanol — Applied procedure to obtain paper glue from the waste liquor	Kamm et al., 2006 Sindall, 1906 Watt, 1890
1895	A. Boehringer	— Industrial lactic acid fermentation	Benninga, 1990
The End of the Nineteenth Century		— Ethanol was used in farm machinery and introduced in the automobile market	Lee and Lavore, 2013
1900		— Development of pulp and paper mils (5200 worldwide)	Kamm et al., 2006 Paulik, 2011
1901	A. Classen	— The first commercial process of wood saccharification (German Patent 130980) with sulfuric acid	Kamm et al., 2006 Hajny, 1981
1902	W. Normann	— Liquid plant oils are converting into tempered fat by augmentation of hydrogen — Hydration of liquid catalytic (Ni), resulting tempered stearic acid	Kamm et al., 2006 WEF, 2010
1909	M. Ewen G. Tomlinson	— The first commercial process of wood working with dilute sulfuric acid (US Patent 938208)	Kamm et al., 2006 Lloyd and Harris, 1955 Otulugbu, 2012
1893-1912	Company Boehringer-Ingelheim	— The pioneer of industrial biotechnology	Bio Deutschland, 2012
Interbelic Period	Friedrich Bergius	— Development technologically viable processes for wood saccharification — Ethanol production from the fermentation of wood sugar	Kamm et al., 2006 Schobert, 2013
1920	Quaker Oats company	— Development of furfural production from pentoses	Marcus, 2005 RIRDC, 2006
1925	W. J. Hale, H. Dow, C. H. Herty	— Chemurgy was founded in USA, having as an objective the utilization of agricultural resources in industry	Kamm et al., 2006
1927	American Maraton Corporation	— Development of commercial products from the organic solids in the spent sulfite liquor from pulp and paper manufacture as leather tanning agents and dispensing agents	Kamm et al., 2006 WEF, 2010
1932	W. H. Carothers Van Natta	— Discovery and developing a polyester made from lactic acid	Huijser, 2009 Kobayashi, 2010

(Continued)

Key Moment	Place and Actors	Innovations and Activities	References
1934	Cedar rapids, Iowa	— Furfural production was established as an industrial process	Kamm et al., 2006 Peters, 1937
1940	A. E. Staley Dectur Illinois	— Commercial production of levulinic acid in autoclaves — Utilization of hexoses from low cost cellulose production was experimented for the production of levulinic acid	Kamm et al., 2006 Kitano et al., 1975
1941	Henry Ford	— A car 100% biosynthetic composite material made from cellulose meal, soy meal, formaldehyde resin, with methanol as fuel produced from cannabis	Kamm et al., 2006
1990s	Company nature works	— Commercialization of the poly(lactic) acid made from lactic acid	Vink et al., 2003

alternatives to replace the fossil fuels-based products with biomass-based products depends on, among others, the costs involved (Sanders et al., 2005; van Ree and Annavelink, 2007).

There are different paths for biomass utilization (Table 14.3) (Wagemann, 2012):

• integral unmodified or modified biomass, without component separation;

• various individual components of biomass;

• biomass components in a complete way/form at various location;

• the whole biomass in its complete forms.

However, any classification is generic only based on a too large generalization and provides little information on the intimacy of involved processes as well as of the possibility to apply various technological processes to different feedstocks (Cherubini et al., 2009). No classifi­cation criterion allows the combination of different bio­refinery systems by linking different technologies involved in both energy-driven biorefinery systems and material-driven biorefinery systems. Cherubini et al.

(2009) mentioned some examples in this regard: "if the carbohydrate fraction of a lignocellulosic feedstock is used to produce cellulose and xylose, the system is classified as a lignocellulosic feedstock biorefinery; but can also be classified as a forest-based biorefinery and, if the lignin fraction is pyro — lyzed, the same biorefinery is also suitable for classification as a two-platform concept biorefinery".

STRUCTURE OF BIOREFINERY CONCEPT

The biorefinery is more than a fixed technology since it includes a collection of unitary processes, by several different routes from feedstocks to products (Xiu et al.,

2011) . Figure 14.3 shows the structural scheme of bio­refinery concepts, including process types with the uni­tary processes and the primary products and intermediates, as well as secondary products (Hackl and Harvey, 2010).

The economic viability of bio-based products prepa­ration involves different processes and methods: phys­ical, chemical, biological, and thermal. Table 14.3 describes shortly some of these processes and methods.

However, a clear set of criteria to classify the different biorefinery concepts is still missing. van Ree and Annevelink (2007) considered a classification based on the following:

• Raw material input, resulting in some classes of biorefineries, like Green, Whole Crop, Lignocellulosic, Feedstock, and Marine Biorefineries.

• Technologies applied for biomass processing: Two Platform Concept, Thermo, Chemical Biorefineries.

• Products resulted (main, intermediate): Syngas, Sugar, Lignin Platforms.

Due to the complexity of this structure, process integration is the most sustainable approach to ensure the system efficiency and products quality. In an inte­grated configuration, biorefinery systems are struc­tured in various ways by considering the use of raw materials, the environmentally sound character, and the degree of integration as follows (van Ree and Annevelink, 2007, Martin and Grossmann, 2012, Wagemann, 2012):

• Lignocellulosic feedstock biorefinery is based on the processing of lignocellulosic-rich biomass sources in three steps (Figure 14.4): cellulose (sugar raw material); hemicelluloses (polyses); and lignin. These

TABLE 14.3 Biomass Utilization Paths (Wagemann, 2012)

Biomass Utilization Examples

Wood for wood-based raw materials or sawing products Wood used as fuel Insulating materials made of natural fibers Linseed oil as solvent

Vegetable oil from rape or as component of lacquers/dyes Starch from cereal crops for the production of bioethanol or for the production of paper starch Sugar from sugar beet used as a fermentation raw material

Biogas from corn for local generation of electricity and heat respectively for biomethane as feed-in into grid for use in different locations

Palm oil generation aboard, its transportation to Europe, and its domestic processing

Biorefinery concepts using a platform for the integrated production of a spectrum of products

Source: Adapted with the permission of the coordinator of "Biorefineries Roadmap as part of the German Federal Government action plans for the material and energetic utilization of renewable raw materials" brochure on behalf of The Federal Government, Professor Kurt Wagemann.

processing steps result in feeds, chemicals, biopolymers and other biomaterials. All residues are incinerated for the cogeneration of heat and power (van Ree and Annevelink, 2007).

• Whole crop biorefinery uses raw materials (cereals, maize, and wheat) in the form of grain, flour (meal), and straw (combination of ears, leaves, chaff and nodes), based on dry or wet milling biomass. Their processing results in feeds, chemicals and biomaterials (Figure 14.5).

• Green biorefineries use "nature wet" (fresh) biomass (green grass, clover, alfalfa, and immature cereals), resulting in a fiber-rich press cake and a nutrient-rich press juice (Figure 14.6).

• Thermochemical biorefinery (TCBR) entails the biomass refining into a large portfolio of value-added products, by applying several technologies such as pyrolysis, gasification, torrefaction, and hydrothermal upgrading. The resulting products could be introduced into the existing infrastructures and substituting fossil fuels (de Wild, 2011; Martin
and Grossmann, 2012). A particular concept derived from TCBR and developed by de Wild (2011) relies to Staged Catalytic Biorefinery Concept, which offers the possibility to process biomass in different sequential technological steps, with reducing the severity of the processing conditions using suitable catalysts, and to separate diverse products at different stages.

• Marine biorefinery (MBR) is based on marine crops, i. e. microalgae (diatoms; green, golden, and blue/green algae) and macroalgae (brown, red and green seaweeds), and their derived products (Bowles, 2007; van Ree and Annevelink, 2007; Martin and Grossmann, 2012).

Depending on the materials resulted after primary refinery steps, the leading procedures applied for further transformation and the integration degree of these above mentioned biorefinery systems could be included in various biorefinery platforms: biochem­ical, thermochemical, and microorganism platforms (Cherubini et al., 2009; Kammm et al., 2006; WEF,

2010) (Table 14.4.)

In this context, the biorefinery is "an explicitly inte­grative, multifunctional overall concept that biomass as a diverse source of raw materials for the sustainable gener­ation of a spectrum of different intermediates and prod­ucts (chemicals, materials, bioenergy/biofuels), allowing the fullest possible use of all raw material components. The coproducts can also be food and/or feed. These objec­tives necessitate the integration of a range of different methods and technologies" (Wagemann, 2012).

The integration and multifunctionality in bio­refineries can be performed at four levels raw material, process, product, and industry (Martin and Grossmann, 2012; Wagemann, 2012) (Figure 14.7).