Energy Conversion and Management 51 (2010) 14121421

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Energy Conversion and Management

journal homepage: www.elsevier.com/locate/enconman

The biorenery concept: Using biomass instead of oil for producing energy and chemicals
Francesco Cherubini *
Department of Energy and Process Engineering, Norwegian University of Science and Technology (NTNU), NO-7491 Trondheim, Norway

a r t i c l e

i n f o

a b s t r a c t
A great fraction of worldwide energy carriers and material products come from fossil fuel renery. Because of the on-going price increase of fossil resources, their uncertain availability, and their environmental concerns, the feasibility of oil exploitation is predicted to decrease in the near future. Therefore, alternative solutions able to mitigate climate change and reduce the consumption of fossil fuels should be promoted. The replacement of oil with biomass as raw material for fuel and chemical production is an interesting option and is the driving force for the development of biorenery complexes. In biorenery, almost all the types of biomass feedstocks can be converted to different classes of biofuels and biochemicals through jointly applied conversion technologies. This paper provides a description of the emerging biorenery concept, in comparison with the current oil renery. The focus is on the state of the art in biofuel and biochemical production, as well as discussion of the most important biomass feedstocks, conversion technologies and nal products. Through the integration of green chemistry into bioreneries, and the use of low environmental impact technologies, future sustainable production chains of biofuels and high value chemicals from biomass can be established. The aim of this bio-industry is to be competitive in the market and lead to the progressive replacement of oil renery products. 2010 Elsevier Ltd. All rights reserved.

Article history: Received 22 June 2009 Accepted 29 January 2010 Available online 6 March 2010 Keywords: Biorenery Biomass Biofuels Biochemicals Green chemistry

1. Background and introduction Our strong dependence on fossil fuels comes from the intensive use and consumption of petroleum derivatives which, combined with diminishing petroleum resources, causes environmental and political concerns. There is clear scientic evidence that emissions of greenhouse gases (GHG), such as carbon dioxide (CO2), methane (CH4) and nitrous oxide (N2O), arising from fossil fuel combustion and land-use change as a result of human activities, are perturbing the Earths climate [1]. The Intergovernmental Panel on Climate Change (IPCC) Fourth Assessment Report highlighted that the worlds growing population and per capita energy demand are leading to the rapid increase in greenhouse gas (GHG) emissions. In particular, over the past 10 years, transport has shown the highest rates of growth in GHG emissions in any sector [2]. The worlds primary source of energy for the transport sector (and production of chemicals as well) is oil. World demand is approximately 84 million barrels a day and is projected to increase to about 116 million barrels a day by 2030, with transport accounting for some 60% of such a rising demand [3]. While the transport sector continues to expand in the US and Europe, growth in the emerging economies of India and China is predicted to be substan* Tel.: +4773598942; fax: +4773598943. E-mail address: francesco.cherubini@ntnu.no. 0196-8904/$ - see front matter 2010 Elsevier Ltd. All rights reserved. doi:10.1016/j.enconman.2010.01.015

tially greater, growing by at least 3% per year [4]. Concerning chemicals, their dependence on fossil resources is even stronger. The majority of chemical products are produced from oil renery and almost 4% of oil is worldwide used for chemical and plastic production [5]. In order to simultaneously reduce the dependence on oil and mitigate climate change in transport and chemical sectors, alternative production chains are necessary. It is increasingly recognized that there is not a single solution to these problems and that combined actions are needed, including changes in behavior, changes in vehicle technologies, expansion of public transport and introduction of innovative fuels and technologies [6]. Recently, society began to recognize the opportunities offered by a future sustainable economy based on renewable sources and has been starting to nance R&D activities for its implementation. It is increasingly acknowledged globally that plant-based raw materials (i.e. biomass) have the potential to replace a large fraction of fossil resources as feedstocks for industrial productions, addressing both the energy and non-energy (i.e. chemicals and materials) sectors [7]. At national, regional and global levels there are three main drivers for using biomass in biorenery for production of bioenergy, biofuels and biochemicals. These are climate change, energy security and rural development. The political motivation to support renewable sources of energy and chemicals arises from each

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individual driver or combinations. Policies designed to target one driver can be detrimental to another. For example, policies aimed at ensuring energy security may result in increased GHG emissions where local coal reserves are preferentially exploited at the expense of imported oil or gas. In addition, electricity and heat can be provided by a variety of renewable alternatives (wind, sun, water, biomass and so on), while biomass is very likely to be the only viable alternative to fossil resources for production of transportation fuels and chemicals, since it is the only C-rich material source available on the Earth, besides fossils. As a consequence, the sustainable biomass production is a crucial issue, especially concerning a possible fertile land competition with food and feed industries. This paper investigates the possibilities to use biomass feedstocks as raw materials in biorenery. Firstly, an overview of the current status in biofuel production is provided and then the emerging biorenery concept is described. The latter is done through an overview of the most promising biomass feedstocks, technological processes and nal products. The current oil renery industry is taken as benchmark throughout the paper. Finally, after reviewing the strategic role played by green chemistry in establishing sustainable conversion technologies, some guidelines for future biorenery complexes are proposed. 2. State of the art in biofuel production Currently, transportation fuels based on biomass (i.e. biofuels) are identied as 1st and 2nd generation biofuels. First generation biofuels usually refer to biofuels produced from raw materials in competition with food and feed industries. Because of this competition, these biofuels give rise to ethical, political and environmental concerns. In order to overcome these issues, production of second generation biofuels (i.e. from raw materials based on waste, residues or non-food crop biomass) gained an increasing worldwide interest in the last few years as a possible greener alternative to fossil fuels and conventional biofuels. As a development of 2nd generation biofuel production, the use of biomass in biorenery complexes is expected to ensure additional environmental benets and implement national energy security, thanks to the coproduction of both bioenergy and high value chemicals. 2.1. First generation biofuels First generation biofuels are produced from sugar, starch, vegetable oil or animal fats using conventional technologies. The basic feedstocks are often seeds and grains such as wheat, corn and rapeseed. The most common rst generation biofuels are bioethanol, biodiesel and starch-derived biogas, but also straight vegetable oils, biomethanol and bioethers may be included in this category. Bioethanol is recovered from biomass feedstocks such as sugarcane, sugar beet and starch crops (mainly corn and wheat). In 2006, total world production reached 51.3 billion litres. USA is currently the largest producer of bioethanol with a production of 19.8 billion litres per year, with corn as primary feedstock. Sugarcane is used as primary feedstock in Brazil, currently the worlds second largest producer (17.8 billion litres per year). The European Union produces 3.44 billion litres of bioethanol, mainly from sugar beet and starch crops [8]. Biodiesel is produced from oil based crops such as rapeseed, sunower, soybean but also from palm oil and waste edible oils. World biodiesel production surpassed 6 billion litres in 2006. Germany led biodiesel production in 2006, producing 2.5 billion litres mainly from rapeseed and sunower. The USA are the second largest producer with 0.86 billion litres, but other countries (France, Italy, Austria) are increasing their biodiesel production [8].

Biogas is produced after anaerobic digestion of mixtures of corn derived starch, manure, organic waste and grasses. However, when biogas is mainly derived from waste and residues can be categorized as 2nd generation biofuel, because its feedstock is not in competition with the food and feed industry. The production of biogas is common in most world countries, and in the last few years it has been strong implemented in countries with economic subsides for electricity generation from biogas (especially European countries). In some countries (such as Germany and Sweden), biogas is also used as transportation biofuel, after upgrading to biomethane. For instance, Sweden leads the world in automotive biogas production, with a total eet of approximately 4500 vehicles with 45% of its fuel supplied by biomethane [9]. The main advantages of rst generation biofuels are due to the high sugar or oil content of the raw materials and their easy conversion into biofuel. Many biofuel production chains have been analysed by means of Life Cycle Assessment (LCA) in order to point out their environmental performances [1012]. With the exception of a few studies, most LCAs have found a net reduction in global warming emissions and fossil energy consumption when the most common transportation biofuels (bioethanol and biodiesel) are used to replace conventional diesel and gasoline [1315]. Several LCA studies have also evaluated life cycle impacts under other environmental aspects, including local air pollution, acidication, eutrophication, ozone depletion, land use, etc. These environmental burdens are much more affected by site specic assumptions than GHG and energy balances, showing that it is not that easy to draw simplied conclusions. Studies that have examined these other environmental issues have concluded that most, but not all, biofuels substituting fossil fuels lead to increased negative impacts [16,17]. In addition, 1st generation biofuels are in competition with food and feed industries for the use of biomass and agricultural land, giving rise to ethical implications: as prices for fossil fuels increase, a larger proportion of cereals or agricultural land will be dedicated to biofuel production instead of using it to produce food. In conclusion, rst generation biofuels currently produced from sugars, starches and vegetable oils cause several concerns: these productions compete with food for their feedstock and fertile land, their potential availability is limited by soil fertility and per hectare yields and the effective savings of CO2 emissions and fossil energy consumption are limited by the high energy input required for crop cultivation and conversion [18,19]. These limitations are expected to be partially overcome by developing the so-called 2nd generation biofuels [20]. 2.2. Second generation biofuels Second generation biofuels are produced from a variety of nonfood crops. These include the utilization of lignocellulosic materials, such as residues from agriculture, forestry and industry and dedicated lignocellulosic crops. In the scientic literature, the term 2nd generation shows wide variation in usage and can variably refer to feedstocks (e.g. lignocellulosic material), conversion routes (e.g. thermochemical, ash pyrolysis, enzymatic, etc.) and end products (e.g. gas or synthetic liquid biofuels). Contrarily to rst generation biofuels, where the utilized fraction (grains and seeds), represents only a small portion of the above-ground biomass, second generation biofuels can rely on the whole plant for bioenergy production. In fact, rapeseed grain yield is 3.4 t/ha but the oil content of the grain is only 40%, thus the effective yield is reduced to 1.35 t/ha [21]. Second generation biofuels (e.g. Fisher Tropsch (FT)-diesel from biomass and bioethanol from lignocellulosic feedstock) promise advantages over 1st generation biofuels in terms of land-use efciency and environmental performance, according to most of the

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LCA studies published in the literature [22,23]. Thanks to technology development, environmental performances of 2nd generation biofuels could benet of the use of high quantities of lignocellulosic residues and waste which are already available: they can constitute the main raw material sources, which can be also supplemented with non-food crops such as perennial grasses, and short-rotation forestry. Most processes and technologies for 2nd generation biofuels from biomass residues are still at a precommercial stage, but could enter the market within 1015 years if corresponding investments (R&D, infrastructure) are achieved. On the one side the raw material situation is optimum (widespread, relatively cheap and easily available); on the other side, their use could allow the coproduction of valuable biofuels, chemical compounds as well as electricity and heat, leading to better energy, environmental and economic performances through the development of biorenery concepts [24].

concept, and usually require materials in competition with the food and feed industry. Their exploitation is thereby limited. By contrast, lignocellulosic crops reduce the competition for fertile land, since they can be grown on land which is not suitable for agricultural crops. Moreover, in comparison with conventional crops that can contribute only with a small fraction of the above standing biomass, bioreneries based on lignocellulosic feedstocks can rely on larger biomass per hectare yields, since the whole crop is available as feedstock [24,28]. Concerning the conversion plant, consumption of non-renewable energy resources during biorenery processing should be minimized, along with related environmental impacts, while the complete and efcient biomass use should be maximized. This ecological perspective requires:  analyses of three important agricultural and forestry cycles, namely carbon (respiration, photosynthesis, and organic matter decomposition), water (precipitation, evaporation, inltration, and runoff) and nitrogen (N xation, mineralization, denitrication) and their interdependencies [29],  system performance evaluations at plant scale [30],  environmental impact evaluations carried out by means of Life Cycle Assessment [31]. Biorenery industries are expected to develop as dispersed industrial complexes able to revitalize rural areas. Unlike oil renery, which almost invariably means very large plants, bioreneries will most probably encompass a whole range of different-sized installations. In this context, several bio-industries can combine their material ows in order to reach a complete utilization of all biomass components: the residue from one bio-industry (e.g. lignin from a lignocellulosic ethanol production plant) becomes an input for other industries, giving rise to integrated bio-industrial systems. In addition, biomass resources are locally available in many countries and their use, may contribute to reduce national dependence on imported fossil fuels. 3.2. Feedstocks The term feedstock refers to raw materials used in biorenery. The biomass is synthesized via the photosynthetic process that converts atmospheric carbon dioxide and water into sugars. Plants use the sugar to synthesize the complex materials that are generically named biomass. An important stage in biorenery system is the provision of a renewable, consistent and regular supply of feedstock. Initial processing may be required to increase its energy density to reduce transport, handling and storage costs. Renewable carbon-based raw materials for biorenery are provided from four different sectors: 1. agriculture (dedicated crops and residues), 2. forestry, 3. industries (process residues and leftovers) and households (municipal solid waste and wastewaters), 4. aquaculture (algae and seaweeds). A further distinction can be done between those feedstocks which come from dedicated crops and residues from agricultural, forestry and industrial activities, which can be available without upstream concerns. The main biomass feedstocks can be grouped in 3 wide categories: carbohydrates and lignin, triglycerides and mixed organic residues. 3.2.1. Carbohydrates and lignin Carbohydrates (from starch, cellulose and hemicellulose) are molecules of carbon, hydrogen, and oxygen and are by far the most

3. The biorenery concept 3.1. Denition and perspectives Among the several denition of biorenery, the most exhaustive was recently performed by the IEA Bioenergy Task 42 Bioreneries [25]: Biorening is the sustainable processing of biomass into a spectrum of marketable products and energy. The biorenery concept embraces a wide range of technologies able to separate biomass resources (wood, grasses, corn. . .) into their building blocks (carbohydrates, proteins, triglycerides. . .) which can be converted to value added products, biofuels and chemicals. A biorenery is a facility (or network of facilities) that integrates biomass conversion processes and equipment to produce transportation biofuels, power, and chemicals from biomass. This concept is analogous to todays petroleum renery, which produces multiple fuels and products from petroleum. A forward looking approach is the stepwise conversion of large parts of the global economy/industry into a sustainable biobased society having bioenergy, biofuels and biobased products as main pillars and bioreneries as the basis. Such a replacement of oil with biomass will require some breakthrough changes in the todays production of goods and services: biological and chemical sciences will play a leading role in the generation of future industries and new synergies of biological, physical, chemical and technical sciences must be developed [24]. The efcient production of transportation biofuels is seen as one of the main promoting factors for the future development of bioreneries [26]. In fact, the transportation sector is growing steadily and the demand for renewable (bio-)fuels, which can only be provided from biomass, grows accordingly. As a consequence, the main challenge for biorenery development seems to be the efcient and cost effective production of transportation biofuels, whereas from the coproduced biomaterials and biochemicals additional economic and environmental benets can be gained. The main biobased products are today obtained from conversion of biomass to basic products like starch, oil, and cellulose. In addition, chemicals like lactic acid and amino acids are produced and used in the food industry. Other already commercially available biobased products include adhesives, cleaning compounds, detergents, dielectric uids, dyes, hydraulic uids, inks, lubricants, packaging materials, paints and coatings, paper and box board, plastic llers, polymers, solvents, and sorbents. Some examples of biorenery and non-conventional biomass industries which are already competitive in the market are listed in Cherubini et al. [27], along with some existing pilot and demo plant. Most of the existing biofuels and biochemicals are currently produced in single production chains and not within a biorenery

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common biomass component found in plant feedstocks. Six-carbon, single-molecule monosaccharide sugars (C6H12O6) include glucose, galactose and mannose, while the most common 5-carbon sugars (C5H10O5) are xylose and arabinose. The two most important sugar crops are sugar cane and sugar beet which, together with corn (a starch crop), supply almost all the ethanol that is produced today [32]. Starch (C6H10O5)n is a very large polymer molecule composed of many hundreds or thousands of glucose molecules (polysaccharides), which must be broken down into one or two molecule pieces prior to be fermented. The most widespread starch crops are wheat and corn. Once sugars have been depolymerized (for starch crops) or extracted (for sugar crops) they can be easily fermented to ethanol or used as a substrate for chemical reactions leading to a wide range of chemical products. Lignocellulosic biomass has three major components: cellulose, hemicellulose and lignin. Cellulose (C6H10O6)n has a strong molecular structure made by long chains of glucose molecules (C6 sugar). The distinction with starch is given by the conguration of the bonds formed across the oxygen molecule that joins two hexose units. Starch can be readily hydrolyzed by enzymes or acid attack to the single sugar monomers, while cellulose (3050% of total lignocellulosic dry matter) is much more difcult to hydrolyze and set free individual glucose monomers. Hemicellulose (C5H8O5)n is a relatively amorphous component that is easier to break down with chemicals and/or heat than cellulose; it contains a mix of C6 and C5 sugars. It is the second main component of lignocellulosic biomass (2040% of total feedstock dry matter). Lignin (C9H10O2(OCH3)n), is essentially the glue that provides the overall rigidity to the structure of plants and trees and is made of phenolic polymers. While cellulose and hemicellulose are polysaccharides that can be hydrolyzed to sugars and then fermented to ethanol, lignin cannot be used in fermentation processes, but it may be useful for other purposes (chemical extraction or energy generation). Lignin (1525% of total feedstock dry matter) is the largest noncarbohydrate fraction of lignocellulose. Lignocellulosic biomass can be provided either as a crop or as a residue. Large amounts of cellulosic biomass can be produced via dedicated crops like perennial herbaceous plant species, or short rotation woody crops. Other sources of lignocellulosic biomass are waste and residues, like straw from agriculture, wood waste from the pulp and paper industry and forestry residues. The use of waste biomass offers a way of creating value for society, displacing fossil fuels with material that typically would decompose, with no additional land use for its production [33]. 3.2.2. Triglycerides Oils and fats are triglycerides which typically consist of glycerin and saturated and unsaturated fatty acids (their chain length ranges between C8 and C20, but 16, 18 and 20 carbons are the most common). The sources of oils and fats are a variety of vegetable and animal raw materials. Soybean, palm, rapeseed and sunower oil are the most important in terms of worldwide production [34,35]. Vegetable oils are nowadays used for production of biodiesel by reacting with an alcohol, usually methanol. However, they can also be used as a substrate for chemical reactions thanks to two chemically reactive sites: the double bond in the unsaturated fatty acid chain and the acid group of the fatty acid chain [36]. Like sugar and starch crops, oilseed crops are characterized by low yield and high use of inputs. In the future, non-edible crops like Jatropha curcas and Pongamia pinnata, which require lower inputs and are suited to marginal lands, may become the most widespread oil crops for biorenery purposes, especially in dry and semiarid regions [32,37]. Other sources of vegetable oil for biofuel conversion can be found in waste streams of food industry, where waste edible oil is mainly generated from commercial services and food process-

ing plants such as restaurants, fast food chains and households [38]. 3.2.3. Mixed organic residues Other types of biomass sources that do not fall within the previous categories are organic fraction of the Municipal Solid Waste (MSW), manure, wild fruits and crops, proteins and residues from fresh fruit and vegetable industries. The physical and chemical characteristics of this wide spectrum of biomass resources vary largely. Certain streams such as sewage sludge, manure from dairy and swine farms and residues from food processing are very wet, with moisture contents over 70%. Therefore, these feedstocks are more suited for an anaerobic digestion process to generate biogas, rather than other fuels or chemicals. Other streams, such as organic MSW, may be more or less contaminated with heavy metals or other elements, but represents a high potential for energy recovery [39]. Clearly, the different properties and characteristic of the biomass waste require the application of different conversion technologies. 3.3. Technological processes in biorenery The aim of technological process in biorenery is depolymerizing and deoxygenating the biomass components. In order to convert biomass feedstock into valuable products within a biorenery approach, several technological processes must be jointly applied. They can be divided in four main groups: thermochemical, biochemical, mechanical/physical and chemical processes. 3.3.1. Thermochemical processes There are two main thermochemical processes for converting biomass into energy and chemical products. The rst is gasication, which consists in keeping biomass at high temperature (>700 C) with low oxygen levels to produce syngas, a mixture of H2, CO, CO2 and CH4 [40,41]. Syngas can be used directly as a stationary biofuel or can be a chemical intermediate (platform) for the production of fuels (FT-fuels, dimethyl ether, ethanol, isobutene. . .) or chemicals (alcohols, organic acids, ammonia, methanol and so on). The second thermochemical pathway for converting biomass is pyrolysis, which uses intermediate temperatures (300600 C) in the absence of oxygen to convert the feedstock into liquid pyrolytic oil (or bio-oil), solid charcoal and light gases similar to syngas [42,43]. Their yields vary with process conditions and for biorenery purposes the treatment which maximizes the production of liquid bio-oil is the most desirable (ash pyrolysis). The application of bio-oil as a transportation biofuel is nowadays problematic and its use as a source of chemicals is still under development [44,45]. Together with charcoal, it is generally best suited as a fuel for stationary electric power or thermal energy plants. In addition to gasication and pyrolysis, direct combustion is also included among the thermochemical processes. This is the most common and oldest form of biomass conversion that involves burning biomass in an oxygen-rich environment mainly for the production of heat [46]. 3.3.2. Biochemical processes Unlike thermochemical processes, biochemical processes occur at lower temperatures and have lower reaction rates. The most common types of biochemical processes are fermentation and anaerobic digestion. The fermentation uses microorganisms and/ or enzymes to convert a fermentable substrate into recoverable products (usually alcohols or organic acids). Ethanol is currently the most required fermentation product, but the production of many other chemical compounds (e.g. hydrogen, methanol, succinic acid, among others) is nowadays object of many research and development activities. Hexoses, mainly glucose, are the most fre-

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quent fermentation substrates, while pentoses (sugars from hemicellulose), glycerol and other hydrocarbons required the development of customized fermentation organisms to enable their conversion to ethanol [47]. Anaerobic digestion involves the bacterial breakdown of biodegradable organic material in the absence of oxygen over a temperature range from about 30 to 65 C. The main end product of these processes is biogas (a gas mixture made of methane, CO2 and other impurities), which can be upgraded up to >97% methane content and used as a surrogate of natural gas [48]. 3.3.3. Mechanical processes Mechanical processes are processes which do not change the state or the composition of biomass, but only perform a size reduction or a separation of feedstock components. In a biorenery pathway, they are usually applied rst, because the following biomass utilization requires reduction of the material size within specic ranges, depending on feedstock specie, handling and further conversion processes. Biomass size reduction is a mechanical treatment that refers to either cutting or commuting processes that signicantly change the particles size, shape and bulk density of biomass. Separation processes involve the separation of the substrate into its components, while with extraction methods valuable compounds are extracted and concentrated from a bulk and inhomogeneous substrate [49]. Lignocellulosic pre-treatment methods (e.g. the split of lignocellulosic biomass into cellulose, hemicellulose and lignin) fall within this category, even if some of hemicellulose is also hydrolyzed to single sugars [50]. 3.3.4. Chemical processes Chemical processes are those processes which carry a change in the chemical structure of the molecule by reacting with other substances. The most common chemical processes in biomass conversion are hydrolysis and transesterication, but this group also includes the wide class of chemical reactions where a change in the molecular formula occurs. Hydrolysis uses acids, alkalis or enzymes to depolymerise polysaccharides and proteins into their component sugars (e.g. glucose from cellulose) or derivate chemicals (e.g. levulinic acid from glucose) [50]. Transesterication is the most common method to produce biodiesel today and is a chemical process by which vegetable oils can be converted to methyl or ethyl esters of fatty acids, also called biodiesel. This process involves the coproduction of glycerine, a chemical compound with diverse commercial uses [34]. Other important chemical reactions in biorening are FisherTropsch synthesis, methanisation, steam reforming, among others. 4. From oil renery to biornery 4.1. Biomass vs. fossils as raw materials The structure of biorenery raw materials is totally different from that on which the current oil renery is based. In fact, the crude oil is a mixture of many different organic hydrocarbon compounds. The rst step of oil renery is to remove water and impurities, then distil the crude oil into its various fractions as gasoline, diesel fuel, kerosene, lubricating oils and asphalts. Then, these fractions can be chemically changed further into various industrial chemicals and nal products. Unlike petroleum, biomass composition is not homogeneous, because the biomass feedstock might be made of grains, wood, grass, biological waste and so on, and the elemental composition is a mixture of C, H and O (plus other minor components such as N, S and other mineral compounds). Chemical and elemental composition of some lignocellulosic biomass feedstocks is reported in

Table 1. If compared to petroleum, biomass generally has too little hydrogen, too much oxygen, and a lower fraction of carbon. The compositional variety in biomass feedstocks is both an advantage and a disadvantage. An advantage is that bioreneries can make more classes of products that can petroleum reneries and can rely on a wider range of raw materials. A disadvantage is that a relatively larger range of processing technologies is needed, and most of these technologies are still at a pre-commercial stage [51]. In order to be used for production of biofuels and chemicals, biomass needs to be depolymerized and deoxygenated. Deoxygenation is required because the presence of O in biofuels reduces the heat content of molecules and usually gives them high polarity, which hinders blending with existing fossil fuels [19]. Chemical applications may require much less deoxygenation, since the presence of O often provides valuable physical and chemical properties to the product. Unlike petroleum, biomass experiences seasonal changes, since harvesting is not possible throughout the entire year. A switch from crude oil to biomass may require a change in the capacity of chemical industries, with a requirement to generate the materials and chemicals in a seasonal time-frame. Alternatively, biomass may have to be stabilized prior to long-term storage in order to ensure continuous, year-round, operation of the biorenery [52]. Biorenery represents a change from the traditional oil renery based on large exploitation of natural resources and large waste production towards integrated systems in which all resources are used. An example of how the biorenery of the future will evolve can be found in the history of the existing corn wet-milling industry [53]. Initially the corn wet-milling industry produced starch as the major product. As technology developed and the need for higher value products drove the growth of the industry, the product portfolio expanded from various starch derivatives such as glucose and maltose syrups to high fructose corn syrup. Later on, fermentation products derived from the starch and glucose such as citric acid, gluconic acid, lactic acid, lysine, threonine and ethanol were added. Many other by-products, such as corn gluten, corn oil, corn ber and animal feed are now being produced. The nal picture is that the development of the technical, commercial and political infrastructure of a biomass renery (biorenery) makes it similar to the current oil renery concept. 4.2. Current chemical platforms in oil renery Todays chemical industry processes crude oil into a limited number of base fractions [54]. Using numerous cracking and rening catalysts and using distillation as the dominant separation process, crude oil is rened into fractions such as naphtha, gasoline, kerosene, gas oil and residues. The relative volumes of the fractions formed depend on the processing conditions and the composition of the crude oil. The naphtha fraction is subsequently used as a feedstock for the production of just a few platform chemicals from which all the major bulk chemicals are subsequently derived. An important characteristic of the naphtha feedstock is that, unlike biomass, it is very low in oxygen content. The majority of bulk chemicals can be produced starting from these few platform chemicals (see Fig. 1):     ethylene, propylene, C4-olenes, the aromatics benzene, toluene and xylene (often referred to as BTX).

These hydrogen- and carbon-containing platform chemicals are subsequently used, for instance as solvents (benzene, toluene),

F. Cherubini / Energy Conversion and Management 51 (2010) 14121421 Table 1 Difference in composition of some lignocellulosic feedstocks. Parameter Water LHV Cellulose Glucan (C6) Hemicellulose Xylan (C5) Arabinan (C5) Galactan (C6) Mannan (C6) Lignin Acids Extractives Ash C H O N S Unit (dry) % MJ/kg % % % % % % % % % % % % % % % % Softwood 15 19.6 44.5 44.5 21.9 6.3 1.6 2.56 11.4 27.7 2.67 2.88 0.32 50.3 5.98 42.1 0.03 0.01 Switchgrass 15 18.6 35.4 35.4 26.5 22.4 2.73 0.96 0.39 18.2 2.15 11.5 4.28 46.9 5.54 42 0.62 0.7 Corn stover 15 18.5 38.1 38.1 25.3 20.2 2.03 0.74 0.41 20.2 4.84 4.78 8.59 46.7 5.49 38.4 0.67 0.1 Wheat straw 15 17.6 32.6 32.6 22.6 19.2 2.35 0.75 0.31 16.8 2.24 12.9 10.2 43.9 5.26 38.7 0.63 0.16

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Petroleum

8387 1014 0.11.5 0.12 0.56

Sources: softwood [47]; switchgrass [62] (biomass sample type: switchgrass alamo whole plant #94); corn stover [62] (biomass sample type: corn stover zea mays stalks and leaves w/o cobs #55); wheat straw [62] (biomass sample type: wheat straw (Triticum aestivum) thunderbird whole plant #154); petroleum [63].

Fig. 1. Platform chemicals in oil renery and their main derivatives.

starting material for polymers (ethylene, propylene, butadiene) or are further functionalized via the introduction of elements such as oxygen, nitrogen or chlorine [55]. 4.3. Expected chemical platforms in biorenery A biorenery industry aiming at producing bulk chemicals from biomass will be based on a different selection of simple platforms

than those currently used in the petrochemical industry. Given the chemical complexity of biomass, there is some choice of which platform chemicals to produce since, within limits, different processing strategies of the same material can lead to different breakdown products. Although, in principle, all oil renery platform chemicals can be also derived from biomass, but with lower yields and higher costs (as depicted in [55]), the future bioreneries are expected to be

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based on a limited number of platforms, from which all the other commodity and bulk chemicals can be derived. In particular, the carbohydrate fraction of biomass feedstock (i.e. cellulose and hemicellulose in lignocellulosic biomass) is expected to play the biggest role as a renewable carbon source for biochemical products. In fact, biomass polysaccharides can be effectively hydrolyzed to monosaccharides (e.g., glucose, fructose and xylose) which can then be converted, via fermentations or chemical synthesis, to an array of bio Platform Molecules (bPM building block chemicals with potential use in the production of numerous value-added chemicals), analogous to the petro-platform molecules of the current oil renery. In 2004, a list of the most promising bPMs was compiled by the US Department of Energy, with the intention that research into the area of bPM utilization would focus on those molecules highlighted (Fig. 2) [56]. Some chemicals, such as lactic acid, citric acid and ethanol, were omitted from the list as research into their use was considered to be already extensive and at an advanced stage. Several functional groups are available from this list, offering a huge choice of potential reactions and products. When considering the type of reactions to perform on bPMs, the chemist should ideally consider those that are greenest. Addition reactions are more favourable than substitutions or eliminations as atom economy is higher. Pericyclic reactions, such as DielsAlder, are also inherently green, typically with atom economies of 100%. Any reactions involving extensive use of auxiliaries, such as solvents or stoichiometric reagents, or hazardous species should be avoided. Catalysts should be incorporated into every step, as long as they are recoverable and reusable [57]. In comparison to oil-derived platform molecules (e.g., ethylene, benzene, etc.), bPMs have much higher oxygen content. This will result in an interesting shift in chemistries from the often harsh and environmentally damaging oxidation procedures to largely greener reduction chemistry; for example using hydrogen gas over

a heterogeneous catalyst. As opposed to adding functionality, as it normally occurs in the petroleum-based chemical industry, there will be a switch to where a large part of the desired functionality or pre-functionality is already present in the substrate [57]. An example of the applications of one of these biobased platform chemicals is the following. Levulinic acid (C5H8O3) is formed by acid hydrolysis of C6 sugars and can be converted to a large number of chemical derivatives thanks to its high reactivity: since it has both a ketone carbonyl group and an acidic carboxyl group, it can react as a ketone and as a fatty acid. Firstly, cellulose is hydrolyzed to C6 sugars and then levulinic acid is obtained through hydroxymethylfuran (HMF) with an efciency of 50% [58]. Then, levulinic acid is converted to the desired products, either chemicals or fuel additives. Among the possible alternatives, the main interesting derivatives are [58,59]:  methyltetrahydrofuran (MTHF, a biofuel which can be blended with gasoline and is obtained by dehydratation and hydrogentation of levulinic acid),  d-aminolevulinic acid (a herbicide which can be produced after a chemical synthesis process),  diphenolic acids (a polymer constituent produced by reaction of levulinic acid with phenols),  ethyl levulinate (a transportation biofuel, produced after reaction with ethanol, which can be added to conventional diesel without engine modications). 5. Biorenery products The products of biorenery systems can be grouped in two broad categories: material products and energy products. Energy products are those products which are used because of their energy content, providing electricity, heat or transportation service. On the other hand, material products are not used for an energy generation

Fig. 2. Top 14 biomass platform molecules [56].

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purpose but for their chemical or physical properties. In some cases, a further distinction for the characterization of products is needed because some products like biohydrogen or bioethanol might be used either as fuels or as chemical compound in chemical synthesis. In these cases, it is necessary to identify the addressed markets, for instance the transportation sector for H2 and bioethanol. The products of a biorenery must be able to replace fossil fuel based products coming from oil renery, both chemicals and energy carriers. Concerning the chemicals, this objective can be met by producing the same chemical species from biomass instead of from fossils (e.g. phenols), or producing a molecule having a different structure but an equivalent function. Concerning the fuels, a biorenery must replace conventional fossil fuels (mainly gasoline, diesel, heavy oil, coal and natural gas) with biofuels coming from biomass upgrading. The most important energy products which can be produced in bioreneries are:  gaseous biofuels (biogas, syngas, hydrogen, biomethane),  solid biofuels (pellets, lignin, charcoal),  liquid biofuels for transportation (bioethanol, biodiesel, FT-fuels, bio-oil). The most important chemical and material products are the following:  chemicals (ne chemicals, building blocks, bulk chemicals),  organic acids (succinic, lactic, itaconic and other sugar derivatives),  polymers and resins (starch-based plastics, phenol resins, furan resins),  biomaterials (wood panels, pulp, paper, cellulose),  food and animal feed,  fertilizers. 6. The role of green chemistry In order to establish a sustainable future production of these biofuels and biochemicals, the integration of green chemistry into bioreneries, along with the use of low environmental impact technologies, is mandatory. Green chemistry can be considered as a set of principles for the manufacture and application of products that aim at eliminating the use, or generation, of environmentally harmful and hazardous chemicals. It offers a tool kit of techniques and underlying principles that any researcher could, and should, apply when developing the next generation of bioreneries. The overall goal of green chemistry combined with a biorenery is the production of genuinely green and sustainable chemical products [52]. Green chemistry offers a protocol when developing biorenery processes and may play an important role in facilitating production of commodity chemicals from biomass. During chemical product manufacture, and indeed during the whole product life cycle, energy demands should be minimized, safer processes used, and hazardous chemical use and production avoided. The nal product should be non-toxic, degradable into innocuous chemicals and with minimum production of waste. Green chemistry methodologies and techniques can be used to reach these goals. For instance, supercritical carbon dioxide is recognized as a green solvent, since it is non-ammable, non-toxic, available as byproduct of many conversion technologies (e.g. biomass fermentation) and gives no solvent residues. Other technologies with great potential as energy efcient extraction methods are microwaves and ultrasounds [60]. In addition, there are numerous natural polymers directly available from biomass with potential for physical and chemical modications. These include starches, cellulose, hemicellulose, lignin,

proteins and lipids. Modication of natural polymers is of extreme interest, since they can replace fossil derived polymers like plastics and textiles. For instance, lignin is a highly complex matrix of aromatic units and can be a renewable source of aromatic compounds so widely used in chemical industry. Breakdown of lignin to individual aromatic units, such as vanillin, is object of research and development activities, but current technology is low-yielding even under extreme conditions [61]. The range of chemicals and materials that future bioreneries could produce is extensive, and with further research the selection will become larger. As argued by Clark et al., environmental impact evaluation methodologies like LCA and metrics such as atom economy should become as important in measuring the sustainability of a chemical process as yield and selectivity are today [52]. 7. Guidelines for future bioreneries With all this, some nal guidelines for the development of biorenery complexes can be elaborated. A biorenery, similarly to what occurs in oil renery, should be based on feedstock upgrading processes, where raw materials are continuously upgraded and rened. This means that a biorenery should separate all the biomass feedstock components, and leading, through a chain of several processes, to a high concentration of pure chemical species (e.g. ethanol) or a high concentration of molecules having similar, well identied functions (e.g. the mixture of C alkanes in FT-fuels). As a consequence, a feedstock cannot be directly burnt without any previous treatment, since the aim of a biorenery is to increase the value of the different biomass components as material and energy source: the most desirable option is to send to combustion, for heat and electricity production, only the residues and leftovers of previous technological treatments and conversion processes. This concept leads to the following remarks:  a biorenery should produce at least one high value chemical/ material product, besides low-grade and high-volume products (like animal feed and fertilizers), according to the specications given above,  a biorenery should produce at least one energy product besides heat and electricity; the production of at least one biofuel (liquid, solid or gaseous) is then required. A biorenery plant should also aim at running in a sustainable way: all the energy requirements of the several biomass conversion processes should be internally supplied by the production of heat and electricity from combustion of residues (within a properly sized set of processes/technologies). For instance, in a lignocellulosic ethanol plant, lignin, after separation from cellulose and hemicellulose, can be burnt to provide the heat and electricity required by the plant. Since lignin can also be used to produce chemicals and polymers, direct external fossil energy inputs are allowed if they ensure overall economic benets and do not unduly burden the life-cycle environmental concerns. Similarly, solid, liquid and gaseous waste should be minimized. This target can be achieved in two ways: using all the different biomass components for producing a wide spectrum of multiple products in one location, or setting up industrial bio-clusters, where material ow exchanges among different plants are promoted in order to transform a downstream residue of a plant into an upstream raw material for another plant. 8. Conclusions The use of biomass as raw materials for bioenergy and biochemical production is encouraged by a reduction of fossil CO2

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F. Cherubini / Energy Conversion and Management 51 (2010) 14121421 LowCVP fuels working group. WTW sub-group. FWG-P-04-024; October 2004. Kim S, Dale BE. Life Cycle Assessment of various cropping systems utilized for producing biofuels: bioethanol and biodiesel. Biomass Bioenergy 2005;29:42639. Blottnitz von H, Curran MA. A review of assessments conducted on bio-ethanol as a transportation fuel from a net energy, greenhouse gas, and environmental life cycle perspective. J Clean Prod 2007;15:60719. Larson ED. A review of life-cycle analysis studies on liquid biofuel systems for the transport sector. Energy for Sustainable Development 2006;10:10926. Zah R, Boni H, Gauch M, Hischier R, Lehmann M, Wager P. Life Cycle Assessment of energy products: environmental assessment of biofuels. Final report. EMPA technology and society lab, Auftrag des Bundesamtes fr Energie, des Bundesamtes fr Umwelt und des Bundesamtes fr Landwirtschaft, Bern; 2007. Marris E. Sugar cane and ethanol: drink the best and drive the rest. Nature 2006;444:6702. Lange JP. Lignocellulose conversion: an introduction to chemistry, process and economics. Biofuels Bioprod Bioref 2007;1:3948. Cherubini F, Bird N, Cowie A, Jungmeier G, Schlamadinger B, Woess-Gallasch S. Energy and GHG-based LCA of biofuel and bioenergy systems: key issues, ranges and recommendation. Resour Conserv Recycling 2009;53:43447. Venturi P, Venturi G. Analysis of energy comparison for crops in European agricultural systems. Biomass Bioenergy 2003;25(3):23555. Searcy E, Flynn PC. Processing of Straw/Corn Stover: comparison of life cycle emissions. International Journal of Green Energy 2008;5:42337. Fleming JS, Habibi S, MacLean HL. Investigating the sustainability of lignocellulose-derived fuels for light-duty vehicles. Transportation Research Part D: Transport and Environment 2006;11:14659. Kamm B, Kamm M, Gruber PR, Kromus S. Biorenery systems an overview. 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emissions, the need for a secure energy supply, and a revitalization of rural areas. Biomass energy and material recovery is maximized if a biorenery approach is considered, where many technological processes are jointly applied to different kinds of biomass feedstock for producing a wide range of bioproducts. A lot of biorenery pathways, from feedstock to products, can then be established, according to the different types of feedstock, conversion technologies and products. Biorenery concept is analogous to todays petroleum renery, which produces multiple fuels and products from petroleum. A key driver for the development and implementation of bioreneries is the growth in demand for energy, fuels, and chemicals. Accordingly, the aim of research is in developing new technologies and creating novel processes, products, and capabilities to ensure the growth is sustainable from economic, environmental and social perspectives. Further research and technology adoption will indicate which new products and processes contribute to more sustainable performances compared to conventional fossil based systems. The term itself of sustainability needs an agreement on a common denition and criteria for its evaluation. This will be necessary for communication with nongovernmental organizations (NGOs), the general public, regulators and policy makers about, for example, CO2 reductions. When developing chemistry for future bioreneries, it is important that the methods and techniques used minimize impact to the environment and the nal products are truly green and sustainable. The use of sustainable feedstock is not enough to ensure a prosperous future for later generation; protection of the environment using greener methodologies is also required. References
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