Energy Conversion and Management 51 (2010) 1412–1421

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Energy Conversion and Management
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The biorefinery 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 refinery. 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 biorefinery complexes. In biorefinery, 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 biorefinery concept, in comparison with the current oil refinery. 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 final products. Through the integration of green chemistry into biorefineries, 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 refinery products. Ó 2010 Elsevier Ltd. All rights reserved.

Article history: Received 22 June 2009 Accepted 29 January 2010 Available online 6 March 2010 Keywords: Biorefinery 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 scientific 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 Earth’s climate [1]. The Intergovernmental Panel on Climate Change (IPCC) Fourth Assessment Report highlighted that the world’s 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 world’s 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: 0196-8904/$ - see front matter Ó 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 refinery 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 finance 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 biorefinery 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

In 2006.g. eutrophication. 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. after reviewing the strategic role played by green chemistry in establishing sustainable conversion technologies. As a consequence. because its feedstock is not in competition with the food and feed industry. This paper investigates the possibilities to use biomass feedstocks as raw materials in biorefinery. starches and vegetable oils cause several concerns: these productions compete with food for their feedstock and fertile land. these biofuels give rise to ethical. Finally.g. These limitations are expected to be partially overcome by developing the so-called 2nd generation biofuels [20]. Many biofuel production chains have been analysed by means of Life Cycle Assessment (LCA) in order to point out their environmental performances [10–12]. starch. such as residues from agriculture. Studies that have examined these other environmental issues have concluded that most. biofuels) are identified as 1st and 2nd generation biofuels. biomass and so on). sunflower. Sugarcane is used as primary feedstock in Brazil. ozone depletion. 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 [13–15]. In addition. Austria) are increasing their biodiesel production [8]. Germany led biodiesel production in 2006. In conclusion. forestry and industry and dedicated lignocellulosic crops.19].e. Policies designed to target one driver can be detrimental to another.g. political and environmental concerns. sugar beet and starch crops (mainly corn and wheat). technological processes and final products. acidification.g.) and end products (e. production of second generation biofuels (i. Sweden leads the world in automotive biogas production. The basic feedstocks are often seeds and grains such as wheat. organic waste and grasses. electricity and heat can be provided by a variety of renewable alternatives (wind. First generation biofuels First generation biofuels are produced from sugar. 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. represents only a small portion of the above-ground biomass. while biomass is very likely to be the only viable alternative to fossil resources for production of transportation fuels and chemicals. biofuels substituting fossil fuels lead to increased negative impacts [16. However. gas or synthetic liquid biofuels). showing that it is not that easy to draw simplified conclusions. since it is the only C-rich material source available on the Earth. The main advantages of first generation biofuels are due to the high sugar or oil content of the raw materials and their easy conversion into biofuel. State of the art in biofuel production Currently. The USA are the second largest producer with 0.3 billion litres. In some countries (such as Germany and Sweden). currently the world’s second largest producer (17. from raw materials based on waste.2. including local air pollution. Bioethanol is recovered from biomass feedstocks such as sugarcane. etc. World biodiesel production surpassed 6 billion litres in 2006. but not all. enzymatic.e. with a total fleet of approximately 4500 vehicles with 45% of its fuel supplied by biomethane [9]. For instance. corn and rapeseed. Cherubini / Energy Conversion and Management 51 (2010) 1412–1421 1413 individual driver or combinations.8 billion litres per year. and in the last few years it has been strong implemented in countries with economic subsides for electricity generation from biogas (especially European countries). biomethanol and bioethers may be included in this category. These include the utilization of lignocellulosic materials. after upgrading to biomethane. producing 2. a larger proportion of cereals or agricultural land will be dedicated to biofuel production instead of using it to produce food. Because of this competition. but also straight vegetable oils. biogas is also used as transportation biofuel. rapeseed grain yield is 3. flash pyrolysis. when biogas is mainly derived from waste and residues can be categorized as 2nd generation biofuel. but other countries (France. First generation biofuels usually refer to biofuels produced from raw materials in competition with food and feed industries. an overview of the current status in biofuel production is provided and then the emerging biorefinery concept is described.1. Italy. Second generation biofuels (e. Biodiesel is produced from oil based crops such as rapeseed. In order to overcome these issues.5 billion litres mainly from rapeseed and sunflower. 2. where the utilized fraction (grains and seeds). land use.86 billion litres. thermochemical. thus the ‘effective’ yield is reduced to 1. Firstly. In fact. These environmental burdens are much more affected by site specific assumptions than GHG and energy balances. Contrarily to first generation biofuels. soybean but also from palm oil and waste edible oils. according to most of the . With the exception of a few studies. The production of biogas is common in most world countries. especially concerning a possible fertile land competition with food and feed industries. 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. 1st generation biofuels are in competition with food and feed industries for the use of biomass and agricultural land. besides fossils.F. In the scientific literature. The current oil refinery industry is taken as benchmark throughout the paper.17]. some guidelines for future biorefinery complexes are proposed.4 t/ha but the oil content of the grain is only 40%. the term 2nd generation shows wide variation in usage and can variably refer to feedstocks (e. giving rise to ethical implications: as prices for fossil fuels increase.35 t/ha [21]. The latter is done through an overview of the most promising biomass feedstocks. transportation fuels based on biomass (i. Several LCA studies have also evaluated life cycle impacts under other environmental aspects. vegetable oil or animal fats using conventional technologies.8 billion litres per year). biodiesel and starch-derived biogas. 2. For example. thanks to the coproduction of both bioenergy and high value chemicals. conversion routes (e. mainly from sugar beet and starch crops [8]. Biogas is produced after anaerobic digestion of mixtures of corn derived starch. second generation biofuels can rely on the whole plant for bioenergy production. The European Union produces 3. the sustainable biomass production is a crucial issue. As a development of 2nd generation biofuel production. total world production reached 51. USA is currently the largest producer of bioethanol with a production of 19. manure. sun. the use of biomass in biorefinery complexes is expected to ensure additional environmental benefits and implement national energy security. The most common first generation biofuels are bioethanol. 2. water. with corn as primary feedstock. Fisher Tropsch (FT)-diesel from biomass and bioethanol from lignocellulosic feedstock) promise advantages over 1st generation biofuels in terms of land-use efficiency and environmental performance. first generation biofuels currently produced from sugars. lignocellulosic material). etc. Second generation biofuels Second generation biofuels are produced from a variety of nonfood crops. In addition.44 billion litres of bioethanol.

By contrast. In addition. In this context. consistent and regular supply of feedstock. Initial processing may be required to increase its energy density to reduce transport. cellulose and hemicellulose) are molecules of carbon.  environmental impact evaluations carried out by means of Life Cycle Assessment [31]. On the one side the raw material situation is optimum (widespread. and chemicals from biomass. along with some existing pilot and demo plant. agriculture (dedicated crops and residues).g. Carbohydrates and lignin Carbohydrates (from starch. plastic fillers. Concerning the conversion plant. aquaculture (algae and seaweeds). chemicals like lactic acid and amino acids are produced and used in the food industry. handling and storage costs. and organic matter decomposition). 3. since the whole crop is available as feedstock [24. the main challenge for biorefinery development seems to be the efficient and cost effective production of transportation biofuels. chemical and technical sciences must be developed [24]. the most exhaustive was recently performed by the IEA Bioenergy Task 42 ‘‘Biorefineries” [25]: ‘‘Biorefining is the sustainable processing of biomass into a spectrum of marketable products and energy”. triglycerides and mixed organic residues. the transportation sector is growing steadily and the demand for renewable (bio-)fuels. mineralization. biorefineries will most probably encompass a whole range of different-sized installations. which can be also supplemented with non-food crops such as perennial grasses. corn. [27].  system performance evaluations at plant scale [30]. and oxygen and are by far the most 3.1414 F. namely carbon (respiration. As a consequence. polymers.2. environmental performances of 2nd generation biofuels could benefit of the use of high quantities of lignocellulosic residues and waste which are already available: they can constitute the main raw material sources. . their use could allow the coproduction of valuable biofuels. giving rise to integrated bio-industrial systems. infrastructure) are achieved. The biorefinery concept 3. Renewable carbon-based raw materials for biorefinery are provided from four different sectors: 1. which can only be provided from biomass. . on the other side. in comparison with conventional crops that can contribute only with a small fraction of the above standing biomass. Other already commercially available biobased products include adhesives. A forward looking approach is the stepwise conversion of large parts of the global economy/industry into a sustainable biobased society having bioenergy. and usually require materials in competition with the food and feed industry.23]. Unlike oil refinery. Their exploitation is thereby limited.1. Most processes and technologies for 2nd generation biofuels from biomass residues are still at a precommercial stage. Cherubini / Energy Conversion and Management 51 (2010) 1412–1421 LCA studies published in the literature [22. water (precipitation. This concept is analogous to today’s petroleum refinery.) into their building blocks (carbohydrates. grows accordingly. triglycerides. An important stage in biorefinery system is the provision of a renewable. grasses. physical. since they can be grown on land which is not suitable for agricultural crops.1. Feedstocks The term ‘‘feedstock” refers to raw materials used in biorefinery. dyes. dielectric fluids. forestry. The main biomass feedstocks can be grouped in 3 wide categories: carbohydrates and lignin. In fact. environmental and economic performances through the development of biorefinery concepts [24]. cleaning compounds. Biorefinery industries are expected to develop as dispersed industrial complexes able to revitalize rural areas. 3. whereas from the coproduced biomaterials and biochemicals additional economic and environmental benefits can be gained. and runoff) and nitrogen (N fixation. several bio-industries can combine their material flows in order to reach a complete utilization of all biomass components: the residue from one bio-industry (e. Thanks to technology development.) which can be converted to value added products. Such a replacement of oil with biomass will require some breakthrough changes in the today’s 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.28]. The efficient production of transportation biofuels is seen as one of the main promoting factors for the future development of biorefineries [26]. 3. The biomass is synthesized via the photosynthetic process that converts atmospheric carbon dioxide and water into sugars. leading to better energy. 2. while the complete and efficient biomass use should be maximized. paper and box board. biofuels and biobased products as main pillars and biorefineries as the basis. paints and coatings. solvents. A biorefinery is a facility (or network of facilities) that integrates biomass conversion processes and equipment to produce transportation biofuels. and cellulose. but could enter the market within 10–15 years if corresponding investments (R&D. In addition. which produces multiple fuels and products from petroleum. The main biobased products are today obtained from conversion of biomass to basic products like starch. denitrification) and their interdependencies [29]. proteins. hydrogen. detergents. industries (process residues and leftovers) and households (municipal solid waste and wastewaters). 4. lubricants. power. evaporation. and short-rotation forestry. relatively cheap and easily available). . Some examples of biorefinery and non-conventional biomass industries which are already competitive in the market are listed in Cherubini et al. Definition and perspectives Among the several definition of biorefinery. which almost invariably means very large plants. oil. packaging materials. Plants use the sugar to synthesize the complex materials that are generically named biomass. may contribute to reduce national dependence on imported fossil fuels. which can be available without upstream concerns. forestry and industrial activities. biofuels and chemicals. consumption of non-renewable energy resources during biorefinery processing should be minimized. biomass resources are locally available in many countries and their use. Most of the existing biofuels and biochemicals are currently produced in single production chains and not within a biorefinery .2. chemical compounds as well as electricity and heat. infiltration. hydraulic fluids. lignocellulosic crops reduce the competition for fertile land. lignin from a lignocellulosic ethanol production plant) becomes an input for other industries. A further distinction can be done between those feedstocks which come from dedicated crops and residues from agricultural. inks. Moreover. along with related environmental impacts. This ecological perspective requires:  analyses of three important agricultural and forestry cycles. concept. The biorefinery concept embraces a wide range of technologies able to separate biomass resources (wood. . biorefineries based on lignocellulosic feedstocks can rely on larger biomass per hectare yields. photosynthesis. and sorbents.

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). such as organic MSW. methanol.3. Hemicellulose (C5H8O5)n is a relatively amorphous component that is easier to break down with chemicals and/or heat than cellulose. which consists in keeping biomass at high temperature (>700 °C) with low oxygen levels to produce syngas. isobutene. direct combustion is also included among the thermochemical processes.1. organic acids.3. rather than other fuels or chemicals. ammonia. Lignin (C9H10O2(OCH3)n). but it may be useful for other purposes (chemical extraction or energy generation). Large amounts of cellulosic biomass can be produced via dedicated crops like perennial herbaceous plant species. 3. succinic acid. while the most common 5-carbon sugars (C5H10O5) are xylose and arabinose. rapeseed and sunflower oil are the most important in terms of worldwide production [34. Thermochemical processes There are two main thermochemical processes for converting biomass into energy and chemical products. non-edible crops like Jatropha curcas and Pongamia pinnata. 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. several technological processes must be jointly applied. Technological processes in biorefinery The aim of technological process in biorefinery is depolymerizing and deoxygenating the biomass components. It is the second main component of lignocellulosic biomass (20–40% of total feedstock dry matter). The two most important sugar crops are sugar cane and sugar beet which. Other sources of vegetable oil for biofuel conversion can be found in waste streams of food industry. CO. oilseed crops are characterized by low yield and high use of inputs. but represents a high potential for energy recovery [39]. lignin cannot be used in fermentation processes. However. proteins and residues from fresh fruit and vegetable industries. while cellulose (30–50% of total lignocellulosic dry matter) is much more difficult to hydrolyze and set free individual glucose monomers. which must be broken down into one or two molecule pieces prior to be fermented. CO2 and CH4 [40. solid charcoal and light gases similar to syngas [42. which require lower inputs and are suited to marginal lands.2. may be more or less contaminated with heavy metals or other elements. mainly glucose. where waste edible oil is mainly generated from commercial services and food process- ing plants such as restaurants. hydrogen. The first is gasification. . The distinction with starch is given by the configuration of the bonds formed across the oxygen molecule that joins two hexose units. mechanical/physical and chemical processes. Starch can be readily hydrolyzed by enzymes or acid attack to the single sugar monomers. Lignin (15–25% of total feedstock dry matter) is the largest noncarbohydrate fraction of lignocellulose. ethanol. these feedstocks are more suited for an anaerobic digestion process to generate biogas. They can be divided in four main groups: thermochemical. hemicellulose and lignin. which uses intermediate temperatures (300–600 °C) in the absence of oxygen to convert the feedstock into liquid pyrolytic oil (or bio-oil). 3.F.) or chemicals (alcohols. Cellulose (C6H10O6)n has a strong molecular structure made by long chains of glucose molecules (C6 sugar). Vegetable oils are nowadays used for production of biodiesel by reacting with an alcohol. Hexoses. like straw from agriculture. Starch (C6H10O5)n is a very large polymer molecule composed of many hundreds or thousands of glucose molecules (polysaccharides). it is generally best suited as a fuel for stationary electric power or thermal energy plants. galactose and mannose. The physical and chemical characteristics of this wide spectrum of biomass resources vary largely. Ethanol is currently the most required fermentation product. or short rotation woody crops. Certain streams such as sewage sludge. wood waste from the pulp and paper industry and forestry residues. biochemical processes occur at lower temperatures and have lower reaction rates. are the most fre- . Therefore.43]. Lignocellulosic biomass can be provided either as a crop or as a residue. it contains a mix of C6 and C5 sugars. is essentially the glue that provides the overall rigidity to the structure of plants and trees and is made of phenolic polymers. manure. wild fruits and crops.3. the different properties and characteristic of the biomass waste require the application of different conversion technologies. Like sugar and starch crops.2. . While cellulose and hemicellulose are polysaccharides that can be hydrolyzed to sugars and then fermented to ethanol.35]. displacing fossil fuels with material that typically would decompose. together with corn (a starch crop). 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. with moisture contents over 70%. single-molecule ‘‘monosaccharide” sugars (C6H12O6) include glucose. 3. The second thermochemical pathway for converting biomass is pyrolysis. The most widespread starch crops are wheat and corn.41]. Syngas can be used directly as a stationary biofuel or can be a chemical intermediate (platform) for the production of fuels (FT-fuels. Their yields vary with process conditions and for biorefinery purposes the treatment which maximizes the production of liquid bio-oil is the most desirable (flash pyrolysis). Soybean. fast food chains and households [38]. may become the most widespread oil crops for biorefinery purposes. Other sources of lignocellulosic biomass are waste and residues.45]. 3. dimethyl ether. a mixture of H2. methanol and so on). Other streams. Together with charcoal. biochemical. 3. among others) is nowadays object of many research and development activities. 18 and 20 carbons are the most common). In addition to gasification and pyrolysis. usually methanol. with no additional land use for its production [33].37]. Clearly. Six-carbon.g. supply almost all the ethanol that is produced today [32]. The use of waste biomass offers a way of creating value for society.3. but the production of many other chemical compounds (e. 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). Biochemical processes Unlike thermochemical processes. Cherubini / Energy Conversion and Management 51 (2010) 1412–1421 1415 common biomass component found in plant feedstocks. palm. 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]. The sources of oils and fats are a variety of vegetable and animal raw materials. 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]. manure from dairy and swine farms and residues from food processing are very wet. In order to convert biomass feedstock into valuable products within a biorefinery approach. 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.2. especially in dry and semiarid regions [32. but 16.2. In the future.

crude oil is refined into fractions such as naphtha.1416 F. An example of how the biorefinery of the future will evolve can be found in the history of the existing corn wet-milling industry [53].g. Other important chemical reactions in biorefining are Fisher–Tropsch synthesis. Many other by-products.and carbon-containing platform chemicals are subsequently used. commercial and political infrastructure of a biomass refinery (biorefinery) makes it similar to the current oil refinery concept. Mechanical processes Mechanical processes are processes which do not change the state or the composition of biomass. Biomass size reduction is a mechanical treatment that refers to either cutting or commuting processes that significantly change the particles size. From oil refinery to biorfinery 4. operation of the biorefinery [52]. fermentation products derived from the starch and glucose such as citric acid. Unlike petroleum. threonine and ethanol were added. Using numerous cracking and refining catalysts and using distillation as the dominant separation process. An advantage is that biorefineries can make more classes of products that can petroleum refineries and can rely on a wider range of raw materials. glucose from cellulose) or derivate chemicals (e. A disadvantage is that a relatively larger range of processing technologies is needed. An important characteristic of the naphtha feedstock is that.4. toluene and xylene (often referred to as BTX). and most of these technologies are still at a pre-commercial stage [51]. hemicellulose and lignin) fall within this category. The most common chemical processes in biomass conversion are hydrolysis and transesterification. Unlike petroleum. S and other mineral compounds). because the biomass feedstock might be made of grains. handling and further conversion processes. lactic acid. As technology developed and the need for higher value products drove the growth of the industry. grass. gluconic acid.g.3. The compositional variety in biomass feedstocks is both an advantage and a disadvantage. Initially the corn wet-milling industry produced starch as the major product. levulinic acid from glucose) [50]. In fact. glycerol and other hydrocarbons required the development of customized fermentation organisms to enable their conversion to ethanol [47]. since the presence of O often provides valuable physical and chemical properties to the product. biomass experiences seasonal changes. In a biorefinery pathway. These hydrogen. among others. and a lower fraction of carbon. it is very low in oxygen content. gas oil and residues. while pentoses (sugars from hemicellulose). Chemical processes Chemical processes are those processes which carry a change in the chemical structure of the molecule by reacting with other substances. Chemical and elemental composition of some lignocellulosic biomass feedstocks is reported in Table 1. alkalis or enzymes to depolymerise polysaccharides and proteins into their component sugars (e. since harvesting is not possible throughout the entire year. 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. Biorefinery represents a change from the traditional oil refinery based on large exploitation of natural resources and large waste production towards integrated systems in which all resources are used. toluene). but only perform a size reduction or a separation of feedstock components. kerosene. The first step of oil refinery is to remove water and impurities. . If compared to petroleum. biomass may have to be stabilized prior to long-term storage in order to ensure continuous. such as corn gluten.1. Separation processes involve the separation of the substrate into its components. fossils as raw materials The structure of biorefinery raw materials is totally different from that on which the current oil refinery is based. and the elemental composition is a mixture of C. Hydrolysis uses acids. depending on feedstock specie. 1):     ethylene. 3. 4. corn fiber and animal feed are now being produced. gasoline. 4. C4-olefines.2. the product portfolio expanded from various starch derivatives such as glucose and maltose syrups to high fructose corn syrup. which can be upgraded up to >97% methane content and used as a surrogate of natural gas [48]. biomass generally has too little hydrogen.3. diesel fuel. which hinders blending with existing fossil fuels [19]. while with extraction methods valuable compounds are extracted and concentrated from a bulk and inhomogeneous substrate [49]. Cherubini / Energy Conversion and Management 51 (2010) 1412–1421 quent fermentation substrates. a chemical compound with diverse commercial uses [34]. the split of lignocellulosic biomass into cellulose.3. year-round. lubricating oils and asphalts. The main end product of these processes is biogas (a gas mixture made of methane. the aromatics benzene. 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. because the following biomass utilization requires reduction of the material size within specific ranges. but this group also includes the wide class of chemical reactions where a change in the molecular formula occurs. 3. even if some of hemicellulose is also hydrolyzed to single sugars [50]. with a requirement to generate the materials and chemicals in a seasonal time-frame. This process involves the coproduction of glycerine. too much oxygen. Later on. methanisation. steam reforming. Then. A switch from crude oil to biomass may require a change in the capacity of chemical industries. the crude oil is a mixture of many different organic hydrocarbon compounds. they are usually applied first. shape and bulk density of biomass. In order to be used for production of biofuels and chemicals. The final picture is that the development of the technical. then distil the crude oil into its various fractions as gasoline.g. Lignocellulosic pre-treatment methods (e. Transesterification 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. lysine. The majority of bulk chemicals can be produced starting from these few platform chemicals (see Fig. Alternatively. CO2 and other impurities). kerosene. Chemical applications may require much less deoxygenation. these fractions can be chemically changed further into various industrial chemicals and final products. biomass composition is not homogeneous. H and O (plus other minor components such as N. Deoxygenation is required because the presence of O in biofuels reduces the heat content of molecules and usually gives them high polarity. for instance as solvents (benzene. propylene. biomass needs to be depolymerized and deoxygenated. The relative volumes of the fractions formed depend on the processing conditions and the composition of the crude oil. wood. also called biodiesel. Current chemical platforms in oil refinery Today’s chemical industry processes crude oil into a limited number of base fractions [54]. unlike biomass. Biomass vs. biological waste and so on. corn oil.

corn stover [62] (biomass sample type: corn stover zea mays stalks and leaves w/o cobs #55).1 Wheat straw 15 17.8 2.03 0.3 5.6 22. the future biorefineries are expected to be .F.7 0.35 0.54 42 0.5–6 Sources: softwood [47].39 18.01 Switchgrass 15 18.74 0. petroleum [63].59 46.4 27.5 44.6 2.9 10.7 2.78 8. within limits.3.1–1.49 38.3 20. Expected chemical platforms in biorefinery A biorefinery 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.98 42. different processing strategies of the same material can lead to different breakdown products. nitrogen or chlorine [55].5 22. starting material for polymers (ethylene.7 Corn stover 15 18.2 43. switchgrass [62] (biomass sample type: switchgrass alamo whole plant #94). Although.96 0.15 11.2 2.84 4. 4.9 5. wheat straw [62] (biomass sample type: wheat straw (Triticum aestivum) thunderbird whole plant #154).4 26.73 0.5 38.7 5.1–2 0.2 2.4 2.2 2.63 0. 1.4 35. all oil refinery platform chemicals can be also derived from biomass.26 38.3 1.41 20.6 35.88 0. there is some choice of which platform chemicals to produce since. propylene. Cherubini / Energy Conversion and Management 51 (2010) 1412–1421 Table 1 Difference in composition of some lignocellulosic feedstocks.16 1417 Petroleum 83–87 10–14 0.2 4. in principle.5 0.9 6. Given the chemical complexity of biomass.62 0.56 11.1 25.1 0.32 50.9 5.24 12.5 4.6 32.28 46. butadiene) or are further functionalized via the introduction of elements such as oxygen.5 21.67 0.6 44. Platform chemicals in oil refinery and their main derivatives.31 16. but with lower yields and higher costs (as depicted in [55]).1 38. Fig.03 0.6 32.4 0.67 2. 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 19.75 0.

typically with atom economies of 100%. benzene. a list of the most promising bPMs was compiled by the US Department of Energy. levulinic acid is converted to the desired products. it can react as a ketone and as a fatty acid. cellulose and hemicellulose in lignocellulosic biomass) is expected to play the biggest role as a renewable carbon source for biochemical products. to an array of bio Platform Molecules (bPM – building block chemicals with potential use in the production of numerous value-added chemicals). from which all the other commodity and bulk chemicals can be derived. such as solvents or stoichiometric reagents. there will be a switch to where a large part of the desired functionality or pre-functionality is already present in the substrate [57]. Catalysts should be incorporated into every step. As opposed to adding functionality.g. Firstly. When considering the type of reactions to perform on bPM’s. were omitted from the list as research into their use was considered to be already extensive and at an advanced stage. bPMs have much higher oxygen content. etc. such as lactic acid. In 2004. 2) [56].e. cellulose is hydrolyzed to C6 sugars and then levulinic acid is obtained through hydroxymethylfuran (HMF) with an efficiency of 50% [58]. providing electricity. Among the possible alternatives. In fact. are also inherently green. the carbohydrate fraction of biomass feedstock (i.. An example of the applications of one of these biobased platform chemicals is the following. via fermentations or chemical synthesis. Then. with the intention that research into the area of bPM utilization would focus on those molecules highlighted (Fig. Any reactions involving extensive use of auxiliaries. for example using hydrogen gas over a heterogeneous catalyst.  ethyl levulinate (a transportation biofuel.g.59]:  methyltetrahydrofuran (MTHF. citric acid and ethanol. Top 14 biomass platform molecules [56]. biomass polysaccharides can be effectively hydrolyzed to monosaccharides (e. Cherubini / Energy Conversion and Management 51 (2010) 1412–1421 based on a limited number of platforms. Biorefinery products The products of biorefinery systems can be grouped in two broad categories: material products and energy products.  d-aminolevulinic acid (a herbicide which can be produced after a chemical synthesis process).).1418 F. material products are not used for an energy generation Fig. heat or transportation service. Addition reactions are more favourable than substitutions or eliminations as atom economy is higher.  diphenolic acids (a polymer constituent produced by reaction of levulinic acid with phenols). fructose and xylose) which can then be converted. This will result in an interesting shift in chemistries from the often harsh and environmentally damaging oxidation procedures to largely greener reduction chemistry. as it normally occurs in the petroleum-based chemical industry. Some chemicals. Several functional groups are available from this list. offering a huge choice of potential reactions and products. In particular. a biofuel which can be blended with gasoline and is obtained by dehydratation and hydrogentation of levulinic acid). In comparison to oil-derived platform molecules (e. which can be added to conventional diesel without engine modifications). Energy products are those products which are used because of their energy content. ethylene. the main interesting derivatives are [58. either chemicals or fuel additives. 2. On the other hand. . glucose. the chemist should ideally consider those that are greenest. or hazardous species should be avoided. Pericyclic reactions. such as Diels–Alder. 5. produced after reaction with ethanol. analogous to the petro-platform molecules of the current oil refinery. as long as they are recoverable and reusable [57]. 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..

for instance the transportation sector for H2 and bioethanol. and hazardous chemical use and production avoided. biomass fermentation) and gives no solvent residues. it is necessary to identify the addressed markets. The most important chemical and material products are the following:  chemicals (fine chemicals. where raw materials are continuously upgraded and refined. In some cases. along with the use of low environmental impact technologies. cellulose. both chemicals and energy carriers. can be burnt to provide the heat and electricity required by the plant. The role of green chemistry In order to establish a sustainable future production of these biofuels and biochemicals. lignin. to a high concentration of pure chemical species (e. or generation. according to the specifications given above. or setting up industrial ‘‘bio-clusters”.g. Cherubini / Energy Conversion and Management 51 (2010) 1412–1421 1419 purpose but for their chemical or physical properties. of environmentally harmful and hazardous chemicals. phenols). paper. Concerning the chemicals. Other technologies with great potential as energy efficient extraction methods are microwaves and ultrasounds [60]. A biorefinery. lignin. phenol resins. where material flow exchanges among different plants are promoted in order to transform a downstream residue of a plant into an upstream raw material for another plant. Similarly. since it is non-flammable.g.g. solid. The range of chemicals and materials that future biorefineries could produce is extensive.  a biorefinery should produce at least one energy product besides heat and electricity. Concerning the fuels. liquid and gaseous waste should be minimized. Conclusions The use of biomass as raw materials for bioenergy and biochemical production is encouraged by a reduction of fossil CO2 . such as vanillin. available as byproduct of many conversion technologies (e. this objective can be met by producing the same chemical species from biomass instead of from fossils (e. biodiesel. In addition.  fertilizers. itaconic and other sugar derivatives). Modification of natural polymers is of extreme interest. The most important energy products which can be produced in biorefineries are:  gaseous biofuels (biogas.  biomaterials (wood panels. charcoal). in a lignocellulosic ethanol plant. apply when developing the next generation of biorefineries. ethanol) or a high concentration of molecules having similar. pulp. furan resins). and leading. The final product should be non-toxic.. 7. As argued by Clark et al. Green chemistry can be considered as a set of principles for the manufacture and application of products that aim at eliminating the use. should be based on feedstock upgrading processes. for heat and electricity production. This means that a biorefinery should separate all the biomass feedstock components. For instance. 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].  solid biofuels (pellets. is object of research and development activities. diesel. and with further research the selection will become larger. This concept leads to the following remarks:  a biorefinery should produce at least one high value chemical/ material product. Guidelines for future biorefineries With all this. direct external fossil energy inputs are allowed if they ensure overall economic benefits and do not unduly burden the life-cycle environmental concerns. proteins and lipids. 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 offers a tool kit of techniques and underlying principles that any researcher could. hemicellulose. lignin. syngas. the mixture of C alkanes in FT-fuels). 8.  liquid biofuels for transportation (bioethanol. some final guidelines for the development of biorefinery complexes can be elaborated. lignin is a highly complex matrix of aromatic units and can be a renewable source of aromatic compounds so widely used in chemical industry. through a chain of several processes. The products of a biorefinery must be able to replace fossil fuel based products coming from oil refinery. energy demands should be minimized. As a consequence. These include starches. FT-fuels. A biorefinery 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). or producing a molecule having a different structure but an equivalent function. Green chemistry offers a protocol when developing biorefinery processes and may play an important role in facilitating production of commodity chemicals from biomass. Breakdown of lignin to individual aromatic units. For instance. and indeed during the whole product life cycle. but current technology is low-yielding even under extreme conditions [61].g. after separation from cellulose and hemicellulose. For instance. the integration of green chemistry into biorefineries.F. since they can replace fossil derived polymers like plastics and textiles. lactic.  food and animal feed. coal and natural gas) with biofuels coming from biomass upgrading.  organic acids (succinic. 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. only the residues and leftovers of previous technological treatments and conversion processes. Since lignin can also be used to produce chemicals and polymers. the production of at least one biofuel (liquid. safer processes used. well identified functions (e. biomethane). a biorefinery must replace conventional fossil fuels (mainly gasoline. During chemical product manufacture. solid or gaseous) is then required. since the aim of a biorefinery is to increase the value of the different biomass components as material and energy source: the most desirable option is to send to combustion. non-toxic. building blocks. hydrogen. Green chemistry methodologies and techniques can be used to reach these goals. similarly to what occurs in oil refinery. degradable into innocuous chemicals and with minimum production of waste. a feedstock cannot be directly burnt without any previous treatment. besides low-grade and high-volume products (like animal feed and fertilizers). cellulose). The overall goal of green chemistry combined with a biorefinery is the production of genuinely green and sustainable chemical products [52]. bio-oil).  polymers and resins (starch-based plastics. is mandatory. supercritical carbon dioxide is recognized as a green solvent. there are numerous natural polymers directly available from biomass with potential for physical and chemical modifications. heavy oil. 6. and should. bulk chemicals).

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