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Biomass is the biodegradable fraction of products and waste of biological origin. Biomass comes from activities such as agriculture, forestry, as well as the biodegradable fraction of industrial and municipal waste. A large amount of biomass encourages the proposal of projects aimed at the integrated use of these wastes to obtain products with high added value. In fact, the use of this waste avoids negative ecological impact on agricultural fields, rivers, and lakes, and supports new technologies that can feasibly solve the pollution problem. The presentation of studies related to the use of these wastes as raw material to produce compounds of industrial interest in areas such as agriculture, second and third-generation biofuels, biogas, pharmaceuticals, chemical industry, human and animal nutrition, through chemical, physical, thermochemical, and biological processes, is the objective of this chapter.
Autonomous University of Guadalajara, Guadalajara, Jalisco, Mexico
*Address all correspondence to: dulce.diaz@edu.uag.mx
1. Introduction
One of the challenges of the twenty-first century is to develop processes for the elaboration of products of industrial interest, with the following characteristics:
environmentally friendly processes,
quality products and services, and
products that satisfy the needs of the consumer.
The above is to meet the needs of the inhabitants of each country and avoid environmental pollution and contribute to the reduction of global warming.
Directive (EU) 2018/2001 of the European Parliament and of the Council defines biomass as the biodegradable fraction of products and waste of biological origin.
Biomass is generated in activities such as agricultural activities of plant and animal origin, forestry, and related industries such as fishing and aquaculture, as well as the biodegradable fraction of industrial and municipal waste of biological origin.
According to the above, biomass covers a wide range of organic materials that are characterized by their heterogeneity, both in terms of their origin and nature.
In 2009 alone, it has been calculated that almost 3.3 Gt of waste was generated, which makes it an inexhaustible source of carbon due to the large amount of biomass produced each year, being a resource that can be used as raw material for the large-scale production of a variety of products of industrial interest, which will be presented in this chapter.
In fact, the use of these residues avoids the negative ecological impact on agricultural fields, rivers, and lakes, and supports new technologies that can feasibly solve the problem of pollution, since biomass, being a neutral resource, reduces CO2 emissions, greenhouse gas (GHG) emissions, and finally provides economic benefits to society [1].
The abundance of biomass and the favorable techno-economic associated with the production of a wide range of products have recently changed the global perception of the use of biomass as a valuable resource and not as a waste. It should be emphasized that failure to utilize biomass can lead to serious environmental hazards, converting biomass into large volumes of waste and causing serious problems for society.
This chapter delves into the research carried out and the development of value-added products from the different types of biomasses. The chapter is divided into the origin and classification of biomass, to continue presenting the different biomass treatment methods and production processes that are currently used for the development of value-added products, and finally, several products of industrial interest and their technology are presented.
Agricultural and forestry practices generate large amounts of residues [1]. The agricultural farming system generates residues in the harvesting of vegetables, fruits, grains, and other crops creating substantial amounts of residues called biomass. Especially agricultural cereal crops contribute significantly to biomass generation [1]. Centore et al. [2] published that globally 66% of residual plant biomass comes from cereal straw (stalk, leaves, and pods), and in second place are sugarcane stalks and leaves [2]. In the EU alone, about 23 Mton/year of dry biomass is available as residual cereal straw [3]. Tripathi et al. [1] mention that in 2009 alone almost 3.3 Gt of residues (fresh weight)/year were generated, considering the main world crops (wheat, corn, rice, soybean, barley, rapeseed, sugarcane, and sugar beet) in the selected countries/regions with high biomass potential (EU, Europe, Canada, Brazil, Argentina, China, and India). To this amount of biomass, it is necessary to include the biomass generated in the following activities: livestock, wood industry, agri-food, among others.
Due to the wide range of biomass that exists in the world, it can be classified according to its: (a) origin, (b) physical state and (c) chemical composition as shown in Figures 1 and 2 [4, 5].
Figure 1.
Classification of biomass according to its origin, physical state, and chemical composition.
Figure 2.
Biomass classification by chemical composition.
2.1 Classification of biomass according to its origin
Biomass classified according to its origin is divided into natural and residual.
Natural: Biomass that occurs spontaneously in nature, in ecosystems that have not suffered human intervention. Firewood or branches are an example of this type of biomass and constitute the main energy source in small towns and developing countries.
Residual: This is the biomass that comes from waste generated by human activities, such as agriculture, livestock, the timber industry, or the agri-food industry.
In addition, biomass is classified into dry and wet, or solid and liquid, and among them can be cited:
Residues from agricultural, forestry, and gardening activities, such as cereal straws, corn husks, agricultural surpluses, those originated in forestry treatments, etc.
Waste from agricultural and forestry industries, such as olive oil production, olive pomace oil, wine and alcohol industry, dried fruit production, wood trimmings, sawdust, etc.
Urban solid waste and urban wastewater.
Livestock waste: mainly slurry.
Agro-industrial waste: dairy industries, paper mills, distilleries, oil mills, canneries, etc.
Used food oils.
Energy crops: These are agricultural crops that are not intended for food, but to produce energy; they are called agro-energy crops. Agro-energy crops are selected according to the biomass production required, so they are usually species characterized by their robustness, high cellulose concentration, to reduce cultivation costs, and the price of biomass, among the examples we have: Ethiopian rapeseed and thistle.
2.2 Classification according to physical state
Biomass can be classified according to its physical state, this can be:
Solid Biomass: The best-known biomass, it includes wood and forest residues, residues from wood processing and pulp and paper industries, agricultural residues (straw) and wood waste, residues obtained from pruning and cleaning of parks and gardens, energy crops, peat, agro-industrial residues (pomace, sawdust, olive pits), organic fraction of municipal solid waste, etc.
Liquid Biomass: This group includes biodegradable livestock and industrial waste, urban wastewater, oils, and biofuels.
Gaseous Biomass: This is methane or biogas obtained from animal waste, agro-food waste, landfills, waste dumps, etc.
2.3 Classification according to chemical composition
The classification of biomass according to its chemical composition can be oleaginous, alcoholic, amylaceous/inulinic, and lignocellulosic. The following is the relation of biomass according to its chemical composition.
Oleaginous: In this group are the lipids obtained from seeds and grains, as well as animal fat.
Alcoholic: Monosaccharides and disaccharides represent this group, for example, sugar pulp, sugar cane, sweet sorghum, and beet.
Amylaceous/Inulinic: In this group are starch and inulin, which are present in potato tuber, cereal grains, dahlia rhizomes, chicory, etc.
Lignocellulosic: This group is represented by cellulose and hemicellulose polysaccharides found in lignocellulosic residues such as wood in general, agricultural residues, etc.
In the same way, from an ecological point of view, it is possible to differentiate biomasses of different orders: primary, secondary, and tertiary (Figures 3–5).
Figure 3.
Primary biomass.
Figure 4.
Secondary biomass.
Figure 5.
Tertiary biomass.
2.4 Classification of biomass from an ecological point of view
Primary biomass: Primary biomass includes organic matter formed directly by photosynthetic organisms (algae, green plants, and other autotrophic organisms). This group includes natural and anthropogenic biomass (Figure 3). Natural biomass is that which is produced spontaneously in nature without any human intervention. The resources generated in the natural pruning of a forest are an example of this type of biomass. Anthropogenic biomass includes biomass obtained by human activity such as agricultural residues. Primary biomass is classified into energy crops, agricultural residues, and forestry residues. This group includes all plant biomass, including energy crops (rape, thistle, eucalyptus), algal biomass (microalgae and macroalgae), agricultural waste (straw or pruning residues), and forestry waste (forestry treatments: obtaining firewood, cleaning to prevent fires and improve access).
Secondary biomass: Secondary biomass falls into the category of anthropogenic biomass, which includes waste generated in the agri-food, animal, and forestry industries, such as hulls, stems, leaves, pods, bones, agro-industrial waste, animal slaughterhouse waste, and wood industry waste (Figure 4).
Tertiary biomass: Tertiary biomass includes municipal solid waste and sludge from wastewater treatment plants (Figure 5).
Waste valorization is a process that converts waste materials into valuable products, such as chemicals, materials, and fuels. The transformation of biomass into value-added products is increasing worldwide due to the following characteristics [6, 7, 8, 9]:
As for chemicals and materials, biomass is an accessible and low-cost feedstock. Different forms of biomass are converted into products of industrial interest.
As renewable energy, biomass is resource neutral, as it is generally cleaner burning than fossil fuels.
Certain types of biomass can be used directly, without any or almost no treatment, such as wood residues, such as sawmill residues, logging residues, and municipal wood residues from plants and crops, which are used as fertilizer; in other cases, pretreatment is required to condition the biomass before it is subjected to processes to obtain a product of industrial interest [8]. The most common pretreatment methods are mechanical shredding, acid or alkaline hydrolysis, extraction of the components by organic solvents or ionic liquids, and steam explosion treatment, as some examples [10, 11].
The technologies applied to modify biomass properties are grouped into 4:
Thermochemical processes
Chemical processes
Biological processes
Physical processes
Figure 6 illustrates a graphic representation of the most common technologies used in biomass valorization.
Figure 6.
Biomass transformation processes.
3.1 Thermochemical process
Thermochemical processes are based on the use of high temperatures to convert biomass into energy (Figure 7). These processes involve irreversible chemical reactions carried out at high temperatures and a wide range of oxidation conditions [12]. These technologies have the potential to produce mainly heat, electricity, and fuels. Thermochemical transformation processes comprise liquefaction, pyrolysis, gasification, and combustion (Figure 8) [11, 12, 13, 14, 15].
Figure 7.
Thermochemical and chemical processes of biomass and its resulting products.
Figure 8.
Physical and biological processes of biomass transformation and resulting products.
3.1.1 Biomass liquefaction
Liquefaction aims to maximize the production of liquids from biomass, with the use of low temperatures (250–400°C) and high pressures (5–20 MPa) in the absence of oxygen and presence of catalysts such as carbonates and metals (zinc, copper, nickel, ruthenium) during processing. In this process the complex molecules of cellulose and lignin are fragmented by heating with steam and carbon monoxide, oxygen is removed, and hydrogen atoms are added at the same time. The product of this chemical reaction is a mixture of hydrocarbons called heavy oils, which on cooling condense into a liquid fraction [13]. The heavy oil or bio-oil produced contains less oxygen since it has less water, therefore, it has a higher calorific value.
3.1.2 Pyrolysis of biomass
Pyrolysis is a process that consists of the thermal decomposition of biomass in the absence of oxygen. Pyrolysis requires temperatures up to 550°C, although it can be carried out at even higher temperatures (700–900°C), depending on the biomass treated. The product is a synthesis gas with considerable calorific value. During the pyrolysis process, solid or carbonized products, liquid products (bio-oils, tars, and water), and a gas mixture consisting mainly of CO2, CO, H2, and CH4 are generated [9, 15].
3.1.3 Biomass gasification
Gasification consists of the conversion of biomass, normally of woody origin by thermal decomposition through partial oxidation reactions using a gasifying agent, such as steam, oxygen, air, or a mixture of the above and high temperatures (700–900°C), to obtain a synthesis gas also called as syngas with a considerable calorific value. Depending on the final feedstock conversion requirements, different temperature and pressure ranges can be used, as well as different types of gasifying agents, such as air, oxygen, steam, hydrogen, or carbon dioxide. The gas produced contains CO, H2, CH4, N2, and steam, which is used in internal combustion engines and gas turbines. Fuel gas is mainly used to produce electricity or thermal energy [15].
3.1.4 Biomass combustion
Combustion is a thermochemical process used for heat production, consisting of a chemical reaction in the presence of oxygen at temperatures between 800 and 1000°C, in which fuel is oxidized, and a large amount of energy is released in the form of heat (exothermic reaction). Depending on the amount of oxygen present in the process, combustion can be complete when the amount of air is sufficient to oxidize all the organic elements that make up the fuel to produce mainly CO2 and H2O, or incomplete when the concentration of air is insufficient to oxidize the fuel and generate CO. This process converts the stored chemical energy of the biomass into heat, mechanical energy or electricity depending on the process equipment used such as furnaces, boilers, steam turbines, turbo generators, etc. [12, 15].
3.2 Chemical processes
Chemical processes include structural modifications or breaking of chemical bonds to either alter or form new molecules, as well as to hydrolyze macromolecules. Several of the chemical processes presented in this section are used as pretreatments to improve the efficiencies of biological processes, enzymatic reactions, such as fermentation and anaerobic digestion of biomass.
3.2.1 Hydrolysis
Chemical hydrolysis treatments are classified into acid hydrolysis and alkaline hydrolysis.
In alkaline hydrolysis, effective lignin removal and low inhibitor formation have been observed, although the reaction times are relatively long and the cost of the alkaline catalyst is high; however, it does not degrade sugars. The most commonly used reagents in alkaline hydrolysis are NaOH, NH3, CaO, and Ca(OH)2, and unlike acid hydrolysis, the temperatures are lower, in the range of 50–90°C. The use of an alkali causes the degradation of the ester and side chains, altering the structure of the lignin. This causes a loss of cellulose crystallinity and partial solvation of hemicellulose [16].
It has been reported that acid hydrolysis of biomass removes hemicellulose and partially lignin at high reaction rates; the limitation of acid hydrolysis is the corrosion of the reactor material, as well as a high formation of sugar degradation inhibitors. In acid hydrolysis, dilute or concentrated acid is used, the most used being H2SO4; the biomass is subjected to temperatures in the range of 100–160°C [17].
3.2.2 Solvent extraction
In recent years, research has been conducted on the generation of third-generation biofuels, also called advanced biofuels due to the raw materials and technological processes used for their production. The raw material for third-generation fuels are microalgae, which promise a high production of biodiesel per unit area due to their high lipid content, which surpasses all biodiesel sources currently used. Microalgae are cultivated in photobioreactors, which only need a liquid culture medium, some nutrients, and sunlight to stimulate the growth of the microalgae biomass. This makes it feasible to use land that is not suitable for the cultivation of human and animal food products for the assembly of photobioreactors. Studies for the extraction of oil from algae for subsequent transformation into biodiesel, either chemically or enzymatically, have been the subject of numerous investigations in numerous countries [18].
The study of the extraction process of lipids from microalgae begins with the knowledge of the composition of the cell wall of the algal biomass to be extracted, to select the solvents that allow high extraction efficiency and the lowest cost of the process. A wide variety of organic solvents have been used in the extraction of algal oil, the most popular being hexane and ethanol, with the extraction of more than 98% of the fatty acids present in the algal biomass [19]. Since ethanol is a polar solvent, its selectivity towards lipids is relatively low compared to other solvents, so that other components of the microalgae such as sugars, pigments, or amino acids (primary and secondary metabolites) may appear in extractions with ethanol.
3.2.3 Supercritical fluids
Supercritical fluids (SCFs) are good solvents due to their ability to dissolve substances in a similar way to organic solvents, and because their viscosity and diffusion coefficient are close to those of gases, thus facilitating the transport properties of these fluids. Moreover, since the surface tension of FSCs is equal to zero, these fluids are particularly suitable for the extraction of substances contained in solid matrices such as lignocellulosic biomass to obtain cellulose, hemicellulose, and lignin [18, 20]. A fluid is called supercritical when it is forced to remain at conditions of pressure and temperature higher than its critical pressures and temperatures, under these conditions, the fluid has characteristics of both a gas and a liquid, which gives it some special properties such as low viscosity and high relative diffusivity, which allows them to easily penetrate the solids and provide a faster extraction.
All supercritical solid extraction processes consist of two stages: extraction and separation of the solvent from the extract produced. In extraction, supercritical CO2 flows through the solid and dissolves the extractable components. The solvent loaded with the extract is evacuated from the extractor and fed to the separator, where the pressure is reduced so that the solute is not soluble and precipitates. Another advantage is the use of FSCs is the possibility of changing their solvating power by variations of the pressure and/or temperature of the fluid, thus allowing fractional extraction of the solutes, and complete recovery of the solvent by simple pressure adjustments [20, 21].
Of all the supercritical fluids that have been studied, carbon dioxide (CO2) is the most widely used due to its low critical temperature (TC = 31°C) and pressure (PC = 74 bar), non-toxicity, availability, and low cost. CO2 is a “green” solvent that is found in the atmosphere, in food and beverages, and of which no minimum content needs to be fixed in extracts, so it can be safely used [21]. In fact, it is considered a GRAS solvent. The supercritical fluid method emerged as an alternative to the traditional use of large quantities of toxic solvents for extractions, being this type of processes the most promising, besides these techniques are characterized by having short extraction times and high selectivities [20].
3.3 Physical processes
The physical processes most used in the transformation of biomass into value-added products are presented.
3.3.1 Mechanical crushing
The reduction of wood to a size compatible with the subsequent process is the first step in the pretreatment of biomass. The reduction of lignocellulosic materials through a combination of chipping and/or grinding can be applied to reduce cellulose crystallinity, increase mass transfer due to a larger contact area and increase the efficiency of the subsequent process, whether chemical, thermochemical, or biological. The size of the materials is usually 10–30 mm after chipping and 0.2–2 mm after milling [22].
3.3.2 Mechanical extraction
Mechanical extraction is usually performed through an expeller press also called screw or extruder press. This press is a continuous mechanical extractor, where the oil is extracted from the raw material in a single step, with high pressure. Mechanical extraction has been used as a tool for the extraction of microalgae components and includes several kinds of mechanical devices such as cell homogenizers, ball mills, pressing systems [10], concluding that the highest percentage of oil extraction was obtained when using a ball mill with 1 mm crystal spheres for one minute. Mechanical extraction methods have the disadvantage of difficulty in recovering the extracted oil, so these kinds of methods are used in combination with chemical solvent methods.
3.3.3 Biomass briquetting
Biomass briquettes are a biofuel, made mostly from dried and compressed green waste and other organic materials (rice and groundnut hulls, bagasse, municipal solid waste, and agricultural residues), which can be used in boilers to generate steam or electricity from it, also used in ovens for cooking and heating. Briquettes are burned together with coal to generate heat through combustion, generating low total net greenhouse gas emissions compared to fossil fuels. The dimensions of briquettes are diameter > 5 cm and length between 50 and 80 cm [23].
3.4 Biological processes
Biological processes use biological agents (microorganisms, algae, or enzymes) to convert biomass into value-added products such as electricity, heat, bioproducts, and fuels. Biological processes can be divided into biocatalysis (enzymes are used as biocatalysts), fermentation, and anaerobic digestion.
3.4.1 Enzymatic process
Enzymatic processes are present in several areas of biotechnology, such as pharmaceuticals, food, energy, detergents, textiles, as well as in the environment, mainly in water and waste treatment processes and in the formation of biofuel, specifically biodiesel. Biodiesel can be generated from the triglycerides of tallow, vegetable oil, or microalgae oil by transesterification [24].
It is important to highlight that in the processes of bioethanol and biogas formation and other products of interest by microbial means from biomass, there is a critical step, which is the release of fermentable sugars from the polysaccharides of the biomass to be converted with high yields into high value-added products. Therefore, the most recent research in the field of bioresources has focused on the development of certain biomass pretreatments, such as delignification and enzymatic hydrolysis of cellulose, in which a low production of inhibitory compounds and high release of fermentable sugars are achieved so that they can be efficiently transformed into value-added products via microbial means and with a low environmental impact [25].
3.4.2 Anaerobic digestion of biomass
In this process, organic matter (lignocellulosic biomass, municipal waste, livestock, and agricultural industry waste) is degraded to form biogas by the action of anaerobic bacteria at temperatures of approximately 30°C. Anaerobic digestion is the cheapest, most stable, and well-established technique that recovers a greater amount of energy from the source; the process consists of three fundamental stages: hydrolysis-acidogenesis, homoacetogenesis-acetogenesis, and methanogenesis [26]. The first stage involves acid-forming bacteria that use carbohydrates as raw material, the second stage involves acetic acid-forming bacteria that can be inhibited by H2, and the third stage involves acetophilic and hydrogenophilic bacteria that use acetic acid, carbon monoxide, and hydrogen to generate the product of digestion, which is biogas.
Biogas is a mixture of methane (CH4), carbon dioxide (CO2), small amounts of hydrogen (H2), hydrogen sulfide (SH2), and nitrogen (N2). Biogas can be used as an important energy source in the combustion process carried out in engines, turbines, or boilers operated in the industry. In addition, the degraded biomass that remains as a residue of the biogas production process is an excellent fertilizer for agricultural crops [27].
3.4.3 Biomass fermentation
Fermentation is an anaerobic process where the substrate is transformed into organic products through the action of microorganisms. The types of fermentation that exist, according to the microorganism present in the process are alcoholic, malic, lactic, acetic, propionic, and butyric.
The substrate is mainly fermentable sugars, obtained from starch, cellulose, fruits, vegetables, and in general from lignocellulosic biomass. Table 1 shows some of the products that have been obtained by fermentation using biomass [11, 16, 28, 29].
Product
Organism
Use
Product
Organism
Use
Ethanol
Saccharomyces cerevisiae, Zymomonas mobilis
Biofuel
Lactic acid
Lactobacillus
Chemical and food, cosmetics, pharmaceutical, and plastics industries
Biobutanol
Clostridium beijerinckii
Biofuel
Propionic acid
Propionibacteria
Food preservative
Acetone-butanol-ethanol (ABE)
Clostridium
Biofuel
Succinic acid
Anaerobiospirillum succinici
Chemical and food industry, cosmetics, pharmaceuticals, and plastics
Summary of the various products derived from biomass.
The transformation of biomass into chemical products and biofuels is increasing worldwide. Table 1 shows some products obtained by fermentation from lignocellulosic biomass. Biomass is a neutral and economical resource, however, to transform biomass into value-added products, a pretreatment of delignification and saccharification is necessary to release fermentable sugars.
The environmental impact of using biomass is the reduction of CO2 emissions due to the substitution of fossil fuels and the valorization of certain wastes as raw materials. The use of indigenous biomass helps to convert potentially problematic waste for the future into available resources. In addition, this action would reduce forest fires and contribute to the positive management of ecosystems and to the mitigation of climate change.
The social impact of the use of biomass is to stimulate the economy of the region through the employment of groups linked to rural areas and to stop the depopulation of rural areas and the economic savings that the use of waste allows. Finally, the economic value of biomass utilization requires the mobilization of a series of human and capital resources and an intense relationship with suppliers, as biomass has to be supplied to industries. This benefits the primary sector (agriculture, forestry, and livestock), as well as the secondary sector (agri-food, forestry, chemical, pharmaceutical, food, materials, etc.).
Biomass is a valuable renewable and undervalued source of chemicals for use in the processing industry and can be used directly or indirectly to produce platform molecules or bioproducts by chemical, physical, microbial, or enzymatic treatments. Nowadays, biomass can be used for many purposes, such as chemicals, pharmaceuticals, food, biofuels (biogas/bioethanol), or energy and fodder production, which contribute significantly to the economic growth of countries.
It should be noted that as urbanization increases, more waste will be generated by society, so the integral valorization of biomass is a fundamental pillar of sustainable development. Given the origin of this biomass, as well as its composition, biomass is a vast resource for society.
Due to the diversity that biomass presents in its chemical composition, biomass is a vast resource that requires research to further develop technologies and processes with a multidisciplinary approach. It should be noted that biomass pretreatment is a critical point in the production processes to achieve high yields and productivity. This is necessary to overcome the complete transition of our production systems from a petroleum-based economy to a bio-based economy.
The author is grateful to the Autonomous University of Guadalajara for its support in the realization of this work.
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Written By
Dulce María Diaz-Montaño
Submitted: 28 February 2022Reviewed: 01 March 2022Published: 12 April 2022
Open access peer-reviewed chapter
