Biorefineries: Integrated Biochemical Processes for Liquid Biofuels
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Biorefineries outlines the processes and steps to successfully scale up production of two types of biofuels, butanol and ethanol, from cellulosic residues for commercial purposes. It covers practical topics, including biomass availability, pretreatment, fermentation, and water recycling, as well as policy and economic factors. This reflects the unique expertise of the editor team, whose backgrounds range from wood and herbaceous feedstocks to process economics and industrial expertise. The strategies presented in this book help readers to design integrated and efficient processes to reduce the cost of production and achieve an economically viable end product
- Outlines the economic benefits of designing a single operational process.
- Includes all currently available processes on pretreatment, fermentation and recovery
- Covers all pretreatment, fermentation, and product recovery options
- Focuses on biofuels but acts as a stepping stone to develop cost-efficient processes for an array of commodity chemicals
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Biorefineries - Nasib Qureshi
Part I
Cellulosic Biomass Processing & Biorefinery Road Map
Chapter 1
An Overview of Existing Individual Unit Operations
Solmaz Aslanzadeh; Mofoluwake M. Ishola; Tobias Richards; Mohammad J. Taherzadeh* Swedish Centre for Resource Recovery, University of Borås, Borås, Sweden
* Corresponding author: Mohammad.Taherzadeh@hb.se
Abstract
This chapter presents an overview of the different unit operations of biochemical platforms used in biorefineries producing ethanol and butanol. Biochemical platforms primarily convert lignocellulosic biomass into mixed sugars and then liquid fuels. Biochemical conversion processes rely on biocatalysts, such as enzymes and microorganisms, in combination with heat, chemical catalysts, and solvents, to convert the carbohydrate fraction of lignocellulosic biomass (hemicellulose and cellulose) into an intermediate sugar stream, which serves as the substrate for ethanol and butanol fermentation. Future biorefineries can benefit from the various combinations of diverse raw materials, conversion processes, technologies, and product portfolios associated with these platforms. Biochemical conversion routes apply biocatalysts, such as enzymes and microbial cells, plus heat and chemicals, to convert biomass into an intermediate sugar mix stream and then to ethanol or butanol. Thermochemical conversion technologies use heat and/or physical catalysts to convert biomass into a gaseous intermediate that primarily consists of H2 and CO, and a subsequent chemical or biological step converts the intermediate into biofuels. Fully understanding these processes requires knowledge of each step. Therefore, this chapter offers a summary of the individual unit operations involved in these processes.
Keywords
Ethanol
Butanol
Lignocellulose
Pretreatment
Fermentation
1.1 Introduction
Biorefineries are integrated biomass-conversion processes used to generate biobased products such as biofuels (e.g., biobutanol and bioethanol), bioenergy (heat and power), and biobased chemicals and materials [1,2]. Biorefineries are analogous to present day petroleum refineries. As with petroleum refineries, which manufacture products from natural resources, biorefineries use integrated processes to produce biofuels and chemicals from bioresources, including various types of biomass, such as wastes and agricultural residuals [1,2]. Biorefinery facilities can be categorized according to feedstock materials, generated products, technologies employed, or a combination of these factors. In reality, the many available combinations of feedstocks, technologies, and products indicate the complexity of integrated biorefineries [3]. A simple biorefinery can be built on different platforms
designed for different product routes [2]. The biochemical platform is based on biochemical conversion processes focused on the fermentation of sugars extracted from biomass feedstocks. On the other hand, the thermochemical platform relies on thermochemical conversion processes, and it involves the gasification of feedstocks and the manipulation of subsequent by-products. Currently, the gasification of carbonaceous materials is a common practice (e.g., syngas generation from coal), but the gasification of lignocellulosic biomass is still an emerging technology. Consideration must be given to exactly how this process would fit into the biorefinery concept. For example, in what way might the heat and power generated from these processes be combined [2]?
Regardless of the importance of biobased products for many industries, technical, strategic, and commercial hurdles must be overcome before any large-scale commercialization can be successful [2]. The development of the industry now largely depends on the competition between different uses for biomass resources, which will significantly impact whether biorefineries arise primarily from the chemicals, fuels, or forestry products industries. The situation has emerged rapidly, and numerous next-generation biorefineries are already in operation. A biorefinery in Finland now utilize food industry waste as feedstock and operate bioethanol or biogas plants. In addition, the company is designing bioethanol production based on lignocellulosic sawdust material with a production capacity of 10 million liters of bioethanol annually. Borregaard, located in Norway, is today producing cellulose, ethanol, lignin derivatives, and vanillin [3]. The power company Fortum is commissioning a fluidized bed fast pyrolysis oil production based on woody biomass with an annual capacity of 50,000 tons [3].
Lignocellulosic material and multiple feedstocks currently dominate the research, reflecting the necessity of finding appropriate feedstocks to substitute for agricultural and energy crops in future biorefineries [3]. In comparison to fossil-based materials, biobased feedstock and products have lower carbon efficiency and contrasting molecular structures, and these differences are concerns that must be addressed regarding the biorefineries. Unlike fossil fuels, biomass components contain high percentages of oxygen [4], and the molar ratios of H/C and O/C are essential. Higher O/C ratios offer new options for producing molecules such as butanol, methyltetrahydrofuran, and ethers [5]. Monomers, such as carboxylic acids, are oxygen-rich and are gaining attention as biopolymers [6], and numerous other chemical routes for exploiting succinic acid are acknowledged as well [7]. Research on product valorization and optimal biorefinery design is growing rapidly, decreasing the gap between the production of petrochemicals and their biobased counterparts [8]. In order for biorefineries to be widely adopted, they must be well integrated into a current infrastructure [9]. The aromatic building blocks of lignin (benzene, toluene, and xylene) dominate the research in this regard. The aromatic chemicals isolated from lignin can be used in conventional petrochemical processes, which convert bulk aromatics into nylons, resins, polymers, and other compounds [10].
Companies are pursuing numerous sugar conversion technologies and processes for the production of fuels or monomers for polymer production. Hydroxymethylfurfural (HMF) is produced through the chemical dehydration of six carbon sugars into a range of furan derivatives such as 2,5-furandicarboxylic acid, which has been proposed as a replacement for terephthalic acid in the production of polyester. Six- and five-carbon sugars can undergo selective dehydration, hydrogenation, and oxygenation to give rise to useful products such as sorbitol, furfural, glucaric acid, HMF, and levulinic acid. The biorefinery industry is expected to experience its strongest growth in the production of secondary chemicals such as polylactic acid (PLA), polyhydroxyalkanoates, and polyethylene from biobased ethanol. Some companies are currently commercializing n-butanol and isobutanol production. Acrylic acid is also used as an important chemical building block in the production of polyacrylates and commodity acrylates created via the fermentation and hydrogenation of carbohydrates to 3-hydroxypropionicacid (HPA). The fermentation of carbohydrates into biohydrocarbons such as isoprene is the latest trend in biobased chemical production. In part, the growing attention paid to carbohydrate fermentation results from recent progresses in synthetic biology, which is allowing industry to design microbes for the production of a new range of molecules [9]. Lactic acid produced by fermentation can be transformed chemically to methyl lactate, lactide, and PLA [11]. PLA is a fully biodegradable replacement for polyethylene terephthalates [12]. Effective processes for transforming biologically produced lactic acid and HPA to methacrylic and acrylic acids are under development. DuPont has developed an economically competitive fermentation route for producing 1,3-propanediol, the main building block in poly(propylene terephthalate) synthesis [13]. Fermentation by numerous microorganisms has been used to produce succinic acid [14,15], and it could perhaps substitute maleic anhydride currently produced from butane, in future. Chemical companies, such as Dow Chemical, Huntsman, Cargill and Archer Daniels Midland, have proposed glycerol as an inexpensive building block for the production of high-value propylene glycol. Additionally, Dow and Solvay are investigating the production of epichlorohydrin from glycerol, as epichlorohydrin could later be manufactured into epoxy resins and epichlorohydrin elastomers [16]. Biofuels generated from biomass are predicted to replace the first-generation biofuels market slowly but steadily, and the required infrastructure may come from the infrastructure of existing petroleum and sugar industries, as these industries can consume the bioproducts before they finally become major fuel products [17].
This chapter primarily focuses on different unit operations used for the production of ethanol and butanol via biochemical and thermochemical processes. Biochemical conversion routes apply biocatalysts, such as enzymes and microbial cells, plus heat and chemicals, to convert biomass into an intermediate sugar mix stream and then into ethanol or butanol. On the other hand, thermochemical conversion technologies depend on heat and/or physical catalysts for the conversion of biomass into a gaseous intermediate that largely consists of H2 and CO, and a subsequent chemical or biological step converts that intermediate to biofuels (Figure 1.1). Truly understanding these processes requires knowledge of each step. This chapter offers a summary of the individual unit operations involved in these processes.
Figure 1.1 An overview of the biochemical and thermochemical conversion routes of lignocellulosic biomass for ethanol and butanol production.
1.2 Biochemical Processes
In the last few decades, the biorefining of biomass has attracted considerable attention. Mainly as a result of growing energy and environmental concerns, interest in biofuels and biochemical production from biomass has also grown rapidly. Biorefineries utilizing lignocellulosic biomass seem to have the most promise. The proposed reason is optimal raw material availability, as well as the possibility of good integration of the conversion products into the traditional petrochemical and future biobased product markets [18]. About half of the total global biomass yield is estimated to be lignocellulose, with 75% of the lignocellulose consisting of carbohydrates that are a potential future source of fermentable carbohydrates for the production of liquid biofuels, commodity chemicals, and biodegradable chemicals [18]. The cellulose and hemicellulosic polymers of lignocellulose can be enzymatically or chemically hydrolyzed into their monomeric sugars, followed by fermentation to biofuels [19]. The release of fermentable sugars from lignocellulosic material is considered to be a bottle-neck for the industrial development of lignocellulose-based biorefineries [18]. Overcoming biomass recalcitrance and making the cellulose accessible for the enzymes is still a challenge [19]. The purpose of pretreating lignocelluloses is to develop and enhance the reactivity of cellulose and hemicellulose in the subsequent steps. For the pretreatment, the lignocelluloses are exposed to heat, chemicals, and/or enzymes (Figure 1.2). Pretreatment technologies are generally classified into the physical, chemical, physicochemical, and biological methods summarized in Table 1.1.
Figure 1.2 The pretreatment process using heat, acids, bases, and other chemicals to open up the lignocellulosic structures and make them available for the enzymatic hydrolysis.
Table 1.1
A Summary of Pretreatment Methods for Lignocellulosic Biomass
It is not easy to evaluate and compare pretreatment technologies, because these technologies entail upstream and downstream processing costs, capital investment, chemical recycling, and waste treatment systems. Nevertheless, if pretreatment is considered to be an integrated division of an industrial system or biorefinery, mass-and-energy balance analysis could be used to evaluate the efficiency of a pretreatment method with a given feedstock [48]. A cost-effective and efficient pretreatment technology must be developed in order for lignocellulosic biofuels to become commercially possible [49].
1.2.1 Biomass Pretreatment Technologies and Their Challenges
The recalcitrant nature of cellulose in lignocellulosic materials results from the compact arrangements of polymer chains that are water insoluble, as well as its resistance to depolymerisation [50,51]. Hence, it is vital that pretreatment make changes in the structure of the lignocellulose to make the cellulose more accessible to hydrolysis. The resistance of lignocellulosic material to hydrolysis is attributed to many factors, such as the substance’s heterogeneous nature, crystallinity, accessible surface area, particle size, and degree of polymerization (DP), as well as the size of the lignin and hemicellulose shield protecting the cellulose [50,52,53]. However, the economics of downstream processing ought to be balanced against the cost of the pretreatment technology used in an integrated biorefinery. Thus, the trade-off concerning the operation, capital, and input (biomass) costs must be elucidated when selecting a pretreatment technique for a biorefineries [54,55]. There is challenge present in the interpretation of pretreatment effects that should be taken into consideration. For instance, altering one factor influencing the reactivity of the substrate after pretreatment could alter other factors that could impact the reactivity as well [52,56,57]. Disconnecting these effects remains a challenge. For example, enzymatic hydrolysis improves with hemicellulose removal, due to an increase in cellulose yields, and the removal of the lignin can further improve the rate, as well as the yield of cellulose. While the lignin is still present in the solid substrate, hemicellulose hydrolysis can also modify the nature of lignin, especially at elevated temperatures, affecting enzymatic digestibility [58]. Despite the wealth of research, the field has yet to produce a cost-effective pretreatment process that can fulfill all the requirements and be applicable to a wide variety of biomass feedstock with high yields.
1.2.2 Physical Pretreatment
In physical pretreatment, the biomass is reduced into particles of smaller size via mechanical comminution, or the surface area of the biomass is increased without size reduction. The surface area can often be increased through mechanical refining during which the biomass is subjected to shear-induced fibrillation
. Physical pretreatment provides cellulases with greater access to the biomass surface by increasing the surface area and thereby improving hydrolysis yields [19,59,60]. Physical pretreatment is often an essential step prior to or following chemical or biochemical processing [61,62]. However, the information about the mode of action, such as how physical pretreatment modifies the chemical composition or how it affects the cell wall structure, is limited, although physical pretreatment does appear to cause changes in the cell wall similar to changes produced by technologies for the mechanical pulping of wood, such as thermomechanical pulping, grinding, and pressure grinding. Some forms of physical pretreatment have been observed to alter the lignin structure [61,63]. A weakness of physical pretreatment is its lack of ability to remove the lignin, which limits the enzymes’ access to cellulose [64,65]. Other drawbacks of this pretreatment method are its high energy consumption, the prohibitive costs of its large-scale implementation, and the huge environmental and safety concerns related to it [48]. Investigations show that delignification of the feedstock could be the reason for the high energy consumption of physical pretreatment methods [66], and as such, physical pretreatment can ultimately affect the overall energy efficiency of a biorefinery [62].
1.2.3 Chemical and Physicochemical Pretreatment
The primary objective of chemical pretreatments is to enhance the biodegradability of cellulose by removing lignin and/or hemicellulose, thus potentially altering the DP and crystallinity of the cellulose [13]. After feedstock cost, the pretreatment of biomass is estimated to comprise the largest cost in biofuel production [49]. Generally, chemical pretreatment technologies display a high degree of selectivity for the biomass constituents, and they require quite harsh reaction conditions, which may not be desirable for integration into a biorefinery scheme, because of possible effects on downstream biological processing [40,50]. For instance, oxidative lime pretreatment is effective but requires high oxygen pressure [67]. Organic solvent pretreatments require additional catalysts, and the solvents have to be entirely removed and recycled afterwards because of their inhibitory effect on downstream saccharification and fermentation [68]. Organosolv pretreatments are effective at solubilizing lignin [69], which can be recovered and utilized for a range of applications such as precursors for various chemicals or fuel in a biorefinery. The challenge with this pretreatment is that, in order to be feasible, high recovery yields of the organic solvent (e.g., by distillation) are necessary. The pretreated material has to be separated from the solvent as well, in order to avoid potential inhibitors causing negative effects on subsequent enzymatic hydrolysis or fermentation. In the case of ethanol as solvent, however, solvent recovery could be simplified because plants usually have the technology necessary for handling ethanol when it is a final product [70]. Diluted acid pretreatment is quite effective in solubilizing the hemicellulose, although the generation of polysaccharide degradation products at elevated temperatures is a drawback. These products can inhibit microorganisms in downstream fermentation, leading to lower overall ethanol yields [20,71]. Furthermore, recycling and concentrating the acid are generally too costly as well