Pretreatment of Biomass: Processes and Technologies

Pretreatment of Biomass

Processes and Technologies

Editors

Ashok Pandey

Centre for Biofuels & Biotechnology Division, CSIR-National Institute for Interdisciplinary Science & Technology, Trivandrum, India

Sangeeta Negi

Department of Biotechnology, Motilal Nehru National Institute of Technology, Allahabad, India

Parameswaran Binod

Centre for Biofuels & Biotechnology Division, CSIR-National Institute for Interdisciplinary Science & Technology, Trivandrum, India

Christian Larroche

Institut Pascal, Polytech Clermont-Ferrand University Blaise Pascal Clermont-Ferrand, France

Table of Contents

Cover image

Title page

Copyright

List of Contributors

Section A. Lignocellulosic Biomass

Chapter 1. Introduction

1.1. Overview

1.2. The Role of Pretreatment

1.3. Methods of Pretreatment

1.4. Summary

Chapter 2. Analysis of Lignocellulosic Biomass Using Infrared Methodology

2.1. Introduction

2.2. Physical Principles of IRS and Its Application

2.3. Composition and Structure of Lignocellulosic Biomass

2.4. Biomass Analysis via Fourier Transform NIRS

2.5. Biomass Analysis via Fourier Transform Mid-infrared Spectroscopy

2.6. Conclusion

Chapter 3. Acidic Pretreatment

3.1. Introduction

3.2. Acid-Catalyzed Reaction of Lignocellulose

3.3. Inhibitors and Detoxification

3.4. Process Configurations for Acidic Pretreatment

Chapter 4. Alkaline Treatment

4.1. Introduction

4.2. Types of Alkali

4.3. Conditions of Alkali Pretreatment

4.4. Mechanism of Alkali Pretreatment

4.5. Physicochemical Characterization of Alkali Pretreated Biomass

4.6. Prospects and Consequences

4.7. Commercialization Aspects

4.8. Conclusion

Chapter 5. Hydrothermal Treatment

5.1. Introduction

5.2. Pretreatment of Lignocellulosic Biomass

5.3. Hydrothermal Treatment of Lignocellulosic Biomass

5.4. The Properties of Hydrolysate and Pretreated Biomass Obtained from Hydrothermal Treatment

5.5. Utilization of Hydrolysate and Pretreated Biomass Obtained from Hydrothermal Treatment

Chapter 6. Steam Explosion

6.1. Introduction

6.2. Mechanism

6.3. Key Parameters

6.4. Operation Mode

6.5. Chemical Addition

6.6. Physicochemical Variation of Biomass

6.7. Perspective

Chapter 7. Ozonolysis

7.1. Introduction

7.2. Applications of Ozonolysis

7.3. Ozonolysis Chemical Reactions and Structural Changes

7.4. Effect of Process Parameters

7.5. Challenges, Possibilities and Future Perspectives

Chapter 8. Ionic Liquid Pretreatment

8.1. Introduction

8.2. Ionic Liquids

8.3. Potency as Solvent for Lignocellulosic Biomass

8.4. Recent Research and Practices in IL Pretreatment

8.5. IL Pretreatment in Combination With Other Conventional Methods

8.6. Synthesis

8.7. Technoeconomic Factors Affecting Commercialization of IL Pretreatment

8.8. Conclusions

Chapter 9. Microwave Pretreatment

9.1. Introduction

9.2. MW Application

9.3. MW Pretreatment Reactors

9.4. Summary and Prospects

Chapter 10. Torrefaction

10.1. Introduction

10.2. Torrefaction Classification

10.3. Nonoxidative Torrefaction

10.4. Property Variation of Biomass

10.5. Oxidative Torrefaction

10.6. Wet Torrefaction and Steam Explosion

10.7. Applications

Section B. Algal Biomass

Chapter 11. Algal Biomass: Physical Pretreatments

11.1. Microalgal Biomass

11.2. Applications

11.3. Potential Biofuel Products

11.4. Pretreatments of Microalgae

11.5. Energy and Environmental Assessment

11.6. Conclusion and Final Remarks

Chapter 12. Chemical Pretreatment of Algal Biomass

12.1. Introduction

12.2. Choice of Pretreatment of Algal Biomass for the Production of Biofuels

12.3. Pretreatments of Algal Biomass for the Production of Bioethanol, Biogas, and Biohydrogen

12.4. Pretreatments for Lipid Extraction and Biodiesel Production

12.5. Recent Approaches of Biofuel Production from Algal Biomass

12.6. Future Prospects of Algal Pretreatment

Index

Copyright

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List of Contributors

Young Hoon Jung,     Department of Biotechnology, Korea University Graduate School, Seoul, Republic of Korea

Parameswaran Binod,     Centre for Biofuels, Biotechnology Division, CSIR – National Institute for Interdisciplinary Science and Technology, Trivandrum, India

Hélène Carrère,     INRA, UR0050, Laboratoire de Biotecnologie de l’Environnement, Avenue des Etangs, Narbonne, France

Wei-Hsin Chen,     Department of Aeronautics and Astronautics, National Cheng Kung University, Tainan, Taiwan, Republic of China

Jinghuan Chen,     Beijing Key Laboratory of Lignocellulosic Chemistry, Beijing Forestry University, Beijing, China

J.L. Colodette,     Pulp and Paper Laboratory, Department of Forestry Engineering, Federal University of Viçosa, Viçosa, Minas Gerais, Brazil

Ivet Ferrer,     GEMMA – Group of Environmental Engineering and Microbiology, Department of Hydraulic, Maritime and Environmental Engineering, Universitat Politècnica de Catalunya·BarcelonaTech, Barcelona, Spain

C. Marangon-Jardim,     Pulp and Paper Laboratory, Department of Forestry Engineering, Federal University of Viçosa, Viçosa, Minas Gerais, Brazil

So-Yeon Jeong,     Department of Forest Products and Technology, Chonnam National University, Gwangju, Republic of Korea

Kyoung Heon Kim,     Department of Biotechnology, Korea University Graduate School, Seoul, Republic of Korea

Jae-Won Lee,     Department of Forest Products and Technology, Chonnam National University, Gwangju, Republic of Korea

Sangeeta Negi,     Department of Biotechnology, Motilal Nehru National Institute of Technology, Allahabad, Uttar Pradesh, India

M. Morales-Otero,     Laboratory of Environmental Microbiology and Biotechnology, School of Environmental & Natural Resources Engineering, University of Valle, Santiago de Cali, Colombia

Ajay Kumar Pandey,     Department of Biotechnology, Motilal Nehru National Institute of Technology, Allahabad, Uttar Pradesh, India

Ashok Pandey,     Centre for Biofuels, Biotechnology Division, CSIR – National Institute for Interdisciplinary Science and Technology, Trivandrum, India

Min S. Park

Department of Chemical & Biomolecular Engineering, Korea Advanced Institute of Science and Technology, Yuseong-gu, Daejeon, Republic of Korea

Advanced Biomass R&D Center, Yuseong-gu, Daejeon, Republic of Korea

Fabiana Passos,     GEMMA – Group of Environmental Engineering and Microbiology, Department of Hydraulic, Maritime and Environmental Engineering, Universitat Politècnica de Catalunya·BarcelonaTech, Barcelona, Spain

S. Bolado-Rodríguez,     Department of Chemical Engineering and Environmental Technology, University of Valladolid, Valladolid, Spain

Raveendran Sindhu,     Centre for Biofuels, Biotechnology Division, CSIR – National Institute for Interdisciplinary Science and Technology, Trivandrum, India

Shao-Ni Sun,     Beijing Key Laboratory of Lignocellulosic Chemistry, Beijing Forestry University, Beijing, China

Run-Cang Sun

Beijing Key Laboratory of Lignocellulosic Chemistry, Beijing Forestry University, Beijing, China

State Key Laboratory of Pulp and Paper Engineering, South China University of Technology, Guangzhou, China

R. Travaini,     Department of Chemical Engineering and Environmental Technology, University of Valladolid, Valladolid, Spain

Enrica Uggetti,     GEMMA – Group of Environmental Engineering and Microbiology, Department of Hydraulic, Maritime and Environmental Engineering, Universitat Politècnica de Catalunya·BarcelonaTech, Barcelona, Spain

Kun Wang,     Beijing Key Laboratory of Lignocellulosic Chemistry, Beijing Forestry University, Beijing, China

Donghai Wang,     Department of Biological and Agricultural Engineering, Kansas State University, Manhattan, KS, USA

Feng Xu,     Department of Biological and Agricultural Engineering, Kansas State University, Manhattan, KS, USA

Jian Xu,     National Key Laboratory of Biochemical Engineering, Institute of Process Engineering, Chinese Academy of Sciences, Beijing, China

Ji-Won Yang

Department of Chemical & Biomolecular Engineering, Korea Advanced Institute of Science and Technology, Yuseong-gu, Daejeon, Republic of Korea

Advanced Biomass R&D Center, Yuseong-gu, Daejeon, Republic of Korea

Gursong Yoo,     Department of Chemical & Biomolecular Engineering, Korea Advanced Institute of Science and Technology, Yuseong-gu, Daejeon, Republic of Korea

Section A

Lignocellulosic Biomass

Outline

Chapter 1. Introduction

Chapter 2. Analysis of Lignocellulosic Biomass Using Infrared Methodology

Chapter 3. Acidic Pretreatment

Chapter 4. Alkaline Treatment

Chapter 5. Hydrothermal Treatment

Chapter 6. Steam Explosion

Chapter 7. Ozonolysis

Chapter 8. Ionic Liquid Pretreatment

Chapter 9. Microwave Pretreatment

Chapter 10. Torrefaction

Chapter 1

Introduction

Parameswaran Binod,  and Ashok Pandey     Centre for Biofuels, Biotechnology Division, CSIR – National Institute for Interdisciplinary Science and Technology, Trivandrum, India

Abstract

Conversion of lignocellulosic biomass to fuel involves three major operating steps: pretreatment, hydrolysis and fermentation. Pretreatment is the first and most important step in lignocellulosic biomass processing. It is the key process by which the recalcitrant lignocellulosic biomass could be modified so as to make it amenable to further processes or reactions in order to convert it into biofuel or other products. The chapter discusses the purpose of pretreatment and gives a brief outline of different pretreatment techniques in use for the processing of lignocellulosic biomass.

Keywords

Acid treatment; Algal biomass; Alkali treatment; Hydrothermal treatment; Lignocellulosic biomass; Microwave; Treatment; Thermochemical treatment; Torrefaction

1.1. Overview

Lignocellulosic biomass is a promising feedstock for future renewable fuels. It constitutes a substantial renewable substrate for bioethanol production that does not compete with food and animal feed. Lignocellulosic materials predominantly contain a mixture of carbohydrate polymers such as cellulose and hemicelluloses and lignin. Cellulose is an unbranched linear polymer of glucose. Hemicelluloses belong to a group of heterogenous polysaccharides containing both 6-carbon and 5-carbon sugars. Lignin is a very complex molecule with phenylpropane units linked in a three-dimensional structure. Lignocellulosic plant materials also contain other proteins and extractives represent a minor fraction (between 5% and 15%). Extractives contain large numbers of lipophilic and hydrophilic constituents.

The amount of cellulose, hemicelluloses and lignin depends on the type of material. Usually the cellulose content may vary between 30% and 50%, hemicelluloses 20–40% and lignin 10–30%. Pretreatment is the first and most important step in lignocellulosic biomass processing. It is the key process by which the recalcitrant lignocellulosic biomass could be modified so as to make it amenable to further processes or reactions in order to convert it into biofuel or other products.

The carbohydrate polymers in the lignocellulosic material are to be converted to simple sugars before fermentation. There are several hydrolysis methods are available for this conversion; they can be broadly classified into physical, chemical and biological. Among these, biological means of hydrolysis using enzymes is the preferred one due to its several advantages over the other two methods. Due to the heterogenous and very complex nature of the lignocellulosic biomass, enzymatic hydrolysis is not an efficient method for native biomass. Hence the biomass has to be pretreated so as to make it amenable to enzyme action. This book describes various methods of pretreatment generally adopted for removing the recalcitrance of the lignocellulosic biomass.

The enzymatic hydrolysis of lignocellulosic materials is limited by several factors, such as cellulose crystallinity, degree of polymerization, moisture content, surface area and lignin content. Decreased particle size improves the available surface area, which in turn improves the enzymatic hydrolysis. The pore size of the substrate in relation to the size of the enzymes is another limiting factor in enzymatic hydrolysis. Removal of hemicelluloses during pretreatment (mainly by acid pretreatment) increases the mean pore size of the substrate and thereby improves the hydrolysis process. Drying of pretreated biomass at higher temperatures generally decreases the sugar yield during enzymatic hydrolysis because of the collapse in pore structure. Hence it is highly recommended to dry the pretreated biomass at lower or ambient temperatures. The presence of lignin in the biomass limits the rate of hydrolysis as lignin irreversibly binds with cellulases. Hence the pretreatment method has to address most of these issues related to the enzymatic hydrolysis so as to make the process more economical.

1.2. The Role of Pretreatment

Pretreatment generally refers to the disruption of the naturally resistant carbohydrate-lignin shield that limits the accessibility of enzymes to cellulose and hemicelluloses. The choice of pretreatment technology is very significant. The pretreatment must take into account the sugar release patterns and solid concentrations for each pretreatment in conjunction with their compatibility with the overall process, feedstock, enzymes and organisms to be applied. The economics of the whole process must be considered while selecting a pretreatment method. The need for chemicals in pretreatment and subsequent neutralization and prefermentation conditioning should be minimal and inexpensive. Because milling of biomass to small particle sizes is energy-intensive and costly, pretreatment technologies that require limited size reduction are desirable. High yields of fermentable hemicellulose sugars of close to 100% should be achieved through pretreatment. The concentration of sugars from the coupled operations of pretreatment and enzymatic hydrolysis should be high enough to ensure that ethanol concentrations are adequate to keep recovery and other downstream costs manageable. Pretreatment reactors should be low in cost through minimizing their volume, not requiring exotic materials of construction due to highly corrosive chemical environments and keeping operating pressures reasonable. The liquid hydrolysate from pretreatment must be fermentable following a low-cost, high-yield conditioning step. However, it is highly desirable to eliminate conditioning to reduce costs and to reduce yield losses. The chemicals formed during hydrolysate conditioning in preparation for subsequent biological steps should not present processing or disposal challenges (e.g. gypsum). Cellulose from pretreatment should be highly digestible, with yields of greater than 90% in less than five and preferably less than three days with low cellulase loadings of less than 10  FPU/g cellulose. Lignin and other constituents should be recovered for conversion to valuable co-products and to simplify downstream processing. The distribution of sugar recovery between pretreatment and subsequent enzymatic hydrolysis should be compatible with the choice of organisms to ferment the sugars in hemicellulose. The heat and power demands for pretreatment should be low and/or be compatible for being thermally integrated with the rest of the process [1].

1.3. Methods of Pretreatment

A variety of physical (comminution, hydrothermolysis), chemical (acid, alkali, solvents, ozone), physicochemical (steam explosion, ammonia fiber explosion) and biological pretreatment techniques have been developed to improve the accessibility of enzymes to cellulosic fibers [2].

Acid pretreatment involves the use of sulfuric, nitric or hydrochloric acids to remove hemicellulose components and expose cellulose for enzymatic digestion while alkali pretreatment refers to the application of alkaline solutions to remove lignin and various uronic acid substitutions on hemicellulose that lower the accessibility of enzymes to the hemicellulose and cellulose. Generally, alkaline pretreatment is more effective on materials having high lignin content. Peroxide pretreatment enhances enzymatic conversion through oxidative delignification and reduction of cellulose crystallinity.

Hydrothermal treatments can be conducted over wide ranges of operating conditions. The treatment time can also vary widely (from a few seconds to several hours). Such is also the case with the liquid/solid ratio, which can be set at values from 2 to 40  g water/g material but usually falls within the range 8–10  g/g. pH has a strong influence on cellulose degradation.

Among the physicochemical processes, steaming with or without explosion (autohydrolysis) has received substantial attention. The pretreatment removes most of the hemicellulose, thus improving the enzymatic digestion. In steam explosion, the pressure is suddenly reduced and makes the materials undergo an explosive decompression. High pressure and consequently high temperature, typically between 160 and 260  °C, for a few seconds (e.g. 30  s) to several minutes (e.g. 20  min), are used in steam explosion. The steam explosion process is well documented and was tested in laboratory and pilot processes by several research groups and companies. Its energy cost is relatively moderate, and it satisfies all the requirements of the pretreatment process. Steam pretreatment can be performed with addition of sulfur dioxide (SO2); the aim of adding this chemical is to improve recovery of both cellulose and hemicellulose fractions. The treatment can be carried out by 1–4% SO2 (w/w substrate) at elevated temperatures, e.g. 160–230  °C, for a period of e.g. 10  min.

Ozonation is another attractive pretreatment method that does not leave strong acidic, basic or toxic residues in the treated material. The effect of ozone pretreatment has been found to be essentially limited to lignin degradation. Ozonation has been widely used to reduce the lignin content of both agricultural and forestry wastes. The pretreatment is usually carried out at room temperature and does not lead to the generation of inhibitory compounds. However, ozonolysis might be expensive due to the requirement of large amounts of ozone.

The use of microwave energy in the presence of a chemical reagent is another method of pretreatment. This is a more effective pretreatment than the conventional heating chemical pretreatment in terms of accelerating reactions during the pretreatment process [3]. The enzymatic hydrolysis of pretreated rice straw showed that the pretreatment by microwave/acid/alkali/H2O2 had the highest hydrolysis rate and glucose content in the hydrolysate [4].

Microorganisms can also be used to treat the lignocelluloses and enhance enzymatic hydrolysis. The applied microorganisms usually degrade lignin and hemicellulose but very little cellulose, since cellulose is more resistant than the other parts of lignocelluloses to the biological attack. Several fungi, e.g. brown-, white- and soft-rot fungi, have been used for this purpose. White-rot fungi such as Phanerochaete chrysosporium, Trametes versicolor, Ceriporiopsis subvermispora and Pleurotus ostreatus are among the most effective microorganisms for biological pretreatment of lignocelluloses. Low energy requirement, no chemical requirement, and mild environmental conditions are the main advantages of biological pretreatment. However, the treatment rate is very low in most biological pretreatment processes.

Torrefaction is a relatively mild thermochemical process that uses low temperature, generally 200–300  °C, and inert gas atmosphere to produce homogenous solid fuels with higher hydrophobicity and lower oxygen content relative to the feed biomass [5]. During this process, cellulose, hemicelluloses and lignin present in the biomass undergo different chemical transformations because of their distinct chemical and thermal reactivity. It has been reported that compared to cellulose and lignin fractions, most of the hemicelluloses degrade into volatile components at low torrefaction temperatures [6]. Due to the fuel value of torrefied biomass, it has been used as a replacement for coal, in co-combustion with other fuels and in the production of pellets or briquettes.

1.4. Summary

Pretreatment of biomass play a key role in the development of bioprocesses and products from lignocellulosic and algal biomass, working on the principle of biorefinery. The production of bioethanol (second-generation biofuel) from lignocellulosic feedstock, other than food materials, has been developed in recent years and third-generation biofuels are considered to be a technically viable alternative bioenergy resource devoid of major drawbacks. Marine resources have played an important role in biotechnology, particularly in the past decade. There are several macro-algae that contain intracellular carbohydrates and have a potential for production of biofuels, e.g. bioethanol and bio-oil. Different pretreatment methodologies are to be adopted to derive the useful components from the algal biomass.

Acknowledgment

The authors acknowledge the financial support for the Centre for Biofuels by the TIFAC, New Delhi and MNRE, New Delhi.

References

[1] Bin Y, Charles W.E. Pretreatment: the key to unlocking low-cost cellulosic ethanol. Biofuels Bioprod Biorefin. 2008;2:26–40.

[2] Moiser N, Wyman C, Dale B, Elander R, Lee Y.Y, Holtzapple M, et al. Features of promising technologies for pretreatment of lignocellulosic biomass. Bioresour Technol. 2005;96:673–686.

[3] Binod P, Satyanagalakshmi K, Sindhu R, Janu K.U, Sukumaran K.R, Pandey A. Short duration microwave assisted pretreatment enhances the enzymatic saccharification and fermentable sugar production from sugarcane bagasse. Renew Energy. 2012;37:109–116.

[4] Vani S, Binod P, Kuttiraja M, Sindhu R, Sandhya S.V, Preeti V.E, et al. Energy requirement for alkali assisted microwave and high pressure reactor pretreatments of cotton plant residue and its hydrolysis for fermentable sugar production for biofuel application. Bioresour Technol. 2012;112:300–307.

[5] Park J, Meng J, Lim K.H, Rojas O.J, Park S. Transformation of lignocellulosic biomass during torrefaction. J Anal Appl Pyrolysis. 2013;100:199–206.

[6] Peng Y.Y, Wu S. The structural and thermal characteristics of wheat straw hemicellulose. J Anal Appl Pyrolysis. 2010;88:134–139.

Chapter 2

Analysis of Lignocellulosic Biomass Using Infrared Methodology

Feng Xu,  and Donghai Wang     Department of Biological and Agricultural Engineering, Kansas State University, Manhattan, KS, USA

Abstract

Numerous energy crop species and various processing methods provide thousands of biomass samples that need quick, low-cost analysis. Infrared methodology can provide high-throughput analysis of cellulosic biomass. The conventional method for biomass analysis is time-consuming, labor-intensive and unable to provide structural information. Use of infrared spectroscopy allows qualitative and quantitative analysis of biomass samples without destruction of samples, which is beneficial for in situ or in-field measurement. Chemometric analysis is able to make calibration models robust and reliable. The progress of infrared techniques and their applications in biomass study is introduced. A comparison of infrared methods and the conventional method is also summarized. We also review recent infrared applications in biomass analysis and discuss the prospects for applications of infrared techniques.

Keywords

Biomass; Cellulose; Chemometric analysis; Infrared spectroscopy; Lignin

2.1. Introduction

Lignocellulosic biomass for biofuel production has attracted much attention because of its abundance and renewability [1]. The three major components of lignocellulosic biomass, cellulose, hemicellulose and lignin, could be candidates for further biological/chemical utilization [2]. Second-generation ethanol, or bioethanol, for example, is being developed from polysaccharides with microbial fermentation [3,4]. Lignin, a phenolic polymer, is also an important material in industrial applications such as development of adhesive resin [5,6] and lignin gels [7,8]. Lignin and cellulose are being utilized in the synthesis of biodegradable polymers [9]. Biomass composition varies by variety and production location/conditions [10], which, in turn, significantly affects processing strategies; for example, alkali pretreatment is more effective in biomass with low lignin content [11]. Biomass composition changes significantly during processing [12], so a fast and accurate determination of biomass composition is critical to accelerating biomass utilization.

Current biomass composition analysis methods are unable to meet the requirements of high-throughput biomass processing. Classic wet chemical methods of biomass determination, which employ two-step sulfuric acid hydrolysis, have been used for over a century, and improvements have adapted them to different objects and conditions [13,14]. The National Renewable Energy Laboratory distributed a series of procedures for biomass determination that have become the de facto process for biomass analysis [15]. These wet chemical methods provide reliable information about biomass composition and have been proven to work well with both wood and herbaceous feedstock, but they are labor-intensive, time-consuming and expensive, which makes them inappropriate for industrial applications or large numbers of samples; for example, a complete analysis using wet chemical methods costs $800–$2000 per sample [16]. Recent developments in the wet chemical method include a small-scale, high-throughput method that is able to process a large number of samples in less time [17], but the instruments/devices (e.g. powder/liquid-dispensing systems) are costly, and these methods require further refinement because some components of biomass (e.g. acid-soluble lignin and ash) are not determined. Other disadvantages of wet chemical methods are that they require preconditioning to remove extractives, and they generate reliable results only from samples within a certain range of particle size [18]. In addition, chemical methods are unable to differentiate among types of hemicellulose, such as xyloglucan and arabinoxylan [19]. Thus, a reliable low-cost, time-saving method is urgently needed for biomass analysis.

Infrared spectroscopy (IRS) has been widely used for qualitative and quantitative analysis in various areas, such as the food and pharmaceutical industries [20–23]; for example, the composition of protein and oil in meat products, cereal crops and food products was predicted successfully using near-infrared spectroscopy (NIRS) [24–26], as were Brix value and starch content in fruits [27]. The cost of analysis of grain materials using NIRS ($13 per sample) is lower than that using feed analysis (over $17 per sample) [28]. IRS also has been proven able to produce qualitative and quantitative results for biomass application [16,29]; for example, Fourier transform infrared spectroscopy (FTIR) has been used successfully for compositional analysis of lignocellulosic biomass [30]. The main advantages of IRS technology are that sample preparation is simple, analysis is fast and precise, and many constituents can be analyzed at the same time. Thus, the cost of biomass sample analysis could be reduced to about $10 for each sample [16]. One exclusive characteristic of the IRS method is that it is nondestructive, so the sample could be used for other analysis after IRS measurement. IRS analysis also uses no hazardous chemicals. A comparison of IRS and wet chemical methods in biomass analysis is shown in Figure 2.1. In addition to determining the major polysaccharides in biomass, IRS is capable of providing other structural information. Although numerous chemicals or reagents, such as enzymes and alkali, could be used to extract the polymeric components in plant cell walls, the complicated cross-linkages between polymer chains may not be well elucidated by chemical extraction. The IRS techniques could be used for composition and structural analysis, such as detection of functional groups [31]. Only a few studies have been reported for the determination of biomass composition, because earlier IRS analysis suffered from blanket absorption of water [32], but the development of Fourier transform data processing and computer modeling could solve this problem.

FIGURE 2.1   Comparison of the compositional analysis methods for biomass (IR: infrared; MV-PLS: multivariate partial least squares regression; HPLC: high-performance liquid chromatography; UV–Vis: ultraviolet–visible spectroscopy).

This chapter, in addition to summarizing the basic principle of IRS and the characterization of biomass, discusses the applications of IRS in biomass utilization.

2.2. Physical Principles of IRS and Its Application

IRS is usually a result of the fundamental molecular vibration mechanism, which refers to energy–matter interaction [33]. Upon interaction of infrared radiation with an oscillating dipole moment associated with a vibrating bond, absorption of the radiation corresponds to a change in dipole moment. Generally, different functional groups correspond to different components of the infrared spectrum; therefore, the spectral features could be used for structural analysis. The infrared region consists of three regions according to wavelength range: near-infrared (780–2500  nm or 12,800–4000 cm−¹), mid-infrared (2500–25,000  nm or 4000–400 cm−¹), and far-infrared (25,000–1,000,000  nm or 400–10 cm−¹) [34]. Mid-infrared is used to investigate the fundamental vibrations and related structures, whereas near-infrared (NIR) analysis provides information on molecular overtones and combinations of vibrations. One interesting feature in NIRS is the overtone, which consists of numerous combinations of vibrational bands. Even for some simple molecules with few fundamental vibration modes, many overtone bands could be shown in NIR spectra, depending on their various combinations; chloroform, for example, has six fundamental modes but about 34 overtone modes [34]. Although the NIR spectra appear complicated, they are not a random mix, which makes it possible to analyze structural information with chemometric techniques.

The components of the IRS system usually include lenses, a radiation source, filters, a detector and a data processing unit (Figure 2.2(A)) [35]. The filter system is used to define wavelength range, which makes it a crucial component in the infrared system. Several types of filters are available: fixed filters, variable filters and tilting filters. IRS typically measures light absorption, and light reflectance mode is used for solid biomass [16]. Attenuated total reflectance (ATR) is widely used with FTIR in biomass measurement, which simplifies sample preparation. In the NIR system, one diffuse reflection approach is an integrating sphere (Figure 2.2(B)) in which light is directed onto a sample. The integrating sphere is suitable for measuring inhomogeneous samples such as biomass material (e.g. stover, wood chips) because the sampling area is large. Numerous NIR systems have been developed for applications from indoor laboratory to field uses; for example, a field spectrometer has been developed that can be carried in a backpack [36], and remote techniques can be coupled with outdoor spectrometers for field monitoring [37].

A computerized spectrophotometry system has been widely used to perform advanced investigation. With a combination of microscopy and spectroscopy, FTIR could be used to quantify the chemical composition of microscopic samples [38]. Both FTIR and NIR imaging techniques that provide spatially resolved chemical information have been applied in the pharmaceutical [39,40] and food industries [41]. The imaging techniques are helpful in gaining better understanding of biomass structure. In situ FTIR microscopy, for instance, was employed to monitor the structural changes of native plant cell walls with enzymatic treatment [42], which revealed the intrinsic mechanism of enzymatic hydrolysis and biomass recalcitrance to enzymes. More study of biomass structure with infrared microscopy is suggested.

FIGURE 2.2   (A) Block diagram of infrared measurement system; (B) diagram of Thermo NIR integrating sphere.

Image courtesy of Thermo Scientific.

2.3. Composition and Structure of Lignocellulosic Biomass

Lignocellulosic biomass has become a promising alternative source of materials for industrial applications [9]. Plant cell wall is the major component of most biomass. Plant cell wall naturally protects the cell from outside erosion and allows turgor. Different layers of the cell wall play different roles and perform special physiological functions [43]. The primary wall, for example, contains 1–10% cellulose and allows cell expansion, and the secondary wall provides a barrier against potential pathogens [44]. The major components of the plant cell wall are cellulose, hemicellulose and lignin, of which cellulose and hemicellulose are generally referred to as polysaccharides.

Cellulose (molecular formula (C6H10O5)n) is one of the most important polysaccharides in the plant cell wall and has been widely studied in the paper industry [45]. With an ordered structure in the plant cell wall, cellulose consists of hundreds of glucose molecules linked by glucosidic linkage [46]. The glucan chains are usually connected by hydrogen bonds to form microfibrils in the cell wall. There are four different types of cellulose (I, II, III and IV) [47], and cellulose I is considered native cellulose. FTIR is widely used to study native cellulose; for example, FTIR was employed to study the conversion from cellulose Iα, which is enriched in some microbes, to Iβ, which is found primarily in the plant cell wall [48]. The two types of cellulose I