Introduction to Renewable Biomaterials E-Book
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- Herausgeber: John Wiley & Sons
- Kategorie: Wissenschaft und neue Technologien
- Sprache: Englisch
Covers the entire evolutionary spectrum of biomass, from its genetic modification and harvesting, to conversion technologies, life cycle analysis, and its value to the current global economy
This original textbook introduces readers to biomass—a renewable resource derived from forest, agriculture, and organic-based materials—which has attracted significant attention as a sustainable alternative to petrochemicals for large-scale production of fuels, materials, and chemicals. The current renaissance in the manipulation and uses of biomass has been so abrupt and focused, that very few educational textbooks actually cover these topics to any great extent. That’s why this interdisciplinary text is a welcome resource for those seeking a better understanding of this new discipline. It combines the underpinning science of biomass with technology applications and sustainability considerations to provide a broad focus to its readers.
Introduction to Renewable Biomaterials: First Principles and Concepts consists of eight chapters on the following topics: fundamental biochemical & biotechnological principles; principles and methodologies controlling plant growth and silviculture; fundamental science and engineering considerations; critical considerations and strategies for harvesting; first principles of pretreatment; conversion technologies; characterization methods and techniques; and life cycle analysis. Each chapter includes a glossary of terms, two to three problem sets, and boxes to highlight novel discoveries and instruments. Chapters also offer questions for further consideration and suggestions for further reading.
- Developed from a successful USDA funded course, run by a partnership of three US universities: BioSUCEED - BioProducts Sustainability, a University Cooperative Center for Excellence in Education
- Covers the entire evolutionary spectrum of biomass, from genetic modification to life cycle analysis
- Presents the key chemistry, biology, technology, and sustainability aspects of biomaterials
- Edited by a highly regarded academic team, with extensive research and teaching experience in the field
Introduction to Renewable Biomaterials: First Principles and Concepts is an ideal text for advanced academics and industry professionals involved with biomass and renewable resources, bioenergy, biorefining, biotechnology, materials science, sustainable chemistry, chemical engineering, crop science and technology, agriculture.
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Veröffentlichungsjahr: 2017
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Table of Contents
Cover
Title Page
Copyright
List of Contributors
Preface
Chapter 1: Fundamental Biochemical and Biotechnological Principles of Biomass Growth and Use
1.1 Learning Objectives
1.2 Comparison of Fossil-Based versus Bio-Based Raw Materials
1.3 The Nature of Bio-Based Raw Materials
1.4 General Considerations Surrounding Bio-Based Raw Materials
1.5 Research Advances Made Recently
1.6 Prominent Scientists Working in this Arena
1.7 Summary
1.8 Study Problems
1.9 Key References
References
Chapter 2: Fundamental Science and Applications for Biomaterials
2.1 Introduction
2.2 What are the Biopolymers that Encompass the Structure and Function of Lignocellulosics?
2.3 Chemical Reactivity of Cellulose, Heteropolysaccharides, and Lignin
2.4 Composite as a Unique Application for Renewable Materials
2.5 Question for Further Consideration
References
Chapter 3: Conversion Technologies
3.1 Learning Objectives
3.2 Energy Scenario at Global Level
3.3 Biomass
3.4 Biomass Conversion Methods
3.5 Metrics to Assist the Transition Towards Sustainable Production of Bioenergy and Biomaterials
3.6 Summary
3.7 Key References
References
Chapter 4: Characterization Methods and Techniques
4.1 Philosophy Statement
4.2 Understanding the Characteristics of Biomass
4.3 Taking Precautions Prior to Setting Up Experiments for Biomass Analysis
4.4 Classifying Biomass Sizes for Proper Analysis
4.5 Moisture Content of Biomass and Importance of Drying Samples Prior to Analysis
4.6 When the Carbon is Burned
4.7 Structural Cell Wall Analysis, What To Look For
4.8 Hydrolyzing Biomass and Determining Its Composition
4.9 Determining Cell Wall Structures Through Spectroscopy and Scattering
4.10 Examining the Size of the Biopolymers: Molecular Weight Analysis
4.11 Intricacies of Understanding Lignin Structure
4.12 Questions for Further Consideration
References
Chapter 5: Introduction to Life-Cycle Assessment and Decision Making Applied to Forest Biomaterials
5.1 Introduction
5.2 LCA Components Overview
5.3 Life-Cycle Assessment Steps
5.4 LCA Tools for Forest Biomaterials
References
Chapter 6: First Principles of Pretreatment and Cracking Biomass to Fundamental Building Blocks
6.1 Introduction
6.2 What Difference Should Be Considered Between Wood and Agricultural Biomass?
6.3 Define Pretreatment
6.4 Steps of Production of Cellulosic Ethanol
6.5 What Are the Key Considerations for Making a Successful Pretreatment Technology?
6.6 What Are the General Methods Used in Pretreatment?
6.7 What Is Currently Being Done and What Are the Advances?
6.8 Summary
References
Chapter 7: Green Route to Prepare Renewable Polyesters from Monomers: Enzymatic Polymerization
7.1 Philosophic Statement
7.2 Introduction
7.3 Lipase-Catalyzed Ring-Opening Polymerizations of Cyclic Monomeric Esters (Lactones and Lactides)
7.4 Lipase-Catalyzed Polycondensation
List of Abbreviations
References
Chapter 8: Oil-Based and Bio-Derived Thermoplastic Polymer Blends and Composites
8.1 Introduction
8.2 Oil-Based and Bio-Derived Thermoplastic Polymer Blends
8.3 Thermoplastic Composites with Natural Fillers
8.4 Conclusion
8.5 Questions for Further Consideration
References
Index
End User License Agreement
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Guide
Cover
Table of Contents
Preface
Begin Reading
List of Illustrations
Chapter 1: Fundamental Biochemical and Biotechnological Principles of Biomass Growth and Use
Figure 1.1 Global chemical clusters.
Figure 1.2 Biomass applications and material flow (Germany 2008) (Raschka and Carus, [2012]; Anton and Steinicke, [2012]).
Figure 1.3 Expected biomass trade routes by 2020 (TWh) (King and Hagan, [2010]).
Chapter 2: Fundamental Science and Applications for Biomaterials
Figure 2.1 The archetypal structures of the most abundant biomaterials on the planet. (a) The repeating unit (
N
-acetylglucosamine) of the biopolymer chitin. (b) The repeating unit (glucose) of the biopolymer cellulose.
Figure 2.2 A simplified representation of the stereochemical asymmetry present in cellulose: the existence of a non-reducing end group (NREG) versus an opposite reducing end group (REG) give cellulose different terminal chemistries.
Scheme 2.1 A simplified pictorial summary of the contextual development of cellulose fibers: the evolution of cellulose chains into microfibrils, an elementary unit in cellulose, which contribute to the higher order elementary structures (e.g., the macrofibril is composed of a bundle of microfibrils).
Figure 2.3 A representation of the unit cell mode of chain packing for cellulose. (a) The triclinic unit cell (Iα). (b) The monoclinic unit cell (Iβ).
Figure 2.4 Various structural representations of xylan. (a) Simple xylan backbone composed of non-functionalized xylose monomers. (b) Xylan backbone with a pendant 4-
O
-methylhexenuronic acid residue at the 2-carbon. (c) Representation of a xylan backbone decorated with pendant acetyl groups.
Figure 2.5 Representative structure of the galactoglucomannan heteropolysaccharide. Note that the glucomannan backbone has several Ac (acetyl) groups decorating it, while it possesses a pendant galactose residue on the 6 carbon of a mannose residue.
Figure 2.6 A generic representation of the lignin that is believed to be localized within angiosperm wood cells.
Figure 2.7 The generic lignin monomeric structural motifs that constitute the totality of all of the lignin polymers that are extant in nature.
Figure 2.8 A fluorescence micrograph obtained from a cross-section of wood cells. Shown in the micrograph are the major elements of the wood cell starting from the inner lumen (dark, no fluorescence), normal lignified cell wall (second part extending from the inner dark sphere), to the outer middle lamella.
Figure 2.9 Shown is a simple cartoon that illustrates the effect of introducing water molecules within the H-bonded network structure of cellulose.
Figure 2.10 Chemical structures and physical schematic representation of (a) amylose starch and (b) amylopectin starch.
Figure 2.11 Schematic representation of the phase transitions of starch during thermal processing and aging.
Figure 2.12 Growth of the plastics worldwide.
Chapter 3: Conversion Technologies
Figure 3.1 Simple theoretical models of the combined output from a group of gas or oil fields: both graphs assume that fields are found 1 year apart, larger fields are found earlier. (a) Field production follows a trapezoidal profile, possibly typical of gas fields. (b) Field production follows a profile typical of oil fields, that is, a rapid build up, followed by a slow decline.
Figure 3.2 Relationship between EROI of an energy resource and percentage of available energy that can be used per unit of this resource. Light grey area represents fraction of energy of the resource that can be delivered to the economy, dark grey area represents fraction of energy of the resource that is spent to extract/produce resource itself. Please note the net energy cliff at EROI lower than 10.
X
-axis in reverse order.
Figure 3.3 Biomass and fossil fuels – origins and energy content. Biomass is an important element of carbon cycle. In the process of photosynthesis, carbon dioxide and water are converted into carbohydrates and other structures called biomass. Biomass can be then digested or combusted to recover stored chemical energy and release oxidised compounds: carbon dioxide and water. Fossil fuels are biomass that underwent fossilisation process, that is, slow partial decomposition in the absence of oxygen powered by heat and pressure from geological sources. In a process of fossilisation, biomass lost significant content of oxygen and became composed of hydrocarbons having higher energy content than original biomass.
Figure 3.4 Ultimate biological compounds produced via CO
2
fixation in chloroplasts during the process of photosynthesis divided according to their function and chemical structures.
Figure 3.5 Energy released (Δ
E
) from complete combustion of typical fuels and their major combustion products. Note: discontinuous y axis; * bituminous coal; ** herbaceous biomass. Values from GREET, The Greenhouse Gases, Regulated Emissions, and Energy Use In Transportation Model. US DOE.
Figure 3.6 Complete combustion of methane, overview of bond energy changes. Energy investment phase in marked with upward arrows, energy payoff phase with downward arrows. The net energy gain is the difference in energy between reactants and products.
Figure 3.7 Schematic view of the variety of commercial (solid lines) and developing bioenergy routes (dotted lines) from biomass feedstocks through thermochemical, chemical, biochemical and biological conversion routes to heat, power, CHP and liquid or gaseous fuels. Note: commercial products are marked with an asterisk;
1
Parts of feedstock can be used in other routes;
2
Routes can yield co-products;
3
Biomass upgrading can include densification;
4
Anaerobic digestion also produces minor gasses;
5
Including related thermochemical routes like liquefaction.
Figure 3.8 Summary of thermochemical transformations in thermochemical conversion processes. Four major transformation steps are annotated in grey boxes; major products from each transformation are outlined in solid lines; common processes are in solid arrows, specific routes are in dashed arrows, abbreviations: C, combustion; G, gasification; P, pyrolysis.
Figure 3.9 Examples of reactions associated with catalytic bio-oil upgrading.
Figure 3.10 Scheme of transesterification. Biodiesel is synthesised in a chemical reaction of transesterification of an oily feedstock, triglyceride with a short-chain alcohol, usually methanol in the presence of a catalyst. Transesterification yields alkyl esters of fatty acids (biodiesel) and a by-product, glycerol. R
I,II,III
alkyl chains of fatty acid (usually C14–C22), and R
1
alkyl group of an alcohol (usually methyl or ethyl).
Figure 3.11 Schematic representation of stepwise oxidation of glucose in an organism compared to its combustion in oxygen. On the left biological decomposition of glucose into compounds of lower energy and ultimately into CO
2
and H
2
O with most of the energy collected by carrier molecules such as ATP and NADH. On the right complete combustion of glucose in oxygen with activation energy from external heat source. Please note that substrates and products of both reactions are identical.
Figure 3.12 Overview of major metabolic pathways used for bioenergy production and aerobic respiration. Biomass used as a feedstock for fermentative production of bio-fuels and biochemicals is decomposed into glucose and enters glycolysis or bio-fuel-producing organism. Note: Other hexoses are converted into glucose
in vivo
, and pentoses will enter the pathway at later stages of glycolysis through pentose phosphate pathway). Oily feedstocks can enter through β-oxidation pathway as acetyl-CoA. * Glucose is split into two pyruvate molecules during glycolysis; ** Butyryl-CoA is formed through condensation of two Acetyl-CoA.
Chapter 4: Characterization Methods and Techniques
Figure 4.1 Biomass characterization diagram shows common characterization techniques for carbohydrates and lignin.
Figure 4.2 HPLC chromatogram of four monosaccharide standards separated by Bio-Rad® Aminex 87P column at 60 °C, flow rate of 06 ml min
−1
of 4 mM H
2
SO
4
.
Figure 4.3 X-ray diffraction spectra of microcrystalline cellulose (Avicel PH-101) shows three methods for calculating Crl: (a) Segal method; (b) peak deconvolution method; and (c) amorphous subtraction method.
Figure 4.4 Illustration of information obtained from CP/MAS
13
C NMR spectrum of microcrystalline cellulose. C
4
and C
6
regions are typically used for Crl determination and evaluation of changes in inter-/intramolecular hydrogen bonding.
Figure 4.5
13
C NMR spectrum of MWL isolated from pine shows various spectral regions.
Figure 4.6 Phosphorylation of lignin with 2-chloro-4,4,5,5-tetramethyl-1,3,2-dioxaphospholane (TMDP) is fast and reaction products (c) are shown in
31
P NMR spectrum (b) and lignin modified (a).
Figure 4.7 The 2D HSQC spectra of enzymatic mild acidolysis lignin (EMAL) isolated from hardwood [108].
Chapter 5: Introduction to Life-Cycle Assessment and Decision Making Applied to Forest Biomaterials
Figure 5.1 The three pillars of the triple-bottom-line perspective of sustainability.
Figure 5.2 System boundary diagram of a cradle-to-grave bio-fuels process but excludes indirect land-use change.
Figure 5.3 System boundary diagram of a cradle-to-gate biomass production system excluding processing.
Figure 5.4 Life-cycle inventory data from product systems.
Figure 5.5 Life-cycle assessment software structure.
Figure 5.6 Life-cycle assessment stages.
Figure 5.7 Impact assessment ISO mandatory and optional steps (ISO 14044, 2006).
Figure 5.8 The relationship between end point and midpoint impacts as proposed by the ILCD Handbook (Wolf
et al
., 2012).
Figure 5.9 Classification of LCI data into midpoint indicators.
Figure 5.10 LCA interest group response to weighting survey used for Eco-indicator 99 weighting method (Goedkoop and Spriensma, 2001).
Chapter 6: First Principles of Pretreatment and Cracking Biomass to Fundamental Building Blocks
Figure 6.1 General structure of lignocellulosic materials.
Figure 6.2 Schematic structure of cellulose molecule.
Figure 6.3 Demonstration of the hydrogen bonding that allows the parallel arrangement of the cellulose polymer chains.
Figure 6.4 (a) Formation of micro- and macrofibrils (fibers) of cellulose and their position in the wall. (b) Magnified view of cellulose microfibril.
Figure 6.5 A schematic structure of the hemicellulose backbone.
Figure 6.6
p
-Coumaryl-, coniferyl-, and sinapyl alcohol: major building components of the three-dimensional polymer lignin.
Figure 6.7 Schematic structure of softwood lignin.
Figure 6.8 Cleavage of the ether bond of lignin in alkaline solution (Lin and Lin, 2002).
Figure 6.9 Hydrolysis of cellulose in acidic media (Krassig and Schurz, 2002).
Figure 6.10 Hydrolysis of cellulose in alkaline conditions (Krassig and Schurz, 2002).
Figure 6.11 Schematic mechanism of effects of pretreatment on lignocellulosic biomass.
Figure 6.12 The major mechanism of acid hydrolysis of glycosidic bonds.
Figure 6.13 Separation of lignocellulosic biomass components in acidic and alkaline pretreatment conditions.
Figure 6.14 The mechanism of enzymatic hydrolysis of cellulose to glucose.
Chapter 7: Green Route to Prepare Renewable Polyesters from Monomers: Enzymatic Polymerization
Figure 7.1 The chemical structure of some lactones derived from renewable resources.
Figure 7.2 Lipase-catalyzed ROP of lactones.
Figure 7.3 Lipase-catalyzed polycondensation to obtain polyester via (a) AB-type monomers, (b) AA-, BB-type monomers.
Figure 7.4 Lipase-catalyzed synthesis of bio-based polyester via a two-stage method in diphenyl ether.
Figure 7.5 Lipase-catalyzed polycondensation to prepare linear polyester with free hydroxyl pendant groups [78].
Figure 7.6 Lipase-catalyzed polycondensation of ricinoleic acid or methyl ricinoleate followed by cross-linking reaction using dicumyl peroxide [89].
Figure 7.7 N435-catalyzed polycondensation of dimethyl 2,5-furandicarboxylate and aliphatic diol using two-stage method in diphenyl ether.
Chapter 8: Oil-Based and Bio-Derived Thermoplastic Polymer Blends and Composites
Figure 8.1 Influence of TEC (a) and ATBC (b) on glass transition temperature of PLA ref. [5].
Figure 8.2 Stress–strain curves of neat PLA and PLA modified with four different ionic liquids.
Figure 8.3 (a) The influence of plant sources in derived starch products. (b) The different stress and strain behaviour of pure amylopectin (1) and pure amylose (2).
Figure 8.4 (a) Tensile strength of low-density polyethylene/thermoplastic starch with and without zeolite 5A. (b) Elongation at break of low-density polyethylene/thermoplastic starch blend with and without zeolite 5A.
Figure 8.5 Thermal analysis results for low-density polyethylene/PLA blend with 4 phr of low-density polyethylene-graft-maleic anhydride.
Figure 8.6 SEM analysis of (a) PBAT/TPS (b) PBAT-
g
-MA/TPS (c) PBAT/TPS/C30B (d) PBAT-
g
-MA/TPS/C30B.
Figure 8.7 Image of 50 kGy irradiated Pc080/TPS20.
Figure 8.8 Effect of irradiation on the variation of Young's modulus for different amounts of starch contained in the blends.
Figure 8.9 Trabant car, produced in 1958 in the German Democratic Republic with main parts made of composites with natural fillers.
Figure 8.10 Example of wood–plastic composites application in decking market [7trust.com, green products].
Figure 8.11 Example of turbo mixer, developed by Valente
et al
. (University of Rome, La Sapienza) [ref. 51] to optimize and analyse the effect of compatibilizing agent in natural fibre–polymer composites. The turbo mixer works through kinetic energy developed by rotating blades as only heat source. Valente
et al
. 2016 [52]. Reproduced with permission of Elsevier.
Figure 8.12 Polypropylene-grafted-maleic anhydride.
Figure 8.13 Working mechanism of polyolefin-grafted-maleic anhydride as coupling agent (elliptical shape is the maleic anhydride graft): (a) compound formation because of the weak interaction between plant fibres (hydrophilic) and polymers (hydrophobic); (b) composite formation thanks to the interaction of MAPP maleated graft with plant fibres and polymeric MAPP chains mixing with polymer matrix.
Figure 8.14 Tensile strength trend of polypropylene-rice husk flour (PP-RHF) neat and with five different compatibilizing agents.
Figure 8.15 Izod impact strength trend of polypropylene-rice husk flour (PP-RHF) neat and with five different compatibilizing agents.
Figure 8.16 Tensile modulus trend of recycled HDPE from milk bottles, with 30 wt% of Aspen hardwood and 2 or 5 wt% of MAPP.
Figure 8.17 Influence of exothermic (a) and endothermic (b) blowing agents on PVC/wood flour density.
Figure 8.18 Dimensional stability of polypropylene (PP), high-impact polypropylene (HIPP), high-density polyethylene (HDPE) and low-density polyethylene (LDPE) with different percentages of paper sludge.
Figure 8.19 Flexural strength of polypropylene (PP), high-impact polypropylene (HIPP), high-density polyethylene (HDPE) and low-density polyethylene (LDPE) with different percentages of paper sludge.
List of Tables
Chapter 1: Fundamental Biochemical and Biotechnological Principles of Biomass Growth and Use
Table 1.1 Composition (%) and heat value (MJ kg
−1
) (Herrmann and Weber, [2011]) of fossil feedstock
Table 1.2 Use of fossil feedstock in different global regions (%) (EKT Interactive Oil and Gas Training, [2014])
Table 1.3 Feedstock mix (%) in German chemical industries (2011) (Benzing, 2013)
Table 1.4 Oil-refinery output from low to high distillation temperature
Table 1.5 Global production volume of bulk chemicals (2010) (Davis, [2011]) and content of carbon
Table 1.6 Milestones in chemical innovation
Table 1.7 Cost of oil production (US$ per barrel) (Birol, [2008])
Table 1.8 Static lifetime (years) of fossil resources (Harald Andruleit, [2011])
Table 1.9 Annual CO
2
emission from various fossil feedstock (million tons; 2012) (Marland, Boden, and Andres, [2007]; Olivier
et al.,
[2014])
Table 1.10 Chemical industry nation's sales and market share (2013)
Table 1.11 Chemical industry region's sales and market share (2013)
Table 1.12 Composition (%) (Michelsen, [1941]) and heat value (MJ kg
−1
) (Herrmann and Weber, [2011]) of vegeTable biomass and biomass compounds
Table 1.13 World consumption of major vegeTable oil (2007/2008) (USDA, [2009]) and carbon content (75% average assumed)
Table 1.14 The biggest sugar producers, production volume (2012) (USDA, [2013]), and carbon content (43% C in sucrose assumed)
Table 1.15 Most important corn-producing nations 2012 (Statista, [2014]) and carbon content (43% C in sucrose assumed)
Table 1.16 Most important potato-producing nations 2009 (Landesverband der Kartoffelkaufleute Rheinland-Westfalen, [2013])
Table 1.17 Global starch crop production 2013 (FAO, [2014]) (except potato; 2012) and theoretical starch and starch–carbon content according composition given in the text
Table 1.18 Approximate yield derived from 1 ton no. 2 yellow corn with 15.5% moisture (International Starch Institute, [2014])
Table 1.19 Performance of microalgae, corn, and short-rotation trees (Fachagentur nachwachsende Rohstoffe, [2012])
Table 1.20 Leading GM crops (global, 2013) (Compass, 2014)
Table 1.21 Leading areas in GM crop cultivation (million hectare; 2013) (Compass, 2014)
Table 1.22 Renewable energy share of global final energy consumption (2012) (Zervos, [2014])
Table 1.23 Global growth rate of renewable energy capacity and bio-fuels production (%; end 2008–2013) (Zervos, [2014])
Table 1.24 Some semisynthetic antibiotics and their global annual production volume (Franssen, Kircher, and Wohlgemuth, [2010])
Table 1.25 Indications to be treated by monoclonal antibodies and sales volume (Pohl-Appel, [2011])
Table 1.26 Global bioplastics capacities by material type (1000 tons per year; 2013) (European Bioplastics, [2014])
Table 1.31 Share (%) of cost factors in bio-based production of bulk chemicals (Kircher, 2014)
Table 1.27 Options for carbon sources from agricultural, forestry, and industrial side streams and carbon content (global; million tons per year) (Kircher, [2012])
Table 1.28 GHG emission associated with biomass production (% CO
2
fixed in harvested biomass) (Haberl
et al.,
[2012])
Table 1.29 Greenhouse gas sources and climate impact factor as well as share of climate impact weighted for the climate changing potential over the next 100 years (EPA US Environmental Protection Agency, 2014)
Table 1.30 Density, bulk density, and carbon per volume (t m
−3
) of various materials
Chapter 3: Conversion Technologies
Table 3.1 Typical bond energies present in energy carriers and products
Table 3.2 Pyrolysis methods and their variants
Chapter 4: Characterization Methods and Techniques
Table 4.1 Selected characterization methods of structural carbohydrates and lignin
Table 4.2 Advantages and disadvantages of biomass characterization methods and techniques
Table 4.3
13
C NMR chemical shift ranges and integration regions of all moieties
Table 4.4
31
P NMR chemical shift ranges and integration regions of hydroxyl moieties
Table 4.5 Assignments of carbohydrates/lignin
13
C–
1
H correlation peaks in the 2D HSQC
Chapter 5: Introduction to Life-Cycle Assessment and Decision Making Applied to Forest Biomaterials
Table 5.1 Three common LCA software package options
Table 5.2 US LCI inventory for wood product manufacturing/sawmills
Table 5.3 Midpoint indicators with associated emissions and scale (Bare
et al
., 2006)
Table 5.4 Greenhouse gas lifetime before decomposition and corresponding global warming potential (GWP) for a 20-year time horizon and a 100-year time horizon (Myhre
et al.
, 2013)
Table 5.5 Normalization factors based on a US citizen's impact over the course of a year in 2008 (Ryberg
et al
., 2014)
Table 5.6 Ecoindicator weighting values and survey responses (Goedkoop and Spriensma, 2001)
Chapter 6: First Principles of Pretreatment and Cracking Biomass to Fundamental Building Blocks
Table 6.1 Composition of different lignocellulosic materials (Jorgensen
et al
., 2007)
Table 6.2 Summary of linkages between the monomer units that form the individual polymer lignin, cellulose, and hemicellulose, and between the polymers to form lignocellulosic biomass
Table 6.3 Functional groups of lignocellulosic biomass
Table 6.4 Main types of fermentation inhibitors and their chemical structures
Table 6.5 The different types of pretreatments and their effects on lignocellulosic biomass
Chapter 8: Oil-Based and Bio-Derived Thermoplastic Polymer Blends and Composites
Table 8.1 Some PLA mechanical features in comparison to traditional polyolefin
Table 8.2 Tensile test results of pure PLA and PLA modified with polyethylene glycol (PEG) and acetyl tri-
n
-butyl citrate (ATBC) in different percentages
Table 8.3 Influence of molecular weight and content of triethyl citrate (TEC) and acetyl tributyl citrate (ATBC) on polylactic acid thermal properties
Table 8.4 The effect of four different ionic liquids on PLA mechanical properties
Table 8.5 Effect of four different ionic liquids on PLA thermal properties
Table 8.6 Main properties of thermoplastic starch plasticized by glycerol and 1-butyl-3-methylimidazolium chloride [BMIM]Cl
Table 8.7 Composition of polyethylene/thermoplastic starch blend with and without zeolite 5A in the amount of 1–3–5%
Table 8.8 Glass transition temperature and crystallization temperature of low-density polyethylene/thermoplastic starch blend with and without zeolite 5A
Table 8.9 Mechanical and thermal properties of neat PBAT and PBAT/TPS blend modified with maleic anhydride and nanoclay C30B addition
Table 8.10 Comparison between natural and glass fibres [can natural fibres replace glass?]
Table 8.11 Mechanical properties of some natural fibres in comparison to traditional fibres and polymers
Table 8.12 Properties of five MAPP with different maleic anhydride content (MA%), molecular weight () and melt flow index (MFI)
Table 8.13 Thermal properties of neat high-density polyethylene (HDPE) in comparison to HDPE with 20–30–40–50–60 wt% of wood
Table 8.14 Influence of CBAs on average cell size
Table 8.15 Influence of N
2
amount, injection speed, weight reduction and mold temperature on shrinkage, warpage, mechanical properties and cell density of WPC foams
Table 8.16 Comparison of properties and cost between HDPE and WPC foam (weight reduction of 20%)
Table 8.17 Mechanical properties of polyolefin–old newspaper composites compared to polyolefin–glass fibre composites
Introduction to Renewable Biomaterials
First Principles and Concepts
Edited by
Ali S. Ayoub
Archer Daniels Midland Company, Chicago, IL, United States North Carolina State University, Raleigh, NC, United States
Lucian A. Lucia
North Carolina State University Raleigh, NC, United States
This edition first published 2018
© 2018 John Wiley & Sons Ltd
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The right of Ali S. Ayoub and Lucian A. Lucia to be identified as the authors of the editorial material in this work has been asserted in accordance with law.
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Library of Congress Cataloging-in-Publication Data
Names: Ayoub, Ali S., 1977- editor. | Lucia, Lucian A., editor.
Title: Introduction to renewable biomaterials : first principles and concepts / edited By Ali S. Ayoub, Lucian A. Lucia.
Description: Hoboken, NJ : John Wiley & Sons, 2018. | Includes bibliographical references and index. |
Identifiers: LCCN 2017019395 (print) | LCCN 2017036356 (ebook) | ISBN 9781118698594 (pdf) | ISBN 9781118698587 (epub) | ISBN 9781119962298 (cloth)
Subjects: LCSH: Biomass. | Renewable natural resources.
Classification: LCC TP339 (ebook) | LCC TP339 .I595 2017 (print) | DDC 662/.88-dc23
LC record available at https://lccn.loc.gov/2017019395
Cover design by Wiley
Cover image: © VL2607954/shutterstock
List of Contributors
Ali S. Ayoub
Archer Daniels Midland Company
ADM Research
Chicago, IL
USA
and
North Carolina State University
Department of Forest Biomaterials
Raleigh, NC
USA
Amir Daraei Garmakhany
Department of Food Science and Technology
Toyserkan Faculty of Industrial Engineering
Buali Sina University
Hamedan
Iran
Maurycy Daroch
School of Environment and Energy
Peking University
Shenzhen
China
Jesse Daystar
Department of Forest Biomaterials
North Carolina State University
Raleigh, NC
USA
Manfred Kircher
KADIB-Kircher Advice in Bioeconomy Kurhessenstr.
Frankfurt am Main
Germany
Lucian A. Lucia
Department of Forest Biomaterials
North Carolina State University
Raleigh, NC
USA
Valerie Massardier
INSA de Lyon
IMP/CNRS 5223
Lyon
France
Toufik Naolou
Institute of Biomaterial Science and Berlin-Brandenburg Centre for Regenerative Therapies
Helmholtz-Zentrum Geesthacht
Teltow
Germany
Alessia Quitadamo
INSA de Lyon
IMP/CNRS 5223
Lyon
France
Scott Renneckar
Department of Sustainable Biomaterials
Virginia Tech
Blacksburg, VA
USA
Noppadon Sathitsuksanoh
Department of Chemical Engineering
University of Louisville
Louisville, KY
USA
Somayeh Sheykhnazari
Department of Wood and Paper Technology
Gorgan University of Agricultural Sciences & Natural Resources
Gorgan
Iran
Marco Valente
Department of Chemical and Material Engineering
University of Rome La Sapienza
Rome
Italy
Richard Venditti
Department of Forest Biomaterials
North Carolina State University
Raleigh, NC
USA
Preface
Over the past few decades the ratio of production to new discoveries has gradually fallen and is currently estimated to about three to one. For every discovered barrel of oil, we consume three. At the same time, more and more regions of the world are seeking high-quality lifestyles that are resource intensive. Until relatively recently (about 30 years ago), high consumption of energy was reserved for the developed economies of the “West.” Since then, rapid development of other countries such as China, India, and Brazil has resulted in a huge increase in demand for energy sources worldwide. The entire population of OECD countries is estimated as about 1.25 billion people, and their primary energy use as 4.37 toe per capita. When China, India, and Brazil, altogether about 2.75 billion people, approach even conservative “European” levels of fossil resources usage (3.29 toe per capita), an additional supply exceeding current use of all OECD countries will be required. It is difficult to envisage how this demand could be met with nonrenewable resources in the medium to long term. It is therefore evident that resources at our disposal are shrinking fast. Moreover, most of these petroleum polymers are not biodegradable and, thus, cannot be decomposed naturally. Furthermore, the addition of carbon dioxide to the atmosphere at the end of its life cycle has increased the need to use materials from renewable and CO2-neutral resources. There is more carbohydrate on earth than all other organic materials combined. Carbohydrates are readily biodegradable and tend to degrade in biologically active environments like soil, sewage, and marine locations where bacteria are active. However, the basic construct of biopolymer matrices remains a virtually insurmountable obstacle to the “best laid plans of mice and men” of providing products to compete with petro-based chemicals and associated commodity items. A more robust and precise understanding of the factors that limit the widespread use of lignocellulosic substrates in society is perhaps the most pressing challenge that the emergent bio-economy faces. The goal, therefore, of this book is to elucidate the fundamental physicochemistry and characterization of the biomaterials, emphasize their value proposition for supplanting petrochemicals, tackle the challenges of conversion, and ultimately provide a milieu of possibilities for the biomaterials. The reader will be conversant and knowledgeable of the critical issues that surround the field of lignocellulosic intransigence, possible successful strategies to cope with their inertness, and potential pathways for the successful use of lignocellulosics and starch in the new bio-economy.
Turning the bio-economy into reality is more than a technical issue. From an abstract point of view, it needs scientific and technical push as well as market pull to make the bio-innovation leap. Therefore, the future role of biomass and its life cycle analysis as industrial feedstock to provide fuel and chemicals is discussed in this book with an analysis of the fossil economy, especially the chemical sector. But first and foremost it needs visionary people: devoted scientists, future-oriented entrepreneurs, a supportive political framework and last but not least a willing general public.
Ali S. AyoubJuly 2017 Chicago, USA
Chapter 1Fundamental Biochemical and Biotechnological Principles of Biomass Growth and Use
Manfred Kircher
KADIB-Kircher Advice in Bioeconomy Kurhessenstr, Frankfurt am Main, Germany
For the first time in history, we face the risk of a global decline. But we are also the first to enjoy the opportunity of learning quickly from developments in societies anywhere else in the world today, and from what has unfolded in societies at any time in the past.
Jared Diamond, [2005]
1.1 Learning Objectives
This chapter discusses about vegetable biomass and its future role as industrial feedstock to provide fuel and chemicals. In the transition phase from the current fossil-based into the bio-based economy, vegetable biomass needs to face up to competition against the fossil benchmark, which is at mineral oil. Therefore, this chapter starts with an analysis of the fossil economy, especially in the chemical sector.
In future, when fossil feedstock inevitably becomes scarce and the bio-economy increasingly unfolds, vegetable biomass must meet the industrial feedstock demand for a growing global population. While further serving the traditional food, feed, and fiber markets, this is no easy challenge. More sustainable carbon sources and applications are another topic of this chapter.
Turning the bio-economy into reality is more than a technical issue. From an abstract point of view, it needs scientific and technical push as well as market pull to make the bio-innovation leap. But first and foremost, it needs people with visionary: devoted scientists, future-oriented entrepreneurs, a supportive political framework, and last but not least a willing general public. These so-called pillars of competitiveness are presented as well.
The learning objectives of this chapter are
1.
the significance of carbon in our economy;
2.
the fundamental biochemical and biotechnological principles of fossil- and bio-based carbon sources concerning nature, production, and processing; and
3.
the complex challenges in making vegetable biomass the dominant sustainable feedstock.
1.2 Comparison of Fossil-Based versus Bio-Based Raw Materials
1.2.1 The Nature of Fossil Raw Materials
The current global economy is very much based on fossil resources to produce energy (electricity, fuel, heat) and organic chemicals. The initial source of these feedstock has been biomass transformed through geological processes into crude oil, natural gas, black coal as well as lignite and peat. What makes these materials valuable for use in energy and chemistry processes is their high energy as well as carbon content (Table 1.1). The most valuable fossil resources are the hydrocarbons that consist only of carbon and hydrogen. Subgroups are, for example, alkanes (saturated hydrocarbons; CnH2n+2), cycloalkanes (CnH2n), alkenes (unsaturated hydrocarbons; CnH2n), and aromatics (ring-shaped molecules) differing in the number of carbon and hydrogen and molecular structure.
Table 1.1 Composition (%) and heat value (MJ kg−1) (Herrmann and Weber, [2011]) of fossil feedstock
C
H
N
O
S
MJ kg
−1
Natural gas
75–85
9–24
Traces
Traces
Traces
32–45
Mineral oil
83–87
10–14
0.1–2
0.5–6
0.5–6
43
Black coal
60–75
6
Traces
17–34
0.5–3
25–33
Lignite
58–73
4.5–8.5
Traces
21–36
3
22
Peat
50–60
5–7
1–4
30–40
0.2–2
15
Coal, especially black coal, is the oldest fossil resource. Formed from terrestrial plant biomass, it has been consolidated between other rock strata and altered to form coal seams by the combined impact of pressure and heat under low-oxygen conditions over about 300 million years. Black coal is extracted by open-cast mining as well as deep mining (up to a depth of 1500 m). It is composed primarily of carbon.
Fossil oil has been formed over a time period of about 100 million years by the exposure to similar conditions on sedimentation layers of marine organisms such as algae and plankton. Under such conditions, the long-chain organic molecules of the vegetable biomass are split into short-chain compounds forming liquid oil. It accumulates in specific geological formations called crude oil reservoirs.
Some fractions even split down to molecules with only one carbon and become gaseous methane (CH4). Therefore, oil deposits (and coal mines) always contain methane of more or less similar age. Methane sources covered by nonpermeable geological layers lead to real methane deposits. From such geological formations, the gas can be extracted in the form of natural gas. Natural gas can also be the result of biological catabolic processes degrading biomass. These deposits are also found under nonpermeable geological formations but have been formed over a period of about 20 million years.
As oil and gas generation needs high-pressure conditions the corresponding deposits are highly pressurized. If such sites are drilled, oil and gas escape through the well – a process called primary recovery allowing to exploit 5–10% of the total oil and gas. By pumping (secondary recovery) and more sophisticated methods (tertiary recovery) more oil and gas can be extracted. Obviously exploiting an oil and gas deposit is easy in the beginning but becomes more and more technically complex and costly with time.
Lignite has a similar origin as black coal. It has been exposed to the harsh geological conditions for up to 65 million years and can be extracted by open-cast mining. The carbon content is lower than that in black coal, but extraction costs are in average more beneficial.
Peat is another fossil resource. It is as well formed from terrestrial plants under aplent moor conditions when the biomass decays for several 1000 years under low-oxygen conditions. Peat contains the lowest carbon and highest water share under fossil resources. It is recovered from ground.
All fossil resources have the following common characteristics: (i) they are rich in carbon and energy; (ii) their composition is not very complex and quite homogeneous; (iii) they can be produced at moderate, though growing cost; and (iv) fossil resources can be shipped easily by railway, tankers, and pipelines.
1.2.2 Industrial Use
1.2.2.1 Energy
All fossil feedstocks are characterized by high energy content. By oxidation (adding oxygen) the chemical energy stored in the molecules is released in the form of heat – a process called burning in everyday language. Therefore, fossil feedstock is an efficient and easy material to produce energy. In 1709, it was used for the first time in England for industrial purposes when black coal instead of wood-based charcoal was used for iron melting in a coke blast furnace. Discovering this energy source came just in time to start metal-based industrialization because charcoal production had significantly decimated the area under forests. Since then black coal is one of the most relevant primary energy carriers. In 1859, the Pennsylvania Rock Oil Company drilled the first oil well in Titusville (Pennsylvania, USA). Only 10 years later, John. D. Rockefeller founded the Standard Oil Company in 1870, thus starting the era of multinational companies serving the global energy markets. Gas exploitation followed in 1920 in the United States and in 1960 in Europe. Table 1.2 shows the share of fossil material use in different global regions.
Table 1.2 Use of fossil feedstock in different global regions (%) (EKT Interactive Oil and Gas Training, [2014])
North America
Europe
Asia Pacific
Mineral oil
55
40
37
Natural gas
30
38
12
Coal
15
22
51
In summary, production of heat, fuel, and electrical power from fossil resources has been the starting point of industrialization and is still today by far the dominant application. Ninety-three percent of oil, 98% of gas and coal, and 100% of peat are going into energy markets (Höfer, [2009a]; Ulber et al., [2011b]). It is estimated that even in 2040 mineral oil, natural gas, and coal will serve more than three-fourths of total world energy supply (US Energy Information Administration, 2013). The mix of fossil feedstock differs among global regions dependent on regional resources and trade routes.
1.2.2.2 Chemicals
The cheap and seemingly unlimited availability of fossil resources not only triggered an energy-hungry industrialization but also the innovation leap into today's chemical industry. High carbon content in combination with easy logistics through pipelines and tankers made especially oil and gas an ideal industrial feedstock. Seven percent of the global oil and about 2% of world natural gas consumption go into chemicals demonstrating that fossil oil still dominates the global chemical industry (70–80% of chemicals are derived from oil, 8–10% from gas, 10–13% from biomass, and only 1–2% from coal; compare Table 1.3)
Table 1.3 Feedstock mix (%) in German chemical industries (2011) (Benzing, 2013)
Naphtha
Natural gas
Coal
Bio-based feedstock
71
14
2
13
Since ancient times chemicals and biochemicals had been produced from natural reservoirs or from biological resources, respectively. For example, sodium carbonate was imported by Europe from soda lakes in Egypt and Turkey or extracted from water plants. The alkaline solution of soda ash (sodium carbonate) is in fact named after Arabic “al kalja” for the ashes of water plants. In 1771, an alternative method changed the world when Nicolas Leblanc (1742–1806) in France invented the chemical synthesis of sodium carbonate by using coal as the carbon source. This real innovation is today acknowledged as the starting point of chemical industries.
Structural Materials
Since the mid-nineteenth century natural product chemistry tried to use biomaterials as a feedstock to organic chemicals. For example, cellulose, the most abundant plant polysaccharide, has been investigated intensively. The fact that in 1846 three German chemists simultaneously but independently invented a method to produce nitrocellulose from cellulose demonstrates how the time was right for such an innovation. It marked the change from biomaterials to bio-based materials. Though highly inflammable, nitrocellulose entered the market with great success because it was able to replace expensive materials such as whale baleens especially used in ladies costumes as well as silk. Later in 1910 viscose was developed from cellulose in Germany as a fiber material that is still in use. Another example of the efforts to gain independence from natural starting materials by developing synthetic materials is the invention of galalith plastic from casein in 1897 again by German chemists. Obviously, there was a market waiting for more materials from modified biological sources, and there were scientists exploring chemistry.
Dyes
Whereas the examples mentioned so far represent more structural materials for fibers and tissues, instruments, and housing, the next group demonstrates the boosting power of added-value chemicals. Color design mostly does not directly determine the utility of a product, but it adds value and makes a difference. Since ancient times dyestuffs were produced at considerable expense from plants, animals, and minerals. At the end of the nineteenth century, chemistry paved the way to cheap dyestuffs and a world full of colors for the first time, thus ending the industrial era of dye plants. The synthesis of the red dye Alizarin in 1869 by German chemists Carl Graebe (1841–1927) and Carl Liebermann (1842–1914) replaced the natural dye made from dyer's madder (Rubia tinctorum) within a short time period. Alizarin became one of the first products of BASF, founded in 1865 in Mannheim, Germany, by Friedrich Engelhorn (1821–1902). Another red dye, fuchsin, first synthesized in 1858 became the starting point for Hoechst AG, founded by Carl Friedrich Wilhelm Meister (1827–1895), Eugen Lucius (1834–1903), and Ludwig August Müller (1846–1895) in Hoechst close to Frankfurt and only 80 km (50 miles) from Mannheim. In 1878 followed Indigo, another synthetic dye, which was developed by Adolf von Baeyer (1835–1917). Indigo gained industrial relevance at BASF and Hoechst when Johannes Pfleger (1867–1957), chemist at Degussa AG in Frankfurt/Main, improved the process economics significantly. Until the early twentieth century, dye products were dominating commercial chemistry and even the whole industry was called dye chemistry.
Receptive markets and growing chemical science were now joined by entrepreneurs. It is important to understand the significance of these three factors working together. But in the end, industry is made by competent individuals who complement each other, build friendship, realize the business option, and take the chance. The men mentioned here – many friends since university studies – formed such a network that became the starting point of the German chemical industry.
Drugs
As of today successful companies use scientific and technical competence to broaden their product portfolio, develop new application fields, and enter profitable markets. In the early twentieth century, the potential of synthetic drugs had been realized and especially the German dye industry started to invest in research and development. Arsphenamine (Salvarsan®), a syphilis drug, developed by the German physician Paul Ehrlich (1854–1915) and the Japanese bacteriologist Sahachiro Hata (1873–1931) in 1910 became a cash cow to Hoechst AG. In 1935 followed Prontosil®, the first sulfonamide developed by Fritz Mietzsch (1896–1958) and Josef Klarer (1898–1953) at Bayer AG in Wuppertal. Noticeably, this chemical group is also used as azodyes demonstrating how competence in a specific field can lead to a spillover invention in a very different application. Gerhard Domagk (1895–1964) discovered the antibacterial effect and received the Nobel Prize in 1939. These examples not only demonstrate how gaining experience in synthetic chemistry in one field (materials, dyes) led to exploring very different markets (pharmaceuticals) but also how chemical industries early integrated microbiological competence.
The pharmaceutical business opened the door for biotechnology in chemical industries when the Scottish bacteriologist Alexander Fleming (1881–1955) explored antibiotics in 1928. He realized that the fungi Penicillium secretes the antibiotic penicillin, a discovery that was honored with the Nobel Prize in 1945. Since 1942 in England Glaxo (pharma company; founded in 1873 and originally in the baby food business) and ICI (chemical industry, founded in 1926) but especially in the US Merck & Co (1917; separated from Merck KGaA, a German pharma company founded in 1668) and Pfizer & Co (founded in 1849; biological pesticides) developed fermentative production processes based on the cultivation of Penicillium chrysogenum. Companies with very different backgrounds in chemistry, synthetic drugs, and food production got involved in developing early fermentation methods. It should be emphasized that those companies focused on fermentation because there was no technical alternative. Penicillin antibiotics were not available by chemical synthesis. The production of penicillin is therefore seen as the starting point of industrial biotechnology (in contrast to traditional food biotechnology using microbial processes such as yogurt, beer, and wine fermentation).
Drugs added a quite different quality to the chemical industry's product portfolio. This chemical product sector is characterized by extremely high functionality to fight diseases, thus adding real value and commercial profit. In addition, this sector is extremely knowledge based – documented by Nobel Prize–winning research.
Polymers
A combination of extensive science and the availability of carbon sources triggered in the 1930s another chemical success story: polymers. Increasing capacities in oil refineries not only provided gasoline and diesel but with naphtha (Table 1.4) also the fraction of long-chain hydrocarbons to be cracked down to methane, ethylene, and propylene. Platform intermediates like these are till today the biggest chemicals by production volume. Their carbon content is the share of carbon of the molecule's molecular mass (g mol−1). Ethylene, for example, consists of two carbon (atomic mass 12 u) and four hydrogen atoms (atomic mass 1 u), which gives a molecular mass of 28 g mol−1 and a share of carbon of 85.7% (Table 1.5).
Table 1.4 Oil-refinery output from low to high distillation temperature
25 °C
>
>
>
>
>
350 °C
Refinery gas
Gasoline
Naphtha
Kerosene
Diesel oil
Fuel oil
Residue
Bottled gas
Automotive fuel
Chemical feedstock
Aircraft fuel
Truck fuel, bus fuel
Ship fuel, power generation
Bitumen for road construction
Table 1.5 Global production volume of bulk chemicals (2010) (Davis, [2011]) and content of carbon
Chemical category
Chemical
C (%)
Production (million tons)
C content (million tons)
Olefins
Ethylene
C
2
H
4
85.7
123
105
Propylene
C
3
H
6
85.7
75
64
Butadiene
C
4
H
6
88.9
10
9
Hexane
C
6
H
14
83.7
5
4
Aromatics
Xylenes
C
8
H
10
90.6
43
39
Benzene
C
6
H
6
92.3
40
37
Toluene
C
7
H
6
91.3
20
18
Not only the availability of a cheap and easy-to-handle feedstock pushed chemical industries but also the often highly advantageous stoichiometric product yield. For example, ethylene (MW 28.05 g mol−1) and propylene (42.08 g mol−1) are available from hexane (86.18 g mol−1) with a yield of 98% kg kg−1.
Already in 1912 the Chemische Fabrik Griesheim-Elektron (later a production site of Hoechst AG) close to Frankfurt (Germany) tried to find new applications for ethylene, which was produced by oil refineries in big amounts. Finally, the chemist Fritz Klatte (1880–1934) synthesized vinyl chloride from acetylene (C2H2; synthesized by dehydrating ethylene) and hydrogen chloride. From 1928 (several companies in the United States; 1930 BASF in Germany) started production and polymerization to polyvinylchloride (PVC) on large scale. PVC became the first synthetic material not starting from any natural building block and a real milestone in chemical innovation, which had been induced by the availability of a new feedstock. Nylon, patented in 1935 by the chemist Wallace Hume Carothers (1896–1937) at E. I. du Pont de Nemours in Wilmington (Delaware, USA), turned out to be the next big step in polymer innovation. The theoretical base of polymer chemistry had been laid at the University of Freiburg (Germany) by Hermann Staudinger (1881–1965) who received the Nobel Prize in Chemistry in 1953. Today, polymers represent the biggest chemical product group in a volume of 241 million tons in 2012 (Statista, [2013]). China leads with a market share of 23.9%, followed by Europe (20.4%) and the NAFTA region (19.9%).
With polymers the chemical industry finally left also in the field of bulk chemicals the level of craftsmanship, which had characterized this industry in the beginning. From then on science and fast advance in knowledge (documented in patents) became a primary competitive driver (Table 1.6).
Table 1.6 Milestones in chemical innovation
1900
1920
1940
1960
1980
Pharmaceuticals
Salvarsan®Aspirin®
Antibiotics
Birth-control pill
Anti-AIDS protease-inhibitor
Paints and coatings
Acryl lacquer
Water-based lacquer
Adhesives
Phenolic resin
UV-crosslinked adhesives
Solvent-free adhesives
Surfactants
Biologically degradable tensides
Phosphate-free tenside
Polymers
Synthetic rubberViscose
Nylon
TeflonStyropore
Microfibers
Agrochemicals
Haber–Bosch process
Linking herbicide and plant breeding
Energy
Solar cell
1.2.3 Expectancy of Resources
Common sense suggests that fossil resources are limited and will be consumed eventually. From a physical point of view, such a statement sounds simple and is absolutely right. Economically, it is more complex because geological resources differ in cost of exploitation (Table 1.7).
Table 1.7 Cost of oil production (US$ per barrel) (Birol, [2008])
Near East
North America
Deep sea
Enhanced oil recovery
Arctic
3–14
10–40
32–65
30–82
32–100
Geological deposits too costly to be explored today may become competitive tomorrow. An example is today's shale gas boom especially in the United States and the earlier oil sand exploitation in Canada. Both deposits remained untouched and were not included in oil statistics for decades but reached competitiveness because the rising oil price allowed more expensive oil production methods. Therefore, we need to differentiate between reserves and resources. Resources define the total volume of fossil feedstock deposited underground, whereas reserves give an idea of what is exploitable today with the state-of-the-art profitable methods. Economists therefore calculate the “static lifetime,” which is the time range within which a given feedstock will be available under current economical conditions with current technical means under consideration or the current consumption.
The total resources in fossil oil are estimated to amount to 752 billion tons. Out of this volume, 383 billion tons is known as exploitable with today's technical means at feasible coast; 167 billion tons or 44% has already been delivered since the beginning of industrial oil production. About 4 billion tons is produced annually. Nonetheless, oil resources are of course limited but are not to be expected to run out within a short term. The very same is true for gas and coal (Table 1.8). Static lifetime expectancy is an important issue because as long as fossil feedstock is on the market it will be the competitive benchmark for bio-based raw materials.
Table 1.8 Static lifetime (years) of fossil resources (Harald Andruleit, [2011])
Static lifetime of reserves
Static lifetime of resources
Mineral oil
54
146
Natural gas
59
233
Black coal
114
2712
Lignite
282
4400
1.2.4 Green House Gas (GHG) Emission
Nevertheless, in view of the climate change, we need to ask whether it is wise to use fossil resources completely. Undoubtedly, producing energy from oil, gas, and coal by burning leads to CO2 (molecular mass 44 g mol−1), which is emitted into the atmosphere; 27.3% of it is carbon (Table 1.9).
Table 1.9 Annual CO2 emission from various fossil feedstock (million tons; 2012) (Marland, Boden, and Andres, [2007]; Olivier et al., [2014])
Mineral oil
Natural gas
Coal
Sum
CO
2
emission
14,500
6840
13,160
34,500
Carbon content
4000
1900
3500
9400
As atmospheric CO2 reduces global infrared emission into space the consumption of fossil resources has a warming effect on the atmosphere, which is broadly agreed to contribute to man-made (anthropogenic) climate change. Due to the already occurred emission an increase in global temperature by 1.3 °C seems unavoidable in the long run of which 0.8 °C increase is already proven (because of the climate system's inertia it is a slow process). However, to limit global warming to 2 °C CO2 emission should not exceed a cumulative volume of 750,000 million tons till 2050 (Wicke, Schellnhuber, and Klingefeld, 2012). This is equivalent to only 21 years of current emission activity of 34,500 million tons. Already the common people are affected by the climate change by sea-level rise in Bangladesh, desertification in Spain, and drought in the United States. Climate change is one of the most pressing current issues forcing governments and industries to reduce the consumption of fossil resources.
1.2.5 Regional Pillars of Competitiveness
When looking on the global map of fossil resources, it is interesting to note that the sites of deposits and production (Middle East, North America, Russia) are mostly not identical with the sites of processing (Figure 1.1). For example, Belgium, Germany, and Netherlands are among the five biggest global chemical regions. Because this region depends on importing oil, it is called after its harbors and rivers which, however, not only serve as the logistics backbone but also as production sites: ARRR (Antwerp, Rotterdam, Rhine, Ruhr).
Figure 1.1 Global chemical clusters.
Although it must be considered that the starting point of industrial activities in this region has been the availability of coal and a little fossil oil the ongoing success of its industries does not depend on feedstock directly on site. More relevant is an efficient regional logistics system for high-volume feedstock imports and processed goods exports through railroad, pipeline, and river and sea transport. Other equally relevant pillars of competitiveness are academic research and education facilities, skilled workforce, effective governmental and public administrative institutions, and last but not least public acceptance.
How the integration of these factors leads to the innovation leap of successful industries producing marketable goods, creating jobs, and inducing a real innovation cycle with a continuous product pipeline is demonstrated by the history of chemical industries. In the nineteenth century, Germany's universities trained excellent chemists who often kept lifelong friendship and formed an effective business network. They used the new raw material of mineral oil, which was easily available along the river Rhine to develop products for receptive markets like dyestuff and more. With academic excellence, entrepreneurs and investors started production facilities for a society honoring innovation. Nobel Prize and global players in chemical industries were the result. Similar chemical clusters evolved in the United States and Japan (ranking today number 1 and 2). China surpassed Germany a few years ago; its industry grew in the beginning due to beneficial cost but has increasingly gained relevance also because of top-ranking science. Germany's chemical industry still ranks number 4 (Table 1.10). When looking at global regions, the Asian chemical industry is today leading (Table 1.11) especially due to China.
Table 1.10 Chemical industry nation's sales and market share (2013)
China
United States
Japan
Germany
Brazil
Sales (billion US$)
1245
815
335
250
145
Share (%)
24.9
16.3
6.7
5.5
2.9
Table 1.11 Chemical industry region's sales and market share (2013)
Asia
EU(27)
NAFTA
Latin America
Africa
Sales (billion US$)
2435
1070
920
260
55
Share (%)
48.7
21.4
18.4
5.2
1.1
1.2.6 Questions for Further Consideration
What makes fossil feedstock a valuable industrial feedstock?
What are the most important applications of fossil feedstock? What is their share in fossil feedstock use?
What are key success factors of leading fossil-based chemical production sites?
Should fossil feedstock be used till running out? Why not?
1.3 The Nature of Bio-Based Raw Materials
Bio-based raw materials for producing energy and chemicals are provided by agriculture (plant cultivation and animal breeding), forestry, and from marine resources. Plant products and vegetable biomass from agriculture and forestry are most relevant today and will be tomorrow.
Vegetable oil appears in the form of fatty acid esters of glycerol (triglycerides). A typical example is linoleic acid (C18H32O2).
Sugar defines a group of carbohydrates. Monosaccharides include glucose (C6H12O6), fructose (C6H12O6), and galactose (C6H12O6). Disaccharides consist of two sugar molecules such as sucrose (C12H22O11; fructose + glucose). Longer chains of sugars are called oligo- or polysaccharides.
Starch is a polysaccharide (C6H10O5)n consisting of α-d-glucose units. It represents one of the most relevant plant reserve molecules stored in special organelles (grain kernel, corn cobs, potato tuber). Most relevant starch crops are wheat, corn, potato, and manioc.
Lignocellulose is the basic material of plant biomass. It is composed of carbohydrate polymers (cellulose ((C12H20O10)[n]) made of glucose dimers, hemicellulose made of d-xylose (C5H10O5) and l-arabinose (C5H10O5)) and an aromatic polymer (lignin). The carbohydrate polymer fraction contains different sugar monomers (six and five carbon sugars). Lignocellulose is the most abundant plant material available, for example, from agricultural crops and residuals, forest trees, or steppe vegetation.
Vegetable biomass is characterized by (i) complex polymeric structures and (ii) compound diversity and (in contrast to fossil materials) the presence of oxygen (Table 1.12)
Table 1.12 Composition (%) (Michelsen, [1941]) and heat value (MJ kg−1
