Table of Contents
Cover
Title Page
Copyright
List of Contributors
Preface
Chapter 1: AkzoNobel: Biobased Raw Materials
1.1 AkzoNobel's Biobased Raw Materials Strategy in Context
1.2 AkzoNobel in the Value Chain
1.3 Drivers Behind Development of the Biobased Raw Material Strategy
1.4 Conclusions of the Biobased Chemicals Strategy
1.5 Implementing the Strategy: Striking Partnerships
1.6 Experience to Date
1.7 Measuring, Reporting, and Ensuring Sustainable Sourcing of Biomass
1.8 Book and Claim
1.9 Sustainability in the Value Chain: LCA
Chapter 2: Arizona Chemical: Refining and Upgrading of Bio-Based and Renewable Feedstocks
2.1 Company Introduction
2.2 History of Pine Chemicals
2.3 Modern Biorefining
2.4 The Kraft Pulping Process
2.5 Cradle-to-Gate
2.6 Outlook
2.7 Case Study: Tackifiers From Renewable Pine-Based Crude Tall Oil and Crude Sulfate Turpentine for Adhesive Applications
Acknowledgments
References
Chapter 3: Arkema: Castor Reactive Seed Crushing Process to Promote Castor Cultivation
3.1 Arkema: Context for Biorenewables
3.2 Introduction to Castor Oil
3.3 Experimental Details
3.4 Results
3.5 Discussion
3.6 Conclusion
Acknowledgments
References
Chapter 4: Avantium Chemicals: The High Potential for the levulinic product tree
4.1 Introduction
4.2 Levulinic Production Routes
4.3 The Levulinic Acid Product Tree
4.4 Conclusions and Outlook
References
Chapter 5: C5LT: Biorenewables at C5 Ligno Technologies AB
5.1 Introduction
5.2 Lignocellulosic Ethanol Production: Process
5.3 C5LT Gene Package Technology
5.4 Fermentation of Lignocellulosic Hydrolysates: Remaining Challenges
5.5 Conclusions
Acknowledgments
References
Chapter 6: Cepsa: Towards The Integration of Vegetable Oils and Lignocellulosic Biomass into Conventional Petroleum Refinery Processing Units
6.1 About Cepsa
6.2 Vegetable Oils
6.3 Lignocellulosic Biomass
6.4 Concluding Remarks
References
Chapter 7: DuPont: Biorenewables at E.I. DU Pont DE Nemours & Co
7.1 DuPont History and Strategic Priorities
7.2 DuPont's Innovation Philosophy
7.3 DuPont's Industrial Biorenewable Portfolio 2013
7.4 Case History #1: Bio-PDO and Sorona
7.5 Case History #2: Development of Yeast-based Omega-3s for Verlasso Harmoniously Raised Salmon
7.6 Future Directions for DuPont in Industrial Biorenewables
7.7 Summary
References
Chapter 8: Evonik: Bioeconomy and Biobased Products
8.1 Introduction
8.2 Biobased and Bioprocessed Products (1)
8.3 Products Produced from Biobased Feedstock by Conventional Catalysis (2)
8.4 Biodegradable Products (3)
8.5 Enabling Chemicals (4)
References
Chapter 9: Market Structure and Growth Rates of Industrial Biorenewables
9.1 Background for Industrial Biorenewables and Data Sources
9.2 Market Overview and Growth Rates
9.3 Examples for Biotechnology-Based Products Related to Biorenewables
References
Chapter 10: Göteborg Energi: Vehicle Fuel From Organic Waste
10.1 The Company
10.2 Sweden's Renewable Energy Targets and the Role that Biogas Will Play in Meeting these
10.3 Biogas in Transportation: Case Studies Within Göteborg Energi
10.4 The Role of Gasification Technology in the Future as the Demand for Biomass-based Energy and Fuel Grows
Recommended Academic References for Further Reading
Chapter 11: Greasoline: Biofuels From Non-food Materials and Residues
11.1 Fuels and Chemicals: Necessity of Renewables
11.2 Evolving Markets for Greasoline® Technology
11.3 Technology Overview Greasoline®
11.4 Description of Business Model
11.5 Diesel from Different Raw Materials
References
Chapter 12: Green Applied Solutions: Customized Waste Valorization Solutions for a Sustainable Future
12.1 Introduction
12.2 The Company
12.3 Projects and Future
12.4 Conclusions and Prospects
Acknowledgments
References
Chapter 13: Grove Advanced Chemicals: Flox® Coagulants – Environmentally Friendly Water and Wastewater Treatment Using Biodegradable Polymers From Renewable Forests
13.1 Introduction
13.2 Company Overview
13.3 Coagulation and Flocculation in Water Treatment
13.4 Flox® Coagulants
13.5 Company and Product Certifications
13.6 Case Studies
13.7 Future Perspectives
References
Chapter 14: Heliae Development, LLC: An Industrial Approach to Mixotrophy in Microalgae
14.1 Preamble
14.2 Introduction to Heliae Development LLC
14.3 Mixotrophy
14.4 Implementation of Industrial Mixotrophy: A Case Study
Acknowledgments
References
Chapter 15: InFiQuS: Making the Best of Leftovers
15.1 Brief Description of InFiQuS
15.2 Valuable by-products Under Research by InFiQuS
15.3 Examples of Products Co-developed by InFiQuS
15.4 Market Situation
15.5 Needs of Research: Synergies Between Industry and Academia
References
Chapter 16: Biorenewables at Mango Materials
16.1 Motivation: the Problems with Plastics Today
16.2 The Bioplastics Industry: An Overview
16.3 Mango Materials – a Novel PHA Production Process
16.4 Mango Materials, the Story
16.5 The Future – new Ideas for Potential Research
Acknowledgments
References
Chapter 17: Novamont: Perspectives on Industrial Biorenewables and Public-Private Needs
17.1 State of the Art and Challenges Faced by Biobased Industries
17.2 Wisdom in the Use of Renewable Raw Materials: The Cascading Use of Biomass
17.3 Case Study: Bioplastics in Italy: Going For Growth Despite the Crisis
17.4 The EU Policy Framework and Related Policy Gaps: The EU Strategy on Bioeconomy and the Role of Industrial Policies
References
Chapter 18: Novozymes: How Novozymes Thinks About Biomass
18.1 The Company
18.2 Case Study: The Transformation of Cellulose to Ethanol
References
Chapter 19: Organoclick: Applied Eco-Friendly and Metal-Free Catalysis for Wood and Fiber Modifications
19.1 Introduction
19.2 Eco-friendly and Organocatalytic Surface Modification of Lignocellulose
19.3 Organocatalytic Cross-linking Between Polysaccharides
19.4 OC Modification of Lignocellulose
References
Chapter 20: Petrobras: The Concept of Integrated Biorefineries Applied to the Oleochemistry Industry: Rational Utilization of Products and Residues via Catalytic Routes
20.1 Introduction
20.2 Glycerol Fermentation
20.3 Hydrotreating
20.4 Decarboxylation
20.5 Conclusions
References
Chapter 21: Phytonix: Cyanobacteria for Biobased Production Using CO2
21.1 Background: The Coming Co2 Economy and Circular Economy Principles
21.2 Technology for Cyanobacteria and Direct Photobiological Production
21.3 Phytonix: Path Toward Full Commercialization of the Technology
21.4 n -Butanol: A Valuable Industrial Chemical and Potential “Drop-in” Gasoline Replacement
References
Chapter 22: Phytowelt Green Technologies: Fermentation Processes and Plant Breeding as Modules for Enhanced Biorefinery Systems
22.1 Introduction
22.2 The Next Step: Beyond Energy Production
22.3 Material Uses of Renewable Poplar Biomass
22.4 Fermentative Production of High-value Compounds
22.5 Cooperations with Chemical Industry
22.6 Toward Optimized Biorenewables: Time-Lapse and Smart Breeding
22.7 Next-Generation Poplars/Plants
22.8 Toward Novel Biorefineries: Networking for Success
References
Chapter 23: Biorenewables at Shell: Biofuels
23.1 Introduction
23.2 Shell and Biofuels
23.3 Development of Advanced Biofuels in Shell
23.4 Challenges Leading to More Research
23.5 Conclusions
References
Index
End User License Agreement
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Guide
Cover
Table of Contents
Preface
Begin Reading
List of Illustrations
Chapter 1: AkzoNobel: Biobased Raw Materials
Figure 1.1 Wider chemical industry and AKZONOBEL use of renewable raw materials.
Figure 1.2 Three-workstream approach.
Figure 1.3 Example matrix.
Figure 1.4 Example of a detail scorecard.
Figure 1.5 Potential green supply chain.
Chapter 2: Arizona Chemical: Refining and Upgrading of Bio-Based and Renewable Feedstocks
Figure 2.1 Crude tall oil products and its applications.
Figure 2.2 Monoterpene biosynthesis route (stereochemistry omitted).
Figure 2.3 Chemical structures of common unsaturated monoterpenes (stereochemistry omitted).
Figure 2.4 Chemical structures of most common rosin acids.
Figure 2.5 Kraft chemical recovery process.
Figure 2.6 Kraft pulping process.
Figure 2.7 Flow of products: acidulation and distillation plant.
Figure 2.8 Kraft pulping process and the resulting products.
Figure 2.9 Typical refinery main fractions of CTO distillation. The dashed lines schematically represent inter-distillation column mass transfers.
Figure 2.10 Major tall oil fatty acid (TOFA) components. Abundance percentages were taken from Zinkel and Russell.
Figure 2.11 CTO distillation into its main components and their derivative products.
Figure 2.12 Cascading use of scarce raw materials to maximize value.
Figure 2.13 Disproportionation of abietic acid.
Figure 2.14 Rosin dimerization (stereochemistry omitted).
Figure 2.15 Rosin acid hydrogenation (stereochemistry in the fully hydrogenated product is partly omitted).
Figure 2.16 Examples of commonly used polyols in rosin ester syntheses.
Figure 2.17 Three distinct equilibria in the esterification reaction of rosin acid with a three-functional-group polyol (glycerol).
Figure 2.18 Hildebrand solubility parameters of different tackifiers in relation to most common adhesive polymers.
Figure 2.19 Application performance of different SYLVARES™ grades in Newton in a foam tape application, coat weight , formulation based on industry standard acrylic polymer tackified with 25 w/w% terpene phenol resin. polyethylene, , , , and .
Chapter 3: Arkema: Castor Reactive Seed Crushing Process to Promote Castor Cultivation
Figure 3.1 Current operating bio-based products and plants.
Figure 3.2 On-going developments.
Figure 3.3 Ricinus communis plant.
Figure 3.4 Obtained castor seeds via the conventional process (a) or the novel approach (b).
Figure 3.5 Obtained methyl ricinoleate via the conventional process (a) or the novel approach (b).
Chapter 4: Avantium Chemicals: The High Potential for the levulinic product tree
Figure 4.1 Maleic anhydride route to levulinic acid.
Figure 4.2 C6 and C5 sugar-based routes to levulinic acid.
Figure 4.3 Enzymatic cascade for glucose to levulinic acid.
Figure 4.4 BioFine process scheme.[47]
Figure 4.5 Chemical products derived from levulinic acid and its esters.
Figure 4.6 Reaction scheme of ML to GVL.
Figure 4.7 Reaction scheme of ML to DPA.
Figure 4.8 Reaction scheme of GVL to PA.
Figure 4.9 Reaction scheme of ML to MeTHF.
Figure 4.10 Base-assisted formation of SA from LA.
Figure 4.11 Reaction scheme of the reaction of LA and glycerol into ketals.
Chapter 5: C5LT: Biorenewables at C5 Ligno Technologies AB
Figure 5.1 Configurations used for the conversion of biomass to ethanol. The dotted line indicates SSF configuration.
Figure 5.2 Variety of different raw materials, pretreatment and hydrolysis methods, and process configurations. As the various options each three categories can be combined in almost any combination, the number of resulting ethanol production processes is almost infinite. This generates a wide variety of different lignocellulosic hydrolysates and requirements for the fermenting microorganism.
Figure 5.3 The initial xylose conversion pathways in fungi (XR–XDH) and bacteria (XI).
Figure 5.4 Schematic illustration of the C5LT gene package technology to generate xylose-fermenting yeast strains.
Figure 5.5 Anaerobic fermentation of mineral medium (a) and lignocellulosic hydrolysate (b) using the same C5LT strain. Xylose – squares; glucose – diamonds; ethanol – triangles; xylitol – circles.
Figure 5.6 Sugar yield (diamonds), C6 fermentability (circles), and estimated C5 fermentability (squares) as function of the combined severity values.
Figure 5.7 Anaerobic batch fermentation of corn stover (a), wheat straw (b), and bagasse (c) using three different C5LT strains. Xylose – squares; glucose – diamonds; ethanol – triangles; biomass – crosses; xylitol – circles.
Figure 5.8 Anaerobic batch fermentation of lignocellulosic hydrolysate using 2 g/L (a) or 5 g/L (b) of initial yeast cell dry weight concentration. Xylose – squares; glucose – diamonds; ethanol – triangles.
Chapter 6: Cepsa: Towards The Integration of Vegetable Oils and Lignocellulosic Biomass into Conventional Petroleum Refinery Processing Units
Figure 6.1 International Petroleum Investment Company (IPIC).
Figure 6.2 Current presence of Cepsa worldwide.
Figure 6.3 Product distribution portfolio of Cepsa refineries.
Figure 6.4 Cepsa R&D&I center.
Figure 6.5 Simplified flowchart of a refinery.
Figure 6.6 Transesterification reaction of triglycerides to form FAME.
Figure 6.7 Possible reaction pathways in the hydrotreating of vegetable oil.
Figure 6.8 Simplified scheme of the pilot plant used in the hydrotreating of vegetable oils.
Figure 6.9 Gas Chromatography analysis of mineral Diesel (dark gray) and the one obtained by coprocessing of mineral and vegetable oil (light gray).
Figure 6.10 Used frying oil and two hydrotreated products.
Figure 6.11 Observed exothermic behavior through the catalytic bed during the hydrotreating of 100% of SRGO and during the coprocessing of used frying oil in the refinery in Tenerife.
Figure 6.12 Proportion profiles of n -paraffin obtained when hydrotreating sunflower, soybean, and used frying oils in operational units at moderate pressure.
Figure 6.13 Cepsa partners in the project ALGINDCO2.
Figure 6.14 Places close to the refinery of Huelva, where microalgae were isolated (indicated by numbers).
Figure 6.15 Two of the used systems for the project. (a) Raceway (300 L). (b) Horizontal photobioreactor (PBR) of 5 m3 .
Figure 6.16 Algae-based oil and HAO.
Figure 6.17 Profile of n -paraffin of HAO under diesel hydrotreating conditions.
Figure 6.18 Simplified scheme of the production of biofuel from algae oil.
Figure 6.19 Coconut, camelina, and UFO.
Figure 6.20 Profile of n -paraffin in HVO obtained at 55 bar, LHSV = 2 h−1 and 372 °C for camelina, 375 °C for refined coconut oil, and 366 °C for nonrefined UFO.
Figure 6.21 Isomer distribution after isomerization of HVO derived from refined coconut oil between 330 and 350 °C at P = 30 bar and LHSV = 2.7 h−1 .
Figure 6.22 Cold flow properties of coconut oil HVO isomerized.
Figure 6.23 Cold flow properties of kerosene fraction obtained after hydrocracking process using crude frying oil as raw material.
Figure 6.24 Alternatives for the production of biokerosene using vegetable oils as raw material.
Figure 6.25 Envisaging the integration of vegetable oils as raw materials for a conventional petroleum refinery.
Figure 6.26 Main components of lignocellulosic biomass.
Figure 6.27 Furfural production from hemicellulose.
Figure 6.28 Integration of DRAGO project within a pulp and paper industry.
Figure 6.29 Pine residues used by the University of La Laguna in Tenerife (Canary Islands, Spain).
Figure 6.30 Pilot plant for hydrodeoxygenation of furan-based molecules and diesel fuel obtained after the process.
Figure 6.31 Density of the blend of SRGO and LCO with the synthetized biobooster of the DRAGO project.
Chapter 7: DuPont: Biorenewables at E.I. DU Pont DE Nemours & Co
Figure 7.1 DuPont's 2013 sales by business unit.
Figure 7.2 DuPont's scientific competencies. This breadth and depth in a variety of disciplines enables successful development of industrial biorenewables.
Figure 7.3 Metabolic pathways for the production of PDO and biomass. Reactions inserted from Saccharomyces are in the blue background, and those inserted from Klebsiella in the green background. Initial and final products are in yellow backgrounds. Important redox and energy cofactors are in red.
Figure 7.4 Alterations made in the E. coli genome in the course of making the PDO biocatalyst. Changes were made to glucose transport, glycerol metabolism, glycolysis (Entner–Doudoroff, pentose phosphate, and tricarboxylic acid cycles), respiration, amino acid biosynthesis pathways, anaplerotic reactions, and global regulators. Not shown – the plasmid containing the pathway genes.
Figure 7.5 Distribution of skills of project team members year by year over the course of the Bio-PDO™ project.
Figure 7.6 Progress toward key objectives year by year over the course of the project.
Figure 7.7 Schematic diagram of aerobic pathways for EPA biosynthesis.
Figure 7.8 Workflow of strain and fermentation process development.
Figure 7.9 Microfermenters can be used for strain screening (bar graph on top) and for optimization of fermentation conditions (scatter plot below).
Figure 7.10 Omega-3 fermentation as a two-stage, fed-batch process developed primarily in lab-scale fermenters. During the first stage, biomass is grown to a specified cell density. During the second stage, lipid containing EPA/DHA is accumulated in the prepared biomass.
Figure 7.11 Example use of a predictive fermentation model.
Chapter 8: Evonik: Bioeconomy and Biobased Products
Figure 8.1 Following our definition, products contribute to the bioeconomy if they are biobased, bioprocessed, biodegradable, or if they are indispensable to enable value creation in the bioeconomy.
Figure 8.2 Each nation, institution, and company need to have a sustainability or CR strategy for keeping the balance of all three sustainability aspects in order to keep mankind's well-being on earth.
Figure 8.3 Lighthouse investment projects at Evonik.
Figure 8.4 The public-private partnership SPIRE.
Figure 8.5 Traditional aquaculture requires up to 3 kg of wild-catch fish, which is fed in form of fish meal. Costly and scarce fish meal can be replaced by plant protein sources and amino acids. Supplementing amino acids effectively reduces fish meal requirements from 40% to only 15%.
Figure 8.6 Cargill biorefinery concept at Blair, Nebraska, United States. Cargill will build a “Blair 2” in Castro, Brazil, startup 2015.
Figure 8.7 OOO DonBioTech biorefinery concept Volgodonsk, Russia.
Figure 8.8 Biocatalysis improves the sustainability of emollient ester production.
Figure 8.9 Comparison of the chemical and the new biotechnological way for the PA12 synthesis developed at Evonik.
Figure 8.10 Synthesis of the different Evonik's VESTAMID® Terra products.
Figure 8.11 Global biobased succinic acid capacity.
Chapter 9: Market Structure and Growth Rates of Industrial Biorenewables
Figure 9.1 Market size of industrial renewables in 2010, 2015, and 2020.
Figure 9.2 Chemical and biorenewable sales per segment in 2010.
Figure 9.3 Biorenewable sales per region in 2010.
Figure 9.4 Biorenewable sales per subsegment in 2010.
Figure 9.5 Chemical sales and biorenewable sales per segment in 2015.
Figure 9.6 Biorenewable sales per subsegment in 2015.
Figure 9.7 Chemical sales and biorenewable sales per segment in 2020.
Figure 9.8 Biorenewable sales per subsegment in 2020.
Figure 9.9 Structural formulas of molecules produced by biotechnological processes.
Chapter 10: Göteborg Energi: Vehicle Fuel From Organic Waste
Figure 10.1 The Gasendal process.
Figure 10.2 The Air Liquide technology.
Figure 10.3 Facilities of the GoBiGas plant.
Chapter 11: Greasoline: Biofuels From Non-food Materials and Residues
Figure 11.1 Simplified flow sheet of the Greasoline® technology.
Figure 11.2 Lower part of pilot plant showing feed system, preheater, evaporator, and product quench.
Figure 11.3 Pilot atmospheric distillation.
Figure 11.4 Pilot rotary kiln for catalyst reactivation. (Outside (a) and inside (b) view of kiln.)
Figure 11.5 Greasoline: Suited raw materials and possible products.
Figure 11.6 Different phenotypes of jatropha.
Figure 11.7 Distillation curve of water quenched crude product mixture in pilot plant.
Figure 11.8 GC-MS: 25 biggest peaks of crude product mixture making up 41% by mass of total.
Chapter 12: Green Applied Solutions: Customized Waste Valorization Solutions for a Sustainable Future
Figure 12.1 Pretreatment of rice husk (a) to fine sieved powder (b) via milling prior to processing.
Figure 12.2 Conversion of rice husks into sodium carbonate.
Figure 12.3 Mechanochemical production of designer nanomaterials from various polysaccharides.
Figure 12.4 From slaughterhouse/tannery waste to biocollagenic polymers with applications in tissue regeneration.
Chapter 13: Grove Advanced Chemicals: Flox® Coagulants – Environmentally Friendly Water and Wastewater Treatment Using Biodegradable Polymers From Renewable Forests
Figure 13.1 Samples of the commercial solution of coagulants Flox®-QT, Flox®-QTH, and Flox®-QTP (25%, w/w).
Figure 13.2 Generic representation of the chemical structure of Flox® coagulants.
Figure 13.3 Schematic representation of the wastewater treatment process in a particular ceramics industry after the implementation of Flox®-QTH coagulant.
Figure 13.4 Schematic representation of the wastewater treatment process in a particular fish canning industry after the implementation Flox®-QT/ Flox®-QTH coagulants.
Figure 13.5 Schematic representation of the wastewater treatment process in a particular poultry abattoir after the implementation of Flox®-QT coagulant.
Figure 13.6 Schematic representation of the wastewater treatment process in a particular medium-density fiberboard (MDF) industry after the implementation of Flox®-QT coagulant.
Figure 13.7 Schematic representation of the wastewater treatment process in a particular dairy industry after the implementation of Flox®-QT coagulant.
Chapter 14: Heliae Development, LLC: An Industrial Approach to Mixotrophy in Microalgae
Figure 14.1 The supplementation with CO2 does not improve the mixotrophic growth of HS26 in 20 L carboys. Inorganic carbon enrichment is only necessary when HS26 was grown phototrophically.
Figure 14.2 The mixotrophic growth of HS26 in shake flasks is above the photoautotrophic as well as the heterotrophic treatment (a). Light in mixotrophic cultures improves acetic acid yields (0.4) above those obtained in heterotrophic cultures (0.3 g CDW per g of acetic acid) (b). All treatments were analyzed in duplicates. Data and Figure retrieved from literature.[29]
Figure 14.3 Mixotrophic growth of HS26 in 20 L flat panel photobioreactor with an acetic acid auxostat system (squares) is threefold more productive than the traditional phototrophic system (cycles). All treatments were operated in duplicates. Retrieved from literature.[29]
Figure 14.4 Mixotrophic growth and biomass productivities of HS26 in two replicate (1000 L) open reactors. Harvesting was made semicontinuously with 50–80% daily harvest throughout a 10 d period, whereas bacterial levels were maintained below 106 CFU/mL. The results reflect typical values obtained in production.[29]
Figure 14.5 Large-scale bioreactors for the mixotrophic cultivation of microalgae.
Figure 14.6 Mixotrophic growth and biomass productivities of HS26 in a 100,000 L open reactor. Harvesting was made semicontinuously with 20–80% daily harvest throughout a 29 d of stable operation. The results reflect typical values obtained in production.[29]
Figure 14.7 Overview of Heliae algae cultivation facilities in Phoenix, AZ.
Chapter 15: InFiQuS: Making the Best of Leftovers
Figure 15.1 By-products used by our company from different industries.
Figure 15.2 Overview of crustacean shell management.
Figure 15.3 Isolation of valuable by-products from crustacean shells.
Figure 15.4 Preparation of chitin derivatives.
Figure 15.5 Chemical structure of chitin and chitosan (chitosan m > 0.6).
Figure 15.6 Scheme of beer production and main uses of yeast.
Figure 15.7 Uses of cardoon.
Figure 15.8 Solid cake cardoon composition.
Figure 15.9 Chitin and chitosan market.
Chapter 16: Biorenewables at Mango Materials
Figure 16.1 The closed-loop system of Mango Materials.
Figure 16.2 (a) Chemical structure of a generic PHA. (b) Chemical structure of PHB.
Figure 16.3 The location of methane production at landfill point sources in the continental United States.
Figure 16.4 Comparison of revenue generated using methane for plastic production versus using methane to generate electricity.
Figure 16.5 Timeline of significant events in the growth of Mango Materials.
Chapter 18: Novozymes: How Novozymes Thinks About Biomass
Figure 18.1 Novozymes overview.
Figure 18.2 Enzymatic synergies in plant biomass deconstruction. Panel a – schematic representation of the enzymatic hydrolysis of cellulose by synergizing cellobiohydrolases (CBH I and CBH II), an endoglucanase, and a β-glucosidase; Panel b – schematic representation of the enzymatic hydrolysis of hemicellulose by synergizing xylanase, β-xylosidase, and xylan-debranching enzymes; Panel c – illustration of a typical bacterial cellulosome; Panel d – illustration of the increase of the accessible cellulose surface area in biomass as a result of hemicellulose degradation by an endo-β-1,4-xylanase; Panel e – illustration of the release of a nonproductively bound to lignin cellulase by a laccase; Panel f – effect of a swollenin on cellulose microfibril bundles; Panel g – oxidation of the anomeric carbon by LPMOs. List of abbreviations used in the figure: NR – nonreducing cellulose end; R – reducing cellulose end; CBH I – an R-end-acting exo-β-1,4-glucanase (EC 3.2.1.176), the Hypocrea jecorina (formerly Trichoderma reesei ) Cel7A (formerly cellobiohydrolase I or CBH I); CBH II – an NR-end-acting exo-β-1,4-glucanase (EC 3.2.1.91), the H. jecorina Cel6A (formerly cellobiohydrolase II or CBH II); EG – an endo-β-1,4-glucanase (EC 3.2.1.4); β-G – a β-glucosidase (EC 3.2.1.21); XYN – an endo-β-1,4-xylanase (EC 3.2.1.8), which cleaves the main xylan backbone; β-XYL – a β-d -xylosidase (EC 3.2.1.37), which hydrolyses the released xylooligosaccharides to xylose; α-AF – an α-l -arabinofuranosidase (EC 3.2.1.55), active on arabinans; α-GAL – an α-d -galactosidase (EC 3.2.1.22), active on nonreducing α-d -galactose residues; α-GLU – an α-d -glucuronidase (EC 3.2.1.131), active on α-d -1,2-(4-O-methyl) glucuronosyl links; FE – a feruloyl esterase (EC 3.1.1.73), which releases ferulic acid by cleaving ester bonds; AXE – an acetylxylan esterase (EC 3.1.1.72), which catalyzes the release of acetyl groups; LPMOs – lytic polysaccharide monooxygenases (formerly, GH61); AA9 – CAZy auxiliary activity family 9 comprising LPMOs; GH61 – CAZy glycoside hydrolase family 61; R′, R – glycosyl groups; C1 – anomeric carbon. (Illustration by Vera M. Gutman.)
Figure 18.3 Common flow diagrams for a biomass to ethanol process, utilizing dilute acid in the pretreatment with a “whole slurry” concept. (a) Simultaneous saccharification and fermentation (SSF); (b) Separate hydrolysis and cofermentation (SHF); (c) Separate hydrolysis and parallel fermentation (SHPF). Alternative processes can separate and/or wash liquid streams generated during the pretreatment and conditioning step to remove impurities or create parallel process streams.
Figure 18.4 Diagram illustrating the block construction technoeconomic model used by Novozymes to estimate current and future state B2E concepts. (MESP = minimum ethanol selling price, ICC = installed capacity cost, EUC = enzyme use cost.)
Figure 18.5 Example relationship of hydrolysis time to minimum ethanol selling price for several different assumed hydrolysis tank costs, using an enzyme performance correlation based upon laboratory data.
Figure 18.6 Common production cost breakdown for a dilute acid pretreatment process for biomass to ethanol. Note the negative cost associated with the electricity export.
Figure 18.7 Illustration of the impact of improvements in enzyme efficiency (current Cellic CTec3 vs future) on the optimal reaction time and conversion targets for a whole slurry acid pretreated-type enzyme hydrolysis step. Enzyme improvement can be leveraged to increase the target cellulose conversion (75%/Current 4 days to 83%/Future 4 days). Changes in hydrolysis time can also be made (4 days Current to 3 days Future), but for the same tank type, the MESP benefit, if any, is small. The right side of the lowest delta MESP points for each curve illustrates the cost impact of targeting a higher conversion than the current technology will provide.
Figure 18.8 Comparison of several sugar platforms with ethanol processes to an ethanol only biomass process for varying sugar price in USD per metric ton dry weight sugars. (dMT = metric ton dry weight sugars, uw = unwashed substrate, sq = S/L separation process without washing, w = S/L separation process with washing.)
Figure 18.9 Impact of feedstock cost and internal rate of return (IRR) on the minimum ethanol selling price (MESP) for a Novozymes benchmark process model case with whole slurry converting biomass into ethanol. Other process layouts can lead to changes in the absolute and relative values. For high IRR requirements, the interest payments can be as large as the rest of the production costs combined.
Figure 18.10 Typical concentration diagram for a pentose-fermenting ethanologen in a batch fermentation. The physical (sugar transporters on cell wall) as well as energetic/metabolic traits (intercellular enzyme pathways for sugar conversion to ethanol) often give considerable preferential activity on glucose over other sugars, including other hexoses (shown as phase lasting to about 36 h). After the glucose is consumed, the uptake rate of other sugars increases (36–60 h), until a critical point where the cells begin to be stressed by the ethanol concentration and/or the cells struggle as a result of reduced available maintenance energy.
Chapter 19: Organoclick: Applied Eco-Friendly and Metal-Free Catalysis for Wood and Fiber Modifications
Scheme 19.1 Examples of organocatalytic reactions for the synthesis of heterocycles.
Scheme 19.2 Direct poly(caprolactone) derivatization of solid cellulose.
Scheme 19.3 Organocatalytic cross-linking of cellulose fibers.
Scheme 19.4 “OrganoClick” surface modification of heterogeneous polysaccharides.
Figure 19.1 Water drops on a polyester-based textile treated with OrganoTex™.
Chapter 20: Petrobras: The Concept of Integrated Biorefineries Applied to the Oleochemistry Industry: Rational Utilization of Products and Residues via Catalytic Routes
Figure 20.1 Potential use of vegetable oils as raw material in nonconventional chemical routes.
Figure 20.2 Main products from glycerol.
Figure 20.3 Coprocessing flow sheet.
Figure 20.4 Reaction pathways starting from an ordinary triglyceride.
Chapter 21: Phytonix: Cyanobacteria for Biobased Production Using CO2
Figure 21.1 Shading in a photobioreactor.
Figure 21.2 Bubble flow in a reactor volume that mixes the reactor contents.
Figure 21.3 Porous membrane used to mix PBR with air.
Figure 21.4 Production cost structure. Projected n -butanol production costs according to Phytonix estimations. See data in literature for comparison.[15]
Figure 21.5 Mass balance for the Phytonix's n -butanol production.
Chapter 22: Phytowelt Green Technologies: Fermentation Processes and Plant Breeding as Modules for Enhanced Biorefinery Systems
Figure 22.1 The biorefinery concept. A simplified graphical representation of Phytowelt's concept of a poplar-based biorefinery. Tree biomass produced in short rotation coppices serves a biomass source. Residues not suited for immediate energetic use like bark and branches will enter the primary refinement extracting carbohydrates, preformed high-value compounds, as well as raw materials. These intermediate products will serve as feedstock for fermentative production of high-value compounds such as carotenoids and for production of additional products for chemical or biochemical treatment. Wastes produced during all steps will again be used to generate energy, first used to cover the requirements of the biorefinery processes. While running the biorefinery desirable improvements of the input biomass will be revealed. This directly translates into new breeding targets to be realized using Phytowelt's time-lapse breeding techniques and closes the feedback loop.
Figure 22.2 Schematic view of terpene biosynthesis. Essential feedstock for the synthesis of all terpenes are IPP and DMAPP and, depending on the terpene class, either the condensation products GPP, FPP, or GGPP. In most bacteria (like E. coli ) IPP can only be synthesized via the MEP pathway and GGPP cannot be produced. The additional implementation of the MVA pathway increases IPP production capacities resulting in increased terpene yields. Final product formation requires a range of additional reactions such as condensations, desaturations, cyclisations, and oxidations. Examples of terpene structures belonging to the different classes are given.
Figure 22.3 Tools for metabolic engineering of microbial hosts. Design and cloning of suitable individual expression units for a given gene of interest or operon-like multigene constructs require availability of various DNA elements such as promoters, ribosome binding site (RBS), and their flanking untranslated regions (UTR), as well as transcriptional termination signals (terminators). Phytowelt has generated collections of functional proprietary sequences for each of these elements as genetic toolbox for metabolic engineering.
Figure 22.4 Fermentative production of high-value compounds. (a) Structures of some of the carotenoids produced by Phytowelt's metabolically engineered E. coli strains. (b) Omega oxidation of plant oil-derived fatty acids results in feedstocks for polymer chemistry. (c) Biosynthesis of diterpene compounds currently under investigation.
Figure 22.5 Cytochrome reductase (CPR) enables activity of P450 enzymes. (a) In the cell CPR mediates the transfer of electrons from cofactor NADPH to the P450 enzymes. (b) Expression and activity optimization of a CPR enzyme developed by Phytowelt. (c) Activities measured for a subset of Phytowelt's CPR library.
Figure 22.6 Enhanced biomass of tetraploid poplar plants derived from protoplast fusion. (a) New poplar line (tetraploid, 4n ) shows significant increases in stem biomass, chloroplast number, and stomata length compared to diploid (2n ) poplar. (b) Corresponding pictures of the plant materials.
Chapter 23: Biorenewables at Shell: Biofuels
Figure 23.1 Routes for converting lignocellulose to fuels and chemicals.
Figure 23.2 Acid hydrolysis of lignocellulose to levulinic acid ( , 5–20 wt% solid, 3–9 wt% , ).
Figure 23.3 Fuel derivatives from furfural and levulinic acid.
Figure 23.4 Selectivity of oligomers (a) and dimer/trimer (b) of the oligomers under standard conditions as well as in the presence of extractant or alternative acid catalysts.
Figure 23.5 Acidic steam stripping of furfural from lignocellulose.
Figure 23.6 Fuel properties of bio-oxygenates.
Figure 23.7 Comparison of FCC yields from vacuum gas oil and blends with rapeseed oil (20%) and marine algae oil (20%) as feed.
Figure 23.8 Schematic path showing the metabolic route to tricyclene.
Figure 23.9 Schematic path showing the metabolic routes to fatty alcohols (AAR: acyl-ACP reductase; ADH alcohol dehydrogenase; FAR fatty alcohol-forming acyl reductase; CAR: carboxylic acid reductase; TES: thioesterase; ACL: fatty acid-CoA ligase; ACR: fatty acyl-CoA reductase).
Figure 23.10 Virent's BioForming technology platform.[79]
Figure 23.11 The pyrolysis oil pathway as investigated by BIOCOUP.
Figure 23.12 Coprocessing of upgraded pyrolysis oils in laboratory-scale hydrotreating unit (feed: blend of gas oil (hydrotreated gas oil), HGO), or straight-run gas oil (SRGO)) and upgraded pyrolysis (UPO; bars refer to boiling range fraction, e.g., being kerosene and being diesel).
Figure 23.13 Acidic hydroliquefaction of lignocellulose (acetic acid as cosolvent, pH , 40–100 bar ).
Figure 23.14 Liquefaction of lignocellulose in phenolic medium (30 min at ).
List of Tables
Chapter 2: Arizona Chemical: Refining and Upgrading of Bio-Based and Renewable Feedstocks
Table 2.1 Major Crude Sulfate Turpentine (CST) Monomer Composition Differences by Comparison of the United States with Swedish CST.[5b]
Table 2.2 Carbon Footprint as a Multiple of CTO-Based Equivalents.[60]
Table 2.3 GHG Emissions for CTO versus Fossil-Based Chemical Companies.[82]
Chapter 3: Arkema: Castor Reactive Seed Crushing Process to Promote Castor Cultivation
Table 3.1 Features of Three Batches of Castor Seeds Processed Under Different Methods
Table 3.2 Flattening of Castor Seeds
Table 3.3 Evaluation of Defatted Castor Seeds and Oil Cake
Table 3.4 Effect of the Catalyst Content on the Processing
Table 3.5 Effect of the Catalyst Content on the Quality of the Methyl Esters Recovered
Table 3.6 Effect of the Amount of Methanol Relative to the Amount of Seed Flakes
Table 3.7 Effect of the Amount of Methanol on the Quality of the Methyl Esters
Table 3.8 Effect of the Reaction Time on the Processability
Table 3.9 Effect of the Reaction Time on the Product Quality
Table 3.10 Effect of the Amount of Acid Used during the Post-Esterification Step
Table 3.11 Effect of the Post-Esterification Step on Product Quality
Table 3.12 Ricin Quantification and Toxicity Measurement by CEA and USDA. (2 Independent Labs)
Table 3.13 Allergenicity Tests
Table 3.14 Evaluation of Acute Toxicity
Table 3.15 Seed Meal Value for Export from India, US $/t
Chapter 4: Avantium Chemicals: The High Potential for the levulinic product tree
Table 4.1 Collected Physical Properties of Levulinic Acid and Methyl and Ethyl Levulinate
Table 4.2 Levulinic Acid and Levulinate Production Routes
Table 4.3 Reported Promising Target Molecules from Levulinic Acid
Chapter 6: Cepsa: Towards The Integration of Vegetable Oils and Lignocellulosic Biomass into Conventional Petroleum Refinery Processing Units
Table 6.1 Properties of HVO Achieved in Pilot Plant in the Coprocessing of SRGO with Used Frying Oil (UFO) and Sunflower Oil
Table 6.2 Theoretical Composition of Fatty Acids of Crude Camelina Oil, Refined Coconut Oil, and Nonrefined Used Frying Oil
Table 6.3 Paraffins, Aromatics, and Alkanes Yield in Hydrocracking Products of UFO (55 bar, LHSV = 1.1 h−1 )
Table 6.4 Properties of Biobooster Synthetized at DRAGO Project
Chapter 7: DuPont: Biorenewables at E.I. DU Pont DE Nemours & Co
Table 7.1 Isolated Genes for EPA Biosynthesis
Chapter 9: Market Structure and Growth Rates of Industrial Biorenewables
Table 9.1 Biorenewable Sales Including Growth Rates for the Different Segments in 2010, 2015, and 2020
Table 9.2 Chemical and Biorenewable Sales per Segment in 2010
Table 9.3 Chemical and Biorenewable Sales per Segment in 2015
Table 9.4 Chemical and Biorenewable Sales per Segment in 2020
Chapter 11: Greasoline: Biofuels From Non-food Materials and Residues
Table 11.1 Chemical Properties of PFAD (e.g., Malaysia)
Table 11.2 Chemical Properties of Preprocessed Jatropha Oil for Greasoline. Physical and Chemical Properties of Jatropha Oil (Extracted by Hot Water Extraction with Aqua High® Technology)
Table 11.3 Properties According to EN590 for Neat Jatropha Oil-Based Greasoline Diesel. Greasoline®-Derived Diesel Produced from Jatropha
Chapter 13: Grove Advanced Chemicals: Flox® Coagulants – Environmentally Friendly Water and Wastewater Treatment Using Biodegradable Polymers From Renewable Forests
Table 13.1 Most Relevant Physicochemical Characteristics of the Commercial Solution of the Flox®-QT Coagulant (25%, w/w)
Table 13.2 Comparison between the Wastewater Treatment Dosages of Coagulants PAC 18% and Flox®-QTH and Alkalinization Agent NaOH in a Ceramics Industry
Table 13.3 Comparison of Quality Parameters (Average Values) of Treated Wastewater Using Coagulants PAC 18% and Flox®-QTH in a Ceramics Industry
Table 13.4 Comparison of Industrial Wastewater Treatments Using Coagulants PAC 18% and Flox®-QT/Flox®-QTH in a Fish Canning Plant (Average Values)
Table 13.5 Comparison of Industrial Wastewater Treatments in a Poultry Abattoir Using Coagulants PAC 18% and Flox®-QT
Table 13.6 Comparison of Wastewater Physicochemical Treatment in a Medium-Density Fiberboard (MDF) Plant Using PAC 18% and Flox®-QT Coagulants
Table 13.7 Comparison of Industrial Wastewater Tertiary Treatment in a Medium-Density Fiberboard (MDF) Plant Using PAC 18% and Flox®-QTH Coagulants
Table 13.8 Comparison of Wastewater Treatments in a Dairy Plant Using PAC 18% and Flox®-QT Coagulants
Table 13.9 Turbidity and pH of River Raw Water and Treated Water Comparative Results Obtained in Laboratory-Scale Tests Using Flox®-QT and Aluminum Sulfate (Al2 (SO4 )3 ) in the Coagulation and Flocculation Process of Drinking Water Treatment (Average Values)
Table 13.10 Turbidity and pH of Raw River Water Comparative Results in the Treated Water Obtained in Laboratory-Scale Tests Using Flox®-QT and Aluminum Sulfate in the Coagulation Process of Drinking Water Treatment
Table 13.11 Turbidity and pH of Raw Lake Water Comparative Results in the Treated Water Obtained in Laboratory-Scale Tests Using Flox®-QT and Aluminum Sulfate in the Coagulation Process of Drinking Water Treatment
Chapter 14: Heliae Development, LLC: An Industrial Approach to Mixotrophy in Microalgae
Table 14.1 Microalgae Classified According to Their Trophic Metabolism and Other Terms Used in the Chapter
Table 14.2 Potential Benefits of Mixotrophic Microalga Growth When Compared to Heterotrophic and Photoautotrophic Growth Models
Table 14.3 Brief Descriptions of Industrial Microbiological Processes That Due To Their Robustness Are Not Necessarily Operated under Axenic Conditions
Table 14.4 Preliminary Economic Assessment of Mixotrophic Process Viability. Using the CO2 Budget Observed in Photoautotrophic Open Pond Cultures with Acetic Acid (Mixotrophic Scenario) Results in Almost a Threefold Increase in Productivity per unit of Investment/Production
Chapter 15: InFiQuS: Making the Best of Leftovers
Table 15.1 InFiQuS in a Nutshell
Table 15.2 Worldwide Crustaceans Harvested in 2011
Table 15.3 Crustacean Shell Composition
Table 15.4 Examples of Chitin and Chitosan Applications
Table 15.5 World's Olive Oil Production in the Period 2007–2013 (International Olive Oil Council (November 2013)).[35]
Table 15.6 Three-Phase Systems versus Two-Phase Systems
Table 15.7 High-Valuable Components Found in Olive Oil Waste.[40]
Chapter 18: Novozymes: How Novozymes Thinks About Biomass
Table 18.1 Some Impacts of Water on Process Steps for B2E
Table 18.2 Various Forms of Coproducts from a Biomass to Ethanol Process
Chapter 19: Organoclick: Applied Eco-Friendly and Metal-Free Catalysis for Wood and Fiber Modifications
Table 19.1 Results from Spray Tests
Chapter 20: Petrobras: The Concept of Integrated Biorefineries Applied to the Oleochemistry Industry: Rational Utilization of Products and Residues via Catalytic Routes
Table 20.1 Different Catalytic Systems for Hydroprocessing VegeTable Oils/Fatty Acids
Chapter 23: Biorenewables at Shell: Biofuels
Table 23.1 Coprocessing of Upgraded Pyrolysis Oils in Laboratory-Scale FCC Unit (Product Distribution of 20 wt% HDO Oil Blends at Constant 60% Conversion. From HDO-1 to HDO-5, the Severity of Upgrading Increases)
Table 23.2 Product Distribution After Catalytic Cracking 100 wt% VGO Compared with 80 wt% VGO and 20 wt% Liquefied Biofeed and 80 wt% VGO and 20% Pyrolysis Oil (at a Constant Cat/Oil Ratio of 3.0 and a Temperature of 520 ° C)
A Practical Viewpoint
Edited by
Pablo Domínguez de María
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