Chemicals and Fuels from Bio-Based Building Blocks E-Book
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- Herausgeber: Wiley-VCH
- Kategorie: Wissenschaft und neue Technologien
- Sprache: Englisch
An up-to-date and two volume overview of recent developments in the field of chemocatalytic and enzymatic processes for the transformation of renewable material into essential chemicals and fuels. Experts from both academia and industry discuss catalytic processes currently under development as well as those already in commercial use for the production of bio-fuels and bio-based commodity chemicals. As such, they cover drop-in commodity chemicals and fuels, as well as bio-based monomers and polymers, such as acrylic acid, glycols, polyesters and polyolefins. In addition, they also describe reactions applied to waste and biomass valorization and integrated biorefining strategies. With its comprehensive coverage of the topic, this is an indispensable reference for chemists working in the field of catalysis, industrial chemistry, sustainable chemistry, and polymer synthesis.
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Veröffentlichungsjahr: 2016
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Table of Contents
Cover
Title Page
Copyright
Volume 1
List of Contributors
Preface
Part I: Drop-in Bio-Based Chemicals
Chapter 1: Olefins from Biomass
1.1 Introduction
1.2 Olefins from Bioalcohols
1.3 Alternative Routes to Bio-Olefins
1.4 Conclusions
References
Chapter 2: Aromatics from Biomasses: Technological Options for Chemocatalytic Transformations
2.1 The Synthesis of Bioaromatics
2.2 The Synthesis of Bio-
p
-Xylene, a Precursor for Bioterephthalic Acid
2.3 The Synthesis of Bioterephthalic Acid without the Intermediate Formation of
p
-Xylene
2.4 Technoeconomic and Environmental Assessment of Bio-
p
-Xylene Production
References
Chapter 3: Isostearic Acid: A Unique Fatty Acid with Great Potential
3.1 Introduction
3.2 Biorefinery and Related Concepts
3.3 Sustainability of Oils and Fats for Industrial Applications
3.4 Fatty Acids
3.5 Polymerization of Fatty Acids
3.6 ISAC
3.7 Other Branched Chain Fatty Acids
3.8 Properties of ISAC
3.9 Applications of ISAC
3.10 Selective Routes for the Production of ISAC
3.11 Summary and Conclusions
Acknowledgments
References
Chapter 4: Biosyngas and Derived Products from Gasification and Aqueous Phase Reforming
4.1 Introduction
4.2 Biomass Gasification
4.3 Aqueous Phase Reforming
References
Chapter 5: The Hydrogenation of Vegetable Oil to Jet and Diesel Fuels in a Complex Refining Scenario
5.1 Introduction
5.2 The Feedstock
5.3 Hydroconversion Processes of Vegetable Oils and Animal Fats
5.4 Chemistry of Triglycerides Hydroconversion
5.5 Life Cycle Assessment and Emission
5.6 The Green Refinery Project
5.7 Conclusions
References
Part II: Bio-Monomers
Chapter 6: Synthesis of Adipic Acid Starting from Renewable Raw Materials
6.1 Introduction
6.2 Challenges for Bio-Based Chemicals Production
6.3 Choice of Adipic Acid as Product Target by Rennovia
6.4 Conventional and Fermentation-Based Adipic Acid Production Technologies
6.5 Rennovia's Bio-Based Adipic Acid Production Technology
6.6 Step 1: Selective Oxidation of Glucose to Glucaric Acid
6.7 Step 2: Selective Hydrodeoxygenation of Glucaric Acid to Adipic Acid
6.8 Current Status of Rennovia's Bio-Based Adipic Acid Process Technology
6.9 Bio- versus Petro-Based Adipic Acid Production Economics
6.10 Life Cycle Assessment
6.11 Conclusions
References
Chapter 7: Industrial Production of Succinic Acid
7.1 Introduction
7.2 Market and Applications
7.3 Technology
7.4 Life Cycle Analysis
7.5 Conclusion
References
Chapter 8: 2,5-Furandicarboxylic Acid Synthesis and Use
8.1 Introduction
8.2 Synthesis of 2,5-Furandicarboxylic Acid by Oxidation of HMF
8.3 Synthesis of 2,5-Furandicarboxylic Acid from Carbohydrates and Furfural
8.4 2,5-Furandicarboxylic Acid-Derived Surfactants and Plasticizers
8.5 2,5-Furandicarboxylic Acid-Derived Polymers
8.6 Conclusion
References
Chapter 9: Production of Bioacrylic Acid
9.1 Introduction
9.2 Chemical Routes
9.3 Biochemical Routes
9.4 Summary and Conclusions
References
Chapter 10: Production of Ethylene and Propylene Glycol from Lignocellulose
10.1 Introduction
10.2 Reaction Mechanism
10.3 Glycol Production
10.4 Direct Formation of Glycols from Lignocellulose
10.5 Technical Application of Glycol Production
10.6 Summary and Conclusion
References
Part III: Polymers from Bio-Based building blocks
Chapter 11: Introduction
References
Chapter 12: Polymers from Pristine and Modified Natural Monomers
12.1 Monomers and Polymers from Vegetable Oils
12.2 Sugar-Derived Monomers and Polymers
12.3 Polymers from Terpenes and Rosin
12.4 Final Considerations
12.5 Acknowledgment
References
Chapter 13: Polymers from Monomers Derived from Biomass
13.1 Polymers Derived from Furans
13.2 Polymers from Diacids, Hydroxyacids, Diols
13.3 Glycerol
13.4 Final Considerations
References
Volume 2
List of Contributors
Preface
Part IV: Reactions Applied to Biomass Valorization
Chapter 14: Beyond H2: Exploiting H-Transfer Reaction as a Tool for the Catalytic Reduction of Biomass
14.1 Introduction
14.2 MPV Reaction Using Homogeneous Catalysts
14.3 MPV Reaction Using Heterogeneous Catalysts
14.4 H-Transfer Reaction on Molecules Derived from Biomass
14.5 Industrial Applications of the MPV Reaction
14.6 Conclusions
Acknowledgments
References
Chapter 15: Selective Oxidation of Biomass Constitutive Polymers to Valuable Platform Molecules and Chemicals
15.1 Introduction
15.2 Selective Oxidation of Cellulose
15.3 Selective Oxidation of Lignin
15.4 Selective Oxidation of Starch
15.5 Conclusions
References
Chapter 16: Deoxygenation of Liquid and Liquefied Biomass
16.1 Introduction
16.2 General Remarks on Deoxygenation
16.3 Deoxygenation of Model Compounds
16.4 Deoxygenation of Liquid and Liquefied Biomass
16.5 Deoxygenation in Absence of Hydrogen
16.6 Conclusions and Outlook
References
Chapter 17: C–C Coupling for Biomass-Derived Furanics Upgrading to Chemicals and Fuels
17.1 Introduction
17.2 Upgrading Strategy for Furanics
17.3 Summary and Conclusion
References
Part V: Biorefineries and Value Chains
Chapter 18: A Vision for Future Biorefineries
18.1 Introduction
18.2 The Concept of Biorefinery
18.3 The Changing Model of Biorefinery
18.4 Integrate CO
2
Use and Solar Energy within Biorefineries
18.5 Conclusions
Acknowledgments
References
Chapter 19: Oleochemical Biorefinery
19.1 Oleochemistry Overview
19.2 Applications and Markets for Selected Oleochemical Products
19.3 Future Perspectives of Oleochemistry in the View of Bioeconomy
19.4 Conclusions
References
Chapter 20: Arkema's Integrated Plant-Based Factories
20.1 Introduction
20.2 Arkema's Plant-Based Factories
20.3 Cross-Metathesis of Vegetable Oil Plant
20.4 Summary and Conclusions
Acknowledgments
References
Chapter 21: Colocation as Model for Production of Bio-Based Chemicals from Starch
21.1 Introduction
21.2 Wet Milling of Cereal Grains: At the Heart of the Starch Biorefinery
21.3 The Model of Colocation
21.4 Examples of Starch-Based Chemicals Produced in a Colocation Model
21.5 Summary and Conclusions
References
Chapter 22: Technologies, Products, and Economic Viability of a Sugarcane Biorefinery in Brazil
22.1 Introduction
22.2 Biorefineries: Building the Basis of a New Chemical Industry
22.3 Sugarcane-Based Biorefineries in Brazil: Status
22.4 A Method for Technical Economic Evaluation
22.5 The Sugarcane Biorefinery of the Future: Model Comparison
22.6 Conclusions
References
Chapter 23: Integrated Biorefinery to Renewable-Based Chemicals
23.1 Introduction
23.2 An Alternative Source of Natural Rubber: Toward a Guayule-Based Biorefinery
23.3 Toward Renewable Butadiene
References
Chapter 24: Chemistry and Chemicals from Renewables Resources within Solvay
24.1 Introduction
24.2 Chemistry from Triglycerides
24.3 Chemistry on Cellulose: Cellulose Acetate
24.4 Guars
24.5 Vanillin
24.6 Summary and Conclusions
References
Chapter 25: Biomass Transformation by Thermo- and Biochemical Processes to Diesel Fuel Intermediates
25.1 Introduction
25.2 Biological Processes
25.3 Thermal Processes
25.4 Conclusions
References
Chapter 26: Food Supply Chain Waste: Emerging Opportunities
26.1 Introduction
26.2 Pretreatment and Extraction
26.3 Bioprocessing
26.4 Chemical Processing
26.5 Technical and Sustainability Assessment and Policy Analysis
26.6 Conclusions and Outlook
Acknowledgments
References
Index
End User License Agreement
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Guide
Cover
Table of Contents
Preface
Part I: Drop-in Bio-Based Chemicals
Begin Reading
List of Illustrations
Chapter 1: Olefins from Biomass
Figure 1.1 Routes from biomass to olefins.
Scheme 1.1 Commonly accepted general mechanism for ethanol dehydration on solid catalysts.
Figure 1.2 Several alternative routes investigated for the synthesis of biobutadiene.
Scheme 1.2 Overall reaction stoichiometry from ethanol to butadiene.
Figure 1.3 Schematic flow diagram of the two-step process for making butadiene from ethanol and acetaldehyde, as inferred from [20]. Symbols: R1: reactor to convert ethanol into acetaldehyde, R2: reactor to convert ethanol and acetaldehyde to butadiene, D: distillation column, S: scrubber, C: compressor, W: water, and V: vapor.
Figure 1.4 1,3-Butadiene selectivity versus ethanol conversion for representative catalysts.
Scheme 1.3 Under the reaction conditions used for the gas-phase Lebedev and Guerbet processes, acetaldol is mainly reversed to acetaldehyde and not upgraded to crotonaldehyde.
Scheme 1.4 General reaction network for the Lebedev and Guerbet processes in the gas phase on oxide catalysts with basic features.
Figure 1.5 Two-step process for biomass/oil upgrading.
Scheme 1.5 Ethylene and 2-butene metathesis to produce propylene.
Figure 1.6 Bio-olefin metathesis flow diagram. GB: guard bed, R: isomerization/metathesis reactor, and S: separation unit.
Scheme 1.6 Mechanism of the metathesis of ethylene with 2-butene (a) and 1-butene with 2-butene (b).
Scheme 1.7 Formation of the initial M-carbene species.
Chapter 2: Aromatics from Biomasses: Technological Options for Chemocatalytic Transformations
Figure 2.1 Main alternative routes for the production of bioaromatics.
Figure 2.2 The BioForming concept.
Figure 2.3 From sugars to aromatics and alkanes according to the technology developed by Virent.
Figure 2.4 General reaction scheme of the transformation of the cellulosic and hemicellulosic fraction of lignocellulosic biomass into aromatics and aliphatic hydrocarbons by means of catalytic fast pyrolysis.
Figure 2.5 Simplified block flow diagram for aromatics production by means of CFP.
Figure 2.6 The general reaction scheme of isobutanol transformation into 2,5-dimethyl-2,4-hexadiene, with the various products formed based on the reaction conditions and catalyst type.
Figure 2.7 Simplified flowchart of the Gevo process for the production of
p
-xylene from isobutanol.
Figure 2.8 The synthesis of bio-PET from lignocellulosic biomass according to the Biochemtex concept: process integration.
Figure 2.9 The section of the Biochemtex process for the transformation of lignin into aromatics (MOGHI process).
Figure 2.10 The Amyris (former Draths) technology for terephthalic acid production from muconic acid.
Chapter 3: Isostearic Acid: A Unique Fatty Acid with Great Potential
Figure 3.1 World production of major vegetable oils and fats in 2014 (in million metric tons) [1, 2].
Figure 3.2 Schematic overview of the different conversion routes of oils and fats and the applications of the oleochemicals derived from them. The “modified fatty acids” group includes conjugated, branched, hydroxylated, and hydrogenated fatty acids.
Scheme 3.1 Clay-catalyzed polymerization of commercial oleic acid, which contains mainly linoleic acid in addition to oleic acid. The reaction product is a complex mixture of branched (monomeric) oleic acid, C
36
dimeric acids, and C
54
trimeric acids (typical structures are shown for each fraction; note that all fractions contain many isomers).
Figure 3.3 Current process for production of isostearic acid and polymerized fatty acids.
Scheme 3.2 Production of “oxo” acids using hydroformylation and oxidation; R is a branched or linear alkyl chain.
Scheme 3.3 Production of neopentanoic acid from isobutene via the two-stage Koch reaction.
Figure 3.4 Production of C
16
–C
17
branched primary alcohols (Neodol® 67) from C
15
to C
16
linear olefins.
Scheme 3.4 Production of 2-ethylhexanoic acid via the aldol condensation of butanal.
Chapter 4: Biosyngas and Derived Products from Gasification and Aqueous Phase Reforming
Figure 4.1 Representation of the biomass transformation during the gasification process.
Figure 4.2 Total energy share of the gas products between sensible heat and chemical energy as function of the oxygen addition (ER) [4].
Figure 4.3 Concept at the base of the bioliq pilot plant in Karlsruhe [4].
Figure 4.4 Gasification, cleaning, and upgrading unit using direct gasification with a fluidized bed.
Figure 4.5 Ni/Mg/Al catalyst derived from hydrotalcite used in reforming after gasification of different feedstocks.
Figure 4.6 Fuel production costs of different gasification technologies. (Adapted from [9].)
Figure 4.7 Process scheme of integrated electrolysis and gasification for fuel production.
Figure 4.8 Gibbs free energy change with temperature for reforming reactions of alkanes and carbohydrates and WGS reaction.
Figure 4.9 Parallel reactions in water for ethylene glycol.
Figure 4.10 H
2
selectivity and alkane selectivity of diluted oxygenated hydrocarbon solutions (1 wt%) at 225 and 265 °C [45].
Figure 4.11 Proposed mechanism for the APR reaction of glycerol. Solid arrows pathways proposed by Lercher and coworkers [54] and dashed arrows from Wang and coworkers [55]. Bold gray arrows represent commonly accepted reaction pathways from glycerol.
Figure 4.12 Proposed mechanism for the production of alkanes from xylitol over bifunctional metal–acid catalyst.
Figure 4.13 Comparison of total organic carbon (TOC) percentage of gaseous products and liquid products after APR reaction over different feeds [58].
Figure 4.14 Schematic Virent APR pilot plant [58].
Figure 4.15 Cost breakdown for the Virent APR process [58].
Figure 4.16 Industrial applications of aqueous phase processes.
Chapter 5: The Hydrogenation of Vegetable Oil to Jet and Diesel Fuels in a Complex Refining Scenario
Figure 5.1 Triglyceride molecule containing linolenic (red), palmitic (blue), and oleic (green) acids.
Figure 5.2 Process scheme of Eni/UOP Ecofining
TM
.
Figure 5.3 Melting points of normal paraffins and iso-paraffins with methyl branching.
Figure 5.4 Green diesel cloud point as a function of
iso
-/
n
-paraffin ratio.
Figure 5.5 Triglyceride conversion: stoichiometry of hydrodeoxygenation, decarbonylation, and decarboxylation reactions. 2× stands for the decrease of hydrogen atoms due to the presence of double bonds. Enthalpy of reaction refers to the model triglyceride molecule triacylglycerol of palmitic acid.
Figure 5.6 Water gas shift and methanation reactions of CO and CO
2
in the range of temperatures between 500 and 700 K.
Figure 5.7 Triglyceride conversion scheme proposed by Huber
et al
.
Figure 5.8 Triglyceride conversion scheme proposed by Kubička
et al
.
Figure 5.9 Effect of Ni/Mo ratio on HDO and DCO pathway for oxygen removal.
Figure 5.10 Reaction scheme for catalytic hydroconversion of methyl laurate to normal paraffin.
Figure 5.11 Molar carbon number distribution in catalytic cracking and hydrocracking of
n
-hexadecane at 50% conversion.
Figure 5.12 Hydroisomerization/hydrocracking reaction scheme of
n
-paraffins on bifunctional catalyst.
Figure 5.13 Reaction scheme for the formation of isomers and cracking products.
Figure 5.14 GHG emission associated with the production of green diesel syndiesel and petroleum fuels.
Figure 5.15 Engine test results comparing emissions from a petroleum diesel and an HRD petroleum diesel blend.
Figure 5.16 Engine test results comparing emissions from a petroleum diesel and neat HVO.
Figure 5.17 Average effect of neat and 85% HVO–15% EN590 blending on tailpipe emissions in Euro II to Euro V vehicles compared to a sulfur-free EN590 diesel fuel.
Chapter 6: Synthesis of Adipic Acid Starting from Renewable Raw Materials
Figure 6.1 Economic opportunity analysis for chemical production from glucose.
Scheme 6.1 Conventional adipic acid production from benzene.
Scheme 6.2 Rennovia's adipic acid production from glucose.
Scheme 6.3 Aerobic oxidation of glucose to glucaric acid over heterogeneous catalyst.
Figure 6.2 Representative data for high-throughput screening of glucose oxidation catalysts.
Scheme 6.4 On-path intermediates in the oxidation of glucose to glucaric acid.
Figure 6.3 Scheme for partial conversion process for glucaric acid production.
Figure 6.4 Long-term stable operation of glucose oxidation catalyst.
Scheme 6.5 Selective hydrodeoxygenation of glucaric acid to adipic acid.
Figure 6.5 High-throughput screening of glucaric acid hydrodeoxygenation.
Figure 6.6 Reaction profile for hydrodeoxygenation of glucaric acid.
Scheme 6.6 High-yield hydrodeoxygenation of glucaric acid to adipic acid.
Figure 6.7 Long-term stable operation of glucaric acid hydrodeoxygenation catalyst.
Scheme 6.7 Reaction of tartaric acid and malic acid under hydrodeoxygenation conditions.
Scheme 6.8 Potential mechanism for coupled hydrodeoxygenation of vicinal diols.
Figure 6.8 Comparison of carbon footprint of petro- and bio-based adipic acid.
Chapter 7: Industrial Production of Succinic Acid
Figure 7.1 Succinic acid [CAS 110-15-6].
Figure 7.2 30 kT BioAmber plant in Sarnia, Canada.
Figure 7.3 Succinic acid applications.
Figure 7.4 Formation of succinic-based polyester polyols.
Figure 7.5 Polyurethane systems using succinic acid.
Figure 7.6 Biochemical pathways for succinic acid production.
Figure 7.7 Growth effects of succinic acid on yeast strains.
Figure 7.8 Performance and scalability of BioAmber yeast process.
Chapter 8: 2,5-Furandicarboxylic Acid Synthesis and Use
Scheme 8.1 Oxidation of HMF.
Figure 8.1 Facilities for the scale-up production of HMF and derivatives as well as related products.
Figure 8.2 DSC thermograms of PEF from (a) melt polymerization and (b) solid-state polymerization.
Chapter 9: Production of Bioacrylic Acid
Scheme 9.1 Chemical routes for the one-step (solid arrow) and two-step (dashed arrows) propene oxidation process to acrylic acid [3].
Scheme 9.2 Glycerol oxidehydration reaction to acrylic acid.
Scheme 9.3 Indirect pathways for acrylic acid synthesis from glycerol.
*
y
stands for yield.
Scheme 9.4 Mechanism of lactate production from glycerol proposed by Dusselier
et al.
[39].
Scheme 9.5 Mechanism of glycerol oxidation to lactate over Au–Pt/TiO
2
.
Scheme 9.6 LA to AA dehydration.
Scheme 9.7 Reactions competing with AA production from LA.
Scheme 9.8 Clusters formed by the alkali (X
+
) and alkaline earth metals with the oxygen atoms from the zeolite NaY lattice.
Figure 9.1 Evaluation of the catalyst stability and of its regeneration under air [77].
Figure 9.2 Acidic and basic site densities of HAPS as a function of the Ca/P ratio (a) or calcination temperature (b). For (a) all the HAPs have been calcined at 360 °C. For (b) all the HAPs have a Ca/P ratio of 1.62 [96].
Scheme 9.9 Simplified scheme of the metabolic pathway of direct reduction with
C. propionicum
.
Scheme 9.10 Schematics of the metabolic routes for acrylate biosynthesis from sugars.
Chapter 10: Production of Ethylene and Propylene Glycol from Lignocellulose
Figure 10.1 Illustration of the main constituents of lignocellulose [2c]. Agnieszka et al.
Scheme 10.1 Different process configurations of the transformation of polysaccharides into glycols covering three (top)-, two (middle)-, and one (bottom)-step processes.
Scheme 10.2 Simplified representation of major undesired reaction pathways for a transformation of cellulose to glycols as selected example (5-HMF – 5-hydroxymethylfurfural). (Please note that also further isomerization reactions can occur, delivering mannose in addition to fructose and mannitol/iditol together with the corresponding dehydration products for sorbitol.)
Scheme 10.3 Simplified representation of (de)hydrogenation mechanism on metal surfaces.
Scheme 10.4 Retro-aldol addition and Lobry de Bruyn–Alberda van Ekenstein (LBE) isomerization under basic conditions.
Scheme 10.5 Reaction network of the retro-aldol-based hydrogenolysis of hexitols.
Scheme 10.6 Simplified representation of the decarbonylation mechanism on metal surfaces.
Scheme 10.7 Successive decarbonylation of hexitols toward ethylene glycol.
Scheme 10.8 Formation of 1,2-propylene glycol and lactic acid from glyceraldehyde.
Scheme 10.9 Hydrodeoxygenation via dehydration and hydrogenation.
Scheme 10.10 Two-step reaction of glucose to C
2
–C
4
components over a Cu–Cr catalyst.
Scheme 10.11 Valorization of xylitol in a trickle-bed reactor.
Chapter 12: Polymers from Pristine and Modified Natural Monomers
Scheme 12.1 Schematic representation of the reactive sites in a general unsaturated triglyceride.
Scheme 12.2 Synthesis and polymerization of VSHA [19].
Scheme 12.3 Polycondensation reaction of epoxidized oleic acid [20].
Scheme 12.4 (a) General scheme for ADMET reaction of jojoba oil and (b) oligomerization of jojoba oil with 1,2-ethanedithiol.
Scheme 12.5 Alternative routes explored to convert triglycerides and their fatty acids into polyisocyanates.
Scheme 12.6 The structure of DDI, a fatty acid-based diisocyanate [28].
Scheme 12.7 Synthesis route of (a) palm oil monoglyceride and (b) palm oil alkyd diols [29].
Scheme 12.8 Reaction pathway for the preparation of soy oil-based cationic aqueous polyurethane dispersions [32].
Scheme 12.9 Synthetic pathway to the lignin–oleic acid macropolyol [38].
Scheme 12.10 Synthesis of AB-type monomers for the preparation of renewable PAs [43].
Scheme 12.11 General procedure for the synthesis of nylon precursors from oleic acid [44].
Scheme 12.12 Isosorbide, isomannide, and isoidide.
Scheme 12.13 Biodegradable copolyesters involving isosorbide, lactide, and aromatic monomers [50, 51].
Scheme 12.14 Chemical recycling of PET with isosorbide and succinic acid for powder coating applications [54, 55].
Scheme 12.15 Fully biobased thermoplastic polyurethanes incorporating isosorbide [28].
Scheme 12.16 Synthesis of new biobased monomers from isomannide [61].
Scheme 12.17 Synthesis of biobased AB monomers [60].
Scheme 12.18 Diacetal monomers derived from sugars.
Scheme 12.19 Copolyesters based on galactitol and galactaric acid derivates [66].
Scheme 12.20 Fully aliphatic polyesters based on mannitol derivatives [65].
Scheme 12.21 Chemical structure of the most common monoterpenes.
Scheme 12.22 Chemical structure of the most common rosin components.
Scheme 12.23 Isomerization and oxidation processes for converting pinenes into other terpenes and a terpenoid.
Scheme 12.24 The cationic polymerization of β-pinene initiated by the AlCl
3
/H
2
O complex [94].
Scheme 12.25 Emulsion polymerization of myrcene [100].
Scheme 12.26 Preparation of terpene-based thiols by the reaction of hydrogen sulfide with monoterpenes [105].
Scheme 12.27 Thiol–ene click chemistry between limonene and thiols [101].
Scheme 12.28 Polyester synthesis through the thiol–ene reaction [108].
Scheme 12.29 Terephthalic acid synthesis from limonene via
p
-cymene [107].
Scheme 12.30 Limonene oxides for the synthesis of polyurethanes, polycarbonates, and polyesters [114].
Scheme 12.31 Hyperbranched polymers obtained from dicyclopentadiene and terpenes by ROMP [117].
Scheme 12.32 ROMP of sesquiterpenes [82].
Scheme 12.33 The two most common terpenoids.
Scheme 12.34 Ring-opening polymerization of menthone [115].
Scheme 12.35 Derivatization of abietic acid for the synthesis of acrylopimaric acid and maleopimaric acid [120].
Chapter 13: Polymers from Monomers Derived from Biomass
Scheme 13.1 The most important furan-based building blocks.
Scheme 13.2 Synthetic pathways to prepare the two basic furan derivatives from biomass.
Scheme 13.3 Synthesis of difuran monomers.
Scheme 13.4 Monomers used in furan-based polyamides.
Scheme 13.5 2-Furamide self-condensation.
Scheme 13.6 Synthesis of furanic polyurethanes.
Scheme 13.7 Reactivity scale of substituted furans in their DA coupling with maleimides.
Scheme 13.8 DA equilibrium between furan and maleimide end groups in a macromolecular synthesis.
Figure 13.1 Schematic representation of a recyclable and self-mendable bio-based polymer system [85].
Scheme 13.9 Synthesis of poly(2,5-furandimethylene succinate) and reversible DA reaction between PFS and a bismaleimide (M
2
) leading to the polymeric network.
Scheme 13.10 Atom transfer radical copolymerization of furfuryl methacrylate and methyl methacrylate.
Scheme 13.11 Paal–Knorr reaction of alternating polyketone with furfurylamine and subsequent DA reaction with BMI.
Scheme 13.12 Structures of oligofurans.
Scheme 13.13 Examples of some important building blocks derived from renewable resources.
Scheme 13.14 Synthetic pathway to a polyamide formed from diethyl succinate and hexamethylenediamine copolymerized with tributyl citrate [144].
Scheme 13.15 Synthesis of thermoplastic polyurethanes based on succinate polyesters [145].
Scheme 13.16 Synthetic pathway to produce glycerol–adipic acid hyperbranched polyesters.
Scheme 13.17 Schematic diagram of the synthesis and degradation of poly(5-hydroxylevulinic acid) [155].
Scheme 13.18 Possible cross-linking mechanism and microstructure of PHLA-diols [156].
Scheme 13.19 Synthesis of levulinic acid-
co
-glycerol oligomers [158].
Scheme 13.20 Synthetic pathway leading to poly(dihydroferulic acid) from vanillin [164].
Scheme 13.21 Chemoenzymatic preparation of bio-based bisphenols [165].
Scheme 13.22 Preparation of aliphatic–aromatic polyesters containing ferulic acid moieties [165].
Scheme 13.23 Synthesis of ferulic acid-derived α,ω-diene monomers [167].
Scheme 13.24 Ferulic acid-derived poly(ester-alkenamer)s [167].
Scheme 13.25 Synthetic pathway to prepare PGS polymers.
Scheme 13.26 Copolymerization of oleic diacid with glycerol [179].
Scheme 13.27 Synthesis of poly(1,3-glycerol carbonate) [181].
Chapter 14: Beyond H2: Exploiting H-Transfer Reaction as a Tool for the Catalytic Reduction of Biomass
Scheme 14.1 Main concept for the hydrogen transfer process (AH
2
hydrogen donor, B hydrogen acceptor).
Scheme 14.2 Meerwein–Ponndorf–Verley reduction and Oppenauer oxidation.
Scheme 14.3 Direct hydrogen transfer processes via six-membered ring intermediate.
Scheme 14.4 Hydrogen transfer via metal hydride pathway.
Scheme 14.5 H-transfer mechanism over metal oxide.
Scheme 14.6 Hydrogen transfer mechanism between an alcohol and a ketone for catalysts carrying both acidic (
A
) and basic (
B
) sites.
Figure 14.1 Reaction pathways for the conversion of γ-valerolactone (GVL) into fuels and chemicals.
Figure 14.2 Reaction pathway for the conversion of ethyl levulinate (EL) toward γ-valerolactone (GVL) via MPV reduction.
Figure 14.3 Production of GVL via MPV reduction starting from raw biomass.
Figure 14.4 Reaction pathways for the conversion of biomass to form methylfuran (MeF) and 2,5-dimethylfuran (DMF).
Figure 14.5 Sketch of the transition state for H-transfer in the presence of strong Lewis basic sites suggested in literature.
Figure 14.6 Possible reaction pathways from glycerol to allyl alcohol via H-transfer process.
Figure 14.7 Mechanism of H-transfer using formic acid as H-donor and self-catalyst.
Chapter 15: Selective Oxidation of Biomass Constitutive Polymers to Valuable Platform Molecules and Chemicals
Figure 15.1 Cellulose structure.
Scheme 15.1 General routes to valuable chemical products via direct selective oxidation of cellulose.
Scheme 15.2 Conversion of cellulose to formic acid.
Scheme 15.3 Conversion of cellulose into gluconic and glycolic acids via hydrolysis and oxidation catalysis.
Scheme 15.4 Conversion of cellobiose to levulinic acid: reaction pathway of converting the cellobiose into glucose and gluconic acid by superoxide radical anions and reaction pathway of converting gluconic acid to levulinic acid via Hofer–Moest decarboxylation followed by consecutive dehydration/rehydration reactions.
Scheme 15.5 Synthesis of a Ru–MNP catalyst for the direct oxidation to succinic acid.
Figure 15.2 Structure of lignin and primary precursors. (a)
trans-p
-Coumaryl alcohol, (b)
trans
-sinapyl alcohol, and (c)
trans
-coniferyl alcohol.
Scheme 15.6 Typical lignin model compounds (
1
,
5
), oxidation products (
2
,
6
,
7
), and C–O bond cleavage products
3
,
3
′ and
4
,
4
′.
Figure 15.3 Homogenous vanadium-based complexes.
Figure 15.4 Vanadium catalysts for the oxidation of lignin models.
Figure 15.5 The structures of starch consisting of (a) amylose and (b) amylopectin.
Scheme 15.7 Schematic representation of starch selective oxidation.
Scheme 15.8 Proposed simplified mechanism of the starch oxidation by CH
3
ReO
3
/H
2
O
2
/Br
−
system.
Chapter 16: Deoxygenation of Liquid and Liquefied Biomass
Figure 16.1 Simplified scheme of product groups obtained by pyrolytic cracking at different temperatures consequently leading to a drop in molecular weight of product molecules.
Figure 16.2 Products obtained by fast pyrolysis (BtO® process) at about 500 °C and a reaction time of 1 s.
Figure 16.3 Typical detected chemical composition of bio-oils.
Scheme 16.1 Proposed reaction pathways of phenol HDO over supported Ni-based catalysts.
Scheme 16.2 Possible reaction pathways of HDO of guaiacol over Ni-based catalysts.
Scheme 16.3 HDO of phenolic dimers on Ni/HZSM-5 catalyst.
Figure 16.4 van Krevelen plot based on the elemental compositions (dry basis) of the mild and deep HDO over various catalysts.
Figure 16.5 Proposed reaction pathway of HPTT and hydrotreating of pyrolysis oils.
Chapter 17: C–C Coupling for Biomass-Derived Furanics Upgrading to Chemicals and Fuels
Scheme 17.1 Base-catalyzed mechanism of enolate formation.
Scheme 17.2 Acid-catalyzed mechanism of enol formation in aqueous environment.
Figure 17.1 Mechanism for aldol condensation of furfural and acetone over dolomite.
Scheme 17.3 Acid-catalyzed mechanism of aldol condensation reaction.
Scheme 17.4 Dimerization of FAc (Furfural-Acetone coupling product).
Figure 17.2 Strategy for furfural (or HMF) upgrading based on aldol condensation and hydrogenation.
Figure 17.3 Condensation–hydrogenation in water–oil emulsions.
Figure 17.4 Reaction pathway for ring opening of aldol condensation products. Reaction condition: 80 °C, 24 h, water–methanol (1:1); (*)100 °C, 3 h, acetic acid–water (1:1).
Figure 17.5 The strategy for aldol condensation products upgrading based on ring opening reaction.
Scheme 17.5 Mechanism of furan hydroxyalkylation–alkylation (HAA).
Scheme 17.6 Reaction scheme for HAA of 2MF and carbonyl compounds.
Scheme 17.7
Figure 17.6 (a) Sulfonic acid-functionalized ionic liquid catalysts: Type 1 (
1a,b
), type 2 (
1c–f
). (b) Silica-supported sulfonic acid-functionalized ionic liquid catalysts (
1g–h
). (c) Silica-supported sulfonic acid catalysts (
2a–c
).
Figure 17.7 Products (with corresponding yields) formed by condensation of various carbonyl compound with 2-methyl furan using catalyst
2c
.
Figure 17.8 Summary of 2-methyl furan upgrading strategy into fuel application.
Figure 17.9 Sylvan process to produce diesel fuel from biomass.
Scheme 17.8 Concerted and stepwise mechanism.
Figure 17.10 Reaction pathway of DMF and ethylene cycloaddition.
Figure 17.11 Zero-point-corrected electronic energy profiles for the conversion of DMF and ethylene to
p
-xylene relative to the reactants' energy at infinite separation.
Figure 17.12 The proposed PET synthesis by using biomass-derived carbon feedstocks.
Figure 17.13 Diels–Alder pathways to TA and DMT (dimethyl terephthalate) starting from biomass-derived HMF using oxidation steps.
Figure 17.14 Road map for the conversion of HMF (furfural) to aromatic products via Diels–Alder reaction.
Scheme 17.9 Mechanism of the furfural conversion to cyclopentanone.
Scheme 17.10 The alternative pathway of ring rearrangement of furfural via the formation of alcohols.
Scheme 17.11 Reaction pathway of furfural hydrogenation.
Figure 17.15 Cyclopentanone upgrading strategy via aldol condensation and hydroxyalkylation.
Figure 17.16 (a) Aldol condensation of cyclopentanone over different solid base catalysts at 423 K for 8 h in a batch reactor. (b) Carbon yields of F1, C
1
–C
5
: light alkanes and C
10
oxygenates (2-cyclopentyl-cyclopentanone and 2-cyclopentyl–cyclopentanol) over different catalysts. Reaction conditions: 503 K, 6 MPa; liquid feedstock (CC in Figure 17.15) flow rate 0.04 ml min
−1
; hydrogen flow rate: 120 ml min
−1
. (c) Hydroxyalkylation of 2-MF and CPO over different solid acid catalysts. Reaction conditions: 338 K, 2 h; 2-MF/CPO molar ratio = 2. (d) Carbon yield of different alkanes obtained by the HDO of hydroxyalkylation products of 2-MF and CPO over the M/SiO
2
–Al
2
O
3
(M = Fe, Co, Ni, Cu) catalysts. Reaction conditions: 533 K; liquid flow rate = 0.04 ml-min, WHSV = 1.3 h
−1
; H
2
flow rate = 120 ml min
−1
. The diesel range alkanes, gasoline range alkanes, and light alkanes account for C
9
–C
15
, C
5
–C
8
, and C
1
–C
4
alkanes, respectively [172, 175]. *S3 is the hydroxyalkylation product between 2MF (2-methyl furan) and 4-oxopentanal (the ring opening product of 2MF).
Scheme 17.12 Pathway of furanics oxidation in gas phase over V
2
O
5
/O
2
system.
Figure 17.17 Non-radical mechanism of furfural oxidation.
Scheme 17.13 Radical-based mechanism for maleic acid and maleic anhydride formation.
Scheme 17.14 Different products obtained from furfural and HMF oxidation.
Figure 17.18 Intermediate between the catalysts and furan ring.
Scheme 17.15
Figure 17.19 Synthesis route to bio-based TA from biomass-derived furfural.
Figure 17.20 Strategy for dicarboxylic acid upgrading via polymerization.
Scheme 17.16 Proposed mechanism for furfural oxidative coupling.
Scheme 17.17 Re-oxidation of palladium under the presence of Cu(II).
Figure 17.21 Road map for furanics upgrading strategy.
Chapter 18: A Vision for Future Biorefineries
Figure 18.1 Simplified scheme of two biorefinery concepts: sugar biorefinery and lignocellulosic biorefinery (biochemical approach).
Figure 18.2 Simplified scheme of two biorefinery concepts: green biorefinery and oilseed biorefinery.
Figure 18.3 (a) Multicriteria analysis and ranking (see text for description of the parameters ED, TSD, ESD, and SPD) of different routes to produce olefins in relation to the future scenario for sustainable chemical production. (b) Indication of the different routes analyzed with respect to conventional naphtha steam cracking (conversion of fossil fuels (conv. FFs)).
Figure 18.4 Selected routes in the conversion of 5-HMF to chemicals and fuels.
Chapter 19: Oleochemical Biorefinery
Figure 19.1 Schematic depiction of the value chain of oleochemistry: section A corresponds to the extraction of oils and fats from raw materials to obtain suitable primary platform chemicals for further processing, section B comprises the conversion of oils and fats to fatty acids and their esters as secondary platform chemicals, and section C indicates the transformation to oleochemical specialties.
Figure 19.2 Schematic depiction of the main products of oleochemistry and their origin; the position in the value chain is indicated with different gray scales.
Figure 19.3 Tallow average price, Cat III, years 2002–2014.
Figure 19.4 Evolution of the actualized price index for glycerine, years 1995–2014.
Chapter 20: Arkema's Integrated Plant-Based Factories
Figure 20.1 Comparison of tropical oils (palm kernel and coconut oils) with metathesized oil cost of production, based on historical data from the 2000 to 2014 period. Note: Historical prices for tropical oils were taken as CIF Rotterdam (meaning delivered in Rotterdam), while rapeseed oil is Free On Board (FOB) (meaning on board of a ship in Rotterdam).
Figure 20.2 Distribution of cost of production from the Monte Carlo simulation, with standard deviations listed in Table 20.9.
Figure 20.3 Tornado plot of the main parameters.
Chapter 21: Colocation as Model for Production of Bio-Based Chemicals from Starch
Figure 21.1 Maize wet milling process yielding a variety of intermediate and end products.
Figure 21.2 Wheat wet milling process yielding a variety of intermediate and end products.
Figure 21.3 General scheme of the downstream processing of a starch slurry, mostly executed at the wet mill site (DE = dextrose equivalent).
Figure 21.4 Total, variable, and fixed costs in function of production output.
Figure 21.5 Overview of the commercial bio-based products described in this chapter.
Chapter 22: Technologies, Products, and Economic Viability of a Sugarcane Biorefinery in Brazil
Figure 22.1 Schematic representation of a biorefinery.
Figure 22.2 How will the chemical chain work for renewable raw materials?
Figure 22.3 Challenges in each step of the chemical production chain for renewable raw materials.
Figure 22.4 Constituent parts of the biomass produced in the world [2].
Figure 22.5 Biorefinery and synthetic biology [12].
Figure 22.6 Braskem's technology roadmapping for chemicals produced from renewable raw materials.
Figure 22.7 Overview of Braskem methodology for renewable chemical evaluation.
Figure 22.8 Routes to biobutadiene.
Figure 22.9 Minimum selling price comparison of biobutanol production considering different levels of integration with the sugarcane mill.
Scheme 22.1 Conventional sugarcane mill.
Figure 22.10 Ethanol MSP conventional mill.
Scheme 22.2 Conventional ethanol and stand-alone cellulosic ethanol plants.
Figure 22.11 Ethanol MSP stand-alone cellulosic plant.
Scheme 22.3 Integrated conventional and stand-alone cellulosic ethanol plant.
Figure 22.12 Ethanol MSP from an integrated conventional and cellulosic ethanol plant.
Scheme 22.4 Biorefinery producing ethanol, raw sugar, and succinic acid.
Figure 22.13 Ethanol MSP from a biorefinery producing ethanol, raw sugar, and succinic acid.
Scheme 22.5 Biorefinery producing ethanol, raw sugar, succinic acid, and butanol.
Figure 22.14 Ethanol MSP from a biorefinery producing ethanol, raw sugar, succinic acid, and butanol.
Figure 22.15 Ethanol minimum selling prices comparison.
Chapter 23: Integrated Biorefinery to Renewable-Based Chemicals
Figure 23.1 Matrica biorefinery based on highly unsaturated vegetable oils.
Figure 23.2 Major sesqui- and triterpenes found in the guayule resin.
Figure 23.3 An integrated scheme for the guayule whole plant valorization. Primary products of a guayule-based biorefinery are shown in the black boxes.
Figure 23.4 Main approaches to renewable butadiene (BDO: butanediol).
Chapter 24: Chemistry and Chemicals from Renewables Resources within Solvay
Scheme 24.1 Traditional epichlorohydrin production from propylene.
Scheme 24.2 Epichlorohydrin production from glycerol.
Figure 24.1 Integrating 1 MT of Epicerol® (instead of classical epichlorohydrin from nonrenewable resource) in a product makes the carbon footprint drop down by 2.56 MT CO
2
equivalent.
Figure 24.2 Chemistry and applications of Augeo solvent family.
Scheme 24.3 Schematic synthesis path of sebacic acid from castor oil.
Figure 24.3 Aging in ZnCl
2
/water 50/50 wt% solution at 80 °C for 200 h: burst pressure of 6 mm × 8 mm plasticized PA 6.10 tubes and tensile strength of 30GF-reinforced PA 6.10 versus PA 12.
Figure 24.4 Permeability at 40 °C versus E10 fuel (10% ethanol, 45% toluene, 45% isooctane) and at 23 °C versus CO
2
and O
2
.
Figure 24.5 Different configurations of micelles.
Figure 24.6 Schematic illustration of the wormlike micelle network.
Scheme 24.4 A simplified chemistry for amphoteric viscoelastic surfactants.
Scheme 24.5 Simplified chemistry of cellulose acetate.
Figure 24.7 A. Eichengrün.
Figure 24.8 Cellulose acetate applications.
Scheme 24.6 Some chemistry of functionalization of guars.
Chapter 25: Biomass Transformation by Thermo- and Biochemical Processes to Diesel Fuel Intermediates
Figure 25.1 Technologies for biomass transformation into advanced biofuels.
Figure 25.2 Oleaginous yeast cell –
Candida curvata
cell grown with limited nitrogen source. Total lipid content approximately 40%. M: mitochondrion and L: lipid bodies.
Figure 25.3 Metabolic pathway for microbial production of hydrocarbons. Adapted from Lee and Choi [19].
Figure 25.4 Process flow for the production of microbial oil from sugar.
Figure 25.5 Microalgae cultivation and algal oil downstream processes.
Figure 25.6 Technologies for lipid-based feedstock conversion to biofuels.
Figure 25.7 Fast pyrolysis reactor system.
Figure 25.8 Multistage bio-oil hydrotreating process.
Chapter 26: Food Supply Chain Waste: Emerging Opportunities
Figure 26.1 The integrated biorefinery as a mixed feedstock source of chemicals, energy, fuels, and materials [2].
Figure 26.2 Components derived from food waste and their applications.
Figure 26.3 Waste orange peel (WOP) valorization to useful end products using microwave-assisted extraction technologies.
Figure 26.4 Oleaginous food waste to valuable products: concept and quantities.
List of Tables
Chapter 1: Olefins from Biomass
Table 1.1 Active systems in the transformation of ethanol to 1,3-butadiene
Table 1.2 Catalysts for the conversion of ethanol into acetaldehyde
Table 1.3 Catalytic systems for the conversion of ethanol into
n
-butanol
Table 1.4 Catalytic systems used for (butane)diol(s) dehydration
Table 1.5 Recent results for propylene production by the metathesis of ethylene with butenes
Chapter 3: Isostearic Acid: A Unique Fatty Acid with Great Potential
Table 3.1 Overview of the major markets and applications of ISAC and its derivatives, based on patent and published literature
Table 3.2 Literature overview for the selective OA alkyl isomerization in presence of zeolites and mesoporous materials
Chapter 4: Biosyngas and Derived Products from Gasification and Aqueous Phase Reforming
Table 4.1 Composition at the exit of gasifier from Varnamo and Gussing plants [4]
Table 4.2 Gasification reaction occurring after pyrolysis in the gasifier [4]
Table 4.3 Comparison of partial oxidation and ATR upgrading downstream of the gasifier [4]
Chapter 5: The Hydrogenation of Vegetable Oil to Jet and Diesel Fuels in a Complex Refining Scenario
Table 5.1 World production 2011/2012 of the main vegeTable oil production
Table 5.2 Fatty acid composition of vegeTable oils
Table 5.3 Characteristics of crude and refined palm oil
Table 5.4 Fatty acid composition of animal fats
Table 5.5 Fatty acid compositions of triglycerides from algae
Table 5.6 Typical yields of Ecofining
TM
process in gas oil mode
Table 5.7 Chemical physical characteristics of normal paraffins
Table 5.8 Product yields and product characteristics
Table 5.9 Comparison of physical properties
Table 5.10 Theoretical paraffin yields and hydrogen consumption associated with DCO
2
and HDO
Table 5.11 β-Scission an isomerization mode occurring during hydroconversion of paraffins. Adapted from Ref. [115]
Table 5.12 Ecofining HRD diesel blend used for engine tests [Eni data]
Chapter 7: Industrial Production of Succinic Acid
Table 7.1 Companies with commercial-scale succinic acid manufacturing facilities
Table 7.2 Comparison of properties of polymers of bio-based succinic acid/PDO copolymers with conventional polymers containing adipic acid
Table 7.3 Summary of the applications involving bio-based succinic acid expected by 2020
Table 7.4 Commercial and semiworks processes for succinic acid production
Chapter 8: 2,5-Furandicarboxylic Acid Synthesis and Use
Table 8.1 Molecular structures of FDCA and PTA
Table 8.2 Comparison of PEF and PET polyester physical properties [13–15]
Table 8.3 Aqueous phase oxidation of HMF
Table 8.4 Oxidation of HMF in acetic acid
Chapter 9: Production of Bioacrylic Acid
Table 9.1 Results of the catalytic tests realized by Huang
et al.
on lanthanide-impregnated zeolites [60, 64]
Table 9.2 Results of the catalytic tests made by Huang
et al.
on potassium-modified zeolites [61, 62]
Table 9.3 Catalytic performance for LA dehydration obtained over sodium phosphate-based catalysts supported on zeolite nanocrystallites [77]
Table 9.4 Catalytic performance for the dehydration of lactic acid to acrylic acid over phosphate-based catalysts [80]
Table 9.5 Main catalysts and their performances for LA dehydration in the gas phase
Chapter 10: Production of Ethylene and Propylene Glycol from Lignocellulose
Table 10.1 Results for ruthenium-based catalysts in the conversion of sorbitol.
Table 10.2 Conversion of xylose and xylitol over CuO/ZnO/Al
2
O
3
(
T
= 245 °C,
p
(H
2
) = 50 bar)
Table 10.3 Conversion of woody biomass over Ni–W
2
C/AC catalyst (
T
= 235 °C,
t
= 4 h,
p
(H
2
) = 60 bar)
Table 10.4 Conversion of corn stalk over different catalysts (
T
= 245 °C,
t
= 2 h,
p
(H
2
) = 60 bar)
Table 10.5 Conversion of glucose over Ni–W
2
C/AC (
T
= 245 °C,
t
= 3 h,
p
(H
2
) = 60 bar)
Chapter 12: Polymers from Pristine and Modified Natural Monomers
Table 12.1 Common fatty acids found in general vegeTable oil compositions [4, 5]
Table 12.2 Common vegeTable oils and their fatty acid content [4, 5]
Table 12.3 Comparison among different aromatic polyesters based on carbohydrates [70]
Chapter 13: Polymers from Monomers Derived from Biomass
Table 13.1 Thermal and mechanical data of furan dicarboxylates
Table 13.2 Comparison among some properties of PEF and PET [34, 58–60]
Chapter 14: Beyond H2: Exploiting H-Transfer Reaction as a Tool for the Catalytic Reduction of Biomass
Table 14.1 List of the most important H-transfer catalysts, with relevant references
Table 14.2 Heterogeneous catalysts used in H-transfer hydrogenation processes of biomass-derived oxygenated compounds. FA = formic acid
Table 14.3 Comparison of the fuel properties of DMF versus ethanol and gasoline [103]
Chapter 15: Selective Oxidation of Biomass Constitutive Polymers to Valuable Platform Molecules and Chemicals
Table 15.1 Catalytic systems for one-pot selective oxidation cellulose to formic acid
Chapter 17: C–C Coupling for Biomass-Derived Furanics Upgrading to Chemicals and Fuels
Table 17.1 Catalysts for aldol condensation reaction of furfural–HMF and acetone
Table 17.2 Yield of ring opening products over different acid catalysts (10 mol% catalyst in 1:1, water–methanol as solvent, 60–80 °C, 24 h). Adapted from Ref. [49]
Table 17.3 Summary for the catalysts of HAA reaction
Table 17.4 Liquid product mixture obtained of HDO with different types of diesel precursors
a
. Adapted from Ref. [58]
Table 17.5 Catalytic performances of bifunctional catalysts for C
8+
production from 2-methylfuran. Adapted from Ref. [81]
Table 17.6 Catalytic conversion of furfural to cyclopentanone on solid catalysts
a
Table 17.7 Aldol condensation of furfural and HMF with cyclopentanone (CPO) [176]
Table 17.8 Average pore diameters and Hammett acidity function (–H
o
) values of the solid acid catalysts [175]
Table 17.9 Catalyst (with additives) scanning for the furfural oxidation to maleic acid
Table 17.10 Furfural oxidation in water using various acid catalysts in the presence of hydrogen peroxide
a
Chapter 20: Arkema's Integrated Plant-Based Factories
Table 20.1 Castor oil to aminoundecanoic acid plant – Marseille Saint-Menet (France) plant data
Table 20.2 Castor oil to sebacic acid plant – Hengshui (China) plant data
Table 20.3 Epoxidation plant – Blooming Prairie (US) plant data
Table 20.4 Feuchy (France) plant data
Table 20.5 Activated carbons from locally sourced pinewood – Parentis (France) plant data
Table 20.6 Fatty acid distribution
Table 20.7 Simple calculation on cost of production
Table 20.8 Correlation matrix for raw materials, coproducts, and benchmarks
Table 20.9 Uncertainty on main parameters assuming a normal (Gaussian) distribution
Chapter 22: Technologies, Products, and Economic Viability of a Sugarcane Biorefinery in Brazil
Table 22.1 Examples of basic and specialty chemicals produced in a one-step conversion from renewable sources to the final chemical via new synthetic biology routes
Table 22.2 Prices of feedstocks and products
Chapter 24: Chemistry and Chemicals from Renewables Resources within Solvay
Table 24.1 Physical properties: comparison of PA 6.10 versus other aliphatic nylons, as a function of increasing CH
2
/amide ratios
Table 24.2 Technological properties of PA6.10 typologies–glass fiber (GF) reinforced and plasticized.
Chapter 25: Biomass Transformation by Thermo- and Biochemical Processes to Diesel Fuel Intermediates
Table 25.1 Lipid accumulation and fatty acid profiles of selected oleaginous yeasts
Table 25.2 Theoretical metabolic yields for lipids compared to ethanol
Table 25.3 Microalgae photosynthetic efficiency in outdoor cultivation
Table 25.4 Lipid production of microalgae compared with most common oleaginous crops
Table 25.5 Product distribution obtained by different pyrolysis modes from wood.
a
Table 25.6 Properties of bio-oils and upgraded bio-oils from wood
Edited by Fabrizio Cavani, Stefania Albonetti, Francesco Basile, and Alessandro Gandini
Chemicals and Fuels from Bio-Based Building Blocks
Volume 1
Edited by Fabrizio Cavani, Stefania Albonetti, Francesco Basile, and Alessandro Gandini
Chemicals and Fuels from Bio-Based Building Blocks
Volume 2
Editors
Prof. Fabrizio Cavani
Dipartimento di Chimica Industriale
Viale Risorgimento 4
40136 Bologna
Italy
Prof. Stefania Albonetti
Dipartimento di Chimica Industriale
Viale Risorgimento 4
40136 Bologna
Italy
Prof. Francesco Basile
Dipartimento di Chimica Industriale
Viale Risorgimento 4
40136 Bologna
Italy
Prof. Alessandro Gandini
Universidade de Sao Paulo
PB 780
13560-970 Sao Carlos, SP
Brazil
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Print ISBN: 978-3-527-33897-9
ePDF ISBN: 978-3-527-69819-6
ePub ISBN: 978-3-527-69822-6
Mobi ISBN: 978-3-527-69821-9
oBook ISBN: 978-3-527-69820-2
Cover Design Formgeber, Mannheim, Germany
List of Contributors
Stefania Albonetti
Alma Mater Studiorum– University of Bologna
Dipartimento di Chimica Industriale “Toso Montanari”
Viale Risorgimento 4
40136 Bologna
Italy
Aristos Aristidou
Cargill Biotechnology R&D
2500 Shadywood Road
Excelsior, MN 55331
USA
Udo Armbruster
Leibniz-Institut für Katalys e.V.
Albert-Einstein-Street 29a
18059 Rostock
Germany
Mehrdad Arshadi
Swedish University of Agricultural Sciences
Department of Forest Biomaterials and Technology
Umea
Sweden
Francesco Basile
Alma Mater Studiorum– University of Bologna
Dipartimento di Chimica Industriale “Toso Montanari”
Viale Risorgimento 4
40136 Bologna
Italy
Anna Katharina Beine
RWTH Aachen University
Institut für Technische und Makromolekulare Chemie
Lehrstuhl für Heterogene Katalyse und Technische Chemie
Worringerweg 2
52074 Aachen
Germany
Giuseppe Bellussi
ENI S.p.A
Downstream R&D Development
Operations and Technology
Via Maritano 26
20097 S. Donato Milanese
Italy
Daniele Bianchi
Eni S.p.A.
Renewable Energy and Environmental R&D Center– Istituto eni Donegani
Via G. Fauser 4
28100 Novara
Italy
Eric Black
Cargill Corn Milling North America
15407 McGinty Road West
Wayzata, MN 55391
USA
Thomas Bonnotte
Univ. Lille
CNRS, Centrale Lille, ENSCL
Univ. Artois
UMR 8181 – UCCS – Unité de Catalyse et Chimie du Solide
F-59000 Lille
France
Thomas R. Boussie
Rennovia Inc.
3040 Oakmead Village Drive
Santa Clara California 95051
USA
Massimo Bregola
Cargill Starches & Sweeteners Europe
Divisione Amidi
Via Cerestar 1
Castelmassa
RO 45035
Italy
Pieter C.A. Bruijnincx
Utrecht University
Faculty of Science
Debye Institute for Nanomaterials Science
Inorganic Chemistry and Catalysis
Universiteitsweg 99
3584 CG Utrecht
The Netherlands
Tuong V. Bui
University of Oklahoma
Chemical, Biological, and Materials Engineering
100 East Boyd Street
Norman, OK 73019
USA
Vincenzo Calemma
ENI S.p.A
Downstream R&D Development
Operations and Technology
Via Maritano 26
20097 S. Donato Milanese
Italy
Federico Capuano
Eni S.p.A.
Refining and Marketing and Chemicals
Via Laurentina 449
00142 Roma
Italy
Alfred Carlson
BioAmber, Inc.
3850 Annapolis Lane North
Plymouth, MN 55447
USA
Roberto Werneck do Carmo
BRASKEMS.A.
Chemical Processes from Renewable Raw Materials
Renewable Technologies
Rua Lemos Monteiro 120
05501-050 São Paulo, SP
Brazil
Fabrizio Cavani
Alma Mater Studiorum– University of Bologna
Dipartimento di Chimica Industriale “Toso Montanari”
Viale Risorgimento 4
40136 Bologna
Italy
Annamaria Celli
University of Bologna
Department of Civil, Chemical, Environmental and Materials Engineering
Via Terracini 28
40131 Bologna
Italy
Gabriele Centi
University of Messina
ERIC aisbl and CASPE/INSTM
Department DIECII
Section Industrial Chemistry
Viale F. Stagno D'Alcontras 31
98166 Messina
Italy
Sanjay Charati
Solvay R&I
Centre de Lyon
Saint Fons 69190
France
Alessandro Chieregato
Alma Mater Studiorum– Università di Bologna
Dipartimento di Chimica Industriale “Toso Montanari”
Viale Risorgimento 4
40136 Bologna
Italy
James H. Clark
University of York
Green Chemistry Centre of Excellence
York
YO10 5DD
UK
Corine Cochennec
Solvay R&I
Centre de Lyon
Saint Fons 69190
France
Bill Coggio
BioAmber, Inc.
3850 Annapolis Lane North
Plymouth, MN 55447
USA
Martino Colonna
University of Bologna
Department of Civil, Chemical, Environmental and Materials Engineering
Via Terracini 28
40131 Bologna
Italy
Steven Crossley
University of Oklahoma
Chemical, Biological, and Materials Engineering
100 East Boyd Street
Norman, OK 73019
USA
Manilal Dahanayake
Solvay R&I
Centre de Lyon
Saint Fons 69190
France
Paulo Luiz de Andrade Coutinho
BRASKEM S.A.
Knowledge Management
Intellectual Property and Renewables
Corporative Innovation
Rua Lemos Monteiro 120
05501-050 São Paulo, SP
Brazil
Jean-Claude de Troostembergh
Cargill Biotechnology R&D
Havenstraat 84
Vilvoorde 1800
Belgium
Gary M. Diamond
Rennovia Inc.
3040 Oakmead Village Drive
Santa Clara California 95051
USA
Eric Dias
Rennovia Inc.
3040 Oakmead Village Drive
Santa Clara California 95051
USA
Jean-Luc Dubois
ARKEMA France
420 Rue d'Estienne d'Orves
92705 Colombes
France
Franck Dumeignil
Univ. Lille
CNRS, Centrale Lille
ENSCL, Univ. Artois
UMR 8181 – UCCS – Unité de Catalyse et Chimie du Solide
F-59000 Lille
France
and
Maison des Universités
Institut Universitaire de France
IUF
103 Bd St-Michel
75005 Paris
France
Alan Barbagelata El-Assad
BRASKEM S.A.
Innovation in Renewable Technologies
Corporative Innovation
Rua Lemos Monteiro 120
05501-050 São Paulo, SP
Brazil
Mihaela Florea
University of Bucharest
Department of Organic Chemistry
Biochemistry and Catalysis
4-12 Regina Elisabeta Boulevard
030016 Bucharest
Romania
Alessandro Gandini
University of São Paulo
São Carlos Institute of Chemistry
Avenida Trabalhador São-carlense 400
CEP 13466-590
São Carlos, SP
Brazil
Nicholas Gathergood
Tallinn University of Technology
Department of Chemistry
Tallinn
Estonia
Patrick Gilbeau
Solvay R&I
Centre de Lyon
Saint Fons 69190
France
Claudio Gioia
University of Bologna
Department of Civil, Chemical, Environmental and Materials Engineering
Via Terracini 28
40131 Bologna
Italy
Gianni Girotti
Versalis S.p.A.
Green Chemistry R&D Centre
Via G. Fauser 4
28100 Novara
Italy
Peter J.C. Hausoul
RWTH Aachen University
