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
Pages
xv
xvi
xvii
xviii
xix
xx
xxi
xxii
xxiii
xxiv
xxv
xxvi
xxvii
1
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62
63
64
65
66
67
68
69
70
71
72
73
74
75
76
77
78
79
80
81
82
83
84
85
86
87
88
89
90
91
92
93
94
95
96
97
98
99
100
101
102
103
104
105
106
107
108
109
110
111
112
113
114
115
116
117
118
119
120
121
122
123
124
125
126
127
128
129
130
131
132
133
134
135
136
137
138
139
140
141
142
143
144
145
146
147
148
149
150
151
153
154
155
156
157
158
159
160
161
162
163
164
165
166
167
168
169
170
171
172
173
174
175
176
177
178
179
180
181
182
183
184
185
186
187
188
189
190
191
192
193
194
195
196
197
198
199
200
201
202
203
204
205
206
207
208
209
210
211
212
213
214
215
217
218
219
220
221
222
223
224
225
226
227
228
229
230
231
232
233
234
235
236
237
238
239
240
241
242
243
245
246
247
248
249
250
251
252
253
254
255
256
257
258
259
260
261
262
263
264
265
266
267
268
269
271
273
274
275
276
277
278
279
280
281
282
283
284
285
286
287
288
289
290
291
292
293
294
295
296
297
298
299
300
301
302
303
304
305
306
307
308
309
310
311
312
313
315
316
317
318
319
320
321
322
323
324
325
326
327
328
329
330
331
332
333
334
335
336
337
338
339
340
341
342
343
344
345
346
347
348
349
350
351
353
354
355
356
357
358
359
360
361
362
363
364
365
366
367
368
369
370
371
372
373
374
375
376
377
378
379
380
381
382
383
384
385
386
387
388
389
390
391
392
393
394
395
396
397
398
399
400
401
402
403
404
405
406
407
408
409
410
411
412
413
414
415
416
417
418
419
420
421
422
423
424
425
426
427
428
429
431
432
433
434
435
436
437
438
439
440
441
442
443
444
445
446
447
448
449
450
451
452
453
454
455
456
457
458
459
460
461
462
463
464
465
466
467
468
469
470
471
472
473
474
475
476
477
478
479
480
481
482
483
484
485
486
487
488
489
490
491
492
493
494
495
497
498
499
500
501
502
503
504
505
506
507
508
509
510
511
512
513
514
515
516
517
518
519
520
521
522
523
524
525
526
527
528
529
530
531
532
533
535
536
537
538
539
540
541
542
543
544
545
546
547
548
549
550
551
552
553
554
555
556
557
558
559
560
561
562
563
564
565
566
567
568
569
570
571
572
573
574
575
576
577
578
579
580
581
582
583
584
585
586
587
588
589
590
591
592
593
594
595
596
597
598
599
600
601
603
604
605
606
607
608
609
610
611
612
613
615
616
617
618
619
620
621
622
623
624
625
626
627
628
629
630
631
632
633
634
635
636
637
638
639
640
641
643
644
645
646
647
648
649
650
651
652
653
654
655
656
657
658
659
660
661
662
663
664
665
667
668
669
670
671
672
673
674
675
676
677
678
679
681
682
683
684
685
686
687
688
689
690
691
692
693
694
695
696
697
698
699
700
701
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.