Table of Contents

Wiley Series in Renewable Resources

Title Page

List of Contributors

Series Preface

Acknowledgements

Chapter 1: Nanoporous Organic Frameworks for Biomass Conversion

1.1 Introduction
1.2 Nanoporous Crystalline Organic Frameworks
1.3 Nanoporous Organic Sulfonated Resins
1.4 Conclusions and Perspective
References

Chapter 2: Activated Carbon and Ordered Mesoporous Carbon-Based Catalysts for Biomass Conversion

2.1 Introduction
2.2 Activated Carbon and Mesoporous Carbon
2.3 Cellulose Conversion
2.4 Lignin Conversion
2.5 Synthesis of Biofuel (Diesel or Jet Fuel) from Lignocellulose
2.5 Summary
References

Chapter 3: Nanoporous Carbon/Nitrogen Materials and their Hybrids for Biomass Conversion

3.1 Introduction
3.2 Dehydrogenation of Formic Acid
3.3 Transfer Hydrogenation of Unsaturated Compounds from Formic Acid
3.4 Synthesis of High-Value-Added Chemicals from Biomass
3.5 Metal-Free Catalyst: Graphene Oxide for the Conversion of Fructose
3.6 Conclusions and Outlook
References

Chapter 4: Recent Developments in the Use of Porous Carbon Materials for Cellulose Conversion

4.1 Introduction
4.2 Overview of Catalytic Cellulose Hydrolysis
4.3 Functionalized Carbon Catalyst for Cellulose Hydrolysis
4.4 Summary and Outlook
References

Chapter 5: Ordered Mesoporous Silica-Based Catalysts for Biomass Conversion

5.1 Introduction
5.2 Sulfated Ordered Mesoporous Silicas
5.3 Ordered Mesoporous Silica-Supported Polyoxometalates and Sulfated Metal Oxides
5.4 Heteroatom-Doped Ordered Mesoporous Silica
5.5 Ordered Mesoporous Silica-Supported Metal Nanoparticles
5.6 Overall Summary and Outlook
References

Chapter 6: Porous Polydivinylbenzene-Based Solid Catalysts for Biomass Transformation Reactions

6.1 Introduction
6.2 Synthesis of Porous PDVB-Based Solid Acids and Investigation of their Catalytic Performances
6.3 Perspectives of PDVB-Based Solid Catalysts and their Application for Biomass Transformations
Acknowledgments
References

Chapter 7: Designing Zeolite Catalysts to Convert Glycerol, Rice Straw, and Bio-Syngas

7.1 Glycerol Conversion to Propanediols
7.2 Rice Straw Hydrogenation
7.3 Bio-Gasoline Direct Synthesis from Bio-Syngas
References

Chapter 8: Depolymerization of Lignin with Nanoporous Catalysts

8.1 Introduction
8.2 Developed Techniques for Lignin Depolymerization
8.3 Oxidative Depolymerization of Lignin
8.4 Hydrolysis of Lignin with Base and Acid Catalysts
8.5 Other Depolymerization Techniques (Cracking, Photocatalysis, Electrocatalysis, and Biocatalysis)
8.6 Conclusions
Acknowledgments
References

Chapter 9: Mesoporous Zeolite for Biomass Conversion

9.1 Introduction
9.2 Production of Biofuels
9.3 Conversion of Glycerol
9.4 Overall Summary and Outlook
References

Chapter 10: Lignin Depolymerization Over Porous Copper-Based Mixed-Oxide Catalysts in Supercritical Ethanol

10.1 Introduction
10.2 Lignin Depolymerization by CuMgAl Mixed-Oxide Catalysts in Supercritical Ethanol
10.3 Conclusions
References

Chapter 11: Niobium-Based Catalysts for Biomass Conversion

11.1 Introduction
11.2 Hydrolysis
11.3 Dehydration
11.4 HMF Hydration to Levulinic Acid
11.5 Hydrodeoxygenation
11.6 C–C Coupling Reactions
11.7 Esterification/Transesterification
11.8 Other Reactions in Biomass Conversion
11.9 Summary and Outlook
References

Chapter 12: Towards More Sustainable Chemical Synthesis, Using Formic Acid as a Renewable Feedstock

12.1 Introduction
12.2 General Properties of FA and Implications for Green Synthesis
12.3 Transformation of Bio-Based Platform Chemicals
12.4 FA-Mediated Depolymerization of Lignin or Chitin
12.5 Upgrading of Bio-Oil and Related Model Compounds
12.6 FA as the Direct Feedstock for Bulk Chemical Synthesis
12.7 Conclusions and Outlook
References

Index

End User License Agreement

List of Illustrations

Chapter 1: Nanoporous Organic Frameworks for Biomass Conversion

Figure 1.1 Illustration of porosity existing in Nature and synthesized frameworks with a decreasing pore size. (a) Bamboo; (b) honeycomb; (c) scanning electron microscopy (SEM) image of alveolar tissue in mouse lung; (d) SEM image of an ordered macroporous polymer; (e) SEM image of an ordered mesoporous polymer from self-assembly of block copolymers; (f) structural representation of the COF structure.
Scheme 1.2 Possible valuable chemicals based on carbohydrate feedstock.
Figure 1.2 Schematic representation of the structure of MIL-101-SO₃H.
Figure 1.3 Bifunctional catalyst MIL-101(Cr)-SO₃H used for glucose conversion to HMF.
Figure 1.4 NUS-6(Hf) used as a heterogeneous catalyst for fructose conversion to HMF.
Figure 1.5 Synthetic routes to MOF-SO₃H and the conversion of fructose into HMF.
Figure 1.6 Ru-PTA/MIL-100(Cr) used as a heterogeneous catalyst for biomass conversion.
Figure 1.7 Scheme of fabrication of functional hybrids of MOFs and polymer networks.
Scheme 1.2 Scheme of fabrication of COF-SO₃H for the conversion of fructose into HMF.
Figure 1.8 Chemical structure of Amberlyst® 15.
Figure 1.9 Nafion® NR50 used for the conversion of fructose into HMF.
Figure 1.10 Transmission electron microscopy (TEM) images of (a) MCF, (b) Nafion®(15)/MCF, (c) Nafion®(30)/MCF, and (d) Nafion®(45)/MCF.

Chapter 2: Activated Carbon and Ordered Mesoporous Carbon-Based Catalysts for Biomass Conversion

Scheme 2.1 Structure of cellulose.
Scheme 2.2 Conversion of cellulose to chemicals over carbon-based catalysts.
Figure 2.1 Reaction mechanism for the hydrolysis of cellulose by carbon materials bearing –SO₃H, –COOH, and phenolic –OH groups.
Scheme 2.3 Catalytic conversion of cellulose into polyols.
Scheme 2.4 The reaction pathway for conversion of cellulose and hemicellulose to EG.
Figure 2.2 Schematic representative structures of lignin.
Figure 2.3 Hydrogenolysis of guaiacylglycerol-β-guaiacyl ether over Ni/AC and Pd/AC [98].
Figure 2.4 The recycling results of Ni-W₂C/AC catalyst for lignin hydrocracking reaction [76b].
Figure 2.5 Conversion of lignin over carbon-supported noble metals catalysts [99].
Figure 2.6 Hydrodeoxygenation of guaiacol with MoS₂/AC catalysts.
Figure 2.7 Aqueous-phase HDO of vanillin with Pd@CN catalyst.
Figure 2.8 Possible reaction pathways from lignin model compounds to cycloalkanes.
Figure 2.9 HDO of phenolic monomers/dimers on Pd/C and HZSM-5 catalysts.
Figure 2.10 Scanning electron microscopy image of the blank ACC FM100. Scale bar = 500 μm [105].
Figure 2.11 Total-ion chromatogram (TIC) of the liquid products.
Figure 2.12 Possible mechanism for the palladium-catalyzed alkylation of acetone [111].
Figure 2.13 Divergent pathway leads to different products [115].
Figure 2.14 One-pot HDO treatment of Me₂-furoin at 393K under 2 MPa H₂ [117].
Figure 2.15 Reaction chemistry for the conversion of xylose oligomers into tridecane [118].

Chapter 3: Nanoporous Carbon/Nitrogen Materials and their Hybrids for Biomass Conversion

Figure 3.1 Schematic view of typical (a) rectifying metal–n-type semiconductor contact. (b) Rectifying metal–p-type semiconductor. (c) Metal–semiconductor ohmic contact.
Figure 3.2 (a) Work functions of typical metals and carbon, and band structures of carbon nitride and N-doped carbon (NC). (b) Schematic view of a Mott–Schottky-type Pd@CN contact (E_F: work function; E_C: conduction band; E_V: valence band
Figure 3.3 Formic acid oxidation at a scan rate of 50 mV s⁻¹ on PtAu/graphene, PtAu/CB, and commercial Etek-Pt/C in N₂-saturated 0.5 M H₂SO₄ + 0.5 M HCOOH.
Figure 3.4 Preparation and application of CoAuPd/C nanocatalyst for formic acid decomposition at 298K.
Figure 3.5 Correlation with the work function of the M core, where M = fcc (111) Ag, Rh, Au, Ru and Pt or hexagonal close-packed (hcp) (0001) Ru. Ag, with the largest difference in work function in relation to Pd, gives the strongest electron promotion to the Pd shell.
Figure 3.6 Volume change of reforming gas with time for 60 mg of the synthesized catalyst in 5 ml of solution containing 6.64 M formic acid and 6.64 M sodium formate at a reaction temperature of 92 °C.
Figure 3.7 Proposed mechanisms for the synthesis of Pd-PANI/CNT catalysts.
Figure 3.8 Electrohydrogenation mechanism for CO₂ reduction on Pd/C.
Figure 3.9 Procedures or parameters for varying the catalytic performance of supported noble metal nanocrystals. A highly coupled interface is the third aspect to be considered for the design of highly efficient catalysts.
Figure 3.10 The rapid separation of ethylbenzene after the hydrogenation reaction of styrene. After the reaction, the as-formed ethylbenzene was separated automatically from the water phase, within 10 min. The solid catalyst was precipitated automatically at the bottom and easily separated from the oil phase by filtration or decantation. The reaction conditions were: 10 mmol styrene, 250 ml H₂O, 30 mmol formic acid (FA), and 500 mg Pd/CN, at 298K.
Figure 3.11 Screening of catalysts for the hydrogenation of levulinic acid (LA) to γ-valerolactone (GVL).
Figure 3.12 Structure of AgPd@g-C₃N₄.
Figure 3.13 Proposed possible mechanism of disproportion and transfer hydrogenation.
Figure 3.14 The hydrodeoxygenation of vanillin, depicting a plausible mechanism.
Figure 3.15 Conversion of fructose into 5-hydroxymethylfurfural (HMF) and 2,5-diformylfuran (DFF), catalyzed by functionalized g-C₃N₄.
Figure 3.16 Schematic illustration of the fabrication of Pt@CN nanosheets.
Figure 3.17 Effect of the addition of Ru/C catalyst on furfural conversion and product yield for the indicated homogeneous Lewis acid catalysts.
Figure 3.18 Reaction pathway of 5-hydroxymethylfurfural (HMF) hydrogenation in supercritical CO₂.
Figure 3.19 Pathways for the hydrogenation of levulinic acid to γ-valerolactone.
Figure 3.20 Multiphase recycling procedure for conversion of levulinic acid (LA) to γ-valerolactone (GVL).
Figure 3.21 Oxidation products of 5-hydroxymethylfurfural (HMF) derived from fructose dehydration. The byproducts are 2,5-diformylfuran (DFF), 5-hydroxymethyl-2-furancarboxylic acid (HMFCA), 5-formyl-2-furancarboxylic acid (FFCA), and 2,5-furandicarboxylic acid (FDCA).
Figure 3.22 The conversion of carbohydrates to 5-ethoxymethylfurfural (EMF), catalyzed by graphene oxide (GO).
Figure 3.23 Conversion of HMF into products for biofuels applications.

Chapter 4: Recent Developments in the Use of Porous Carbon Materials for Cellulose Conversion

Scheme 4.1 Hydrolysis of cellulose to glucose.
Figure 4.1 Applications of cellulose-derived glucose for chemical synthesis [5].
Figure 4.2 Schematic of lignocellulose showing the three components and molecular structure of cellulose with hydrogen bonding.
Figure 4.3 Mechanism of acid hydrolysis of cellulose [32].
Figure 4.4 Enzymatic hydrolysis of cellulose. EG: endoglucanase; CBH: cellobiohydrolase; BG: β-glucosidase [5].
Figure 4.5 Structure of the sulfonated carbon catalyst. Reprinted with permission from Ref. [74]. Copyright 2008, American Chemical Society.
Figure 4.6 Correlation between total amount of weak acid functional groups on the catalyst surface and the glucose yield. Reproduced with permission from Ref. [38]. Copyright 2016, Springer.
Figure 4.7 Proposed structure of E-Carbon containing an aromatic framework and weakly acidic functional groups [92].
Figure 4.8 Catalytic cycle for the use of E-Carbon produced by air-oxidation for the hydrolysis of Eucalyptus [92]. HC indicates xylan as a hemicellulose.
Figure 4.9 Schematic representation of synergy between adjacent carboxylic acid groups for hydrolysis of β-1,4-glucans.

Chapter 5: Ordered Mesoporous Silica-Based Catalysts for Biomass Conversion

Figure 5.1 Conversion of levulinic acid (LA) to fuel additives.
Figure 5.2 Reaction pathways for the conversion of cellulose. The reactions include (A) hydrolysis, (B) isomerization, (C) dehydration, (D) rehydration, (E) hydrogenation, and (F) hydrogenolysis.
Figure 5.3 Yield of levulinic acid (LA) over different acid catalysts. Reaction conditions: 0.1 g catalyst or 0.03 mol l⁻¹ H₂SO₄; 0.1 g cellulose; 5 ml H₂O; 473K; 1000 rpm; 4 h.
Figure 5.4 The conversion of xylose to furfural.
Figure 5.5 Structures of PrSO₃H-MCM-41 and MPrSO₃H-MCM-41.
Figure 5.6 Schematic representation of the influence of surface hydrophobicity on catalytic activity. Top: HPAs/SiO₂-Ta₂O₅. Alkyl-functionalized HPAs/SiO₂-Ta₂O₅ sample synthesized by a co-condensation technique (middle) and a post-synthesis grafting method (bottom).
Figure 5.7 Locations of the Brønsted and Lewis acid sites on metal oxides (MO_x) and sulfated metal oxides (SO₄^2–/MO_x).
Figure 5.8 (a) The synthesis of S-Sn-OH; (b) Scanning transmission electron microscopy image; (c–e) O, Si, and Sn energy-dispersive X-ray spectroscopy (EDS) elemental maps of S-Sn-OH, respectively. The scale bars in images (b) to (e) are 10, 8, 8, and 8 nm, respectively.
Figure 5.9 (a) Formation of 1,1-bisylvylalkanes by hydroxyalkylation/alkylation from Sylvan and an aldehyde with subsequent hydrodeoxygenation to 6-alkyl undecane. (b) Formation and hydrodeoxygenation of 5,5-bisylvyl-2-pentanone. Initially, one molecule of Sylvan is hydrolyzed to 4-oxopentanal by sulfuric acid catalysis; two further sylvan molecules are subsequently hydroxyalkylated and alkylated with the intermediary aldehyde.
Figure 5.10 Transformation of 2-methylfuran and butanal into alkanes over a bifunctional Pt/MCM-41 catalyst.
Figure 5.11 Fragment structure of hardwood lignin.

Chapter 6: Porous Polydivinylbenzene-Based Solid Catalysts for Biomass Transformation Reactions

Figure 6.1 The synthetic process of super superhydrophobic PDVB and scanning electron microscopy images of the resultant PDVB sample.
Figure 6.2 The sulfonation process of PDVB by using HSO₃Cl in CH₂Cl₂ solvent.
Figure 6.3 The synthetic procedures of superhydrophobic PDVB-based solid acids.
Figure 6.4 (A) Absorption capacities for methanol, toluene, ethanol, and sunflower oil over PDVB-SO₃H-24, Amberlyst 15 and SBA-15-SO₃H. (B) Catalytic kinetics curves in the transesterification of tripalmitin with methanol over (a) PDVB-SO₃H-24, (b) H₃PO₄₀W₁₂, (c) SBA-15-SO₃H, (d) Amberlyst 15, and (e) S-ZrO₂.
Figure 6.5 Catalytic activities in the transesterification of sunflower oil with methanol over (a) PDVB-SO₃H-24, (b) H₃PO₄₀W₁₂, (c) SBA-15-SO₃H, (d) Amberlyst 15, and (e) S-ZrO₂.
Figure 6.6 The enhanced acid strength of PDVB-SO₃H-SO₂CF₃ and its applications for catalyzing the depolymerization of crystalline cellulose.
Figure 6.7 (A) Contact angle of (a) a water droplet, (b) a salad oil droplet, (c) a methanol droplet, and (d) a glycerol droplet on a PDVB-type solid base. (B) Scheme for the application of PDVB solid base for catalyzing biodiesel production.
Figure 6.8 Dependences of catalytic activities on time in transesterification of tripalmitin with methanol over (a) PDVB solid base, (b) KOH, and (c) CaO catalysts. Reaction condition: 0.05 g catalyst; tripalmitin 0.84 g; methanol 3.76 ml; 65 °C.
Figure 6.9 (A) Scheme for the synthesis of PDVB-[C₁vim][SO₃CF₃] from PDVB-vim. (B, C) Contact angle for a water droplet on the surface of (B) PDVB-vim and (C) PDVB-[C₁vim][SO₃CF₃]. (D, E) Contact angle of a droplet of (D) methanol and (E) tripalmitin on the surface of PDVB-[C₁vim][SO₃CF₃]. Figure reproduced with permission from Ref. [32]. Copyright 2012, American Chemical Society.
Figure 6.10 The scheme for the synthesis of the mesoporous ionic copolymers and diagrams of their structures.
Figure 6.11 Depolymerization of crystalline cellulose into sugars catalyzed by sulfonic group- and acidic ionic liquid-functionalized nanoporous PDVB.
Figure 6.12 Dehydration of sorbitol over (a and b) P-SO₃H and (c and d) Amberlyst-15 catalysts. Reaction conditions: 100 mg sorbitol; molar ratio of sorbitol to acid sites at 7.2 (a and c) in 5 ml THF or (b and d) in a mixture of 4 ml of THF and 1 ml water; 2 MPa N₂; 175 °C.
Figure 6.13 Transformation of glucose into HMF catalyzed by a superhydrophilic PDVB-based solid base and a superhydrophobic PDVB-based solid acid.

Chapter 7: Designing Zeolite Catalysts to Convert Glycerol, Rice Straw, and Bio-Syngas

Scheme 7.1 Transesterification of triglycerides to create glycerol.
Scheme 7.2 Processes of catalytic conversion of glycerol into useful chemicals.
Scheme 7.3 Proposed mechanisms of glycerol hydrogenolysis to produce propanediols.
Scheme 7.4 The main pathways for the conversion of glycerol into 1,2-propanediol via bifunctional catalysis with Pt/NaY.
Scheme 7.5 (A) Illustration of the tandem reaction process on (a) a general hybrid catalyst and (b) a capsule catalyst. (B) General pathway of glycerol conversion to 1,2-propanediol (1,2-PDO) or 1,3-propanediol (1,3-PDO).
Figure 7.1 (a) Surface scanning electron microscopy (SEM) image (inset: complete morphology under lower magnification) and energy-dispersive X-ray spectroscopy (EDS) analysis of the Ru/Al₂O₃ core catalyst. (b) Surface SEM image and EDS analysis of the zeolite capsule catalyst Ru/Al₂O₃-Pd/S. (c) Cross-sectional SEM image and EDS line analysis of the zeolite capsule catalyst Ru/Al₂O₃-Pd/S.
Scheme 7.6 Direct conversion of rice straw via a solid acid-supported Pt catalyst.
Figure 7.2 Generic biomass gasification process.
Figure 7.3 Effect of temperature on the H₂/CO ratio.
Scheme 7.7 Representative isoparaffin synthesis through FT catalytic systems. (A) Two-step reactor configuration. (B) Hybrid catalyst for the one-step synthesis: (a) zeolite-loaded metal catalyst; (b) physical mixture catalyst; (c) core–shell structure catalyst.
Scheme 7.8 (a) Schematic representation of the sputtering apparatus. (b) One-step synthesis of isoparaffin from syngas on Ru/H-Beta catalyst.
Figure 7.4 (A) Transmission electron microscopy images of beta zeolite with various NaOH concentrations. (a) H-beta; (b) meso-beta-0.05 M NaOH; (c) meso-beta-0.15 M NaOH; (d) meso-beta-0.3 M NaOH; (e) meso-beta-0.5 M NaOH; (f) meso-beta-0.7 M NaOH. (B) Product selectivity for different catalysts.
Scheme 7.9 Representation of the hierarchical zeolite catalyst for one-step isoparaffin synthesis.
Figure 7.5 Product distribution for the prepared catalysts.
Scheme 7.10 The synthesis procedure of the HMOR/FI capsule catalyst without a template.

Chapter 8: Depolymerization of Lignin with Nanoporous Catalysts

Figure 8.1 A two-step route for the depolymerization of lignin and further hydrodeoxygenation to alkanes and methanol in the liquid phase.
Figure 8.2 Schematic representation of an integrated bio-refinery process for the full utilization of lignocellulose.
Figure 8.3 Two-step approach for the hydrodeoxygenation of organosolv lignin, including depolymerization and the liquid-phase reforming (LPR) reaction.
Scheme 8.1 Proposed mechanism for the cleavage and HDO of β-O-4 ether linkage using Pd/C and Zn²⁺ catalysts, and the role of Zn²⁺ and synergy effect with a palladium hydride catalyst.
Figure 8.4 The proposed different mechanisms of cleavage of aryl ether CO bonds in the α-O-4, β-O-4, and 4-O-5 model compounds of lignin over Ni/SiO₂ in the aqueous phase.
Figure 8.5 Conversion of lignosulfonate lignin over various catalysts, using methanol as solvent. The major products included 4-propyl-guaiacol (PA) and 4-ethyl-guaiacol (EA).
Figure 8.6 Conversion of wood over a Cu catalyst in methanol in the absence of hydrogen. PMO: porous metal oxides.
Figure 8.7 (a) Schematic representation of the catalytic bio-refining method over Raney Ni in the mixed solvent of 2-propanol and H₂O. (b) Comparison of lignin-derived bio-oil and the traditional organosolv process.
Figure 8.8 Proposed mechanism of oxidation of lignin to aromatic aldehydes for the LaFe_1–xCu_xO₃ (x = 0, 0.1, 0.2) catalyst. Reprinted with permission from Ref. [65]. Copyright 2009, Molecular Diversity Preservati.
Figure 8.9 The proposed strategies for depolymerization of oxidized lignin via two steps.

Chapter 9: Mesoporous Zeolite for Biomass Conversion

Figure 9.1 Known routes for the production of fuels from biomass.
Figure 9.2 The pyrolysis of sugars to various chemicals over the Ce-modified mesoporous ZSM-5 catalyst.
Figure 9.3 Molar carbon selectivity in the catalytic rapid pyrolysis of glucose over various catalysts. BTX: benzene, toluene, xylene; Naphthalenes: naphthalene, methyl-naphthalene.
Figure 9.4 (a) The molecules in pyrolysis oil. (b) The molecules of corresponding alkane oil.
Figure 9.5 ³¹P NMR spectra of TMPO adsorbed on (a) HZSM-5, (b) HZSM-5-M, and (c) HZSM-5-OM. The peaks at 51–53 ppm correspond to the acid sites in the mesopores or on the external surface of zeolite crystals.
Figure 9.6 Gas and gasoline composition from the cracking of cooking oil over conventional (ZSM-5-P) and mesoporous ZSM-5 (HZ-0.5AAT) catalysts.
Figure 9.7 Preparation procedures for Ni nanoparticles supported on mesoporous ZSM-5 zeolite crystals.
Figure 9.8 Yield and conversion for stearic acid hydrodeoxygenation over (a) Ni/ZSM-5 and (b) Ni/mesoporous ZSM-5 catalysts.
Figure 9.9 Hydroconversion of Jatropha oil (triglycerides and free fatty acids) into hydrocarbons over sulphided Ni–Mo catalysts supported on high-surface-area semi-crystalline (HSASC) and low-surface-area crystalline (LSAC) hierarchical mesoporous H-ZSM-5. (a) Conversion (▪, ▴) and C₉–C₁₅ hydrocarbon yield (○,▿) over LSAC (▴,▿) and HSASC (▪, ○) supports. (b) Distribution of isomer/normal alkane (C₉–C₁₅) ratio over LSAC (□) and HSASC (▪) supports; and distribution of isomer/normal alkane (C₇–C₁₈) ratio at different reaction temperatures for HSASC (c) and LSAC (d) supports.
Figure 9.10 Product composition in 1-h reaction for the hydrodeoxygenation of stearic acid over various beta-supported Ni catalysts. The treatment methods used to synthesize the mesoporous beta-catalyst are shown on the x-axis.
Figure 9.11 A simplified scheme of the main reaction pathways in the transformation of triglycerides into biofuels via catalytic processes. (1) Transesterification; (2) Hydrodeoxygenation; (3) Hydrodecarboxylation; (4) Decarbonylation; and (5) Cracking/catalytic cracking.
Figure 9.12 Dependences of glycerol conversion on reaction time over different mesoporous zeolite catalysts.
Figure 9.13 Acrolein selectivity in glycerol conversion over different mesoporous zeolite catalysts.
Figure 9.14 Total chromatogram of liquid products collected between 1 and 2 h in the aromatization of 40% glycerol in methanol at 400 °C over the conventional HZSM-5 zeolite.

Chapter 10: Lignin Depolymerization Over Porous Copper-Based Mixed-Oxide Catalysts in Supercritical Ethanol

Figure 10.1 Schematic view of the structure of hydrotalcites. Bivalent and trivalent cations (e.g., Mg²⁺ and Al³⁺) are sixfold-coordinated to form octahedrals that share edges to constitute infinite layers. Small spheres drawn in the interlayer region represent the compensating anions (e.g., CO₃^2–) [2].
Figure 10.2 GC×GC-MS chromatogram of the product mixture obtained from the catalytic reaction of lignin at 300 °C for 8 h using the CuMgAl mixed-oxide catalyst.
Figure 10.3 GC-MS chromatograms of reaction mixtures obtained from reaction of phenol at 300 °C for 1 h over the Cu₂₀MgAl(2) catalyst in (a) methanol, (b) ethanol, and (c) 50%/50% (v/v) methanol/ethanol solvents. The GC-MS chromatograms were normalized to the internal standard, ISTD [59].
Figure 10.4 GPC chromatograms of reaction mixtures obtained from the reaction at 300 °C for 1 h over the Cu₂₀MgAl(2) catalyst. (a) Using phenol in different solvents; (b) Using different reactants in methanol solvent (the depicted chromatograms have been normalized by the sum of the peak area) [59].
Figure 10.5 The side-chain region of the ¹H–¹³C HSQC NMR spectra of the reaction products of phenol conversion (300 °C; 1 h; CuMgAlO_x catalyst). (a) Spectrum for methanol solvent; (b) Combined spectra of methanol (red) and 50%/50% (v/v/) methanol/ethanol solvent (green). The combined spectra have been normalized by the total peak volume [59].
Scheme 10.1 The roles of alkylation, the Guerbet reaction, and esterification in suppressing char formation during lignin depolymerization over the Cu₂₀MgAl(2) catalyst in supercritical ethanol [59].
Figure 10.6 Monomeric product distribution following lignin reaction at 380 °C for 8h over the Cu₂₀MgAl(2) catalyst in ethanol solvent [59].
Figure 10.7 XRD patterns of the (a) Cu₂₀LDH(y) precursors and (b) mixed-oxide catalysts after calcination at 460 °C for 6 h [60].
Figure 10.8 CO₂-TPD profiles of the mixed-oxide catalysts with different M²⁺/M³⁺ ratios [60].
Scheme 10.2 Proposed reaction network of catalytic depolymerization of lignin in ethanol over the Cu_xMgAl(y) catalysts [60].

Chapter 11: Niobium-Based Catalysts for Biomass Conversion

Figure 11.1 The reactions involved in biomass conversion over niobium-based catalysts.
Figure 11.2 Representative structures of Lewis and Brønsted acid sites in NbOPO₄.
Figure 11.3 Production of sorbitol from cellulose by successive hydrolysis and hydrogenation over Ru/NbOPO₄ bifunctional catalyst.
Figure 11.4 Production of isosorbide from cellulose by a two-step sequential process over a bifunctional Ru/NbOPO₄ catalyst.
Figure 11.5 Schematic reaction pathway of glucose dehydration to HMF over Nb-based catalyst containing both Lewis and Brønsted acid sites.
Figure 11.6 Schematic reaction mechanism for the production of HMF from glucose over NbOPO₄.
Figure 11.7 Production of furfural from xylose via isomerization and dehydration over niobium phosphate.
Figure 11.8 Production of acrolein from glycerol via double dehydration.
Figure 11.9 Schematic reaction pathways in the dehydration of glycerol over NbOPO₄.
Figure 11.10 Schematic reaction pathways for the conversion of glycerol in a two-bed system combining CsPW/Nb₂O₅ and V-Mo/SiC.
Figure 11.11 The rehydration of HMF to levulinic and formic acid catalyzed by acid.
Figure 11.12 Schematic reaction process of cellulose conversion to GVL via sequential hydrolysis, dehydration, rehydration, and hydrogenation.
Figure 11.13 Schematic reactions of dehydration/hydrogenation of C₈-ols over Pt/NbOPO₄ catalyst.
Figure 11.14 Catalytic performance of direct hydrodeoxygenation of furfural-acetone over Pd/NbOPO₄ in a fixed-bed reactor.
Figure 11.15 One-pot conversion of raw woody biomass to liquid alkanes via direct hydrodeoxygenation over multifunctional Pt/NbOPO₄.
Figure 11.16 Glycerol as a byproduct from biodiesel production by transesterification of triglycerides with small alcohols.
Figure 11.17 Aqueous-phase processing of GVL to pentanoic acid over a bifunctional Pd/Nb₂O₅ catalyst.

Chapter 12: Towards More Sustainable Chemical Synthesis, Using Formic Acid as a Renewable Feedstock

Figure 12.1 The concept of formic acid-based biorefinery.
Figure 12.2 Carbon-neutral H₂ store using biorenewable formic acid as an energy carrier.
Figure 12.3 Reactivity portrait of FA.
Figure 12.4 Catalytic conversion of carbohydrate biomass into GVL [68].
Figure 12.5 Mechanistic proposal for reductive amination of LA [68].
Figure 12.6 Proposed mechanism of Pd/ZrP-catalyzed hydrogenolysis of HMF to HDO in the presence of FA [77].
Figure 12.7 Glycerol hydrogenolysis by FA over Ni–Cu/Al₂O₃ catalyst [78].
Figure 12.8 The mechanism proposed for FA-mediated didehydroxylation [80].
Figure 12.9 Pathway for DMF from HMF using FA as a reagent [38].
Figure 12.10 Ru-catalyzed transformation of furfural to LA with FA [83].
Figure 12.11 Lignin depolymerization and HDO in the presence of FA [37].
Figure 12.12 FA-mediated cleavage of the β-O-4′-ether bond of model lignin compounds [87].
Figure 12.13 Depolymerization of aspen lignin with FA [39].
Figure 12.14 The chemical structure of chitin.
Figure 12.15 Proposed major reaction pathways for FA-mediated chitin liquefaction [89].
Figure 12.16 Bio-oil hydroprocessing using FA as an in-situ hydrogen source [90].
Figure 12.17 Proposed pathways for tandem hydrodeoxygenation of vanillin with FA [93].
Figure 12.18 Proposed pathways for the Ir-catalyzed disproportionation of FA to methanol [102].
Figure 12.19 Proposed pathways for the Ru-catalyzed disproportionation of FA to methanol [103].

List of Tables

Chapter 2: Activated Carbon and Ordered Mesoporous Carbon-Based Catalysts for Biomass Conversion

Table 2.1 Hydrolysis of cellulose and lignocellulosic biomass

Chapter 4: Recent Developments in the Use of Porous Carbon Materials for Cellulose Conversion

Table 4.1 Langmuir parameters and thermodynamic values for adsorption of cello-oligosaccharides on K26 [103]

Chapter 5: Ordered Mesoporous Silica-Based Catalysts for Biomass Conversion

Table 5.1 Product selectivities in levulinic acid (LA) conversion over different catalysts. Reaction conditions: 4 mmol LA; 0.2 g catalyst; 10 ml ethanol; 6 h; 523K; 4 MPa H₂.^a

Chapter 6: Porous Polydivinylbenzene-Based Solid Catalysts for Biomass Transformation Reactions

Table 6.1 Yields of sugars and dehydration products in the depolymerization of crystalline cellulose catalyzed by various solid acids
Table 6.2 The textural parameters and catalytic data in transesterification of tripalmitin with methanol over various solid base catalysts.^a
Table 6.3 Activities in transesterification of tripalmitin with methanol over various catalysts.^a
Table 6.4 Yield of sugars and dehydration products in the depolymerization of Avicel catalyzed by various solid acids and mineral acids
Table 6.5 The catalytic yields of HMF from the conversion of glucose over various catalysts.^a

Chapter 7: Designing Zeolite Catalysts to Convert Glycerol, Rice Straw, and Bio-Syngas

Table 7.1 Results of glycerol hydrogenolysis over Ru/C + acid catalyst at 180 °C.^a
Table 7.2 Reaction properties of core catalyst, zeolite capsule catalyst and hybrid catalyst.^a
Table 7.3 H₂ productivity via ethanol steam reforming.^a
Table 7.4 Rice straw conversion and yield of sugar alcohols under different conditions.^a
Table 7.5 FT synthesis performances of various catalysts

Chapter 8: Depolymerization of Lignin with Nanoporous Catalysts

Table 8.1 Data of the depolymerization of lignin with noble metal catalysts
Table 8.2 Data for the depolymerization of lignin with transition metal catalysts in liquid solvents
Table 8.3 Data for the depolymerization of lignin with metal catalysts in the absence of H₂
Table 8.4 Data for the oxidative depolymerization of lignin.
Table 8.5 Data for the hydrolysis of lignin with base and acid catalysts

Chapter 10: Lignin Depolymerization Over Porous Copper-Based Mixed-Oxide Catalysts in Supercritical Ethanol

Table 10.1 Yields of monomers, lignin residues and char following lignin depolymerization in supercritical ethanol at 300 °C for 4 h [37, 59]
Table 10.2 Yields of monomers, lignin residues, and char and the total yields following lignin depolymerization under varying conditions
Table 10.3 Textural properties and chemical composition of mixed oxide catalysts with different M²⁺/M³⁺ ratios [60]
Table 10.4 Product distribution for the reaction of lignin in ethanol at 340 °C for 4 h over mixed oxide catalysts with different M²⁺/M³⁺ ratios [60]
Table 10.5 Product distribution for the reaction of lignin in ethanol at 340 °C for 4 h over mixed oxide catalysts as a function of Cu content [60]

Chapter 11: Niobium-Based Catalysts for Biomass Conversion

Table 11.1 Summary of the catalytic performance of various catalysts for the dehydration of different carbohydrates under their respective optimal conditions
Table 11.2 The catalytic performance of various Nb catalysts for the dehydration of glycerol to acrolein under their respective optimal conditions
Table 11.3 Direct hydrodeoxygenation of furfural-acetone over different Pd-based catalysts in a batch reactor.^a
Table 11.4 Summary of hydrodeoxygenation of various biomass-derived oxygenates over Nb-based bifunctional catalysts

Wiley Series in Renewable Resources

Series Editor:

Christian V. Stevens, Faculty of Bioscience Engineering, Ghent University, Belgium

Titles in the Series:

Wood Modification: Chemical, Thermal and Other Processes

Callum A. S. Hill

Renewables-Based Technology: Sustainability Assessment

Jo Dewulf, Herman Van Langenhove

Biofuels

Wim Soetaert, Erik Vandamme

Handbook of Natural Colorants

Thomas Bechtold, Rita Mussak

Surfactants from Renewable Resources

Mikael Kjellin, Ingegärd Johansson

Industrial Applications of Natural Fibres: Structure, Properties and Technical Applications

Jörg Müssig

Thermochemical Processing of Biomass: Conversion into Fuels, Chemicals and Power

Robert C. Brown

Biorefinery Co-Products: Phytochemicals, Primary Metabolites and Value-Added Biomass Processing

Chantal Bergeron, Danielle Julie Carrier, Shri Ramaswamy

Aqueous Pretreatment of Plant Biomass for Biological and Chemical Conversion to Fuels and Chemicals

Charles E. Wyman

Bio-Based Plastics: Materials and Applications

Stephan Kabasci

Introduction to Wood and Natural Fiber Composites

Douglas D. Stokke, Qinglin Wu, Guangping Han

Cellulosic Energy Cropping Systems

Douglas L. Karlen

Introduction to Chemicals from Biomass, 2nd Edition

James H. Clark, Fabien Deswarte

Lignin and Lignans as Renewable Raw Materials: Chemistry, Technology and Applications

Francisco G. Calvo-Flores, Jose A. Dobado, Joaquín Isac-García, Francisco J. Martín-Martínez

Sustainability Assessment of Renewables-Based Products: Methods and Case Studies

Jo Dewulf, Steven De Meester, Rodrigo A. F. Alvarenga

Cellulose Nanocrystals: Properties, Production and Applications

Wadood Hamad

Fuels, Chemicals and Materials from the Oceans and Aquatic Sources

Francesca M. Kerton, Ning Yan

Bio-Based Solvents

François Jérôme and Rafael Luque

Forthcoming Titles:

Biorefinery of Inorganics: Recovering Mineral Nutrients from Biomass and Organic Waste

Erik Meers, Gerard Velthof

The Chemical Biology of Plant Biostimulants

Danny Geelen

Biobased Packaging: Material, Environmental and Economic Aspects

Mohd Sapuan Salit, Muhammed Lamin Sanyang

Thermochemical Processing of Biomass: Conversion into Fuels, Chemicals and Power, 2nd Edition

Robert C. Brown

All rights reserved. No part of this publication may be reproduced, stored in a retrieval system, or transmitted, in any form or by any means, electronic, mechanical, photocopying, recording or otherwise, except as permitted by law. Advice on how to obtain permission to reuse material from this title is available at http://www.wiley.com/go/permissions.

The right of Feng-Shou Xiao and Liang Wang to be identified as the authors of the editorial material in this work has been asserted in accordance with law.

John Wiley & Sons Ltd, The Atrium, Southern Gate, Chichester, West Sussex, PO19 8SQ, UK

For details of our global editorial offices, customer services, and more information about Wiley products visit us at www.wiley.com.

Wiley also publishes its books in a variety of electronic formats and by print-on-demand. Some content that appears in standard print versions of this book may not be available in other formats.

While the publisher and authors have used their best efforts in preparing this work, they make no representations or warranties with respect to the accuracy or completeness of the contents of this work and specifically disclaim all warranties, including without limitation any implied warranties of merchantability or fitness for a particular purpose. No warranty may be created or extended by sales representatives, written sales materials or promotional statements for this work. The fact that an organization, website, or product is referred to in this work as a citation and/or potential source of further information does not mean that the publisher and authors endorse the information or services the organization, website, or product may provide or recommendations it may make. This work is sold with the understanding that the publisher is not engaged in rendering professional services. The advice and strategies contained herein may not be suitable for your situation. You should consult with a specialist where appropriate. Further, readers should be aware that websites listed in this work may have changed or disappeared between when this work was written and when it is read. Neither the publisher nor authors shall be liable for any loss of profit or any other commercial damages, including but not limited to special, incidental, consequential, or other damages.

List of Contributors

Yong Cao Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, China
Sheng Dai Department of Chemistry, The University of Tennessee, USA
Chi-Linh Do-Thanh Department of Chemistry, The University of Tennessee, USA
Atsushi Fukuoka Institute for Catalysis, Hokkaido University, Japan
Emiel J.M. Hensen Laboratory of Inorganic Materials Chemistry, Schuit Institute of Catalysis, Eindhoven University of Technology, The Netherlands
Xiaoming Huang Laboratory of Inorganic Materials Chemistry, Schuit Institute of Catalysis, Eindhoven University of Technology, The Netherlands
Hirokazu Kobayashi Institute for Catalysis, Hokkaido University, Japan
Jiechen Kong Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engineering, East China Normal University, China
Tamás I. Korányi Laboratory of Inorganic Materials Chemistry, Schuit Institute of Catalysis, Eindhoven University of Technology, The Netherlands
Changzhi Li State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, China
Guangyi Li State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, China
Ning Li State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, China
Shu-Shuang Li Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, China
Xin-Hao Li School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, China
Yao Lin Department of Chemistry and Institute of Materials Science, University of Connecticut, USA
Fei Liu State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, China
Fujian Liu Department of Chemistry, Shaoxing University, China
Yong-Mei Liu Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, China
Zhicheng Luo Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engineering, East China Normal University, China
Xiangju Meng Key Laboratory of Applied Chemistry of Zhejiang Province, Department of Chemistry, Zhejiang University, China
Jifeng Pang State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, China
Abhijit Shrotri Institute for Catalysis, Hokkaido University, Japan
Hui Su School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, China
Lei Tao Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, China
Noritatsu Tsubaki Department of Applied Chemistry, School of Engineering, University of Toyama, Japan
Aiqin Wang State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, China
Hong-Hui Wang School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, China
Liang Wang Key Laboratory of Applied Chemistry of Zhejiang Province, Department of Chemistry, Zhejiang University, China
Yanqin Wang Shanghai Key Laboratory of Functional Materials Chemistry, Research Institute of Industrial Catalysis, School of Chemistry and Molecular Engineering, East China University of Science and Technology, China
Liubi Wu Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engineering, East China Normal University, China
Qineng Xia Shanghai Key Laboratory of Functional Materials Chemistry, Research Institute of Industrial Catalysis, School of Chemistry and Molecular Engineering, East China University of Science and Technology, China
Feng-Shou Xiao Key Laboratory of Applied Chemistry of Zhejiang Province, Department of Chemistry, Zhejiang University, China
Chuang Xing School of Biological and Chemical Engineering, Zhejiang University of Science and Technology, China
Jinming Xu State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, China
Shaodan Xu Key Laboratory of Applied Chemistry of Zhejiang Province, Department of Chemistry, Zhejiang University, China
Guohui Yang Department of Applied Chemistry, School of Engineering, University of Toyama, Japan
Ruiqin Yang School of Biological and Chemical Engineering, Zhejiang University of Science and Technology, China
Tao Zhang State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, China
Chen Zhao Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engineering, East China Normal University, China
Tian-Jian Zhao School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, China
Xiaochen Zhao State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, China
Mingyuan Zheng State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, China
Xiang Zhu Department of Chemistry, The University of Tennessee, USA

Series Preface

Renewable resources, their use and modification are involved in a multitude of important processes with a major influence on our everyday lives. Applications can be found in the energy sector, paints and coatings, and the chemical, pharmaceutical, and textile industry, to name but a few.

The area interconnects several scientific disciplines (agriculture, biochemistry, chemistry, technology, environmental sciences, forestry …), which makes it very difficult to have an expert view on the complicated interaction. Therefore, the idea to create a series of scientific books that will focus on specific topics concerning renewable resources, has been very opportune and can help to clarify some of the underlying connections in this area.

In a very fast changing world, trends are not only characteristic for fashion and political standpoints; science is also not free from hypes and buzzwords. The use of renewable resources is again more important nowadays; however, it is not part of a hype or a fashion. As the lively discussions among scientists continue about how many years we will still be able to use fossil fuels – opinions ranging from 50 to 500 years – they do agree that the reserve is limited and that it is essential not only to search for new energy carriers but also for new material sources.

In this respect, renewable resources are a crucial area in the search for alternatives for fossil-based raw materials and energy. In the field of energy supply, biomass and renewables-based resources will be part of the solution alongside other alternatives such as solar energy, wind energy, hydraulic power, hydrogen technology, and nuclear energy. In the field of material sciences, the impact of renewable resources will probably be even bigger. Integral utilization of crops and the use of waste streams in certain industries will grow in importance, leading to a more sustainable way of producing materials. Although our society was much more (almost exclusively) based on renewable resources centuries ago, this disappeared in the Western world in the nineteenth century. Now it is time to focus again on this field of research. However, it should not mean a “retour à la nature,” but it should be a multidisciplinary effort on a highly technological level to perform research towards new opportunities, to develop new crops and products from renewable resources. This will be essential to guarantee a level of comfort for a growing number of people living on our planet. It is “the” challenge for the coming generations of scientists to develop more sustainable ways to create prosperity and to fight poverty and hunger in the world. A global approach is certainly favoured.

This challenge can only be dealt with if scientists are attracted to this area and are recognized for their efforts in this interdisciplinary field. It is, therefore, also essential that consumers recognize the fate of renewable resources in a number of products.

Furthermore, scientists do need to communicate and discuss the relevance of their work. The use and modification of renewable resources may not follow the path of the genetic engineering concept in view of consumer acceptance in Europe. Related to this aspect, the series will certainly help to increase the visibility of the importance of renewable resources. Being convinced of the value of the renewables approach for the industrial world, as well as for developing countries, I was myself delighted to collaborate on this series of books focusing on different aspects of renewable resources. I hope that readers become aware of the complexity, the interaction and interconnections, and the challenges of this field and that they will help to communicate on the importance of renewable resources.

I certainly want to thank the people of Wiley's Chichester office, especially David Hughes, Jenny Cossham and Lyn Roberts, in seeing the need for such a series of books on renewable resources, for initiating and supporting it, and for helping to carry the project to the end.

Last, but not least, I want to thank my family, especially my wife Hilde and children Paulien and Pieter-Jan, for their patience and for giving me the time to work on the series when other activities seemed to be more inviting.

Christian V. Stevens,

Faculty of Bioscience Engineering

Ghent University, Belgium

Series Editor ‘Renewable Resources’

June 2005