Nanoporous Catalysts for Biomass Conversion E-Book
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- Herausgeber: John Wiley & Sons
- Kategorie: Wissenschaft und neue Technologien
- Serie: Wiley Series in Renewable Resources
- Sprache: Englisch
A comprehensive introduction to the design, synthesis, characterization, and catalytic properties of nanoporous catalysts for the biomass conversion
With the specter of peak oil demand looming on the horizon, and mounting concerns over the environmental impact of greenhouse gas emissions, biomass has taken on a prominent role as a sustainable alternative fuel source. One critical aspect of the biomass challenge is the development of novel catalytic materials for effective and controllable biomass conversion. Edited by two scientists recognized internationally for their pioneering work in the field, this book focuses on nanoporous catalysts, the most promising class of catalytic materials for the conversion of biomass into fuel and other products.
Although various catalysts have been used in the conversion of biomass-derived feedstocks, nanoporous catalysts exhibit high catalytic activities and/or unique product selectivities due to their large surface area, open nanopores, and highly dispersed active sites. This book covers an array of nanoporous catalysts currently in use for biomass conversion, including resins, metal oxides, carbons, mesoporous silicates, polydivinylbenzene, and zeolites. The authors summarize the design, synthesis, characterization and catalytic properties of these nanoporous catalysts for biomass conversions, discussing the features of these catalysts and considering future opportunities for developing more efficient catalysts. Topics covered include:
- Resins for biomass conversion
- Supported metal oxides/sulfides for biomass oxidation and hydrogenation
- Nanoporous metal oxides
- Ordered mesoporous silica-based catalysts
- Sulfonated carbon catalysts
- Porous polydivinylbenzene
- Aluminosilicate zeolites for bio-oil upgrading
- Rice straw Hydrogenation for sugar conversion
- Lignin depolymerization
Timely, authoritative, and comprehensive, Nanoporous Catalysts for Biomass Conversion is a valuable working resource for academic researchers, industrial scientists and graduate students working in the fields of biomass conversion, catalysis, materials science, green and sustainable chemistry, and chemical/process engineering.
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Veröffentlichungsjahr: 2017
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Table of Contents
Wiley Series in Renewable Resources
Title Page
Copyright
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
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Guide
Table of Contents
Begin Reading
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-SO
3
H.
Figure 1.3 Bifunctional catalyst MIL-101(Cr)-SO
3
H 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-SO
3
H 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-SO
3
H 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 –SO
3
H, –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-W
2
C/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 MoS
2
/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 Me
2
-furoin at 393K under 2 MPa H
2
[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 N
2
-saturated 0.5 M H
2
SO
4
+ 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 CO
2
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 H
2
O, 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-C
3
N
4
.
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-C
3
N
4
.
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 CO
2
.
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
H
2
SO
4
; 0.1 g cellulose; 5 ml H
2
O; 473K; 1000 rpm; 4 h.
Figure 5.4 The conversion of xylose to furfural.
Figure 5.5 Structures of PrSO
3
H-MCM-41 and MPrSO
3
H-MCM-41.
Figure 5.6 Schematic representation of the influence of surface hydrophobicity on catalytic activity. Top: HPAs/SiO
2
-Ta
2
O
5
. Alkyl-functionalized HPAs/SiO
2
-Ta
2
O
5
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 (SO
4
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 HSO
3
Cl in CH
2
Cl
2
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-SO
3
H-24, Amberlyst 15 and SBA-15-SO
3
H. (B) Catalytic kinetics curves in the transesterification of tripalmitin with methanol over (a) PDVB-SO
3
H-24, (b) H
3
PO
40
W
12
, (c) SBA-15-SO
3
H, (d) Amberlyst 15, and (e) S-ZrO
2
.
Figure 6.5 Catalytic activities in the transesterification of sunflower oil with methanol over (a) PDVB-SO
3
H-24, (b) H
3
PO
40
W
12
, (c) SBA-15-SO
3
H, (d) Amberlyst 15, and (e) S-ZrO
2
.
Figure 6.6 The enhanced acid strength of PDVB-SO
3
H-SO
2
CF
3
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-[C
1
vim][SO
3
CF
3
] from PDVB-vim. (B, C) Contact angle for a water droplet on the surface of (B) PDVB-vim and (C) PDVB-[C
1
vim][SO
3
CF
3
]. (D, E) Contact angle of a droplet of (D) methanol and (E) tripalmitin on the surface of PDVB-[C
1
vim][SO
3
CF
3
]. 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-SO
3
H 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 N
2
; 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/Al
2
O
3
core catalyst. (b) Surface SEM image and EDS analysis of the zeolite capsule catalyst Ru/Al
2
O
3
-Pd/S. (c) Cross-sectional SEM image and EDS line analysis of the zeolite capsule catalyst Ru/Al
2
O
3
-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 H
2
/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 Zn
2+
catalysts, and the role of Zn
2+
and synergy effect with a palladium hydride catalyst.
Figure 8.4 The proposed different mechanisms of cleavage of aryl ether CO bonds in the α-O-4, β-O-4, and 4-O-5 model compounds of lignin over Ni/SiO
2
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 H
2
O. (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–
x
Cu
x
O
3
(
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
31
P 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 C
9
–C
15
hydrocarbon yield (○,▿) over LSAC (▴,▿) and HSASC (▪, ○) supports. (b) Distribution of isomer/normal alkane (C
9
–C
15
) ratio over LSAC (□) and HSASC (▪) supports; and distribution of isomer/normal alkane (C
7
–C
18
) 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., Mg
2+
and Al
3+
) 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., CO
3
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 Cu
20
MgAl(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 Cu
20
MgAl(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
1
H–
13
C 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 Cu
20
MgAl(2) catalyst in supercritical ethanol [59].
Figure 10.6 Monomeric product distribution following lignin reaction at 380 °C for 8h over the Cu
20
MgAl(2) catalyst in ethanol solvent [59].
Figure 10.7 XRD patterns of the (a) Cu
20
LDH(
y
) precursors and (b) mixed-oxide catalysts after calcination at 460 °C for 6 h [60].
Figure 10.8 CO
2
-TPD profiles of the mixed-oxide catalysts with different M
2+
/M
3+
ratios [60].
Scheme 10.2 Proposed reaction network of catalytic depolymerization of lignin in ethanol over the Cu
x
MgAl(
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 NbOPO
4
.
Figure 11.3 Production of sorbitol from cellulose by successive hydrolysis and hydrogenation over Ru/NbOPO
4
bifunctional catalyst.
Figure 11.4 Production of isosorbide from cellulose by a two-step sequential process over a bifunctional Ru/NbOPO
4
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 NbOPO
4
.
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 NbOPO
4
.
Figure 11.10 Schematic reaction pathways for the conversion of glycerol in a two-bed system combining CsPW/Nb
2
O
5
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 C
8
-ols over Pt/NbOPO
4
catalyst.
Figure 11.14 Catalytic performance of direct hydrodeoxygenation of furfural-acetone over Pd/NbOPO
4
in a fixed-bed reactor.
Figure 11.15 One-pot conversion of raw woody biomass to liquid alkanes via direct hydrodeoxygenation over multifunctional Pt/NbOPO
4
.
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/Nb
2
O
5
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 H
2
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/Al
2
O
3
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 H
2
.
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 H
2
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 H
2
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 M
2+
/M
3+
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 M
2+
/M
3+
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
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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
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Bio-Based Solvents
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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
Nanoporous Catalysts for Biomass Conversion
Edited by
Feng-Shou Xiao and Liang Wang
Zhejiang University, Hangzhou, China
This edition first published 2018
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Library of Congress Cataloging-in-Publication Data
Names: Xiao, Feng-Shou, 1963- editor. | Wang, Liang, 1986- editor.
Title: Nanoporous catalysts for biomass conversion / edited by Feng-Shou
Xiao, Zhejiang University, Hangzhou, China, Liang Wang, Zhejiang
University, Hangzhou, China.
Other titles: Catalysts for biomass conversion
Description: First edition. | Hoboken, NJ : Wiley, 2017. | Includes
bibliographical references and index. |
Identifiers: LCCN 2017013229 (print) | LCCN 2017013683 (ebook) | ISBN
9781119128090 (pdf) | ISBN 9781119128106 (epub) | ISBN 9781119128083
(cloth)
Subjects: LCSH: Biomass conversion. | Porous materials. | Catalysts. |
Nanopores. | Catalysis.
Classification: LCC TP248.B55 (ebook) | LCC TP248.B55 N36 2017 (print) | DDC
620.1/16–dc23
LC record available at https://lccn.loc.gov/2017013229
Cover design by Wiley
Cover image: © georgeclerk/Gettyimages; (Top) © LEONELLO CALVETTI/Gettyimages; (Bottom Left)
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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
Acknowledgements
We would like to thank the National Natural Science Foundation of China for the constant encouragement and financial support (NO. 91634201, 21333009, 21403192, 91645105, and U1462202) to our investigation in Nanoporous Catalyst Synthesis and Biomass Conversion.
We are also grateful to Shagun Chaudhary and Emma Strickland, from Wiley, whose great patience was much appreciated in ‘polishing’ the text of the book.
Chapter 1Nanoporous Organic Frameworks for Biomass Conversion
Xiang Zhu, Chi-Linh Do-Thanh and Sheng Dai
Department of Chemistry, The University of Tennessee, USA
1.1 Introduction
Porosity, a profound concept that helps to understand Nature and create novel fascinating architectures, is inherent to natural processes, as seen in hollow bamboo, hexagonal honeycomb, and the alveoli in the lungs (Figure 1.1) [1, 2]. These advanced natural porous frameworks and their promising applications have widely inspired scientists with the idea of mimicking them in artificial structures down to the micro- and nanoscale range [1, 2]. The rational design and synthesis of advanced nanoporous materials, which play a crucial role in established processes such as catalysis and gas storage and separations and catalysis [3–12], have long been an important science subject and attracted tremendous attention. During the past two decades, the linking of molecular scaffolds by covalent bonds to create crystalline extended structures has afforded a broad family of novel nanoporous crystalline structures [13] such as like metal–organic frameworks (MOFs) [14] and covalent organic frameworks (COFs) [15]. The key advance in this regard has been the versatility of covalent chemistry and organic synthesis techniques, which give rise to a wide variety of target applications for these extended organic frameworks, for example, the use of MOFs and COFs in the context of biomass conversion. In addition to crystalline frameworks, nanoporous organic resins have long been extensively studied as heterogeneous catalysts for the conversion of biomass because of their commercial synthesis [16].
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.
Upgrading biomass into fuel and fine chemicals has been considered a promising renewable and sustainable solution to replacing petroleum feedstocks, owing to the rich family of biomass raw materials, which mainly includes cellulose, hemicellulose, and lignin [17, 18]. For example, the carbohydrates, present in the cellulosic and hemicellulosic parts of biomass, can be converted into renewable platform chemicals such as 5-hydroxymethylfurfural (HMF), via acid-catalyzed dehydration for the production of a wide variety of fuels and chemical intermediates [19]. Despite great progress, including unprecedented yields and selectivities, having been made in biomass conversion using conventional homogeneous catalysts, the cycling abilities have long been the main drawbacks that inhibit their large-scale applications. As a result, heterogeneous nanoporous solid catalysts hold great promise in these diverse reactions [16]. High porosities of nanoporous catalysts may help to access reactants, mass transfer, and functionalization of task-specific active sites, such that the product selectivities can be easily controlled. To this end, nanoporous materials with high surface areas, tunable pore sizes and controllable surface functionalities have been extensively prepared and studied. Significantly, nanoporous crystalline organic frameworks, with well-defined spatial arrangements where their properties are influenced by the intricacies of the pores and ordered patterns onto which functional groups can be covalently attached to produce chemical complexity, exhibit distinct advantages over other porous catalysts. For instance, post-synthetic modification (PSM) techniques [20] provide a means of designing the intrinsic pore environment without losing their long-range order to improve the biomass conversion performance. The inherent ‘organic effect’ enables the architectures to function with task-specific moieties such as the acidic sulfonic acid (–SO3H) group. The desired microenvironment can also be generated by rationally modifying the organic building units or metal nodes. In addition, the attractive large porosity allows the frameworks to become robust solid supports to immobilize active units such as polyoxometalates and polymers [21]. In essence, nanoporous crystalline organic frameworks including MOFs and COFs have demonstrated strong potential as heterogeneous catalysts for biomass conversion [21]. The ability to reticulate task-specific functions into frameworks not only allows catalysis to be performed in a high-yield manner but also provides a means of facile control of product selectivity.
HMF, as a major scaffold for the preparation of furanic polyamides, polyesters, and polyurethane analogs, exhibits great promise in fuel and solvent applications [19, 22]. The efficient synthesis of HMF from biomass raw materials has recently attracted major research efforts [23–29]. Via a two-step acyclic mechanism, HMF can be prepared from the dehydration of C-6 sugars such as glucose and fructose. First, glucose undergoes an isomerization to form fructose in the presence of either base catalysts or Lewis acid catalysts by means of an intramolecular hydride shift [30]. Subsequently, Brønsted acid-catalyzed dehydration of the resultant fructose affords the successful formation of HMF with the loss of three molecules of H2O (Scheme 1.2) [31]. The development of novel nanoporous acidic catalysts for the catalytic dehydration of sugars to HMF is of great interest, and is highly desirable. Hence, design strategies for the construction of nanoporous crystalline organic frameworks that are capable of the efficient transformation of sugars to HMF are discussed in this chapter, and some nanoporous organic resins for the conversion of raw biomass materials are highlighted. By examining the common principles that govern catalysis for dehydration reactions, a systematic framework can be described that clarifies trends in developing nanoporous organic frameworks as new heterogeneous catalysts while highlighting any key gaps that need to be addressed.
Scheme 1.1 Possible valuable chemicals based on carbohydrate feedstock.
1.2 Nanoporous Crystalline Organic Frameworks
1.2.1 Metal–Organic Frameworks
The Brønsted acidity of nanoporous catalysts is very essential for the dehydration of carbohydrates towards the formation of HMF [32–34]. One significant advantage of metal–organic frameworks (MOFs) is their highly designable framework, which gives rise to a versatility of surface features within porous backbones. Whereas, a wide variety of functional groups has been incorporated into MOF frameworks, exploring the Brønsted acidity of MOFs [14], the introduction of sulfonic acid groups in the framework remains a challenge and less explored, mainly because of the weakened framework stability. In this regard, several different synthetic techniques have been developed and adopted to introduce sulfonic acid (–SO3H) groups for MOF-catalyzed dehydration processes: (i) de-novo synthesis using organic linkers with –SO3H moiety; (ii) pore wall engineering by the covalently postsynthetic modification [20] (PSM) route; and (iii) modification of the pore microenvironment through the introduction of additional active sites. These novel MOF materials featuring strong Brønsted acidity show great promise as solid nanoporous acid catalysts in biomass conversion.
1.2.1.1 De-Novo Synthesis
Inspired by the framework MIL-101 [35], which possesses strong stability in aqueous acidic solutions and is fabricated from a chromium oxide cluster and terephthalate ligands in hydrofluoric acid media, Kitagawa et al. for the first time reported the rational design and synthesis of a MIL-like MOF material for cellulose hydrolysis [36]. By, adopting the MIL-101 framework as a platform, these authors created a novel nanoporous acid catalyst with highly acidic –SO3H functions along the pore walls by the innovative use of 2-sulfoterephthalate instead of the unsubstituted terephthalate in MIL-101 (Figure 1.2). The resultant Cr-based MOF MIL-101-SO3H was shown to exhibit a clean catalytic activity for the cellulose hydrolysis reaction, thus opening a new window on the preparation of novel nanoporous catalysts for biomass conversion. On account of the unsatisfactory yields of mono- and disaccharides from cellulose hydrolysis being caused by the poor solubility of crystalline cellulose in water, the same group further studied isomerization reactions from glucose to fructose in aqueous media, where MIL-101-SO3H not only shows a high conversion of glucose but also selectively produces fructose [37]. A catalytic one-pot conversion of amylose to fructose was also achieved because of the high stability of the framework in an acidic solution, which suggests promising applications of compound in the biomass field.
Figure 1.2 Schematic representation of the structure of MIL-101-SO3H.
On account of the HMF formation mechanism, the Lewis acid featuring metal center – for example, chromium (II) – allows for a high-yield isomerization because of the coordinate effect between the Lewis acidic metal sites and glucose [24]. In addition to strong Brønsted acidity caused by the –SO3H moieties, MIL-101-SO3H also bears Cr(III) sites within the structure, which is similar to CrCl2 and may act as active sites for the isomerization of glucose to fructose, whereas the fructose dehydration can be initiated with the aid of –SO3H groups. Bao et al. carried out an integrated process using nanoporous MIL-101-SO3H as the catalyst and biomass-derived solvent (γ-valerolactone; GVL) for the conversion of glucose into HMF (Figure 1.3) [38]. The batch heterogeneous reaction was shown to give a HMF yield of 44.9% and a selectivity of 45.8%. The glucose isomerization in GVL with 10 wt% water was found to follow second-order kinetics, with an apparent activation energy of 100.9 kJ mol−1 according to the reaction kinetics study. Clearly, the bifunctional MIL-101-SO3H framework can serve as a potential platform for the dehydration reaction of biomass-derived carbohydrate to generate platform chemicals.
Figure 1.3 Bifunctional catalyst MIL-101(Cr)-SO3H used for glucose conversion to HMF.
Reproduced with permission from Ref. [38]. Copyright 2016, American Institute of Chemical Engineers.
Solvents play another crucial role in the green biomass conversion processes, and the development of water-based heterogeneous systems for dehydration is important for the industrial reaction of fructose conversion to HMF [19]. Janiak et al. adopted MIL-101Cr (MIL-SO3H) as the heterogeneous catalyst and achieved a 29% conversion of glucose to HMF in a THF : H2O (39 : 1, v : v) mixture [39]. Recently, Du et al. reported a 99.9% glucose conversion and an excellent HMF yield of 80.7% in water using a new bifunctional PCP(Cr)-SO3HCr(III) material [40]. These authors showed that the sulfonic acid group in the framework was the essential function center, and more Lewis acid sites resulted in a better catalyst activity.
Despite the aforementioned nanoporous Cr-based MOF materials displaying promising applications in dehydration processes, the stringent synthetic conditions and toxic inorganic reagents of Cr MOFs greatly limit their real use. Recently, the research group of Zhao reported a modulated hydrothermal (MHT) approach that can be used to synthesize a series of highly stable Brønsted acidic NUS-6(Zr) and NUS-6(Hf) MOFs in a green and scalable way, although the linker 2-sulfotherephthalate was previously reported to make unstable UiO-type frameworks. The hafnium (Hf)-based material NUS-6(Hf) exhibited a superior performance for the dehydration of fructose to HMF (Figure 1.4) [41], outperforming all other presently known MOFs or heterogeneous catalysts with a yield of 98% under the same reaction conditions. Nevertheless, although such a high transformation yield can be achieved in organic dimethyl sulfoxide (DMSO), the attempts at dehydration with the same MOF material in aqueous media resulted in only negligible amounts of HMF (ca. 5%). Therefore, it is very valuable and significant to rationally design and develop stable Brønsted acidic MOF materials for high-performance dehydrations to prepare HMF in green aqueous media, even though this is an enormous challenge.
Figure 1.4 NUS-6(Hf) used as a heterogeneous catalyst for fructose conversion to HMF.
Reproduced by permission of Ref. [41]. Copyright 2012 American Chemical Society.
1.2.1.2 Postsynthetic Modification
In addition to direct synthesis using building linkers to modify MOF materials in situ, the PSM route is becoming an important technique to introduce various functions inside the MOFs for diverse applications, such as heterogeneous catalysis and gas storage and separation [20]. Therefore, PSM provides another means of introducing Brønsted acid groups to MOF backbones for the dehydration of biomasses to HMF. The presence of organic scaffolds in MOFs allows for a convenient employment of a variety of organic transformations. Furthermore, the acid strength on the surface can be precisely controlled by the PSM through varying the grafting rate of the reaction. As shown in Figure 1.5, Chen et al. reported the synthesis of a family of MOF frameworks functionalized with the –SO3H group through the PSM of the organic linkers, using chlorosulfonic acid [42]. The resultant framework MIL-101(Cr) [MIL-101(Cr)-SO3H] exhibited a full fructose conversion with a HMF yield of 90% in DMSO. The –SO3H groups was found to have a significant effect on fructose-to-HMF transformation [42]. Both the conversions of fructose and selectivities towards HMF were increased with the sulfonic acid-site density of the MOF material. Kinetics studies further suggested that the dehydration of fructose to HMF using MIL-101(Cr)-SO3H followed pseudo-first-order kinetics with an activation energy of 55 kJ mol−1.
Figure 1.5 Synthetic routes to MOF-SO3H and the conversion of fructose into HMF.
1.2.1.3 Pore Microenvironment Modification
Pore microenvironment engineering inside MOF frameworks via either the physical impregnation of acidic compounds or in-situ
