Contents
1. Introduction

2. Hydrolysis of cellulose
3. Hydrocracking of cellulose
4. Future outlook

5. Summary
2

Contents
1. Introduction

2. Hydrolysis of cellulose
3. Hydrocracking of cellulose
4. Future outlook

5. Summary3

1-1. Energy demand
Quadrillion Btu

Quadrillion Btu

YearWorld energy consumption
4

Year

World energy consumption
by fuel1-2. Energy-related effects
Billion metric tons

Dollars per barrel

Year

Year

World CO2 emissions
5

World oil prices

1-3. Our task
Now there are sufficient amounts of oil reservoirs to satisfy
our current needs even if the utilization of oil is on the vergeof becoming uneconomical.

However…

We must think about how to develop new resources/methods to replace
the current resources or at least to compensate its consumption in somepercentage toward green and sustainable society.

61-4. Resources
Renewable energy

71-5. Biomass
Biomass = Bio(Living thing) + Mass(Amount)

Biomass = Biological materials derived from living, or recently
living organisms.
Waste biomass

8

Unused biomass

Resource crops

住田町立世田米保育園

1-6. Biorefinery
Conversion of biomass
Chemicals
CO2CO2CO2CO2Biomass
91-7. Conversion of biomass
Cost, selectivity

Cost, selectivity

Cost, selectivity

Cost, selectivity

Green economical
process101-8. Plant-derived biomass
Plants produce carbohydrates such as starch, cellulose,
hemicellulose, lignin.
Structure of cellulose molecules
Structure of starch molecules

a-1,4 or a-1,6 linkages, constituent offood materials
11b-1,4 linkages, constituent ofwood

1-9. Plant-derived biomass

Characterization tools such as
X-ray diffraction (XRD),
NMR spectroscopy

are generally used to check thecrystallinity of cellulose.

Hydrogen bonding in cellulose
121-10. Conversion of cellulose
Cellulose

Hydrolysis Chapter 2Glucose
Chemicals, fuels, foods, medicine

Hydrocracking Chapter 3

Sorbitol, Ethylene glycol
Chemicals, fuels, medicine, PET
13

Contents
1. Introduction

2. Hydrolysis of cellulose
3. Hydrocracking of cellulose
4. Future outlook

5. Summary14

2-0. Hydrolysis of cellulose

GlucoseHydrogen bonding in cellulose
15

2-1. Hydrolysis of cellulose with solid acids
Formation ofby-product
Si/Al ratio=10Si/Al ratio=12
Si/Al ratio=45
Si/Al ratio=75
High stability

16

Hydrophobic

SO3H group
SO3H group
SO3H group2-1. Hydrolysis of cellulose with solid acids
Ball-milling of cellulose
22°

Amorphous cellulose
16°

After34°

BeforeXRD pattern
17

SEM image2-2. Hydrolysis of cellulose with amorphous carbon

High stability

18

Amorphous carbon
gave high activity.

2-2. Hydrolysis of cellulose with amorphous carbon
Amorphous carbon

XRD pattern and Raman spectrum
1580 cm-1
1350 cm-1

Amorphouscarbon

Ca. 1 nmFTIR spectrum and 13C MAS NMR spectrum

SO3H group, polycyclic aromatic carbon
atoms, phenolic OH, COOH group
Elemental analysis and cation-exchange
experiment (CH0.622O0.540S 0.048)
19

2-2. Hydrolysis of cellulose with amorphous carbon

Hydrolysis of cellobiose with thecarbon-based solid catalyst(catalyst 0.1 g, cellobiose0.12 g,water 0.7 g, 363 K)

Hydrolysis of cellohexaose with thecarbon-based solid catalyst(catalyst 0.3 g, cellohexaose 5.25 mg,water 0.7 g, 363 K)

With amorphous carbon glucose was obtained in good yields.
20

2-2. Hydrolysis of cellulose with amorphous carbon
Adsorption of cellobiose and cellohexaose

The carbon-based materials were capable of incorporatingcellobiose and cellohexaose. And, niobic acid which has ahigh density of OH groups was also capable of it.
21

2-2. Hydrolysis of cellulose with amorphous carbon
Adsorption of glucose and β-1,4-glucan

Adsorption of H2O

The carbon-based materials were capable
Although glucose was not adsorbed on thecarbon materials, the amount of β-1,4-glucan of incorporating a large amount of water
into the carbon bulk.
adsorbed on the carbon material increasedwith increasing chain length of β-1,4-glucan.
22

2-2. Hydrolysis of cellulose with amorphous carbon
Catalyst features
Decomposition of thehydrogen bond andβ-1,4-glycosidic bondGood access of reactantsin solution to SO3H groups

Adsorption of β-1,4glucan
232-3. Hydrolysis of cellulose with carbon-supported
rutheniumHighstability

Milled
2.8 MPa, Hot compressed water
CMK-3 converted cellulose to oligomers and glucose along with hot compressed water.
Ru was more effective to increase the glucose yield than CMK-3.
Ru species on CMK-3 worked as an acid catalyst to hydrolyze β-1,4-glycosidic bonds ofoligomers to yield glucose from the result of hydrolysis of cellobiose at 393K.
24

2-3. Hydrolysis of cellulose with carbon-supported
ruthenium
TEM image of 2 wt% Ru/CMK-3, and particle
size distribution
SAXS pattern and XRD pattern

A certain type of Ru nanoparticles
25

2-3. Hydrolysis of cellulose with carbon-supported
ruthenium
Fourier transforms of k3 –weighted
Ru K-edge EXAFS spectra

2 wt% Ru/CMK-3
2 wt% Ru/CMK-3-A

RuO2・2H2O
RuO2Reported structure of RuO2・2H2O
RuCl3
Ru

Ru/CMK-3 was similar to RuO2・2H2O.
26

2-3. Hydrolysis of cellulose with carbon-supported
ruthenium
Catalyst features

One-dimensional chainstructure

27

RuO2・2H2O may give a Brønsted acid.
The dissociation of a water molecule
coordinated on Ru could give a vacantsite with Lewis acidity.

2-4. Hydrolysis of cellulose with simple activatedcarbons and trace hydrochloric acid

High stability
Carboxylic acid, phenolic groups from
TPD measurement88%(catalyst 50 mg, cellulose 324 mg, water 40 mL, 453 K, 20 min)28

2-4. Hydrolysis of cellulose with simple activatedcarbons and trace hydrochloric acid

Salicylic acid gave a high TOF.
The catalytic activities can be
explained by two factors.
One is pKa.
The other is the structure of acids.

(TOF = mol of glucose produced in
the catalytic reaction – blank/2 molof catalyst・reaction time)(catalyst 0.5 mM, cellulobiose 25mM , 443 K)

29

2-4. Hydrolysis of cellulose with simple activatedcarbons and trace hydrochloric acid
Catalyst features

Activated carbon(26)

Phenolic groups form hydrogen bonds with hydroxyl groups of a cellulose
chain, and that adjacent carboxylic acids have an opportunity to hydrolyze
glycosidic bonds.
Interaction predicted by spartan’0830

2-5. Short summary of 2 chapter
Cellulose

Hydrolysis Chapter 2Glucose

Hydrocracking Chapter 3

Sorbitol, Ethylene glycol

31

Contents
1. Introduction

2. Hydrolysis of cellulose
3. Hydrocracking of cellulose
4. Future outlook

5. Summary32

3-0. Hydrocracking of cellulose

GlucoseSorbitol
Ethylene glycol

Hydrogen bonding in cellulose33

3-1. Hydrocracking of cellulose with supported metal
Sorbitol 25%
Mannitol 6%

Supported metal gave goodresults and led to the formationof sugar alcohols from cellulose.

Highstability

34

Hydrogen gas was pressurized in
the autoclave with a supported
metal catalyst.

3-1. Hydrocracking of cellulose with solid acids

Various solid acids gave only
low activity.
No sugar alcohol was observed.
The metal promoted thehydrolysis of cellulose.

35

3-1. Hydrocracking of cellulose with supported metal
Catalyst features

Splitting of hydrogen

Reduction ofglucose

H2Transition
metalCarrier
36

H+ interact withcellulose molecule3-1. Hydrocracking of cellulose with supported metal
Time course of the hydrogenation of cellulose

Rate-determining
stepSlow

Fast37

3-1. Hydrocracking of cellulose with supported metal
Ru/AC gave
good results.

Transfer hydrogenation

H2 pressure reached 0.8 MPa.

Sorbitol 34%
Mannitol 9%(catalyst 50 mg, milled cellulose 324 mg, water 30 mL, 2-propanol 10 mL, 463 K, 18 h)
38

3-2. Hydrocracking of cellulose with supported metalHighstability

Hydrolysis of cellulose (cellulose 0.5 g, water 50 g, 518 K, 6 Mpa H2, 30 min)In the presence of a tungsten-based catalyst, ethylene glycol became the major product.

39

3-2. Hydrocracking of cellulose with supported metal
Catalyst features

Temperature-controlled
phase-transfer catalyst
XRD patternBlue to yellow
40

3-2. Hydrocracking of cellulose with supported metal

41

3-3. Short summary of 3 chapter
Cellulose

Hydrolysis Chapter 2Glucose

Hydrocracking Chapter 3

Sorbitol, Ethylene glycol

42

Contents
1. Introduction

2. Hydrolysis of cellulose
3. Hydrocracking of cellulose
4. Future outlook

5. Summary43

4-0. Future outlook

Lignocellulose

44

Chemicals, fuels,
energy etc.

4-1. Chemoselective metal-free aerobic alcoholoxidation in lignin

One of the most common structuralunits is the alkyl aryl ether unit
containing a β-O-4 linkage

Fragment of lignin
45

4-1. Chemoselective metal-free aerobic alcoholoxidation in lignin

46

4-1. Chemoselective metal-free aerobic alcoholoxidation in lignin

This reaction wasapplied to many lignin
model compounds.
Moreover, it was also
applied to real lignin.

47

4-2. Photodegradation of target oligosaccharides48

4-2. Photodegradation of target oligosaccharides

R=HR=H(glycoside 1.0 nM, catalyst 1.0 nM, 10% MeCN/0.1% phosphate buffer, 298 K,10 min, UV lamp 365 nm 100 W)
49

Contents
1. Introduction

2. Hydrolysis of cellulose
3. Hydrocracking of cellulose
4. Future outlook

5. Summary50

5. Summary
Although great progress has been made in conversion of cellulose, theefficient transformation of real biomass to important bulk chemicals is
still in its infancy.

1. Development of cheaper but more efficient and robust catalyst

2. Development of powerful in situ characterization techniques
3. Achievement of industry-academia-government collaboration
are essential for green and sustainable society.

51

References

52

Appendix Derivatives of glucose and applications

53

Appendix Derivatives of sorbitol and applications

54