2. Outline
Introduction
Renewable energy
Lignocellulosic Biomass
Polysaccharides
Lignin
Conversion Processes of Lignocelluloses to Fuels and
Chemicals
Lignocellulose conversion
Problem Statement
Objectives
Hydrogenolysis
Hydrogenolysis Operation
Hydrogenolysis of Feedstock
Lignin Hydrogenolysis
Polysaccharides Hydrogenolysis
Conclusion
Summary
Future Work
3. Renewable Energy
Need for renewable energy
Depletion of Fossil Fuels
Global Warming due to Greenhouse Gasses (GHGs)
National Security
(Deming, 2000) (Forster et al., 2007)
(Akorede et al., 2012)
Bioenergy
Corn/Sugarcane (1st Generation)
Lignocellulosic Biomass (2nd Generation)
4. Lignocellulosic Biomass
Lignocellulosic Biomass
Hardwood
Softwood
Herbaceous Plants
Lignocellulose Complex
(Murphy and McCarthy, 2005)
Cellulose
Hemicellulose
Lignin
The chemical composition make up of the lignocellulosic materials
(Sun and Cheng, 2002)
Feedstock Cellulose (%) Hemicellulose (%) Lignin (%)
Hardwood 40-50 25-40 18-25
Softwood 45-50 25-35 23-35 (Zhou et al., 2010)
Grasses 25-40 35-50 10-30
5. Polysaccharides
Cellulose
Most abundant organic
chemical on earth.
Homopolymer
7,000 to 15,000 monomeric D-
glucose units
Crystalline and Amorphous
Regions
(Meyers et al., 2008)
Up to 65% crystalline regions in Content and compositional differences between hardwood vs. softwood
wood. (Kögel-Knabner, 2002)
Hemicellulose Polyoses
Deciduous Wood (Hardwood) Coniferous Wood (Softwood)
Content (%) Units Content (%) Units
Branched Heteropolymers Xylose, 4-O- Xylose, 4-O-
Pentoses (β-D-xylose, α-L- Xylans 25-30 methylglucuronic 5-10 methylglucuronic
acid acid
arabinose) Mannose, glucose,
Hexoses (β-D-mannose, β-D- Mannans 3-5 Mannose, glucose 20-25 galactose, acetyl
groups
glucose, α-D-galactose) Galactose,
Galactose,
Galactans 0.5-2 arabinose, 0.5-3
Xylans and Glucomannans rhammose
arabinose
Most significant hemicelluloses.
6. Lignin
An amorphous three-dimensional bio-polymer of
three phenylpropane units randomly cross-linked
with one another.
Derived generally from three monolignols:
Para-coumaryl alcohol
Coniferyl alcohol
Sinapyl alcohol
Monolignols produce phenylpropaniod
units
Para-hydroxyphenol (H-unit)
(Xu, 2010)
Guaiacyl (G-unit)
Syringol (S-unit)
Lignin is produced by free radical generation
followed by chemical coupling processes of the
monolignols.
8. Lignin
(Kögel-Knabner, 2002)
Content of the main linkages in lignin (Faravelli et al., 2010)
(Achyuthan et al., 2010; Pandey and Kim, 2011; Ralph, 2005; Zakzeski et al., 2010)
Linkage Type Softwood (spruce) (%) Hardwood (birch) (%)
β-O-4-Aryl ether 46 60
Dibenzodioxocin 25-30 5-10
β-5-Phenylcoumaran 9-12 6
β-β-(Resinol) 2-6 3-12
4-O-5-Diaryl ether <4 <6.5
β-1-(1,2-Diarylpropnae) 1-2 1-2
α-O-4-Aryl ether A few A few
9. Conversion Processes of Lignocelluloses to
fuels and Chemicals
(Menon and Rao, 2012)
Comparison between the biochemical and thermochemical process (Basu 2010a).
Biochemical Process Thermochemical Process
Reactor Type Batch Continuous
Reaction Time A few Days A few minutes
Temperature 100-200 °C ˃ °C
200
Water Usage (liter/liter ethanol) 3.5-170 <1
11. Problem Statement
Current biochemical
conversion of lignocellulose for
fuels and chemicals
Cellulose and hemicellulose
converted to ethanol
Lignin used as a boiler fuel through
combustion
Non-simultaneous
Inefficient utilization of lignin
2nd most abundant polymer
15-30% of biomass
Higher energy content than
cellulose Celunol Corp. http://zfacts.com/p/85.html. 27, July 2012.
9,000-11,000 Btu/lb vs. 7,300-
7,500 Btu/lb
Production of phenols and phenol
12. Objectives
Thermochemical conversion of feedstock for fuel
and chemical precursors
Polysaccharides followed by lignin conversion
Ethanol and lignin derived chemicals
Simultaneous conversion of feedstock
Polysaccharides and lignin derived chemicals
Hydrogenolysis of feedstock using noble-metal
catalysts
Lignin Hydrogenolysis
Main focus
Depolymerization of lignin into fuel and chemical precursors
Factors affecting lignin hydrogenolysis
Lignin monomer yield
Polysaccharides hydrogenolysis
Conversion of polysaccharides into fuel and chemical precursors
Factors affecting polysaccharide hydrogenolysis
14. Hydrogenolysis of Feedstock
Conversion of feedstock:
Based on the weight of feedstock utilized in the reaction and the
solid recovered after reaction
Amount dissolved
Liquid soluble product
Converted feedstock (%)
Liquid insoluble product
Solid residue
Higher feedstock conversion More fuel
and chemical precursors possible
Due to less solid residueFeedstock Conversion
100
80
Conversion (%)
60
40
20
0
in
r
e
ce
se
in
la
av
n
n
ru
lo
p
ig
lig
g
o
lu
p
A
L
P
S
el
lv
i
al
C
so
lk
o
A
an
rg
O
Feedstock
Conversion of different feedstocks through catalytic hydrogenolysis. The reaction conditions were: Residence
time: 4 hours; temperature: 200 °C; Pressure: 1000 psi; catalyst: 10% (w/w) of Pt/C; phosphoric acid: 40% (w/w);
solvent: H2O (1:1,v/v).
15. Hydrogenolysis of Feedstock
Poplar conversion
(amount dissolved) for Poplar Conversion
different reaction 100
conditions 80
Conversion (%)
Higher conversion 60
Higher temperatures
40
Presence of mineral acid
Water solvent 20
15
10
5
Lower conversion 0
71 a
80
92
39
82
84
72
73
40
47
86
88
90
98
65
67
69
5
9
4
0
2
10
10
10
10
10
Lower temperature Experimental control run a Run #
Absence of mineral acid Poplar feedstock conversion when an operational variable is changed during catalytic hydrogenolysis. The reaction
conditions were: Residence time: 4 hours; temperature: 200 °C; Pressure: 1000 psi; catalyst: 10% (w/w) of Pt/C;
(phosphoric acid) phosphoric acid: 40% (w/w); solvent: H2O (1:1,v/v), while one of the conditions was changed and the rest kept as
Ethanol solvent listed.
No effect on conversion
Catalyst and catalyst
16. Lignin Hydrogenolysis
Lignin depolymerization into fuels and chemical
precursors
Selective cleavage of ether bonds
Lower temperature
No carbon-carbon linkage cleavage
Higher temperature
(Faravelli et al., 2010)
Isolated lignin i.e. organosolv lignin and alkali
lignin
Lignin structure already altered due to isolation
17. Lignin Hydrogenolysis
Selective production of
monomers and/or
dimers
Monomers
Monomer units in the
native lignin linked to
other monomer units by
ether bonds
depolymerized into
monomers
Dimers
A lignin monomer linked
to another monomer unit
through a carbon-carbon
linkage, while at the (Yan et al., 2008)
18. Lignin Hydrogenolysis
Hydrogen molecules react with
catalyst
Hydrogen molecule sigma bond
broken
Weaker metal-hydride bond
formed
The sigma bond in the C-O
bond interacts with the metal
catalyst
Weakens metal hydride bond
Hydrogen atom is transferred to
oxygen(C-O bond)
Second hydrogen atom is
transferred from the catalyst to
carbon
Weakened sigma bond gets (Nagy et
al., 2009)
cleaved
19. Lignin Hydrogenolysis
Ideal monomer theoretical yield
Probability of a monomer linked to two other monomer
through ether linkages is the square of the ether linkages
in lignin.
Ether linkages
(2/3) to (3/4) of lignin linkages
Simplified model
More ether linkages in hardwood than softwood
Guaiacyl lignin contains less ether linkages
Resulting in 44-56% theoretical yield for monomers. (Yan
et al., 2008)
Assumptions
All ether linkages cleaved
Not possible for isolated lignin
Do not know ether content in isolated lignin
20. Lignin Hydrogenolysis
Reference condition
GC/MS
Monomers
Guaiacylpropane
Syringylpropane
Dimers
Not detected
Reaction conditions
Peaks with different
retention times
Not identified
Gas Chromatography and mass spectrum analysis. The reaction conditions were: Residence
Guaiacylpropane and time: 4 hours; temperature: 200 °C; Pressure: 1000 psi; catalyst: 10% (w/w) of Pt/C; acid: 40%
(w/w); solvent: H2O (1:1,v/v); feedstock: poplar.
Syringylpropane still
predominate.
Previous Studies
Guaiacylpropanol and
syringylpropanol in addition to
21. Lignin Hydrogenolysis
Factors affecting lignin hydrogenolysis
The effect of residence time
The effect of temperature
The effect of hydrogen pressure
The effect of feedstock
The effect of noble-metal catalyst
The effect of addition of mineral acid
The effect of solvent
Compared by lignin yield (%,w/w)
Based on initial lignin in feedstock
Guaiacylpropane and syringylpropane end-product
22. Lignin Hydrogenolysis
The effect of residence
Residence Time Effect
time on lignin
60
hydrogenolysis 2 hrs
Time needed to reach maximum 4 hrs
Yield (%,w/w)
temperature included. 6 hrs
40
Linear relationship between 8 hrs
residence time and lignin
yield 20
Linear regression analysis 0
statistically significant
s
s
s
s
hr
hr
hr
hr
Residence time does a
2
4
6
8
somewhat decent job of Residence Time (hours)
predicting lignin monomer yield Lignin product yield during catalytic hydrogenolysis while varying the residence times. The
R2 = 0.73 reaction conditions were: temperature: 200 °C; Pressure: 1000 psi; catalyst: 10% (w/w) of Pt/C;
phosphoric acid: 40% (w/w); solvent: H2O (1:1,v/v); feedstock: poplar.
The residence time
23. Lignin Hydrogenolysis
The effect of temperature
Temperature Effect
on lignin 50
hydrogenolysis 150 (°C)
40 200 (°C)
Significant linear
Yield (%,w/w)
250 (°C)
relationship between 30 300 (°C)
temperature and lignin yield 20
for (150 to 250 ºC)
10
Linear regression analysis not 0
)
)
)
statistically significant between
)
(°C
(°C
(°C
(°C
0
0
0
150 to 300 ºC
0
15
20
25
30
Temperature is not a good Temperature
predictor of lignin monomer Lignin product yield during catalytic hydrogenolysis while varying the temperature. The reaction
yield conditions were: Residence time: 4 hours; Pressure: 1000 psi; catalyst: 10% (w/w) of Pt/C;
phosphoric acid: 40% (w/w); solvent: H2O (1:1,v/v); feedstock: poplar.
R2 = 0.61
The temperature treatments
24. Lignin Hydrogenolysis
The effect of
Pressure Effect
hydrogen pressure
60
on lignin hydrogenolysis 0 psi
250 psi
Yield (%,w/w)
40 1000 psi
A minimal pressure
between 0 and 250 psi is 20
necessary for initiation of
hydrogenolysis 0
No linear relationship
i
i
i
ps
ps
ps
0
0
00
25
between pressure and
10
Pressure (psi)
lignin yield between 250 psiproduct yield during catalytic hydrogenolysis while varying the hydrogen pressure. The
Lignin
and 1000 psi reaction conditions were: Residence time: 4 hours; Temperature: 200 °C; catalyst: 10% (w/w)
of Pt/C; phosphoric acid: 40% (w/w); solvent: H2O (1:1,v/v); feedstock: poplar.
The pressure treatments
were statistically different.
25. Lignin Hydrogenolysis
Feedstock Effect
The effect of feedstock 60
Agave
Poplar
on lignin
Yield (%,w/w)
40 Spruce
Organosolv Lignin
hydrogenolysis 20
Alkali Lignin
The feedstock treatments
were statistically different. 0
in
e
r
e
in
la
v
uc
gn
gn
Poplar generated the highest
ga
op
pr
Li
Li
A
P
S
i
lv
al
so
lk
yield
A
o
an
rg
O
Woods Feedstock
Poplar yield > Spruce yield S/Ga (%) versus Feedstock
S/G ratio 5
Agave
4 Poplar
Spruce contains Guaiacyl
Yield (%,w/w)
Spruce
3
lignin Organosolv lignin
Alkali Lignin
2
Agave 1
S/G ratio ~ 2:1 0
in
in
e
r
ce
la
av
Para-hydroxyphenol unit
n
n
ru
p
lig
ig
g
o
p
A
L
P
S
lv
i
al
so
lk
o
A
an
Isolated lignin O
rg
Feedstock
Organosolv lignin a
S/G: syrignylpropane to guaiacylpropane
Small monomer yield Lignin product yield and monomer selectivity during catalytic hydrogenolysis while varying the
feedstock. The reaction conditions were: Residence time: 4 hours; Temperature: 200 °C;
S/G ratio ~ 4:1 Pressure: 1000 psi; catalyst: 10% (w/w) of Pt/C; phosphoric acid: 40% (w/w); solvent: H 2O
(1:1,v/v).
Alkali lignin
26. Lignin Hydrogenolysis
The effect of noble-metal Catalyst Effect on Poplar
catalyst on lignin 100
Pt/C
80 Pt/G
hydrogenolysis
Yield (%,w/w)
Pd/C
60
Rh/Ca
Poplar 40
Noneb
Catalyst is necessary 20
0
Lowers the activation energy of
Ca
b
C
t/G
t/C
e
d/
on
h/
P
P
P
R
N
reaction Catalyst Type
a
Values greater than theoretical 44%
Allows for homolytic dissociation of b
Same reaction conditions
S/Ga (%) versus Catalyst
H2 molecules
5
Pt/C
The catalyst treatments were not 4 Pt/G
Yield (%,w/w)
Pd/C
statistically different for lignin yield. 3 Rh/C
Rh/C was not included because 2
produced values greater than theoretical 1
yield
0
Outlier
/C
C
/G
/C
h/
Pd
Pt
Pt
R
Catalyst treatments were a
Catalyst Type
S/G: syrignylpropane to guaiacylpropane
statistically significant for S/G ratio.
Lignin product yield and monomer selectivity during catalytic hydrogenolysis while varying the
Pd/C higher S/G ratio catalyst on poplar. The reaction conditions were: Residence time: 4 hours; Temperature: 200
°C; Pressure: 1000 psi; catalyst: 10% (w/w); phosphoric acid: 40% (w/w); solvent: H 2O (1:1,v/v);
Higher selectivity for syringylpropane feedstock: poplar.
27. Lignin Hydrogenolysis
The effect of
noble-metal catalyst Catalyst Effect on Organosolv Lignin
15
on lignin hydrogenolysis Pt/C
Pt/G
Organosolv lignin
Yield (%,w/w)
10 Pd/C
The catalyst treatments Rh/C
were statistically different for
5
lignin yield.
Rh/C produced the highest
yield followed by Pt/G 0
/C
/C
/G
/C
Pd
Rh
Pt
Pt
Tukey’s Multiple comparison Catalyst Type
Lignin product yield during catalytic hydrogenolysis while varying the catalyst on organosolv
test
lignin. The reaction conditions were: Residence time: 4 hours; Temperature: 200 °C; Pressure:
Rh/C statistically different to Pt/C
and Pd/C 1000 psi; catalyst: 10% (w/w); phosphoric acid: 40% (w/w); solvent: H2O (1:1,v/v); feedstock:
Pt/G and Rh/C not statistically poplar.
different.
28. Lignin Hydrogenolysis
The effect of
noble-metal catalyst on
lignin hydrogenolysis
Catalyst loading
Poplar
Linear relationship between
catalyst loading and lignin yield Linear regression of catalalysts loading versus yield of lignin monomers for poplar. The reaction
conditions were: Residence time: 4 hours; temperature: 200 °C; pressure: 1000 psi; catalyst:
Linear regression analysis statistically 10% and 40% (w/w) of Pt/C; phosphoric acid: 40% (w/w); solvent: H2O (1:1,v/v); feedstock:
poplar.
significant
Catalyst loading can predict lignin
monomer yield to a certain accuracy.
R2 = 0.81
10% and 40% are not statistically
different
Organosolv lignin
Linear relationship between Linear regression of catalalysts loading versus yield of lignin monomers for organosolv lignin.
catalyst loading and lignin yield The reaction conditions were: Residence time: 4 hours; temperature: 200 °C; pressure: 1000
psi; catalyst: 10% and 40% (w/w) of Pt/C; phosphoric acid: 40% (w/w); solvent: H 2O (1:1,v/v);
feedstock: organosolv lignin.
Linear regression analysis statistically
significant
29. Lignin Hydrogenolysis
The effect of addition mineral acid
on lignin hydrogenolysis
Many reactions combine heterogeneous Phosphoric Acid Effect
catalysis with acid-catalyzed conditions 50
to assist in the hydrogenolysis reaction No Phosphoric Acid
(Yan et al., 2008) 40 Yes Phosphoric Acid
Yield (% ,w/w)
Poplar
30
The acid treatments were
statistically different for lignin yield. 20
Presence of phosphoric acid 10
increased monomer yield
Assisted in the removal of 0
a
recalcitrance of lignocellulose
r
pla
OL
Po
Organosolv lignin Feedstock
The acid treatments were a
Organosolv Lignin
statistically different for lignin yield. Lignin product yield during catalytic hydrogenolysis with/without mineral acid on poplar and
organosolv lignin. The reaction conditions were: Residence time: 4 hours; Temperature: 200 °C;
Presence of phosphoric acid Pressure: 1000 psi; catalyst: 10% (w/w); solvent: H2O (1:1,v/v); feedstock: poplar, organosolv
lignin..
decreased monomer yield slightly.
Condensation reactions
Lignin condensation reactions under
acidic conditions
30. Lignin Hydrogenolysis
The effect of solvent on lignin Solvent effect on Poplar
60
hydrogenolysis Water/Ethanol (1:1,v/v)
Ethanol
Yield (%,w/w)
40 Water/Dioxane (1:1,v/v)
Poplar Dioxane
Water
20
The solvent treatments were
0
statistically different for lignin
ne
ol
er
v)
)
/v
an
v/
at
xa
,v
1,
W
:1
th
io
1:
(1
E
D
l(
yield.
e
o
n
an
xa
th
io
/E
/D
er
er
at
at
W
W
Water as a solvent did not Solvent
produce guaiacylpropane and a
Values greater than theoretical value
Lignin product yield during catalytic hydrogenolysis while varying solvent on poplar. The
syringylpropane. reaction conditions were: Residence time: 4 hours; Temperature: 200 °C; Pressure: 1000 psi;
catalyst: 10% (w/w) Pt/C; phosphoric acid: 40% (w/w);); feedstock: poplar.
Water/ethanol (1:1, v/v) highest
Solvent effect on Organosolv lignin
yield 8
Ethanol
Dioxane solvent produced the 6
Dioxane
Yield (%,w/w)
W ater
lowest yield. 4
W ater/Dioxane (1:1, v/v)
2
Organosolv lignin 0
The solvent treatments were not
ne
ol
er
)
/v
an
at
xa
,v
W
th
io
:1
E
D
(1
e
n
statistically different for lignin
xa
io
/D
er
at
W
yield. Solvent
Lignin product yield during catalytic hydrogenolysis while varying solvent on organosolv lignin.
Water as a solvent did not
The reaction conditions were: Residence time: 4 hours; Temperature: 200 °C; Pressure: 1000
psi; catalyst: 10% (w/w) Pt/C; phosphoric acid: 40% (w/w);); feedstock: organosolv lignin.
31. Polysaccharides Hydrogenolysis
Polysaccharides are degraded and converted
concurrently with the depolymerization of lignin
during hydrogenolysis
Polysaccharides are converted into
polysaccharide monomers, polysaccharide
derived chemicals and insoluble liquid (solid
residue)
Homolytic dissociation of H2 (g) into H atoms by
noble metal catalysts
Influences hydrolysis
Spill-over effect
Cleavage of carbon-carbon and carbon-oxygen
bonds in cellulose
Hydrogenation
Phosphoric acid
Hydrolysis
(Dhepe and Fukuoka, 2007)
32. Polysaccharides Hydrogenolysis
Changes of polysaccharides during
hydrogenolysis
Liquid soluble products
Polysaccharide monomers and
polysaccharide derived chemicals (PDCs)
Liquid insoluble products
Solid residue
For avicel cellulose, 34% conversion
of initial cellulose into polysaccharides
and polysaccharides derived
chemicals
~6% polysaccharide monomers
identified from original polysaccharides
For poplar, 64% conversion of
feedstock.
~8% polysaccharide monomers Mass balance of cellulose hydrogenolysis. The reaction conditions were:
Residence time: 4 hours; temperature: 200 °C; Pressure: 1000 psi; catalyst: 10% (w/w) of
identified from original polysaccharides Pt/C; phosphoric acid: 40% (w/w); solvent: H2O (1:1,v/v); feedstock: cellulose.
a
theoretical weight of un-identifiable saccharides-derived chemicals.
Reaction conditions produced
statistically significant conversion
percentages of polysaccharides
90-100% conversion of initial
polysaccharides into PDCs and solid
33. Polysaccharides Hydrogenolysis
Trace amounts of
dehydration chemicals
from glucose were
detected
Glucose converted to HMF,
furfural, levulinic acid, formic
acid, acetic acid under
hydrothermal conditions in
the presence of acidic (Liu et al., 2011)
conditions.
Cellulose converted into
polyols such as sorbitol
through hydrogenation
using supported metal
catalysts
Previous experiments (Shrotri et al., Conversion products from catalytic hydrogenolysis of cellulose. (1) glucose, (2)
2012) sorbitol, (3) sorbitan, (4) isosoribde, (5) xylose, (6) erythritol, (7) glycerol, (8) 1,2-
(or1,3)propanediol (9) ethanediol, (10) methanol. (Palkovits et al., 2010).
Chemicals detected by
34. Summary
Thermochemical conversion is capable of converting all
three biopolymers in biomass into fuels and chemical
precursors simultaneously.
Biochemical conversion inefficiently utilizes lignin
Lignin derived chemicals and polysaccharide derived
chemicals were fractionated with non-polar solvents.
Lignin is selectively depolymerized into monomeric
subunits for chemical precursors through catalytic
hydrogenolysis
Syringylpropane
Guaiacylpropane
Reaction conditions affect the monolignol yield.
Polysaccharides were degraded through hydrogenolysis
Polysaccharide monomers
Polysaccharide derived chemicals
No dehydration chemicals
Possible polyols production
Reaction conditions affect the degradation of polysaccharides
35. Future Research
Further investigation of polysaccharide derived
chemicals (PDCs) produced through hydrogenolysis
Accurate mass balance
No assumption necessary
Energy balance for viability of process
Design of Experiment (DOE) methodology
Use factorial experimental designs
Determine interaction effects
Investigation into other catalysts
Increase the selectivity
Decrease the activation energy
36. Acknowledgments
Dr. Xuejun Pan
I am honored to have Dr. Pan as my mentor
He has given me a great deal of academic support in
addition to assistance in my research study.
Dr. Pan’s Research Group
There support and knowledge were vital in my research
studies.
Dr. Ralph’s Research Group
I need to thank Dr. John Ralph for allowing me to use his
laboratory equipment.
Special thanks to Dr. Fachuang Lu for assistance in gas
chromatography and mass spectrometry.
Thesis committee
I need to thank Dr. Troy Runge and Dr. Fachuang Lu for
accepting my invitation to be on my thesis committee
In addition to helping finalize my thesis.
Biological Systems Engineering
For the departments support during my undergraduate and
graduate studies.