mechanocatalytic approaches to biomass conversion
TRANSCRIPT
Mechanocatalytic Approaches to
Biomass Conversion Carsten Sievers
March 10 2015 Atlanta GA
Sievers Research Group
Email carstensieverschbegatechedu Phone 404-385-7685 Fax 404-894-2866
Catalytic Routes for Sustainable Production of Fuels and Chemicals
Synthesis Process Development
Surface Reactions
Characteri-zation
Tailored active sites
Water-tolerant solid
acid
Multi-functional catalysts
Acidity Basicity
Metal particles
Porosity
Crystallinity
In-situ spectroscopy
Inter-mediates
Reaction pathways
Catalytic reactions
Reactor design
Deactivation
RM Ravenelle et al J Phys Chem C 114 (2010) 19582 RM Ravenelle et al ACS Catal 1 (2011) 552 RM Ravenelle et al Top Catal 55 (2012) 162 RM Ravenelle et al ChemCatChem 4 (2012) 492
Stability of Solid Catalysts in Hot Water Objectives Understanding the pathways of catalyst deactivation in
hot liquid water Elucidating the influence of biomass-derived
feedstocks on the stability of solid catalysts Improving the hydrothermal stability of solid catalysts
using protective coatings and additives Approaches Kinetic studies on transformations of solid catalysts in
hot water and solutions of oxygenates Physicochemical characterization (N2 physisorption
XRD TEM SEM IR NMR XPS titration) Development of synthesis techniques for improving
hydrothermal stability Performance studies with stabilized catalysts
2θ deg
ppm
ppm
t h
t h
PtAl3+ + H2O harr H+
O
H+ +H2
Cl
H
OH
Al
AL Jongerius et al ACS Catalysis 3 (2013) 464 MW Hahn et al ChemSusChem 6 (2013) 2304 AH Van Pelt et al Carbon 77 (2014) 143
JR Copeland et al Langmuir 29 (2013) 581 JR Copeland et al Catal Today 205 (2013) 49
H1
C1
O3
H2
H3 H4
H5
H6
H7
H8
C2 C3
O1
O2
O4
Al1 Al2
Surface Chemistry of Oxygenates in Water Objectives Understanding surface interactions of biomass-derived
oxygenates in aqueous media Identification of intermediates and reaction pathways
for reactions such as aqueous phase reforming and hydrodeoxygenation (HDO)
Quantification of rates of individual reaction steps Identification of active sites for specific reaction paths Characterization of solvent effects Approaches IR spectroscopy (in vacuum vapor phase (asymp1 atm)
and liquid phase) NMR spectroscopy Liquid phase adsorption isotherms Inelastic neutron scattering Raman spectroscopy DFT calculations (in collaboration with David Sholl)
Glycerol on γ-Al2O3
ATR IR setup for in-situ studies in liquid phase under flow conditions Feed
InletEffluent
N2 Inlet
IR InletIR Outlet
TC
Heating Element
Gasket
Window
IRE
JR Copeland et al J Phys Chem C 117 (2013) 21413 Foo et al ACS Catalysis 4 (2014) 3180
Continuous Conversion Biomass Objectives Development of stable solid catalysts Reactivity studies with model compounds and real
feedstocks Identification of structure property relationships to
improve selectivity Quantitative description of intrinsic kinetics and
transport limitations Development of suitable regeneration procedures for
spent catalysts Approaches Synthesis and post-synthesis treatments of of solid
catalysts Physicochemical characterization (N2 physisorption
XRD SEM IR NMR XPS Boehm titration) Reactivity studies using a flow reactor setup with
automated sample collection
+ H2O
Foo et al ChemSusChem 8 (2015) 534 AH Van Pelt et al Carbon 77 (2014) 143
Sulfur-Free HDO Catalysts Objectives Development of ceria-zirconia based catalysts for
hydrodeoxygenation of oxygenates in pyrolysis oils These catalysts will not contain noble metals and will not require H2S to be co-fed
Optimization of the composition and morphology of the catalysts
Analysis of reaction kinetics Identification of structure-property relationships Approaches Synthesis mixed-metal oxide catalysts with different
compositions and morphologies Physicochemical characterization (TPR isotopic
scrambling of H2D2 N2 physisorption XRD TEM SEM IR NMR XPS titration)
In-situ spectroscopic studies Reactivity studies using a continuously operated
trickle bed reactor
OH
CexZryOz
H2
HO
H2
H H H
OH H
H2 O
H H H
H H
H H
CexZryOz
CexZryOzCexZryOz
Mechanocatalytic Reactions
Reactants catalysts and milling balls are mixed
No solvents are used during the milling
Separation of products can become more efficient
Q Zhang and F Jerome ChemSusChem 6 (2013) 2042
Shaker Mill
Catalytic Sites in Ball Milling
The rate of CO oxidation over a Cr2O3 catalysts increased dramatically when the shaker mill is running
The effect is completely reversibly and repeatable
Milling creates short lived but highly active catalytic sites
S Immohr M Felderhoff C Weidenthaler F Schuumlth Angew Chem Int Ed 52 (2013) 12688
CO + 12O2 CO2 over Cr2O3
Shaker Mill
Plug Flow Reactor
Shaker Mill
Composition of Biomass
H C C H
O H C [ C H 2 O H ]
H 3 C O O C H
C H 2 O H
C H O H
O C H C H 2 O H
H C O
O C H 3 H 2 C O C H
H 3 C O O C H
C H 2 O H
C H O H
H 3 C O O H O H
O C H 3
C
[ O C ]
O H C O
C H 2 O H H 3 C O
C H O H H C
C H 2 O H O
H 3 C O O
C H O H C H
H 3 C O
H O C H 2 O H
O C H 3
H C O C H 2
C H H C H 2 C C H
O
O C H 3 O H
O C H H O H 2 C C
O
H H 3 C O
C H O H H C O
C H 2 O H
H 3 C O O C H 3
C H O H H C
C H 2 O H O
O C H 3
C H O H C H
O H
C H O H 3 C O H C O
C H 2 O H
C H 2
C H 2
C H 3
C H 2 O H
O
O O
O O
O O
O O H O
H O H 2 C
O H
H O H 2 C H O
H O
O H
O H
H O
H O H 2 C H O H 2 C
O H
O
O O
O O
O O
H O H 2 C
O H H O
O O R O
R O
O H
R O O R
O H
O R
H O
H O H 2 C
H O H 2 C
O H 2 C
O
O R O H
H O H 2 C
Cellulose
Hemicellulose
Lignin
Hydrolysis of Carbohydrates
O H
OH
H
H
OH H
H
OH
O O
OH
H
H
OH OH H
H
OH
O
HO
H
OH
H
H
OH OH H
H
O H
H2O
[H+]
OH
H
O
HO
H
OH
H
H
OH OH H
H
O H
Carbohydrates can be depolymerized by addition of water to the glycosidic bond
Hydrolysis of carbohydrates is catalyzed by acids or enzymes
Solid acid can be used to depolymerize cellulose in a ball mill Grinding provides intimate contact between reactant and catalytically active sites Water-soluble compounds are obtained as main products Dealuminated kaolinite is an efficient catalyst
SM Hick C Griebel DT Restrepo JH Truitt EJ Buker C Bylda RG Blair Green Chem 12 (2010) 468 Blair R G Hick S M Truitt J H US patent 8062428 (2011)
Mechanocatalytic Conversion of Cellulose
Very high yields of water-soluble products can be obtained when cellulose is impregnated with mineral acid before ball milling
Oligosaccharides are the main products Formation of branched oligosaccharides indicates re-polymerization Monosaccharides can be obtained by hydrolysis under mild conditions
N Meine R Rinaldi and F Schuumlth ChemSusChem 5 (2012) 1449-1454 J Hilgert N Meine R Rinaldi and F Schuumlth Energy Environ Sci 6 (2013) 92-96
Mechanocatalytic Conversion of Cellulose ESI-MS spectrum of water-soluble products from cellulose
Lignin Structure
J Zakzeski PCA Bruijnincx AL Jongerius BM Weckhuysen Chem Rev 110 (2010) 3552
Conversion of Lignin
J Zakzeski PCA Bruijnincx AL Jongerius BM Weckhuysen Chem Rev 110 (2010) 3552
Lignin can be cracked over solid acid catalysts at 350 to 400 degC Initial conversion of non-volatiles to volatiles Volatiles can be further converted to light gases
and chars Moderate yields of valuable aromatics
Strong bases catalyze hydrolysis of ether linkages Significant amounts of basic waste are formed
Few processes for the conversion of lignin are economically viable
Possible Products from Lignin
Benzene toluene xylene (BTX) are used in many processes in the chemical industry For example terephthalic acid is produced from p-xylene
Propyl benzene has an octane rating of 125-130 and could be used to improve the quality of gasoline
Mechanocatalytic Conversion of Lignin
Base assisted ball milling facilitates cleavage of β-O-4 linkages in lignin Depolymerization of carbohydrates is observed in parallel Currently the amounts of base (NaOH) required are too large for an
attractive process
T Kleine J Buendia C Bolm Green Chem 15 (2013) 160
Natural clays are generally cheap Certain natural clays are solid acids and bases
Thermal treatments can enhance acid-base
properties Ion exchange of clays can add Lewis acid and
base sites Addition of reduced metal particles (eg Ni Cu)
can facilitate reaction involving hydrogen
Clay Based Catalysts
Adsorption of Probe Molecules Objectives Quantification of the concentration
of acid and base sites on solids Characterization of strength of
sites Approaches Adsorption of probe molecules
(eg pyridine CO2) on solid acid and bases just before the ball mill is turned of Analysis by IR spectroscopy Analysis of desorption
temperatures to obtain a strength distribution JR Copeland IA Santillan SM Schimming JL Ewbank C Sievers J Phys Chem C 117 (2013) 21413
MW Hahn JR Copeland AH Van Pelt C Sievers ChemSusChem 6 (2013) 2304 Y Kuwahara D-Y Kang JR Copeland NA Brunelli SA Didas P Bollini C Sievers T Kamegawa H Yamashita CW Jones J Am Chem Soc 134 (2012) 10757
1560 1540 1520 1500 1480 1460 1440 1420
1540
1450
Abso
rban
ce
au
Wavenumber cm-1
Broslashnsted acid sites
Lewis acid sites
IR band at 1450 cm-1
IR band at 1540 cm-1
Mechanocatalytic Hydrotreating
Metal sites can dissociate molecular hydrogen to atomic hydrogen
Atomic hydrogen can spillover to other sites
WC Conner JL Falconer Chem Rev 95 (1995) 759
Mechanocatalytic Hydrotreating
Atomic hydrogen can quench dangling bonds and prevent radical reactions like graphitization
Removal of oxygen containing functional groups
is facilitated when bonds angles are distorted
O
HO
OH O
HO
OH OH
HO
OH+ 2 H
OH+ 2 HOH
+ H2OShear force
Continuous Removal of Products
Small and deoxygenated lignin fragments are volatile and can be removed as vapors
Hydrogen can be separated from the products using a condenser or membrane
Ball mill Condenser
Liquid products
H2 recycle H2 feed
Lignin feed
Messages From This Presentation bull Possible applications of the insights
techniquesfindingsopportunities in this presentation ndash Conversion of lignin into chemicals and fuel additives ndash Utilization of other solid carbon-based feedstocks
bull Barriers and challenges to success ndash Lack of understanding of mechanocatalytic reactions ndash Energy efficiency of milling processes
bull Additional research opportunities ndash Processes for mechanocatalytic hydrotreating and other
approaches to biomass conversion ndash Improving mechanocatalytic processes based on
understanding their fundamentals
- Mechanocatalytic Approaches to Biomass Conversion
- Sievers Research Group
- Slide Number 3
- Slide Number 4
- Continuous Conversion Biomass
- Sulfur-Free HDO Catalysts
- Mechanocatalytic Reactions
- Catalytic Sites in Ball Milling
- Slide Number 9
- Slide Number 10
- Mechanocatalytic Conversion of Cellulose
- Mechanocatalytic Conversion of Cellulose
- Lignin Structure
- Conversion of Lignin
- Possible Products from Lignin
- Mechanocatalytic Conversion of Lignin
- Clay Based Catalysts
- Adsorption of Probe Molecules
- Mechanocatalytic Hydrotreating
- Mechanocatalytic Hydrotreating
- Continuous Removal of Products
- Slide Number 22
-
Sievers Research Group
Email carstensieverschbegatechedu Phone 404-385-7685 Fax 404-894-2866
Catalytic Routes for Sustainable Production of Fuels and Chemicals
Synthesis Process Development
Surface Reactions
Characteri-zation
Tailored active sites
Water-tolerant solid
acid
Multi-functional catalysts
Acidity Basicity
Metal particles
Porosity
Crystallinity
In-situ spectroscopy
Inter-mediates
Reaction pathways
Catalytic reactions
Reactor design
Deactivation
RM Ravenelle et al J Phys Chem C 114 (2010) 19582 RM Ravenelle et al ACS Catal 1 (2011) 552 RM Ravenelle et al Top Catal 55 (2012) 162 RM Ravenelle et al ChemCatChem 4 (2012) 492
Stability of Solid Catalysts in Hot Water Objectives Understanding the pathways of catalyst deactivation in
hot liquid water Elucidating the influence of biomass-derived
feedstocks on the stability of solid catalysts Improving the hydrothermal stability of solid catalysts
using protective coatings and additives Approaches Kinetic studies on transformations of solid catalysts in
hot water and solutions of oxygenates Physicochemical characterization (N2 physisorption
XRD TEM SEM IR NMR XPS titration) Development of synthesis techniques for improving
hydrothermal stability Performance studies with stabilized catalysts
2θ deg
ppm
ppm
t h
t h
PtAl3+ + H2O harr H+
O
H+ +H2
Cl
H
OH
Al
AL Jongerius et al ACS Catalysis 3 (2013) 464 MW Hahn et al ChemSusChem 6 (2013) 2304 AH Van Pelt et al Carbon 77 (2014) 143
JR Copeland et al Langmuir 29 (2013) 581 JR Copeland et al Catal Today 205 (2013) 49
H1
C1
O3
H2
H3 H4
H5
H6
H7
H8
C2 C3
O1
O2
O4
Al1 Al2
Surface Chemistry of Oxygenates in Water Objectives Understanding surface interactions of biomass-derived
oxygenates in aqueous media Identification of intermediates and reaction pathways
for reactions such as aqueous phase reforming and hydrodeoxygenation (HDO)
Quantification of rates of individual reaction steps Identification of active sites for specific reaction paths Characterization of solvent effects Approaches IR spectroscopy (in vacuum vapor phase (asymp1 atm)
and liquid phase) NMR spectroscopy Liquid phase adsorption isotherms Inelastic neutron scattering Raman spectroscopy DFT calculations (in collaboration with David Sholl)
Glycerol on γ-Al2O3
ATR IR setup for in-situ studies in liquid phase under flow conditions Feed
InletEffluent
N2 Inlet
IR InletIR Outlet
TC
Heating Element
Gasket
Window
IRE
JR Copeland et al J Phys Chem C 117 (2013) 21413 Foo et al ACS Catalysis 4 (2014) 3180
Continuous Conversion Biomass Objectives Development of stable solid catalysts Reactivity studies with model compounds and real
feedstocks Identification of structure property relationships to
improve selectivity Quantitative description of intrinsic kinetics and
transport limitations Development of suitable regeneration procedures for
spent catalysts Approaches Synthesis and post-synthesis treatments of of solid
catalysts Physicochemical characterization (N2 physisorption
XRD SEM IR NMR XPS Boehm titration) Reactivity studies using a flow reactor setup with
automated sample collection
+ H2O
Foo et al ChemSusChem 8 (2015) 534 AH Van Pelt et al Carbon 77 (2014) 143
Sulfur-Free HDO Catalysts Objectives Development of ceria-zirconia based catalysts for
hydrodeoxygenation of oxygenates in pyrolysis oils These catalysts will not contain noble metals and will not require H2S to be co-fed
Optimization of the composition and morphology of the catalysts
Analysis of reaction kinetics Identification of structure-property relationships Approaches Synthesis mixed-metal oxide catalysts with different
compositions and morphologies Physicochemical characterization (TPR isotopic
scrambling of H2D2 N2 physisorption XRD TEM SEM IR NMR XPS titration)
In-situ spectroscopic studies Reactivity studies using a continuously operated
trickle bed reactor
OH
CexZryOz
H2
HO
H2
H H H
OH H
H2 O
H H H
H H
H H
CexZryOz
CexZryOzCexZryOz
Mechanocatalytic Reactions
Reactants catalysts and milling balls are mixed
No solvents are used during the milling
Separation of products can become more efficient
Q Zhang and F Jerome ChemSusChem 6 (2013) 2042
Shaker Mill
Catalytic Sites in Ball Milling
The rate of CO oxidation over a Cr2O3 catalysts increased dramatically when the shaker mill is running
The effect is completely reversibly and repeatable
Milling creates short lived but highly active catalytic sites
S Immohr M Felderhoff C Weidenthaler F Schuumlth Angew Chem Int Ed 52 (2013) 12688
CO + 12O2 CO2 over Cr2O3
Shaker Mill
Plug Flow Reactor
Shaker Mill
Composition of Biomass
H C C H
O H C [ C H 2 O H ]
H 3 C O O C H
C H 2 O H
C H O H
O C H C H 2 O H
H C O
O C H 3 H 2 C O C H
H 3 C O O C H
C H 2 O H
C H O H
H 3 C O O H O H
O C H 3
C
[ O C ]
O H C O
C H 2 O H H 3 C O
C H O H H C
C H 2 O H O
H 3 C O O
C H O H C H
H 3 C O
H O C H 2 O H
O C H 3
H C O C H 2
C H H C H 2 C C H
O
O C H 3 O H
O C H H O H 2 C C
O
H H 3 C O
C H O H H C O
C H 2 O H
H 3 C O O C H 3
C H O H H C
C H 2 O H O
O C H 3
C H O H C H
O H
C H O H 3 C O H C O
C H 2 O H
C H 2
C H 2
C H 3
C H 2 O H
O
O O
O O
O O
O O H O
H O H 2 C
O H
H O H 2 C H O
H O
O H
O H
H O
H O H 2 C H O H 2 C
O H
O
O O
O O
O O
H O H 2 C
O H H O
O O R O
R O
O H
R O O R
O H
O R
H O
H O H 2 C
H O H 2 C
O H 2 C
O
O R O H
H O H 2 C
Cellulose
Hemicellulose
Lignin
Hydrolysis of Carbohydrates
O H
OH
H
H
OH H
H
OH
O O
OH
H
H
OH OH H
H
OH
O
HO
H
OH
H
H
OH OH H
H
O H
H2O
[H+]
OH
H
O
HO
H
OH
H
H
OH OH H
H
O H
Carbohydrates can be depolymerized by addition of water to the glycosidic bond
Hydrolysis of carbohydrates is catalyzed by acids or enzymes
Solid acid can be used to depolymerize cellulose in a ball mill Grinding provides intimate contact between reactant and catalytically active sites Water-soluble compounds are obtained as main products Dealuminated kaolinite is an efficient catalyst
SM Hick C Griebel DT Restrepo JH Truitt EJ Buker C Bylda RG Blair Green Chem 12 (2010) 468 Blair R G Hick S M Truitt J H US patent 8062428 (2011)
Mechanocatalytic Conversion of Cellulose
Very high yields of water-soluble products can be obtained when cellulose is impregnated with mineral acid before ball milling
Oligosaccharides are the main products Formation of branched oligosaccharides indicates re-polymerization Monosaccharides can be obtained by hydrolysis under mild conditions
N Meine R Rinaldi and F Schuumlth ChemSusChem 5 (2012) 1449-1454 J Hilgert N Meine R Rinaldi and F Schuumlth Energy Environ Sci 6 (2013) 92-96
Mechanocatalytic Conversion of Cellulose ESI-MS spectrum of water-soluble products from cellulose
Lignin Structure
J Zakzeski PCA Bruijnincx AL Jongerius BM Weckhuysen Chem Rev 110 (2010) 3552
Conversion of Lignin
J Zakzeski PCA Bruijnincx AL Jongerius BM Weckhuysen Chem Rev 110 (2010) 3552
Lignin can be cracked over solid acid catalysts at 350 to 400 degC Initial conversion of non-volatiles to volatiles Volatiles can be further converted to light gases
and chars Moderate yields of valuable aromatics
Strong bases catalyze hydrolysis of ether linkages Significant amounts of basic waste are formed
Few processes for the conversion of lignin are economically viable
Possible Products from Lignin
Benzene toluene xylene (BTX) are used in many processes in the chemical industry For example terephthalic acid is produced from p-xylene
Propyl benzene has an octane rating of 125-130 and could be used to improve the quality of gasoline
Mechanocatalytic Conversion of Lignin
Base assisted ball milling facilitates cleavage of β-O-4 linkages in lignin Depolymerization of carbohydrates is observed in parallel Currently the amounts of base (NaOH) required are too large for an
attractive process
T Kleine J Buendia C Bolm Green Chem 15 (2013) 160
Natural clays are generally cheap Certain natural clays are solid acids and bases
Thermal treatments can enhance acid-base
properties Ion exchange of clays can add Lewis acid and
base sites Addition of reduced metal particles (eg Ni Cu)
can facilitate reaction involving hydrogen
Clay Based Catalysts
Adsorption of Probe Molecules Objectives Quantification of the concentration
of acid and base sites on solids Characterization of strength of
sites Approaches Adsorption of probe molecules
(eg pyridine CO2) on solid acid and bases just before the ball mill is turned of Analysis by IR spectroscopy Analysis of desorption
temperatures to obtain a strength distribution JR Copeland IA Santillan SM Schimming JL Ewbank C Sievers J Phys Chem C 117 (2013) 21413
MW Hahn JR Copeland AH Van Pelt C Sievers ChemSusChem 6 (2013) 2304 Y Kuwahara D-Y Kang JR Copeland NA Brunelli SA Didas P Bollini C Sievers T Kamegawa H Yamashita CW Jones J Am Chem Soc 134 (2012) 10757
1560 1540 1520 1500 1480 1460 1440 1420
1540
1450
Abso
rban
ce
au
Wavenumber cm-1
Broslashnsted acid sites
Lewis acid sites
IR band at 1450 cm-1
IR band at 1540 cm-1
Mechanocatalytic Hydrotreating
Metal sites can dissociate molecular hydrogen to atomic hydrogen
Atomic hydrogen can spillover to other sites
WC Conner JL Falconer Chem Rev 95 (1995) 759
Mechanocatalytic Hydrotreating
Atomic hydrogen can quench dangling bonds and prevent radical reactions like graphitization
Removal of oxygen containing functional groups
is facilitated when bonds angles are distorted
O
HO
OH O
HO
OH OH
HO
OH+ 2 H
OH+ 2 HOH
+ H2OShear force
Continuous Removal of Products
Small and deoxygenated lignin fragments are volatile and can be removed as vapors
Hydrogen can be separated from the products using a condenser or membrane
Ball mill Condenser
Liquid products
H2 recycle H2 feed
Lignin feed
Messages From This Presentation bull Possible applications of the insights
techniquesfindingsopportunities in this presentation ndash Conversion of lignin into chemicals and fuel additives ndash Utilization of other solid carbon-based feedstocks
bull Barriers and challenges to success ndash Lack of understanding of mechanocatalytic reactions ndash Energy efficiency of milling processes
bull Additional research opportunities ndash Processes for mechanocatalytic hydrotreating and other
approaches to biomass conversion ndash Improving mechanocatalytic processes based on
understanding their fundamentals
- Mechanocatalytic Approaches to Biomass Conversion
- Sievers Research Group
- Slide Number 3
- Slide Number 4
- Continuous Conversion Biomass
- Sulfur-Free HDO Catalysts
- Mechanocatalytic Reactions
- Catalytic Sites in Ball Milling
- Slide Number 9
- Slide Number 10
- Mechanocatalytic Conversion of Cellulose
- Mechanocatalytic Conversion of Cellulose
- Lignin Structure
- Conversion of Lignin
- Possible Products from Lignin
- Mechanocatalytic Conversion of Lignin
- Clay Based Catalysts
- Adsorption of Probe Molecules
- Mechanocatalytic Hydrotreating
- Mechanocatalytic Hydrotreating
- Continuous Removal of Products
- Slide Number 22
-
RM Ravenelle et al J Phys Chem C 114 (2010) 19582 RM Ravenelle et al ACS Catal 1 (2011) 552 RM Ravenelle et al Top Catal 55 (2012) 162 RM Ravenelle et al ChemCatChem 4 (2012) 492
Stability of Solid Catalysts in Hot Water Objectives Understanding the pathways of catalyst deactivation in
hot liquid water Elucidating the influence of biomass-derived
feedstocks on the stability of solid catalysts Improving the hydrothermal stability of solid catalysts
using protective coatings and additives Approaches Kinetic studies on transformations of solid catalysts in
hot water and solutions of oxygenates Physicochemical characterization (N2 physisorption
XRD TEM SEM IR NMR XPS titration) Development of synthesis techniques for improving
hydrothermal stability Performance studies with stabilized catalysts
2θ deg
ppm
ppm
t h
t h
PtAl3+ + H2O harr H+
O
H+ +H2
Cl
H
OH
Al
AL Jongerius et al ACS Catalysis 3 (2013) 464 MW Hahn et al ChemSusChem 6 (2013) 2304 AH Van Pelt et al Carbon 77 (2014) 143
JR Copeland et al Langmuir 29 (2013) 581 JR Copeland et al Catal Today 205 (2013) 49
H1
C1
O3
H2
H3 H4
H5
H6
H7
H8
C2 C3
O1
O2
O4
Al1 Al2
Surface Chemistry of Oxygenates in Water Objectives Understanding surface interactions of biomass-derived
oxygenates in aqueous media Identification of intermediates and reaction pathways
for reactions such as aqueous phase reforming and hydrodeoxygenation (HDO)
Quantification of rates of individual reaction steps Identification of active sites for specific reaction paths Characterization of solvent effects Approaches IR spectroscopy (in vacuum vapor phase (asymp1 atm)
and liquid phase) NMR spectroscopy Liquid phase adsorption isotherms Inelastic neutron scattering Raman spectroscopy DFT calculations (in collaboration with David Sholl)
Glycerol on γ-Al2O3
ATR IR setup for in-situ studies in liquid phase under flow conditions Feed
InletEffluent
N2 Inlet
IR InletIR Outlet
TC
Heating Element
Gasket
Window
IRE
JR Copeland et al J Phys Chem C 117 (2013) 21413 Foo et al ACS Catalysis 4 (2014) 3180
Continuous Conversion Biomass Objectives Development of stable solid catalysts Reactivity studies with model compounds and real
feedstocks Identification of structure property relationships to
improve selectivity Quantitative description of intrinsic kinetics and
transport limitations Development of suitable regeneration procedures for
spent catalysts Approaches Synthesis and post-synthesis treatments of of solid
catalysts Physicochemical characterization (N2 physisorption
XRD SEM IR NMR XPS Boehm titration) Reactivity studies using a flow reactor setup with
automated sample collection
+ H2O
Foo et al ChemSusChem 8 (2015) 534 AH Van Pelt et al Carbon 77 (2014) 143
Sulfur-Free HDO Catalysts Objectives Development of ceria-zirconia based catalysts for
hydrodeoxygenation of oxygenates in pyrolysis oils These catalysts will not contain noble metals and will not require H2S to be co-fed
Optimization of the composition and morphology of the catalysts
Analysis of reaction kinetics Identification of structure-property relationships Approaches Synthesis mixed-metal oxide catalysts with different
compositions and morphologies Physicochemical characterization (TPR isotopic
scrambling of H2D2 N2 physisorption XRD TEM SEM IR NMR XPS titration)
In-situ spectroscopic studies Reactivity studies using a continuously operated
trickle bed reactor
OH
CexZryOz
H2
HO
H2
H H H
OH H
H2 O
H H H
H H
H H
CexZryOz
CexZryOzCexZryOz
Mechanocatalytic Reactions
Reactants catalysts and milling balls are mixed
No solvents are used during the milling
Separation of products can become more efficient
Q Zhang and F Jerome ChemSusChem 6 (2013) 2042
Shaker Mill
Catalytic Sites in Ball Milling
The rate of CO oxidation over a Cr2O3 catalysts increased dramatically when the shaker mill is running
The effect is completely reversibly and repeatable
Milling creates short lived but highly active catalytic sites
S Immohr M Felderhoff C Weidenthaler F Schuumlth Angew Chem Int Ed 52 (2013) 12688
CO + 12O2 CO2 over Cr2O3
Shaker Mill
Plug Flow Reactor
Shaker Mill
Composition of Biomass
H C C H
O H C [ C H 2 O H ]
H 3 C O O C H
C H 2 O H
C H O H
O C H C H 2 O H
H C O
O C H 3 H 2 C O C H
H 3 C O O C H
C H 2 O H
C H O H
H 3 C O O H O H
O C H 3
C
[ O C ]
O H C O
C H 2 O H H 3 C O
C H O H H C
C H 2 O H O
H 3 C O O
C H O H C H
H 3 C O
H O C H 2 O H
O C H 3
H C O C H 2
C H H C H 2 C C H
O
O C H 3 O H
O C H H O H 2 C C
O
H H 3 C O
C H O H H C O
C H 2 O H
H 3 C O O C H 3
C H O H H C
C H 2 O H O
O C H 3
C H O H C H
O H
C H O H 3 C O H C O
C H 2 O H
C H 2
C H 2
C H 3
C H 2 O H
O
O O
O O
O O
O O H O
H O H 2 C
O H
H O H 2 C H O
H O
O H
O H
H O
H O H 2 C H O H 2 C
O H
O
O O
O O
O O
H O H 2 C
O H H O
O O R O
R O
O H
R O O R
O H
O R
H O
H O H 2 C
H O H 2 C
O H 2 C
O
O R O H
H O H 2 C
Cellulose
Hemicellulose
Lignin
Hydrolysis of Carbohydrates
O H
OH
H
H
OH H
H
OH
O O
OH
H
H
OH OH H
H
OH
O
HO
H
OH
H
H
OH OH H
H
O H
H2O
[H+]
OH
H
O
HO
H
OH
H
H
OH OH H
H
O H
Carbohydrates can be depolymerized by addition of water to the glycosidic bond
Hydrolysis of carbohydrates is catalyzed by acids or enzymes
Solid acid can be used to depolymerize cellulose in a ball mill Grinding provides intimate contact between reactant and catalytically active sites Water-soluble compounds are obtained as main products Dealuminated kaolinite is an efficient catalyst
SM Hick C Griebel DT Restrepo JH Truitt EJ Buker C Bylda RG Blair Green Chem 12 (2010) 468 Blair R G Hick S M Truitt J H US patent 8062428 (2011)
Mechanocatalytic Conversion of Cellulose
Very high yields of water-soluble products can be obtained when cellulose is impregnated with mineral acid before ball milling
Oligosaccharides are the main products Formation of branched oligosaccharides indicates re-polymerization Monosaccharides can be obtained by hydrolysis under mild conditions
N Meine R Rinaldi and F Schuumlth ChemSusChem 5 (2012) 1449-1454 J Hilgert N Meine R Rinaldi and F Schuumlth Energy Environ Sci 6 (2013) 92-96
Mechanocatalytic Conversion of Cellulose ESI-MS spectrum of water-soluble products from cellulose
Lignin Structure
J Zakzeski PCA Bruijnincx AL Jongerius BM Weckhuysen Chem Rev 110 (2010) 3552
Conversion of Lignin
J Zakzeski PCA Bruijnincx AL Jongerius BM Weckhuysen Chem Rev 110 (2010) 3552
Lignin can be cracked over solid acid catalysts at 350 to 400 degC Initial conversion of non-volatiles to volatiles Volatiles can be further converted to light gases
and chars Moderate yields of valuable aromatics
Strong bases catalyze hydrolysis of ether linkages Significant amounts of basic waste are formed
Few processes for the conversion of lignin are economically viable
Possible Products from Lignin
Benzene toluene xylene (BTX) are used in many processes in the chemical industry For example terephthalic acid is produced from p-xylene
Propyl benzene has an octane rating of 125-130 and could be used to improve the quality of gasoline
Mechanocatalytic Conversion of Lignin
Base assisted ball milling facilitates cleavage of β-O-4 linkages in lignin Depolymerization of carbohydrates is observed in parallel Currently the amounts of base (NaOH) required are too large for an
attractive process
T Kleine J Buendia C Bolm Green Chem 15 (2013) 160
Natural clays are generally cheap Certain natural clays are solid acids and bases
Thermal treatments can enhance acid-base
properties Ion exchange of clays can add Lewis acid and
base sites Addition of reduced metal particles (eg Ni Cu)
can facilitate reaction involving hydrogen
Clay Based Catalysts
Adsorption of Probe Molecules Objectives Quantification of the concentration
of acid and base sites on solids Characterization of strength of
sites Approaches Adsorption of probe molecules
(eg pyridine CO2) on solid acid and bases just before the ball mill is turned of Analysis by IR spectroscopy Analysis of desorption
temperatures to obtain a strength distribution JR Copeland IA Santillan SM Schimming JL Ewbank C Sievers J Phys Chem C 117 (2013) 21413
MW Hahn JR Copeland AH Van Pelt C Sievers ChemSusChem 6 (2013) 2304 Y Kuwahara D-Y Kang JR Copeland NA Brunelli SA Didas P Bollini C Sievers T Kamegawa H Yamashita CW Jones J Am Chem Soc 134 (2012) 10757
1560 1540 1520 1500 1480 1460 1440 1420
1540
1450
Abso
rban
ce
au
Wavenumber cm-1
Broslashnsted acid sites
Lewis acid sites
IR band at 1450 cm-1
IR band at 1540 cm-1
Mechanocatalytic Hydrotreating
Metal sites can dissociate molecular hydrogen to atomic hydrogen
Atomic hydrogen can spillover to other sites
WC Conner JL Falconer Chem Rev 95 (1995) 759
Mechanocatalytic Hydrotreating
Atomic hydrogen can quench dangling bonds and prevent radical reactions like graphitization
Removal of oxygen containing functional groups
is facilitated when bonds angles are distorted
O
HO
OH O
HO
OH OH
HO
OH+ 2 H
OH+ 2 HOH
+ H2OShear force
Continuous Removal of Products
Small and deoxygenated lignin fragments are volatile and can be removed as vapors
Hydrogen can be separated from the products using a condenser or membrane
Ball mill Condenser
Liquid products
H2 recycle H2 feed
Lignin feed
Messages From This Presentation bull Possible applications of the insights
techniquesfindingsopportunities in this presentation ndash Conversion of lignin into chemicals and fuel additives ndash Utilization of other solid carbon-based feedstocks
bull Barriers and challenges to success ndash Lack of understanding of mechanocatalytic reactions ndash Energy efficiency of milling processes
bull Additional research opportunities ndash Processes for mechanocatalytic hydrotreating and other
approaches to biomass conversion ndash Improving mechanocatalytic processes based on
understanding their fundamentals
- Mechanocatalytic Approaches to Biomass Conversion
- Sievers Research Group
- Slide Number 3
- Slide Number 4
- Continuous Conversion Biomass
- Sulfur-Free HDO Catalysts
- Mechanocatalytic Reactions
- Catalytic Sites in Ball Milling
- Slide Number 9
- Slide Number 10
- Mechanocatalytic Conversion of Cellulose
- Mechanocatalytic Conversion of Cellulose
- Lignin Structure
- Conversion of Lignin
- Possible Products from Lignin
- Mechanocatalytic Conversion of Lignin
- Clay Based Catalysts
- Adsorption of Probe Molecules
- Mechanocatalytic Hydrotreating
- Mechanocatalytic Hydrotreating
- Continuous Removal of Products
- Slide Number 22
-
JR Copeland et al Langmuir 29 (2013) 581 JR Copeland et al Catal Today 205 (2013) 49
H1
C1
O3
H2
H3 H4
H5
H6
H7
H8
C2 C3
O1
O2
O4
Al1 Al2
Surface Chemistry of Oxygenates in Water Objectives Understanding surface interactions of biomass-derived
oxygenates in aqueous media Identification of intermediates and reaction pathways
for reactions such as aqueous phase reforming and hydrodeoxygenation (HDO)
Quantification of rates of individual reaction steps Identification of active sites for specific reaction paths Characterization of solvent effects Approaches IR spectroscopy (in vacuum vapor phase (asymp1 atm)
and liquid phase) NMR spectroscopy Liquid phase adsorption isotherms Inelastic neutron scattering Raman spectroscopy DFT calculations (in collaboration with David Sholl)
Glycerol on γ-Al2O3
ATR IR setup for in-situ studies in liquid phase under flow conditions Feed
InletEffluent
N2 Inlet
IR InletIR Outlet
TC
Heating Element
Gasket
Window
IRE
JR Copeland et al J Phys Chem C 117 (2013) 21413 Foo et al ACS Catalysis 4 (2014) 3180
Continuous Conversion Biomass Objectives Development of stable solid catalysts Reactivity studies with model compounds and real
feedstocks Identification of structure property relationships to
improve selectivity Quantitative description of intrinsic kinetics and
transport limitations Development of suitable regeneration procedures for
spent catalysts Approaches Synthesis and post-synthesis treatments of of solid
catalysts Physicochemical characterization (N2 physisorption
XRD SEM IR NMR XPS Boehm titration) Reactivity studies using a flow reactor setup with
automated sample collection
+ H2O
Foo et al ChemSusChem 8 (2015) 534 AH Van Pelt et al Carbon 77 (2014) 143
Sulfur-Free HDO Catalysts Objectives Development of ceria-zirconia based catalysts for
hydrodeoxygenation of oxygenates in pyrolysis oils These catalysts will not contain noble metals and will not require H2S to be co-fed
Optimization of the composition and morphology of the catalysts
Analysis of reaction kinetics Identification of structure-property relationships Approaches Synthesis mixed-metal oxide catalysts with different
compositions and morphologies Physicochemical characterization (TPR isotopic
scrambling of H2D2 N2 physisorption XRD TEM SEM IR NMR XPS titration)
In-situ spectroscopic studies Reactivity studies using a continuously operated
trickle bed reactor
OH
CexZryOz
H2
HO
H2
H H H
OH H
H2 O
H H H
H H
H H
CexZryOz
CexZryOzCexZryOz
Mechanocatalytic Reactions
Reactants catalysts and milling balls are mixed
No solvents are used during the milling
Separation of products can become more efficient
Q Zhang and F Jerome ChemSusChem 6 (2013) 2042
Shaker Mill
Catalytic Sites in Ball Milling
The rate of CO oxidation over a Cr2O3 catalysts increased dramatically when the shaker mill is running
The effect is completely reversibly and repeatable
Milling creates short lived but highly active catalytic sites
S Immohr M Felderhoff C Weidenthaler F Schuumlth Angew Chem Int Ed 52 (2013) 12688
CO + 12O2 CO2 over Cr2O3
Shaker Mill
Plug Flow Reactor
Shaker Mill
Composition of Biomass
H C C H
O H C [ C H 2 O H ]
H 3 C O O C H
C H 2 O H
C H O H
O C H C H 2 O H
H C O
O C H 3 H 2 C O C H
H 3 C O O C H
C H 2 O H
C H O H
H 3 C O O H O H
O C H 3
C
[ O C ]
O H C O
C H 2 O H H 3 C O
C H O H H C
C H 2 O H O
H 3 C O O
C H O H C H
H 3 C O
H O C H 2 O H
O C H 3
H C O C H 2
C H H C H 2 C C H
O
O C H 3 O H
O C H H O H 2 C C
O
H H 3 C O
C H O H H C O
C H 2 O H
H 3 C O O C H 3
C H O H H C
C H 2 O H O
O C H 3
C H O H C H
O H
C H O H 3 C O H C O
C H 2 O H
C H 2
C H 2
C H 3
C H 2 O H
O
O O
O O
O O
O O H O
H O H 2 C
O H
H O H 2 C H O
H O
O H
O H
H O
H O H 2 C H O H 2 C
O H
O
O O
O O
O O
H O H 2 C
O H H O
O O R O
R O
O H
R O O R
O H
O R
H O
H O H 2 C
H O H 2 C
O H 2 C
O
O R O H
H O H 2 C
Cellulose
Hemicellulose
Lignin
Hydrolysis of Carbohydrates
O H
OH
H
H
OH H
H
OH
O O
OH
H
H
OH OH H
H
OH
O
HO
H
OH
H
H
OH OH H
H
O H
H2O
[H+]
OH
H
O
HO
H
OH
H
H
OH OH H
H
O H
Carbohydrates can be depolymerized by addition of water to the glycosidic bond
Hydrolysis of carbohydrates is catalyzed by acids or enzymes
Solid acid can be used to depolymerize cellulose in a ball mill Grinding provides intimate contact between reactant and catalytically active sites Water-soluble compounds are obtained as main products Dealuminated kaolinite is an efficient catalyst
SM Hick C Griebel DT Restrepo JH Truitt EJ Buker C Bylda RG Blair Green Chem 12 (2010) 468 Blair R G Hick S M Truitt J H US patent 8062428 (2011)
Mechanocatalytic Conversion of Cellulose
Very high yields of water-soluble products can be obtained when cellulose is impregnated with mineral acid before ball milling
Oligosaccharides are the main products Formation of branched oligosaccharides indicates re-polymerization Monosaccharides can be obtained by hydrolysis under mild conditions
N Meine R Rinaldi and F Schuumlth ChemSusChem 5 (2012) 1449-1454 J Hilgert N Meine R Rinaldi and F Schuumlth Energy Environ Sci 6 (2013) 92-96
Mechanocatalytic Conversion of Cellulose ESI-MS spectrum of water-soluble products from cellulose
Lignin Structure
J Zakzeski PCA Bruijnincx AL Jongerius BM Weckhuysen Chem Rev 110 (2010) 3552
Conversion of Lignin
J Zakzeski PCA Bruijnincx AL Jongerius BM Weckhuysen Chem Rev 110 (2010) 3552
Lignin can be cracked over solid acid catalysts at 350 to 400 degC Initial conversion of non-volatiles to volatiles Volatiles can be further converted to light gases
and chars Moderate yields of valuable aromatics
Strong bases catalyze hydrolysis of ether linkages Significant amounts of basic waste are formed
Few processes for the conversion of lignin are economically viable
Possible Products from Lignin
Benzene toluene xylene (BTX) are used in many processes in the chemical industry For example terephthalic acid is produced from p-xylene
Propyl benzene has an octane rating of 125-130 and could be used to improve the quality of gasoline
Mechanocatalytic Conversion of Lignin
Base assisted ball milling facilitates cleavage of β-O-4 linkages in lignin Depolymerization of carbohydrates is observed in parallel Currently the amounts of base (NaOH) required are too large for an
attractive process
T Kleine J Buendia C Bolm Green Chem 15 (2013) 160
Natural clays are generally cheap Certain natural clays are solid acids and bases
Thermal treatments can enhance acid-base
properties Ion exchange of clays can add Lewis acid and
base sites Addition of reduced metal particles (eg Ni Cu)
can facilitate reaction involving hydrogen
Clay Based Catalysts
Adsorption of Probe Molecules Objectives Quantification of the concentration
of acid and base sites on solids Characterization of strength of
sites Approaches Adsorption of probe molecules
(eg pyridine CO2) on solid acid and bases just before the ball mill is turned of Analysis by IR spectroscopy Analysis of desorption
temperatures to obtain a strength distribution JR Copeland IA Santillan SM Schimming JL Ewbank C Sievers J Phys Chem C 117 (2013) 21413
MW Hahn JR Copeland AH Van Pelt C Sievers ChemSusChem 6 (2013) 2304 Y Kuwahara D-Y Kang JR Copeland NA Brunelli SA Didas P Bollini C Sievers T Kamegawa H Yamashita CW Jones J Am Chem Soc 134 (2012) 10757
1560 1540 1520 1500 1480 1460 1440 1420
1540
1450
Abso
rban
ce
au
Wavenumber cm-1
Broslashnsted acid sites
Lewis acid sites
IR band at 1450 cm-1
IR band at 1540 cm-1
Mechanocatalytic Hydrotreating
Metal sites can dissociate molecular hydrogen to atomic hydrogen
Atomic hydrogen can spillover to other sites
WC Conner JL Falconer Chem Rev 95 (1995) 759
Mechanocatalytic Hydrotreating
Atomic hydrogen can quench dangling bonds and prevent radical reactions like graphitization
Removal of oxygen containing functional groups
is facilitated when bonds angles are distorted
O
HO
OH O
HO
OH OH
HO
OH+ 2 H
OH+ 2 HOH
+ H2OShear force
Continuous Removal of Products
Small and deoxygenated lignin fragments are volatile and can be removed as vapors
Hydrogen can be separated from the products using a condenser or membrane
Ball mill Condenser
Liquid products
H2 recycle H2 feed
Lignin feed
Messages From This Presentation bull Possible applications of the insights
techniquesfindingsopportunities in this presentation ndash Conversion of lignin into chemicals and fuel additives ndash Utilization of other solid carbon-based feedstocks
bull Barriers and challenges to success ndash Lack of understanding of mechanocatalytic reactions ndash Energy efficiency of milling processes
bull Additional research opportunities ndash Processes for mechanocatalytic hydrotreating and other
approaches to biomass conversion ndash Improving mechanocatalytic processes based on
understanding their fundamentals
- Mechanocatalytic Approaches to Biomass Conversion
- Sievers Research Group
- Slide Number 3
- Slide Number 4
- Continuous Conversion Biomass
- Sulfur-Free HDO Catalysts
- Mechanocatalytic Reactions
- Catalytic Sites in Ball Milling
- Slide Number 9
- Slide Number 10
- Mechanocatalytic Conversion of Cellulose
- Mechanocatalytic Conversion of Cellulose
- Lignin Structure
- Conversion of Lignin
- Possible Products from Lignin
- Mechanocatalytic Conversion of Lignin
- Clay Based Catalysts
- Adsorption of Probe Molecules
- Mechanocatalytic Hydrotreating
- Mechanocatalytic Hydrotreating
- Continuous Removal of Products
- Slide Number 22
-
Continuous Conversion Biomass Objectives Development of stable solid catalysts Reactivity studies with model compounds and real
feedstocks Identification of structure property relationships to
improve selectivity Quantitative description of intrinsic kinetics and
transport limitations Development of suitable regeneration procedures for
spent catalysts Approaches Synthesis and post-synthesis treatments of of solid
catalysts Physicochemical characterization (N2 physisorption
XRD SEM IR NMR XPS Boehm titration) Reactivity studies using a flow reactor setup with
automated sample collection
+ H2O
Foo et al ChemSusChem 8 (2015) 534 AH Van Pelt et al Carbon 77 (2014) 143
Sulfur-Free HDO Catalysts Objectives Development of ceria-zirconia based catalysts for
hydrodeoxygenation of oxygenates in pyrolysis oils These catalysts will not contain noble metals and will not require H2S to be co-fed
Optimization of the composition and morphology of the catalysts
Analysis of reaction kinetics Identification of structure-property relationships Approaches Synthesis mixed-metal oxide catalysts with different
compositions and morphologies Physicochemical characterization (TPR isotopic
scrambling of H2D2 N2 physisorption XRD TEM SEM IR NMR XPS titration)
In-situ spectroscopic studies Reactivity studies using a continuously operated
trickle bed reactor
OH
CexZryOz
H2
HO
H2
H H H
OH H
H2 O
H H H
H H
H H
CexZryOz
CexZryOzCexZryOz
Mechanocatalytic Reactions
Reactants catalysts and milling balls are mixed
No solvents are used during the milling
Separation of products can become more efficient
Q Zhang and F Jerome ChemSusChem 6 (2013) 2042
Shaker Mill
Catalytic Sites in Ball Milling
The rate of CO oxidation over a Cr2O3 catalysts increased dramatically when the shaker mill is running
The effect is completely reversibly and repeatable
Milling creates short lived but highly active catalytic sites
S Immohr M Felderhoff C Weidenthaler F Schuumlth Angew Chem Int Ed 52 (2013) 12688
CO + 12O2 CO2 over Cr2O3
Shaker Mill
Plug Flow Reactor
Shaker Mill
Composition of Biomass
H C C H
O H C [ C H 2 O H ]
H 3 C O O C H
C H 2 O H
C H O H
O C H C H 2 O H
H C O
O C H 3 H 2 C O C H
H 3 C O O C H
C H 2 O H
C H O H
H 3 C O O H O H
O C H 3
C
[ O C ]
O H C O
C H 2 O H H 3 C O
C H O H H C
C H 2 O H O
H 3 C O O
C H O H C H
H 3 C O
H O C H 2 O H
O C H 3
H C O C H 2
C H H C H 2 C C H
O
O C H 3 O H
O C H H O H 2 C C
O
H H 3 C O
C H O H H C O
C H 2 O H
H 3 C O O C H 3
C H O H H C
C H 2 O H O
O C H 3
C H O H C H
O H
C H O H 3 C O H C O
C H 2 O H
C H 2
C H 2
C H 3
C H 2 O H
O
O O
O O
O O
O O H O
H O H 2 C
O H
H O H 2 C H O
H O
O H
O H
H O
H O H 2 C H O H 2 C
O H
O
O O
O O
O O
H O H 2 C
O H H O
O O R O
R O
O H
R O O R
O H
O R
H O
H O H 2 C
H O H 2 C
O H 2 C
O
O R O H
H O H 2 C
Cellulose
Hemicellulose
Lignin
Hydrolysis of Carbohydrates
O H
OH
H
H
OH H
H
OH
O O
OH
H
H
OH OH H
H
OH
O
HO
H
OH
H
H
OH OH H
H
O H
H2O
[H+]
OH
H
O
HO
H
OH
H
H
OH OH H
H
O H
Carbohydrates can be depolymerized by addition of water to the glycosidic bond
Hydrolysis of carbohydrates is catalyzed by acids or enzymes
Solid acid can be used to depolymerize cellulose in a ball mill Grinding provides intimate contact between reactant and catalytically active sites Water-soluble compounds are obtained as main products Dealuminated kaolinite is an efficient catalyst
SM Hick C Griebel DT Restrepo JH Truitt EJ Buker C Bylda RG Blair Green Chem 12 (2010) 468 Blair R G Hick S M Truitt J H US patent 8062428 (2011)
Mechanocatalytic Conversion of Cellulose
Very high yields of water-soluble products can be obtained when cellulose is impregnated with mineral acid before ball milling
Oligosaccharides are the main products Formation of branched oligosaccharides indicates re-polymerization Monosaccharides can be obtained by hydrolysis under mild conditions
N Meine R Rinaldi and F Schuumlth ChemSusChem 5 (2012) 1449-1454 J Hilgert N Meine R Rinaldi and F Schuumlth Energy Environ Sci 6 (2013) 92-96
Mechanocatalytic Conversion of Cellulose ESI-MS spectrum of water-soluble products from cellulose
Lignin Structure
J Zakzeski PCA Bruijnincx AL Jongerius BM Weckhuysen Chem Rev 110 (2010) 3552
Conversion of Lignin
J Zakzeski PCA Bruijnincx AL Jongerius BM Weckhuysen Chem Rev 110 (2010) 3552
Lignin can be cracked over solid acid catalysts at 350 to 400 degC Initial conversion of non-volatiles to volatiles Volatiles can be further converted to light gases
and chars Moderate yields of valuable aromatics
Strong bases catalyze hydrolysis of ether linkages Significant amounts of basic waste are formed
Few processes for the conversion of lignin are economically viable
Possible Products from Lignin
Benzene toluene xylene (BTX) are used in many processes in the chemical industry For example terephthalic acid is produced from p-xylene
Propyl benzene has an octane rating of 125-130 and could be used to improve the quality of gasoline
Mechanocatalytic Conversion of Lignin
Base assisted ball milling facilitates cleavage of β-O-4 linkages in lignin Depolymerization of carbohydrates is observed in parallel Currently the amounts of base (NaOH) required are too large for an
attractive process
T Kleine J Buendia C Bolm Green Chem 15 (2013) 160
Natural clays are generally cheap Certain natural clays are solid acids and bases
Thermal treatments can enhance acid-base
properties Ion exchange of clays can add Lewis acid and
base sites Addition of reduced metal particles (eg Ni Cu)
can facilitate reaction involving hydrogen
Clay Based Catalysts
Adsorption of Probe Molecules Objectives Quantification of the concentration
of acid and base sites on solids Characterization of strength of
sites Approaches Adsorption of probe molecules
(eg pyridine CO2) on solid acid and bases just before the ball mill is turned of Analysis by IR spectroscopy Analysis of desorption
temperatures to obtain a strength distribution JR Copeland IA Santillan SM Schimming JL Ewbank C Sievers J Phys Chem C 117 (2013) 21413
MW Hahn JR Copeland AH Van Pelt C Sievers ChemSusChem 6 (2013) 2304 Y Kuwahara D-Y Kang JR Copeland NA Brunelli SA Didas P Bollini C Sievers T Kamegawa H Yamashita CW Jones J Am Chem Soc 134 (2012) 10757
1560 1540 1520 1500 1480 1460 1440 1420
1540
1450
Abso
rban
ce
au
Wavenumber cm-1
Broslashnsted acid sites
Lewis acid sites
IR band at 1450 cm-1
IR band at 1540 cm-1
Mechanocatalytic Hydrotreating
Metal sites can dissociate molecular hydrogen to atomic hydrogen
Atomic hydrogen can spillover to other sites
WC Conner JL Falconer Chem Rev 95 (1995) 759
Mechanocatalytic Hydrotreating
Atomic hydrogen can quench dangling bonds and prevent radical reactions like graphitization
Removal of oxygen containing functional groups
is facilitated when bonds angles are distorted
O
HO
OH O
HO
OH OH
HO
OH+ 2 H
OH+ 2 HOH
+ H2OShear force
Continuous Removal of Products
Small and deoxygenated lignin fragments are volatile and can be removed as vapors
Hydrogen can be separated from the products using a condenser or membrane
Ball mill Condenser
Liquid products
H2 recycle H2 feed
Lignin feed
Messages From This Presentation bull Possible applications of the insights
techniquesfindingsopportunities in this presentation ndash Conversion of lignin into chemicals and fuel additives ndash Utilization of other solid carbon-based feedstocks
bull Barriers and challenges to success ndash Lack of understanding of mechanocatalytic reactions ndash Energy efficiency of milling processes
bull Additional research opportunities ndash Processes for mechanocatalytic hydrotreating and other
approaches to biomass conversion ndash Improving mechanocatalytic processes based on
understanding their fundamentals
- Mechanocatalytic Approaches to Biomass Conversion
- Sievers Research Group
- Slide Number 3
- Slide Number 4
- Continuous Conversion Biomass
- Sulfur-Free HDO Catalysts
- Mechanocatalytic Reactions
- Catalytic Sites in Ball Milling
- Slide Number 9
- Slide Number 10
- Mechanocatalytic Conversion of Cellulose
- Mechanocatalytic Conversion of Cellulose
- Lignin Structure
- Conversion of Lignin
- Possible Products from Lignin
- Mechanocatalytic Conversion of Lignin
- Clay Based Catalysts
- Adsorption of Probe Molecules
- Mechanocatalytic Hydrotreating
- Mechanocatalytic Hydrotreating
- Continuous Removal of Products
- Slide Number 22
-
Sulfur-Free HDO Catalysts Objectives Development of ceria-zirconia based catalysts for
hydrodeoxygenation of oxygenates in pyrolysis oils These catalysts will not contain noble metals and will not require H2S to be co-fed
Optimization of the composition and morphology of the catalysts
Analysis of reaction kinetics Identification of structure-property relationships Approaches Synthesis mixed-metal oxide catalysts with different
compositions and morphologies Physicochemical characterization (TPR isotopic
scrambling of H2D2 N2 physisorption XRD TEM SEM IR NMR XPS titration)
In-situ spectroscopic studies Reactivity studies using a continuously operated
trickle bed reactor
OH
CexZryOz
H2
HO
H2
H H H
OH H
H2 O
H H H
H H
H H
CexZryOz
CexZryOzCexZryOz
Mechanocatalytic Reactions
Reactants catalysts and milling balls are mixed
No solvents are used during the milling
Separation of products can become more efficient
Q Zhang and F Jerome ChemSusChem 6 (2013) 2042
Shaker Mill
Catalytic Sites in Ball Milling
The rate of CO oxidation over a Cr2O3 catalysts increased dramatically when the shaker mill is running
The effect is completely reversibly and repeatable
Milling creates short lived but highly active catalytic sites
S Immohr M Felderhoff C Weidenthaler F Schuumlth Angew Chem Int Ed 52 (2013) 12688
CO + 12O2 CO2 over Cr2O3
Shaker Mill
Plug Flow Reactor
Shaker Mill
Composition of Biomass
H C C H
O H C [ C H 2 O H ]
H 3 C O O C H
C H 2 O H
C H O H
O C H C H 2 O H
H C O
O C H 3 H 2 C O C H
H 3 C O O C H
C H 2 O H
C H O H
H 3 C O O H O H
O C H 3
C
[ O C ]
O H C O
C H 2 O H H 3 C O
C H O H H C
C H 2 O H O
H 3 C O O
C H O H C H
H 3 C O
H O C H 2 O H
O C H 3
H C O C H 2
C H H C H 2 C C H
O
O C H 3 O H
O C H H O H 2 C C
O
H H 3 C O
C H O H H C O
C H 2 O H
H 3 C O O C H 3
C H O H H C
C H 2 O H O
O C H 3
C H O H C H
O H
C H O H 3 C O H C O
C H 2 O H
C H 2
C H 2
C H 3
C H 2 O H
O
O O
O O
O O
O O H O
H O H 2 C
O H
H O H 2 C H O
H O
O H
O H
H O
H O H 2 C H O H 2 C
O H
O
O O
O O
O O
H O H 2 C
O H H O
O O R O
R O
O H
R O O R
O H
O R
H O
H O H 2 C
H O H 2 C
O H 2 C
O
O R O H
H O H 2 C
Cellulose
Hemicellulose
Lignin
Hydrolysis of Carbohydrates
O H
OH
H
H
OH H
H
OH
O O
OH
H
H
OH OH H
H
OH
O
HO
H
OH
H
H
OH OH H
H
O H
H2O
[H+]
OH
H
O
HO
H
OH
H
H
OH OH H
H
O H
Carbohydrates can be depolymerized by addition of water to the glycosidic bond
Hydrolysis of carbohydrates is catalyzed by acids or enzymes
Solid acid can be used to depolymerize cellulose in a ball mill Grinding provides intimate contact between reactant and catalytically active sites Water-soluble compounds are obtained as main products Dealuminated kaolinite is an efficient catalyst
SM Hick C Griebel DT Restrepo JH Truitt EJ Buker C Bylda RG Blair Green Chem 12 (2010) 468 Blair R G Hick S M Truitt J H US patent 8062428 (2011)
Mechanocatalytic Conversion of Cellulose
Very high yields of water-soluble products can be obtained when cellulose is impregnated with mineral acid before ball milling
Oligosaccharides are the main products Formation of branched oligosaccharides indicates re-polymerization Monosaccharides can be obtained by hydrolysis under mild conditions
N Meine R Rinaldi and F Schuumlth ChemSusChem 5 (2012) 1449-1454 J Hilgert N Meine R Rinaldi and F Schuumlth Energy Environ Sci 6 (2013) 92-96
Mechanocatalytic Conversion of Cellulose ESI-MS spectrum of water-soluble products from cellulose
Lignin Structure
J Zakzeski PCA Bruijnincx AL Jongerius BM Weckhuysen Chem Rev 110 (2010) 3552
Conversion of Lignin
J Zakzeski PCA Bruijnincx AL Jongerius BM Weckhuysen Chem Rev 110 (2010) 3552
Lignin can be cracked over solid acid catalysts at 350 to 400 degC Initial conversion of non-volatiles to volatiles Volatiles can be further converted to light gases
and chars Moderate yields of valuable aromatics
Strong bases catalyze hydrolysis of ether linkages Significant amounts of basic waste are formed
Few processes for the conversion of lignin are economically viable
Possible Products from Lignin
Benzene toluene xylene (BTX) are used in many processes in the chemical industry For example terephthalic acid is produced from p-xylene
Propyl benzene has an octane rating of 125-130 and could be used to improve the quality of gasoline
Mechanocatalytic Conversion of Lignin
Base assisted ball milling facilitates cleavage of β-O-4 linkages in lignin Depolymerization of carbohydrates is observed in parallel Currently the amounts of base (NaOH) required are too large for an
attractive process
T Kleine J Buendia C Bolm Green Chem 15 (2013) 160
Natural clays are generally cheap Certain natural clays are solid acids and bases
Thermal treatments can enhance acid-base
properties Ion exchange of clays can add Lewis acid and
base sites Addition of reduced metal particles (eg Ni Cu)
can facilitate reaction involving hydrogen
Clay Based Catalysts
Adsorption of Probe Molecules Objectives Quantification of the concentration
of acid and base sites on solids Characterization of strength of
sites Approaches Adsorption of probe molecules
(eg pyridine CO2) on solid acid and bases just before the ball mill is turned of Analysis by IR spectroscopy Analysis of desorption
temperatures to obtain a strength distribution JR Copeland IA Santillan SM Schimming JL Ewbank C Sievers J Phys Chem C 117 (2013) 21413
MW Hahn JR Copeland AH Van Pelt C Sievers ChemSusChem 6 (2013) 2304 Y Kuwahara D-Y Kang JR Copeland NA Brunelli SA Didas P Bollini C Sievers T Kamegawa H Yamashita CW Jones J Am Chem Soc 134 (2012) 10757
1560 1540 1520 1500 1480 1460 1440 1420
1540
1450
Abso
rban
ce
au
Wavenumber cm-1
Broslashnsted acid sites
Lewis acid sites
IR band at 1450 cm-1
IR band at 1540 cm-1
Mechanocatalytic Hydrotreating
Metal sites can dissociate molecular hydrogen to atomic hydrogen
Atomic hydrogen can spillover to other sites
WC Conner JL Falconer Chem Rev 95 (1995) 759
Mechanocatalytic Hydrotreating
Atomic hydrogen can quench dangling bonds and prevent radical reactions like graphitization
Removal of oxygen containing functional groups
is facilitated when bonds angles are distorted
O
HO
OH O
HO
OH OH
HO
OH+ 2 H
OH+ 2 HOH
+ H2OShear force
Continuous Removal of Products
Small and deoxygenated lignin fragments are volatile and can be removed as vapors
Hydrogen can be separated from the products using a condenser or membrane
Ball mill Condenser
Liquid products
H2 recycle H2 feed
Lignin feed
Messages From This Presentation bull Possible applications of the insights
techniquesfindingsopportunities in this presentation ndash Conversion of lignin into chemicals and fuel additives ndash Utilization of other solid carbon-based feedstocks
bull Barriers and challenges to success ndash Lack of understanding of mechanocatalytic reactions ndash Energy efficiency of milling processes
bull Additional research opportunities ndash Processes for mechanocatalytic hydrotreating and other
approaches to biomass conversion ndash Improving mechanocatalytic processes based on
understanding their fundamentals
- Mechanocatalytic Approaches to Biomass Conversion
- Sievers Research Group
- Slide Number 3
- Slide Number 4
- Continuous Conversion Biomass
- Sulfur-Free HDO Catalysts
- Mechanocatalytic Reactions
- Catalytic Sites in Ball Milling
- Slide Number 9
- Slide Number 10
- Mechanocatalytic Conversion of Cellulose
- Mechanocatalytic Conversion of Cellulose
- Lignin Structure
- Conversion of Lignin
- Possible Products from Lignin
- Mechanocatalytic Conversion of Lignin
- Clay Based Catalysts
- Adsorption of Probe Molecules
- Mechanocatalytic Hydrotreating
- Mechanocatalytic Hydrotreating
- Continuous Removal of Products
- Slide Number 22
-
Mechanocatalytic Reactions
Reactants catalysts and milling balls are mixed
No solvents are used during the milling
Separation of products can become more efficient
Q Zhang and F Jerome ChemSusChem 6 (2013) 2042
Shaker Mill
Catalytic Sites in Ball Milling
The rate of CO oxidation over a Cr2O3 catalysts increased dramatically when the shaker mill is running
The effect is completely reversibly and repeatable
Milling creates short lived but highly active catalytic sites
S Immohr M Felderhoff C Weidenthaler F Schuumlth Angew Chem Int Ed 52 (2013) 12688
CO + 12O2 CO2 over Cr2O3
Shaker Mill
Plug Flow Reactor
Shaker Mill
Composition of Biomass
H C C H
O H C [ C H 2 O H ]
H 3 C O O C H
C H 2 O H
C H O H
O C H C H 2 O H
H C O
O C H 3 H 2 C O C H
H 3 C O O C H
C H 2 O H
C H O H
H 3 C O O H O H
O C H 3
C
[ O C ]
O H C O
C H 2 O H H 3 C O
C H O H H C
C H 2 O H O
H 3 C O O
C H O H C H
H 3 C O
H O C H 2 O H
O C H 3
H C O C H 2
C H H C H 2 C C H
O
O C H 3 O H
O C H H O H 2 C C
O
H H 3 C O
C H O H H C O
C H 2 O H
H 3 C O O C H 3
C H O H H C
C H 2 O H O
O C H 3
C H O H C H
O H
C H O H 3 C O H C O
C H 2 O H
C H 2
C H 2
C H 3
C H 2 O H
O
O O
O O
O O
O O H O
H O H 2 C
O H
H O H 2 C H O
H O
O H
O H
H O
H O H 2 C H O H 2 C
O H
O
O O
O O
O O
H O H 2 C
O H H O
O O R O
R O
O H
R O O R
O H
O R
H O
H O H 2 C
H O H 2 C
O H 2 C
O
O R O H
H O H 2 C
Cellulose
Hemicellulose
Lignin
Hydrolysis of Carbohydrates
O H
OH
H
H
OH H
H
OH
O O
OH
H
H
OH OH H
H
OH
O
HO
H
OH
H
H
OH OH H
H
O H
H2O
[H+]
OH
H
O
HO
H
OH
H
H
OH OH H
H
O H
Carbohydrates can be depolymerized by addition of water to the glycosidic bond
Hydrolysis of carbohydrates is catalyzed by acids or enzymes
Solid acid can be used to depolymerize cellulose in a ball mill Grinding provides intimate contact between reactant and catalytically active sites Water-soluble compounds are obtained as main products Dealuminated kaolinite is an efficient catalyst
SM Hick C Griebel DT Restrepo JH Truitt EJ Buker C Bylda RG Blair Green Chem 12 (2010) 468 Blair R G Hick S M Truitt J H US patent 8062428 (2011)
Mechanocatalytic Conversion of Cellulose
Very high yields of water-soluble products can be obtained when cellulose is impregnated with mineral acid before ball milling
Oligosaccharides are the main products Formation of branched oligosaccharides indicates re-polymerization Monosaccharides can be obtained by hydrolysis under mild conditions
N Meine R Rinaldi and F Schuumlth ChemSusChem 5 (2012) 1449-1454 J Hilgert N Meine R Rinaldi and F Schuumlth Energy Environ Sci 6 (2013) 92-96
Mechanocatalytic Conversion of Cellulose ESI-MS spectrum of water-soluble products from cellulose
Lignin Structure
J Zakzeski PCA Bruijnincx AL Jongerius BM Weckhuysen Chem Rev 110 (2010) 3552
Conversion of Lignin
J Zakzeski PCA Bruijnincx AL Jongerius BM Weckhuysen Chem Rev 110 (2010) 3552
Lignin can be cracked over solid acid catalysts at 350 to 400 degC Initial conversion of non-volatiles to volatiles Volatiles can be further converted to light gases
and chars Moderate yields of valuable aromatics
Strong bases catalyze hydrolysis of ether linkages Significant amounts of basic waste are formed
Few processes for the conversion of lignin are economically viable
Possible Products from Lignin
Benzene toluene xylene (BTX) are used in many processes in the chemical industry For example terephthalic acid is produced from p-xylene
Propyl benzene has an octane rating of 125-130 and could be used to improve the quality of gasoline
Mechanocatalytic Conversion of Lignin
Base assisted ball milling facilitates cleavage of β-O-4 linkages in lignin Depolymerization of carbohydrates is observed in parallel Currently the amounts of base (NaOH) required are too large for an
attractive process
T Kleine J Buendia C Bolm Green Chem 15 (2013) 160
Natural clays are generally cheap Certain natural clays are solid acids and bases
Thermal treatments can enhance acid-base
properties Ion exchange of clays can add Lewis acid and
base sites Addition of reduced metal particles (eg Ni Cu)
can facilitate reaction involving hydrogen
Clay Based Catalysts
Adsorption of Probe Molecules Objectives Quantification of the concentration
of acid and base sites on solids Characterization of strength of
sites Approaches Adsorption of probe molecules
(eg pyridine CO2) on solid acid and bases just before the ball mill is turned of Analysis by IR spectroscopy Analysis of desorption
temperatures to obtain a strength distribution JR Copeland IA Santillan SM Schimming JL Ewbank C Sievers J Phys Chem C 117 (2013) 21413
MW Hahn JR Copeland AH Van Pelt C Sievers ChemSusChem 6 (2013) 2304 Y Kuwahara D-Y Kang JR Copeland NA Brunelli SA Didas P Bollini C Sievers T Kamegawa H Yamashita CW Jones J Am Chem Soc 134 (2012) 10757
1560 1540 1520 1500 1480 1460 1440 1420
1540
1450
Abso
rban
ce
au
Wavenumber cm-1
Broslashnsted acid sites
Lewis acid sites
IR band at 1450 cm-1
IR band at 1540 cm-1
Mechanocatalytic Hydrotreating
Metal sites can dissociate molecular hydrogen to atomic hydrogen
Atomic hydrogen can spillover to other sites
WC Conner JL Falconer Chem Rev 95 (1995) 759
Mechanocatalytic Hydrotreating
Atomic hydrogen can quench dangling bonds and prevent radical reactions like graphitization
Removal of oxygen containing functional groups
is facilitated when bonds angles are distorted
O
HO
OH O
HO
OH OH
HO
OH+ 2 H
OH+ 2 HOH
+ H2OShear force
Continuous Removal of Products
Small and deoxygenated lignin fragments are volatile and can be removed as vapors
Hydrogen can be separated from the products using a condenser or membrane
Ball mill Condenser
Liquid products
H2 recycle H2 feed
Lignin feed
Messages From This Presentation bull Possible applications of the insights
techniquesfindingsopportunities in this presentation ndash Conversion of lignin into chemicals and fuel additives ndash Utilization of other solid carbon-based feedstocks
bull Barriers and challenges to success ndash Lack of understanding of mechanocatalytic reactions ndash Energy efficiency of milling processes
bull Additional research opportunities ndash Processes for mechanocatalytic hydrotreating and other
approaches to biomass conversion ndash Improving mechanocatalytic processes based on
understanding their fundamentals
- Mechanocatalytic Approaches to Biomass Conversion
- Sievers Research Group
- Slide Number 3
- Slide Number 4
- Continuous Conversion Biomass
- Sulfur-Free HDO Catalysts
- Mechanocatalytic Reactions
- Catalytic Sites in Ball Milling
- Slide Number 9
- Slide Number 10
- Mechanocatalytic Conversion of Cellulose
- Mechanocatalytic Conversion of Cellulose
- Lignin Structure
- Conversion of Lignin
- Possible Products from Lignin
- Mechanocatalytic Conversion of Lignin
- Clay Based Catalysts
- Adsorption of Probe Molecules
- Mechanocatalytic Hydrotreating
- Mechanocatalytic Hydrotreating
- Continuous Removal of Products
- Slide Number 22
-
Catalytic Sites in Ball Milling
The rate of CO oxidation over a Cr2O3 catalysts increased dramatically when the shaker mill is running
The effect is completely reversibly and repeatable
Milling creates short lived but highly active catalytic sites
S Immohr M Felderhoff C Weidenthaler F Schuumlth Angew Chem Int Ed 52 (2013) 12688
CO + 12O2 CO2 over Cr2O3
Shaker Mill
Plug Flow Reactor
Shaker Mill
Composition of Biomass
H C C H
O H C [ C H 2 O H ]
H 3 C O O C H
C H 2 O H
C H O H
O C H C H 2 O H
H C O
O C H 3 H 2 C O C H
H 3 C O O C H
C H 2 O H
C H O H
H 3 C O O H O H
O C H 3
C
[ O C ]
O H C O
C H 2 O H H 3 C O
C H O H H C
C H 2 O H O
H 3 C O O
C H O H C H
H 3 C O
H O C H 2 O H
O C H 3
H C O C H 2
C H H C H 2 C C H
O
O C H 3 O H
O C H H O H 2 C C
O
H H 3 C O
C H O H H C O
C H 2 O H
H 3 C O O C H 3
C H O H H C
C H 2 O H O
O C H 3
C H O H C H
O H
C H O H 3 C O H C O
C H 2 O H
C H 2
C H 2
C H 3
C H 2 O H
O
O O
O O
O O
O O H O
H O H 2 C
O H
H O H 2 C H O
H O
O H
O H
H O
H O H 2 C H O H 2 C
O H
O
O O
O O
O O
H O H 2 C
O H H O
O O R O
R O
O H
R O O R
O H
O R
H O
H O H 2 C
H O H 2 C
O H 2 C
O
O R O H
H O H 2 C
Cellulose
Hemicellulose
Lignin
Hydrolysis of Carbohydrates
O H
OH
H
H
OH H
H
OH
O O
OH
H
H
OH OH H
H
OH
O
HO
H
OH
H
H
OH OH H
H
O H
H2O
[H+]
OH
H
O
HO
H
OH
H
H
OH OH H
H
O H
Carbohydrates can be depolymerized by addition of water to the glycosidic bond
Hydrolysis of carbohydrates is catalyzed by acids or enzymes
Solid acid can be used to depolymerize cellulose in a ball mill Grinding provides intimate contact between reactant and catalytically active sites Water-soluble compounds are obtained as main products Dealuminated kaolinite is an efficient catalyst
SM Hick C Griebel DT Restrepo JH Truitt EJ Buker C Bylda RG Blair Green Chem 12 (2010) 468 Blair R G Hick S M Truitt J H US patent 8062428 (2011)
Mechanocatalytic Conversion of Cellulose
Very high yields of water-soluble products can be obtained when cellulose is impregnated with mineral acid before ball milling
Oligosaccharides are the main products Formation of branched oligosaccharides indicates re-polymerization Monosaccharides can be obtained by hydrolysis under mild conditions
N Meine R Rinaldi and F Schuumlth ChemSusChem 5 (2012) 1449-1454 J Hilgert N Meine R Rinaldi and F Schuumlth Energy Environ Sci 6 (2013) 92-96
Mechanocatalytic Conversion of Cellulose ESI-MS spectrum of water-soluble products from cellulose
Lignin Structure
J Zakzeski PCA Bruijnincx AL Jongerius BM Weckhuysen Chem Rev 110 (2010) 3552
Conversion of Lignin
J Zakzeski PCA Bruijnincx AL Jongerius BM Weckhuysen Chem Rev 110 (2010) 3552
Lignin can be cracked over solid acid catalysts at 350 to 400 degC Initial conversion of non-volatiles to volatiles Volatiles can be further converted to light gases
and chars Moderate yields of valuable aromatics
Strong bases catalyze hydrolysis of ether linkages Significant amounts of basic waste are formed
Few processes for the conversion of lignin are economically viable
Possible Products from Lignin
Benzene toluene xylene (BTX) are used in many processes in the chemical industry For example terephthalic acid is produced from p-xylene
Propyl benzene has an octane rating of 125-130 and could be used to improve the quality of gasoline
Mechanocatalytic Conversion of Lignin
Base assisted ball milling facilitates cleavage of β-O-4 linkages in lignin Depolymerization of carbohydrates is observed in parallel Currently the amounts of base (NaOH) required are too large for an
attractive process
T Kleine J Buendia C Bolm Green Chem 15 (2013) 160
Natural clays are generally cheap Certain natural clays are solid acids and bases
Thermal treatments can enhance acid-base
properties Ion exchange of clays can add Lewis acid and
base sites Addition of reduced metal particles (eg Ni Cu)
can facilitate reaction involving hydrogen
Clay Based Catalysts
Adsorption of Probe Molecules Objectives Quantification of the concentration
of acid and base sites on solids Characterization of strength of
sites Approaches Adsorption of probe molecules
(eg pyridine CO2) on solid acid and bases just before the ball mill is turned of Analysis by IR spectroscopy Analysis of desorption
temperatures to obtain a strength distribution JR Copeland IA Santillan SM Schimming JL Ewbank C Sievers J Phys Chem C 117 (2013) 21413
MW Hahn JR Copeland AH Van Pelt C Sievers ChemSusChem 6 (2013) 2304 Y Kuwahara D-Y Kang JR Copeland NA Brunelli SA Didas P Bollini C Sievers T Kamegawa H Yamashita CW Jones J Am Chem Soc 134 (2012) 10757
1560 1540 1520 1500 1480 1460 1440 1420
1540
1450
Abso
rban
ce
au
Wavenumber cm-1
Broslashnsted acid sites
Lewis acid sites
IR band at 1450 cm-1
IR band at 1540 cm-1
Mechanocatalytic Hydrotreating
Metal sites can dissociate molecular hydrogen to atomic hydrogen
Atomic hydrogen can spillover to other sites
WC Conner JL Falconer Chem Rev 95 (1995) 759
Mechanocatalytic Hydrotreating
Atomic hydrogen can quench dangling bonds and prevent radical reactions like graphitization
Removal of oxygen containing functional groups
is facilitated when bonds angles are distorted
O
HO
OH O
HO
OH OH
HO
OH+ 2 H
OH+ 2 HOH
+ H2OShear force
Continuous Removal of Products
Small and deoxygenated lignin fragments are volatile and can be removed as vapors
Hydrogen can be separated from the products using a condenser or membrane
Ball mill Condenser
Liquid products
H2 recycle H2 feed
Lignin feed
Messages From This Presentation bull Possible applications of the insights
techniquesfindingsopportunities in this presentation ndash Conversion of lignin into chemicals and fuel additives ndash Utilization of other solid carbon-based feedstocks
bull Barriers and challenges to success ndash Lack of understanding of mechanocatalytic reactions ndash Energy efficiency of milling processes
bull Additional research opportunities ndash Processes for mechanocatalytic hydrotreating and other
approaches to biomass conversion ndash Improving mechanocatalytic processes based on
understanding their fundamentals
- Mechanocatalytic Approaches to Biomass Conversion
- Sievers Research Group
- Slide Number 3
- Slide Number 4
- Continuous Conversion Biomass
- Sulfur-Free HDO Catalysts
- Mechanocatalytic Reactions
- Catalytic Sites in Ball Milling
- Slide Number 9
- Slide Number 10
- Mechanocatalytic Conversion of Cellulose
- Mechanocatalytic Conversion of Cellulose
- Lignin Structure
- Conversion of Lignin
- Possible Products from Lignin
- Mechanocatalytic Conversion of Lignin
- Clay Based Catalysts
- Adsorption of Probe Molecules
- Mechanocatalytic Hydrotreating
- Mechanocatalytic Hydrotreating
- Continuous Removal of Products
- Slide Number 22
-
Composition of Biomass
H C C H
O H C [ C H 2 O H ]
H 3 C O O C H
C H 2 O H
C H O H
O C H C H 2 O H
H C O
O C H 3 H 2 C O C H
H 3 C O O C H
C H 2 O H
C H O H
H 3 C O O H O H
O C H 3
C
[ O C ]
O H C O
C H 2 O H H 3 C O
C H O H H C
C H 2 O H O
H 3 C O O
C H O H C H
H 3 C O
H O C H 2 O H
O C H 3
H C O C H 2
C H H C H 2 C C H
O
O C H 3 O H
O C H H O H 2 C C
O
H H 3 C O
C H O H H C O
C H 2 O H
H 3 C O O C H 3
C H O H H C
C H 2 O H O
O C H 3
C H O H C H
O H
C H O H 3 C O H C O
C H 2 O H
C H 2
C H 2
C H 3
C H 2 O H
O
O O
O O
O O
O O H O
H O H 2 C
O H
H O H 2 C H O
H O
O H
O H
H O
H O H 2 C H O H 2 C
O H
O
O O
O O
O O
H O H 2 C
O H H O
O O R O
R O
O H
R O O R
O H
O R
H O
H O H 2 C
H O H 2 C
O H 2 C
O
O R O H
H O H 2 C
Cellulose
Hemicellulose
Lignin
Hydrolysis of Carbohydrates
O H
OH
H
H
OH H
H
OH
O O
OH
H
H
OH OH H
H
OH
O
HO
H
OH
H
H
OH OH H
H
O H
H2O
[H+]
OH
H
O
HO
H
OH
H
H
OH OH H
H
O H
Carbohydrates can be depolymerized by addition of water to the glycosidic bond
Hydrolysis of carbohydrates is catalyzed by acids or enzymes
Solid acid can be used to depolymerize cellulose in a ball mill Grinding provides intimate contact between reactant and catalytically active sites Water-soluble compounds are obtained as main products Dealuminated kaolinite is an efficient catalyst
SM Hick C Griebel DT Restrepo JH Truitt EJ Buker C Bylda RG Blair Green Chem 12 (2010) 468 Blair R G Hick S M Truitt J H US patent 8062428 (2011)
Mechanocatalytic Conversion of Cellulose
Very high yields of water-soluble products can be obtained when cellulose is impregnated with mineral acid before ball milling
Oligosaccharides are the main products Formation of branched oligosaccharides indicates re-polymerization Monosaccharides can be obtained by hydrolysis under mild conditions
N Meine R Rinaldi and F Schuumlth ChemSusChem 5 (2012) 1449-1454 J Hilgert N Meine R Rinaldi and F Schuumlth Energy Environ Sci 6 (2013) 92-96
Mechanocatalytic Conversion of Cellulose ESI-MS spectrum of water-soluble products from cellulose
Lignin Structure
J Zakzeski PCA Bruijnincx AL Jongerius BM Weckhuysen Chem Rev 110 (2010) 3552
Conversion of Lignin
J Zakzeski PCA Bruijnincx AL Jongerius BM Weckhuysen Chem Rev 110 (2010) 3552
Lignin can be cracked over solid acid catalysts at 350 to 400 degC Initial conversion of non-volatiles to volatiles Volatiles can be further converted to light gases
and chars Moderate yields of valuable aromatics
Strong bases catalyze hydrolysis of ether linkages Significant amounts of basic waste are formed
Few processes for the conversion of lignin are economically viable
Possible Products from Lignin
Benzene toluene xylene (BTX) are used in many processes in the chemical industry For example terephthalic acid is produced from p-xylene
Propyl benzene has an octane rating of 125-130 and could be used to improve the quality of gasoline
Mechanocatalytic Conversion of Lignin
Base assisted ball milling facilitates cleavage of β-O-4 linkages in lignin Depolymerization of carbohydrates is observed in parallel Currently the amounts of base (NaOH) required are too large for an
attractive process
T Kleine J Buendia C Bolm Green Chem 15 (2013) 160
Natural clays are generally cheap Certain natural clays are solid acids and bases
Thermal treatments can enhance acid-base
properties Ion exchange of clays can add Lewis acid and
base sites Addition of reduced metal particles (eg Ni Cu)
can facilitate reaction involving hydrogen
Clay Based Catalysts
Adsorption of Probe Molecules Objectives Quantification of the concentration
of acid and base sites on solids Characterization of strength of
sites Approaches Adsorption of probe molecules
(eg pyridine CO2) on solid acid and bases just before the ball mill is turned of Analysis by IR spectroscopy Analysis of desorption
temperatures to obtain a strength distribution JR Copeland IA Santillan SM Schimming JL Ewbank C Sievers J Phys Chem C 117 (2013) 21413
MW Hahn JR Copeland AH Van Pelt C Sievers ChemSusChem 6 (2013) 2304 Y Kuwahara D-Y Kang JR Copeland NA Brunelli SA Didas P Bollini C Sievers T Kamegawa H Yamashita CW Jones J Am Chem Soc 134 (2012) 10757
1560 1540 1520 1500 1480 1460 1440 1420
1540
1450
Abso
rban
ce
au
Wavenumber cm-1
Broslashnsted acid sites
Lewis acid sites
IR band at 1450 cm-1
IR band at 1540 cm-1
Mechanocatalytic Hydrotreating
Metal sites can dissociate molecular hydrogen to atomic hydrogen
Atomic hydrogen can spillover to other sites
WC Conner JL Falconer Chem Rev 95 (1995) 759
Mechanocatalytic Hydrotreating
Atomic hydrogen can quench dangling bonds and prevent radical reactions like graphitization
Removal of oxygen containing functional groups
is facilitated when bonds angles are distorted
O
HO
OH O
HO
OH OH
HO
OH+ 2 H
OH+ 2 HOH
+ H2OShear force
Continuous Removal of Products
Small and deoxygenated lignin fragments are volatile and can be removed as vapors
Hydrogen can be separated from the products using a condenser or membrane
Ball mill Condenser
Liquid products
H2 recycle H2 feed
Lignin feed
Messages From This Presentation bull Possible applications of the insights
techniquesfindingsopportunities in this presentation ndash Conversion of lignin into chemicals and fuel additives ndash Utilization of other solid carbon-based feedstocks
bull Barriers and challenges to success ndash Lack of understanding of mechanocatalytic reactions ndash Energy efficiency of milling processes
bull Additional research opportunities ndash Processes for mechanocatalytic hydrotreating and other
approaches to biomass conversion ndash Improving mechanocatalytic processes based on
understanding their fundamentals
- Mechanocatalytic Approaches to Biomass Conversion
- Sievers Research Group
- Slide Number 3
- Slide Number 4
- Continuous Conversion Biomass
- Sulfur-Free HDO Catalysts
- Mechanocatalytic Reactions
- Catalytic Sites in Ball Milling
- Slide Number 9
- Slide Number 10
- Mechanocatalytic Conversion of Cellulose
- Mechanocatalytic Conversion of Cellulose
- Lignin Structure
- Conversion of Lignin
- Possible Products from Lignin
- Mechanocatalytic Conversion of Lignin
- Clay Based Catalysts
- Adsorption of Probe Molecules
- Mechanocatalytic Hydrotreating
- Mechanocatalytic Hydrotreating
- Continuous Removal of Products
- Slide Number 22
-
Hydrolysis of Carbohydrates
O H
OH
H
H
OH H
H
OH
O O
OH
H
H
OH OH H
H
OH
O
HO
H
OH
H
H
OH OH H
H
O H
H2O
[H+]
OH
H
O
HO
H
OH
H
H
OH OH H
H
O H
Carbohydrates can be depolymerized by addition of water to the glycosidic bond
Hydrolysis of carbohydrates is catalyzed by acids or enzymes
Solid acid can be used to depolymerize cellulose in a ball mill Grinding provides intimate contact between reactant and catalytically active sites Water-soluble compounds are obtained as main products Dealuminated kaolinite is an efficient catalyst
SM Hick C Griebel DT Restrepo JH Truitt EJ Buker C Bylda RG Blair Green Chem 12 (2010) 468 Blair R G Hick S M Truitt J H US patent 8062428 (2011)
Mechanocatalytic Conversion of Cellulose
Very high yields of water-soluble products can be obtained when cellulose is impregnated with mineral acid before ball milling
Oligosaccharides are the main products Formation of branched oligosaccharides indicates re-polymerization Monosaccharides can be obtained by hydrolysis under mild conditions
N Meine R Rinaldi and F Schuumlth ChemSusChem 5 (2012) 1449-1454 J Hilgert N Meine R Rinaldi and F Schuumlth Energy Environ Sci 6 (2013) 92-96
Mechanocatalytic Conversion of Cellulose ESI-MS spectrum of water-soluble products from cellulose
Lignin Structure
J Zakzeski PCA Bruijnincx AL Jongerius BM Weckhuysen Chem Rev 110 (2010) 3552
Conversion of Lignin
J Zakzeski PCA Bruijnincx AL Jongerius BM Weckhuysen Chem Rev 110 (2010) 3552
Lignin can be cracked over solid acid catalysts at 350 to 400 degC Initial conversion of non-volatiles to volatiles Volatiles can be further converted to light gases
and chars Moderate yields of valuable aromatics
Strong bases catalyze hydrolysis of ether linkages Significant amounts of basic waste are formed
Few processes for the conversion of lignin are economically viable
Possible Products from Lignin
Benzene toluene xylene (BTX) are used in many processes in the chemical industry For example terephthalic acid is produced from p-xylene
Propyl benzene has an octane rating of 125-130 and could be used to improve the quality of gasoline
Mechanocatalytic Conversion of Lignin
Base assisted ball milling facilitates cleavage of β-O-4 linkages in lignin Depolymerization of carbohydrates is observed in parallel Currently the amounts of base (NaOH) required are too large for an
attractive process
T Kleine J Buendia C Bolm Green Chem 15 (2013) 160
Natural clays are generally cheap Certain natural clays are solid acids and bases
Thermal treatments can enhance acid-base
properties Ion exchange of clays can add Lewis acid and
base sites Addition of reduced metal particles (eg Ni Cu)
can facilitate reaction involving hydrogen
Clay Based Catalysts
Adsorption of Probe Molecules Objectives Quantification of the concentration
of acid and base sites on solids Characterization of strength of
sites Approaches Adsorption of probe molecules
(eg pyridine CO2) on solid acid and bases just before the ball mill is turned of Analysis by IR spectroscopy Analysis of desorption
temperatures to obtain a strength distribution JR Copeland IA Santillan SM Schimming JL Ewbank C Sievers J Phys Chem C 117 (2013) 21413
MW Hahn JR Copeland AH Van Pelt C Sievers ChemSusChem 6 (2013) 2304 Y Kuwahara D-Y Kang JR Copeland NA Brunelli SA Didas P Bollini C Sievers T Kamegawa H Yamashita CW Jones J Am Chem Soc 134 (2012) 10757
1560 1540 1520 1500 1480 1460 1440 1420
1540
1450
Abso
rban
ce
au
Wavenumber cm-1
Broslashnsted acid sites
Lewis acid sites
IR band at 1450 cm-1
IR band at 1540 cm-1
Mechanocatalytic Hydrotreating
Metal sites can dissociate molecular hydrogen to atomic hydrogen
Atomic hydrogen can spillover to other sites
WC Conner JL Falconer Chem Rev 95 (1995) 759
Mechanocatalytic Hydrotreating
Atomic hydrogen can quench dangling bonds and prevent radical reactions like graphitization
Removal of oxygen containing functional groups
is facilitated when bonds angles are distorted
O
HO
OH O
HO
OH OH
HO
OH+ 2 H
OH+ 2 HOH
+ H2OShear force
Continuous Removal of Products
Small and deoxygenated lignin fragments are volatile and can be removed as vapors
Hydrogen can be separated from the products using a condenser or membrane
Ball mill Condenser
Liquid products
H2 recycle H2 feed
Lignin feed
Messages From This Presentation bull Possible applications of the insights
techniquesfindingsopportunities in this presentation ndash Conversion of lignin into chemicals and fuel additives ndash Utilization of other solid carbon-based feedstocks
bull Barriers and challenges to success ndash Lack of understanding of mechanocatalytic reactions ndash Energy efficiency of milling processes
bull Additional research opportunities ndash Processes for mechanocatalytic hydrotreating and other
approaches to biomass conversion ndash Improving mechanocatalytic processes based on
understanding their fundamentals
- Mechanocatalytic Approaches to Biomass Conversion
- Sievers Research Group
- Slide Number 3
- Slide Number 4
- Continuous Conversion Biomass
- Sulfur-Free HDO Catalysts
- Mechanocatalytic Reactions
- Catalytic Sites in Ball Milling
- Slide Number 9
- Slide Number 10
- Mechanocatalytic Conversion of Cellulose
- Mechanocatalytic Conversion of Cellulose
- Lignin Structure
- Conversion of Lignin
- Possible Products from Lignin
- Mechanocatalytic Conversion of Lignin
- Clay Based Catalysts
- Adsorption of Probe Molecules
- Mechanocatalytic Hydrotreating
- Mechanocatalytic Hydrotreating
- Continuous Removal of Products
- Slide Number 22
-
Solid acid can be used to depolymerize cellulose in a ball mill Grinding provides intimate contact between reactant and catalytically active sites Water-soluble compounds are obtained as main products Dealuminated kaolinite is an efficient catalyst
SM Hick C Griebel DT Restrepo JH Truitt EJ Buker C Bylda RG Blair Green Chem 12 (2010) 468 Blair R G Hick S M Truitt J H US patent 8062428 (2011)
Mechanocatalytic Conversion of Cellulose
Very high yields of water-soluble products can be obtained when cellulose is impregnated with mineral acid before ball milling
Oligosaccharides are the main products Formation of branched oligosaccharides indicates re-polymerization Monosaccharides can be obtained by hydrolysis under mild conditions
N Meine R Rinaldi and F Schuumlth ChemSusChem 5 (2012) 1449-1454 J Hilgert N Meine R Rinaldi and F Schuumlth Energy Environ Sci 6 (2013) 92-96
Mechanocatalytic Conversion of Cellulose ESI-MS spectrum of water-soluble products from cellulose
Lignin Structure
J Zakzeski PCA Bruijnincx AL Jongerius BM Weckhuysen Chem Rev 110 (2010) 3552
Conversion of Lignin
J Zakzeski PCA Bruijnincx AL Jongerius BM Weckhuysen Chem Rev 110 (2010) 3552
Lignin can be cracked over solid acid catalysts at 350 to 400 degC Initial conversion of non-volatiles to volatiles Volatiles can be further converted to light gases
and chars Moderate yields of valuable aromatics
Strong bases catalyze hydrolysis of ether linkages Significant amounts of basic waste are formed
Few processes for the conversion of lignin are economically viable
Possible Products from Lignin
Benzene toluene xylene (BTX) are used in many processes in the chemical industry For example terephthalic acid is produced from p-xylene
Propyl benzene has an octane rating of 125-130 and could be used to improve the quality of gasoline
Mechanocatalytic Conversion of Lignin
Base assisted ball milling facilitates cleavage of β-O-4 linkages in lignin Depolymerization of carbohydrates is observed in parallel Currently the amounts of base (NaOH) required are too large for an
attractive process
T Kleine J Buendia C Bolm Green Chem 15 (2013) 160
Natural clays are generally cheap Certain natural clays are solid acids and bases
Thermal treatments can enhance acid-base
properties Ion exchange of clays can add Lewis acid and
base sites Addition of reduced metal particles (eg Ni Cu)
can facilitate reaction involving hydrogen
Clay Based Catalysts
Adsorption of Probe Molecules Objectives Quantification of the concentration
of acid and base sites on solids Characterization of strength of
sites Approaches Adsorption of probe molecules
(eg pyridine CO2) on solid acid and bases just before the ball mill is turned of Analysis by IR spectroscopy Analysis of desorption
temperatures to obtain a strength distribution JR Copeland IA Santillan SM Schimming JL Ewbank C Sievers J Phys Chem C 117 (2013) 21413
MW Hahn JR Copeland AH Van Pelt C Sievers ChemSusChem 6 (2013) 2304 Y Kuwahara D-Y Kang JR Copeland NA Brunelli SA Didas P Bollini C Sievers T Kamegawa H Yamashita CW Jones J Am Chem Soc 134 (2012) 10757
1560 1540 1520 1500 1480 1460 1440 1420
1540
1450
Abso
rban
ce
au
Wavenumber cm-1
Broslashnsted acid sites
Lewis acid sites
IR band at 1450 cm-1
IR band at 1540 cm-1
Mechanocatalytic Hydrotreating
Metal sites can dissociate molecular hydrogen to atomic hydrogen
Atomic hydrogen can spillover to other sites
WC Conner JL Falconer Chem Rev 95 (1995) 759
Mechanocatalytic Hydrotreating
Atomic hydrogen can quench dangling bonds and prevent radical reactions like graphitization
Removal of oxygen containing functional groups
is facilitated when bonds angles are distorted
O
HO
OH O
HO
OH OH
HO
OH+ 2 H
OH+ 2 HOH
+ H2OShear force
Continuous Removal of Products
Small and deoxygenated lignin fragments are volatile and can be removed as vapors
Hydrogen can be separated from the products using a condenser or membrane
Ball mill Condenser
Liquid products
H2 recycle H2 feed
Lignin feed
Messages From This Presentation bull Possible applications of the insights
techniquesfindingsopportunities in this presentation ndash Conversion of lignin into chemicals and fuel additives ndash Utilization of other solid carbon-based feedstocks
bull Barriers and challenges to success ndash Lack of understanding of mechanocatalytic reactions ndash Energy efficiency of milling processes
bull Additional research opportunities ndash Processes for mechanocatalytic hydrotreating and other
approaches to biomass conversion ndash Improving mechanocatalytic processes based on
understanding their fundamentals
- Mechanocatalytic Approaches to Biomass Conversion
- Sievers Research Group
- Slide Number 3
- Slide Number 4
- Continuous Conversion Biomass
- Sulfur-Free HDO Catalysts
- Mechanocatalytic Reactions
- Catalytic Sites in Ball Milling
- Slide Number 9
- Slide Number 10
- Mechanocatalytic Conversion of Cellulose
- Mechanocatalytic Conversion of Cellulose
- Lignin Structure
- Conversion of Lignin
- Possible Products from Lignin
- Mechanocatalytic Conversion of Lignin
- Clay Based Catalysts
- Adsorption of Probe Molecules
- Mechanocatalytic Hydrotreating
- Mechanocatalytic Hydrotreating
- Continuous Removal of Products
- Slide Number 22
-
Very high yields of water-soluble products can be obtained when cellulose is impregnated with mineral acid before ball milling
Oligosaccharides are the main products Formation of branched oligosaccharides indicates re-polymerization Monosaccharides can be obtained by hydrolysis under mild conditions
N Meine R Rinaldi and F Schuumlth ChemSusChem 5 (2012) 1449-1454 J Hilgert N Meine R Rinaldi and F Schuumlth Energy Environ Sci 6 (2013) 92-96
Mechanocatalytic Conversion of Cellulose ESI-MS spectrum of water-soluble products from cellulose
Lignin Structure
J Zakzeski PCA Bruijnincx AL Jongerius BM Weckhuysen Chem Rev 110 (2010) 3552
Conversion of Lignin
J Zakzeski PCA Bruijnincx AL Jongerius BM Weckhuysen Chem Rev 110 (2010) 3552
Lignin can be cracked over solid acid catalysts at 350 to 400 degC Initial conversion of non-volatiles to volatiles Volatiles can be further converted to light gases
and chars Moderate yields of valuable aromatics
Strong bases catalyze hydrolysis of ether linkages Significant amounts of basic waste are formed
Few processes for the conversion of lignin are economically viable
Possible Products from Lignin
Benzene toluene xylene (BTX) are used in many processes in the chemical industry For example terephthalic acid is produced from p-xylene
Propyl benzene has an octane rating of 125-130 and could be used to improve the quality of gasoline
Mechanocatalytic Conversion of Lignin
Base assisted ball milling facilitates cleavage of β-O-4 linkages in lignin Depolymerization of carbohydrates is observed in parallel Currently the amounts of base (NaOH) required are too large for an
attractive process
T Kleine J Buendia C Bolm Green Chem 15 (2013) 160
Natural clays are generally cheap Certain natural clays are solid acids and bases
Thermal treatments can enhance acid-base
properties Ion exchange of clays can add Lewis acid and
base sites Addition of reduced metal particles (eg Ni Cu)
can facilitate reaction involving hydrogen
Clay Based Catalysts
Adsorption of Probe Molecules Objectives Quantification of the concentration
of acid and base sites on solids Characterization of strength of
sites Approaches Adsorption of probe molecules
(eg pyridine CO2) on solid acid and bases just before the ball mill is turned of Analysis by IR spectroscopy Analysis of desorption
temperatures to obtain a strength distribution JR Copeland IA Santillan SM Schimming JL Ewbank C Sievers J Phys Chem C 117 (2013) 21413
MW Hahn JR Copeland AH Van Pelt C Sievers ChemSusChem 6 (2013) 2304 Y Kuwahara D-Y Kang JR Copeland NA Brunelli SA Didas P Bollini C Sievers T Kamegawa H Yamashita CW Jones J Am Chem Soc 134 (2012) 10757
1560 1540 1520 1500 1480 1460 1440 1420
1540
1450
Abso
rban
ce
au
Wavenumber cm-1
Broslashnsted acid sites
Lewis acid sites
IR band at 1450 cm-1
IR band at 1540 cm-1
Mechanocatalytic Hydrotreating
Metal sites can dissociate molecular hydrogen to atomic hydrogen
Atomic hydrogen can spillover to other sites
WC Conner JL Falconer Chem Rev 95 (1995) 759
Mechanocatalytic Hydrotreating
Atomic hydrogen can quench dangling bonds and prevent radical reactions like graphitization
Removal of oxygen containing functional groups
is facilitated when bonds angles are distorted
O
HO
OH O
HO
OH OH
HO
OH+ 2 H
OH+ 2 HOH
+ H2OShear force
Continuous Removal of Products
Small and deoxygenated lignin fragments are volatile and can be removed as vapors
Hydrogen can be separated from the products using a condenser or membrane
Ball mill Condenser
Liquid products
H2 recycle H2 feed
Lignin feed
Messages From This Presentation bull Possible applications of the insights
techniquesfindingsopportunities in this presentation ndash Conversion of lignin into chemicals and fuel additives ndash Utilization of other solid carbon-based feedstocks
bull Barriers and challenges to success ndash Lack of understanding of mechanocatalytic reactions ndash Energy efficiency of milling processes
bull Additional research opportunities ndash Processes for mechanocatalytic hydrotreating and other
approaches to biomass conversion ndash Improving mechanocatalytic processes based on
understanding their fundamentals
- Mechanocatalytic Approaches to Biomass Conversion
- Sievers Research Group
- Slide Number 3
- Slide Number 4
- Continuous Conversion Biomass
- Sulfur-Free HDO Catalysts
- Mechanocatalytic Reactions
- Catalytic Sites in Ball Milling
- Slide Number 9
- Slide Number 10
- Mechanocatalytic Conversion of Cellulose
- Mechanocatalytic Conversion of Cellulose
- Lignin Structure
- Conversion of Lignin
- Possible Products from Lignin
- Mechanocatalytic Conversion of Lignin
- Clay Based Catalysts
- Adsorption of Probe Molecules
- Mechanocatalytic Hydrotreating
- Mechanocatalytic Hydrotreating
- Continuous Removal of Products
- Slide Number 22
-
Lignin Structure
J Zakzeski PCA Bruijnincx AL Jongerius BM Weckhuysen Chem Rev 110 (2010) 3552
Conversion of Lignin
J Zakzeski PCA Bruijnincx AL Jongerius BM Weckhuysen Chem Rev 110 (2010) 3552
Lignin can be cracked over solid acid catalysts at 350 to 400 degC Initial conversion of non-volatiles to volatiles Volatiles can be further converted to light gases
and chars Moderate yields of valuable aromatics
Strong bases catalyze hydrolysis of ether linkages Significant amounts of basic waste are formed
Few processes for the conversion of lignin are economically viable
Possible Products from Lignin
Benzene toluene xylene (BTX) are used in many processes in the chemical industry For example terephthalic acid is produced from p-xylene
Propyl benzene has an octane rating of 125-130 and could be used to improve the quality of gasoline
Mechanocatalytic Conversion of Lignin
Base assisted ball milling facilitates cleavage of β-O-4 linkages in lignin Depolymerization of carbohydrates is observed in parallel Currently the amounts of base (NaOH) required are too large for an
attractive process
T Kleine J Buendia C Bolm Green Chem 15 (2013) 160
Natural clays are generally cheap Certain natural clays are solid acids and bases
Thermal treatments can enhance acid-base
properties Ion exchange of clays can add Lewis acid and
base sites Addition of reduced metal particles (eg Ni Cu)
can facilitate reaction involving hydrogen
Clay Based Catalysts
Adsorption of Probe Molecules Objectives Quantification of the concentration
of acid and base sites on solids Characterization of strength of
sites Approaches Adsorption of probe molecules
(eg pyridine CO2) on solid acid and bases just before the ball mill is turned of Analysis by IR spectroscopy Analysis of desorption
temperatures to obtain a strength distribution JR Copeland IA Santillan SM Schimming JL Ewbank C Sievers J Phys Chem C 117 (2013) 21413
MW Hahn JR Copeland AH Van Pelt C Sievers ChemSusChem 6 (2013) 2304 Y Kuwahara D-Y Kang JR Copeland NA Brunelli SA Didas P Bollini C Sievers T Kamegawa H Yamashita CW Jones J Am Chem Soc 134 (2012) 10757
1560 1540 1520 1500 1480 1460 1440 1420
1540
1450
Abso
rban
ce
au
Wavenumber cm-1
Broslashnsted acid sites
Lewis acid sites
IR band at 1450 cm-1
IR band at 1540 cm-1
Mechanocatalytic Hydrotreating
Metal sites can dissociate molecular hydrogen to atomic hydrogen
Atomic hydrogen can spillover to other sites
WC Conner JL Falconer Chem Rev 95 (1995) 759
Mechanocatalytic Hydrotreating
Atomic hydrogen can quench dangling bonds and prevent radical reactions like graphitization
Removal of oxygen containing functional groups
is facilitated when bonds angles are distorted
O
HO
OH O
HO
OH OH
HO
OH+ 2 H
OH+ 2 HOH
+ H2OShear force
Continuous Removal of Products
Small and deoxygenated lignin fragments are volatile and can be removed as vapors
Hydrogen can be separated from the products using a condenser or membrane
Ball mill Condenser
Liquid products
H2 recycle H2 feed
Lignin feed
Messages From This Presentation bull Possible applications of the insights
techniquesfindingsopportunities in this presentation ndash Conversion of lignin into chemicals and fuel additives ndash Utilization of other solid carbon-based feedstocks
bull Barriers and challenges to success ndash Lack of understanding of mechanocatalytic reactions ndash Energy efficiency of milling processes
bull Additional research opportunities ndash Processes for mechanocatalytic hydrotreating and other
approaches to biomass conversion ndash Improving mechanocatalytic processes based on
understanding their fundamentals
- Mechanocatalytic Approaches to Biomass Conversion
- Sievers Research Group
- Slide Number 3
- Slide Number 4
- Continuous Conversion Biomass
- Sulfur-Free HDO Catalysts
- Mechanocatalytic Reactions
- Catalytic Sites in Ball Milling
- Slide Number 9
- Slide Number 10
- Mechanocatalytic Conversion of Cellulose
- Mechanocatalytic Conversion of Cellulose
- Lignin Structure
- Conversion of Lignin
- Possible Products from Lignin
- Mechanocatalytic Conversion of Lignin
- Clay Based Catalysts
- Adsorption of Probe Molecules
- Mechanocatalytic Hydrotreating
- Mechanocatalytic Hydrotreating
- Continuous Removal of Products
- Slide Number 22
-
Conversion of Lignin
J Zakzeski PCA Bruijnincx AL Jongerius BM Weckhuysen Chem Rev 110 (2010) 3552
Lignin can be cracked over solid acid catalysts at 350 to 400 degC Initial conversion of non-volatiles to volatiles Volatiles can be further converted to light gases
and chars Moderate yields of valuable aromatics
Strong bases catalyze hydrolysis of ether linkages Significant amounts of basic waste are formed
Few processes for the conversion of lignin are economically viable
Possible Products from Lignin
Benzene toluene xylene (BTX) are used in many processes in the chemical industry For example terephthalic acid is produced from p-xylene
Propyl benzene has an octane rating of 125-130 and could be used to improve the quality of gasoline
Mechanocatalytic Conversion of Lignin
Base assisted ball milling facilitates cleavage of β-O-4 linkages in lignin Depolymerization of carbohydrates is observed in parallel Currently the amounts of base (NaOH) required are too large for an
attractive process
T Kleine J Buendia C Bolm Green Chem 15 (2013) 160
Natural clays are generally cheap Certain natural clays are solid acids and bases
Thermal treatments can enhance acid-base
properties Ion exchange of clays can add Lewis acid and
base sites Addition of reduced metal particles (eg Ni Cu)
can facilitate reaction involving hydrogen
Clay Based Catalysts
Adsorption of Probe Molecules Objectives Quantification of the concentration
of acid and base sites on solids Characterization of strength of
sites Approaches Adsorption of probe molecules
(eg pyridine CO2) on solid acid and bases just before the ball mill is turned of Analysis by IR spectroscopy Analysis of desorption
temperatures to obtain a strength distribution JR Copeland IA Santillan SM Schimming JL Ewbank C Sievers J Phys Chem C 117 (2013) 21413
MW Hahn JR Copeland AH Van Pelt C Sievers ChemSusChem 6 (2013) 2304 Y Kuwahara D-Y Kang JR Copeland NA Brunelli SA Didas P Bollini C Sievers T Kamegawa H Yamashita CW Jones J Am Chem Soc 134 (2012) 10757
1560 1540 1520 1500 1480 1460 1440 1420
1540
1450
Abso
rban
ce
au
Wavenumber cm-1
Broslashnsted acid sites
Lewis acid sites
IR band at 1450 cm-1
IR band at 1540 cm-1
Mechanocatalytic Hydrotreating
Metal sites can dissociate molecular hydrogen to atomic hydrogen
Atomic hydrogen can spillover to other sites
WC Conner JL Falconer Chem Rev 95 (1995) 759
Mechanocatalytic Hydrotreating
Atomic hydrogen can quench dangling bonds and prevent radical reactions like graphitization
Removal of oxygen containing functional groups
is facilitated when bonds angles are distorted
O
HO
OH O
HO
OH OH
HO
OH+ 2 H
OH+ 2 HOH
+ H2OShear force
Continuous Removal of Products
Small and deoxygenated lignin fragments are volatile and can be removed as vapors
Hydrogen can be separated from the products using a condenser or membrane
Ball mill Condenser
Liquid products
H2 recycle H2 feed
Lignin feed
Messages From This Presentation bull Possible applications of the insights
techniquesfindingsopportunities in this presentation ndash Conversion of lignin into chemicals and fuel additives ndash Utilization of other solid carbon-based feedstocks
bull Barriers and challenges to success ndash Lack of understanding of mechanocatalytic reactions ndash Energy efficiency of milling processes
bull Additional research opportunities ndash Processes for mechanocatalytic hydrotreating and other
approaches to biomass conversion ndash Improving mechanocatalytic processes based on
understanding their fundamentals
- Mechanocatalytic Approaches to Biomass Conversion
- Sievers Research Group
- Slide Number 3
- Slide Number 4
- Continuous Conversion Biomass
- Sulfur-Free HDO Catalysts
- Mechanocatalytic Reactions
- Catalytic Sites in Ball Milling
- Slide Number 9
- Slide Number 10
- Mechanocatalytic Conversion of Cellulose
- Mechanocatalytic Conversion of Cellulose
- Lignin Structure
- Conversion of Lignin
- Possible Products from Lignin
- Mechanocatalytic Conversion of Lignin
- Clay Based Catalysts
- Adsorption of Probe Molecules
- Mechanocatalytic Hydrotreating
- Mechanocatalytic Hydrotreating
- Continuous Removal of Products
- Slide Number 22
-
Possible Products from Lignin
Benzene toluene xylene (BTX) are used in many processes in the chemical industry For example terephthalic acid is produced from p-xylene
Propyl benzene has an octane rating of 125-130 and could be used to improve the quality of gasoline
Mechanocatalytic Conversion of Lignin
Base assisted ball milling facilitates cleavage of β-O-4 linkages in lignin Depolymerization of carbohydrates is observed in parallel Currently the amounts of base (NaOH) required are too large for an
attractive process
T Kleine J Buendia C Bolm Green Chem 15 (2013) 160
Natural clays are generally cheap Certain natural clays are solid acids and bases
Thermal treatments can enhance acid-base
properties Ion exchange of clays can add Lewis acid and
base sites Addition of reduced metal particles (eg Ni Cu)
can facilitate reaction involving hydrogen
Clay Based Catalysts
Adsorption of Probe Molecules Objectives Quantification of the concentration
of acid and base sites on solids Characterization of strength of
sites Approaches Adsorption of probe molecules
(eg pyridine CO2) on solid acid and bases just before the ball mill is turned of Analysis by IR spectroscopy Analysis of desorption
temperatures to obtain a strength distribution JR Copeland IA Santillan SM Schimming JL Ewbank C Sievers J Phys Chem C 117 (2013) 21413
MW Hahn JR Copeland AH Van Pelt C Sievers ChemSusChem 6 (2013) 2304 Y Kuwahara D-Y Kang JR Copeland NA Brunelli SA Didas P Bollini C Sievers T Kamegawa H Yamashita CW Jones J Am Chem Soc 134 (2012) 10757
1560 1540 1520 1500 1480 1460 1440 1420
1540
1450
Abso
rban
ce
au
Wavenumber cm-1
Broslashnsted acid sites
Lewis acid sites
IR band at 1450 cm-1
IR band at 1540 cm-1
Mechanocatalytic Hydrotreating
Metal sites can dissociate molecular hydrogen to atomic hydrogen
Atomic hydrogen can spillover to other sites
WC Conner JL Falconer Chem Rev 95 (1995) 759
Mechanocatalytic Hydrotreating
Atomic hydrogen can quench dangling bonds and prevent radical reactions like graphitization
Removal of oxygen containing functional groups
is facilitated when bonds angles are distorted
O
HO
OH O
HO
OH OH
HO
OH+ 2 H
OH+ 2 HOH
+ H2OShear force
Continuous Removal of Products
Small and deoxygenated lignin fragments are volatile and can be removed as vapors
Hydrogen can be separated from the products using a condenser or membrane
Ball mill Condenser
Liquid products
H2 recycle H2 feed
Lignin feed
Messages From This Presentation bull Possible applications of the insights
techniquesfindingsopportunities in this presentation ndash Conversion of lignin into chemicals and fuel additives ndash Utilization of other solid carbon-based feedstocks
bull Barriers and challenges to success ndash Lack of understanding of mechanocatalytic reactions ndash Energy efficiency of milling processes
bull Additional research opportunities ndash Processes for mechanocatalytic hydrotreating and other
approaches to biomass conversion ndash Improving mechanocatalytic processes based on
understanding their fundamentals
- Mechanocatalytic Approaches to Biomass Conversion
- Sievers Research Group
- Slide Number 3
- Slide Number 4
- Continuous Conversion Biomass
- Sulfur-Free HDO Catalysts
- Mechanocatalytic Reactions
- Catalytic Sites in Ball Milling
- Slide Number 9
- Slide Number 10
- Mechanocatalytic Conversion of Cellulose
- Mechanocatalytic Conversion of Cellulose
- Lignin Structure
- Conversion of Lignin
- Possible Products from Lignin
- Mechanocatalytic Conversion of Lignin
- Clay Based Catalysts
- Adsorption of Probe Molecules
- Mechanocatalytic Hydrotreating
- Mechanocatalytic Hydrotreating
- Continuous Removal of Products
- Slide Number 22
-
Mechanocatalytic Conversion of Lignin
Base assisted ball milling facilitates cleavage of β-O-4 linkages in lignin Depolymerization of carbohydrates is observed in parallel Currently the amounts of base (NaOH) required are too large for an
attractive process
T Kleine J Buendia C Bolm Green Chem 15 (2013) 160
Natural clays are generally cheap Certain natural clays are solid acids and bases
Thermal treatments can enhance acid-base
properties Ion exchange of clays can add Lewis acid and
base sites Addition of reduced metal particles (eg Ni Cu)
can facilitate reaction involving hydrogen
Clay Based Catalysts
Adsorption of Probe Molecules Objectives Quantification of the concentration
of acid and base sites on solids Characterization of strength of
sites Approaches Adsorption of probe molecules
(eg pyridine CO2) on solid acid and bases just before the ball mill is turned of Analysis by IR spectroscopy Analysis of desorption
temperatures to obtain a strength distribution JR Copeland IA Santillan SM Schimming JL Ewbank C Sievers J Phys Chem C 117 (2013) 21413
MW Hahn JR Copeland AH Van Pelt C Sievers ChemSusChem 6 (2013) 2304 Y Kuwahara D-Y Kang JR Copeland NA Brunelli SA Didas P Bollini C Sievers T Kamegawa H Yamashita CW Jones J Am Chem Soc 134 (2012) 10757
1560 1540 1520 1500 1480 1460 1440 1420
1540
1450
Abso
rban
ce
au
Wavenumber cm-1
Broslashnsted acid sites
Lewis acid sites
IR band at 1450 cm-1
IR band at 1540 cm-1
Mechanocatalytic Hydrotreating
Metal sites can dissociate molecular hydrogen to atomic hydrogen
Atomic hydrogen can spillover to other sites
WC Conner JL Falconer Chem Rev 95 (1995) 759
Mechanocatalytic Hydrotreating
Atomic hydrogen can quench dangling bonds and prevent radical reactions like graphitization
Removal of oxygen containing functional groups
is facilitated when bonds angles are distorted
O
HO
OH O
HO
OH OH
HO
OH+ 2 H
OH+ 2 HOH
+ H2OShear force
Continuous Removal of Products
Small and deoxygenated lignin fragments are volatile and can be removed as vapors
Hydrogen can be separated from the products using a condenser or membrane
Ball mill Condenser
Liquid products
H2 recycle H2 feed
Lignin feed
Messages From This Presentation bull Possible applications of the insights
techniquesfindingsopportunities in this presentation ndash Conversion of lignin into chemicals and fuel additives ndash Utilization of other solid carbon-based feedstocks
bull Barriers and challenges to success ndash Lack of understanding of mechanocatalytic reactions ndash Energy efficiency of milling processes
bull Additional research opportunities ndash Processes for mechanocatalytic hydrotreating and other
approaches to biomass conversion ndash Improving mechanocatalytic processes based on
understanding their fundamentals
- Mechanocatalytic Approaches to Biomass Conversion
- Sievers Research Group
- Slide Number 3
- Slide Number 4
- Continuous Conversion Biomass
- Sulfur-Free HDO Catalysts
- Mechanocatalytic Reactions
- Catalytic Sites in Ball Milling
- Slide Number 9
- Slide Number 10
- Mechanocatalytic Conversion of Cellulose
- Mechanocatalytic Conversion of Cellulose
- Lignin Structure
- Conversion of Lignin
- Possible Products from Lignin
- Mechanocatalytic Conversion of Lignin
- Clay Based Catalysts
- Adsorption of Probe Molecules
- Mechanocatalytic Hydrotreating
- Mechanocatalytic Hydrotreating
- Continuous Removal of Products
- Slide Number 22
-
Natural clays are generally cheap Certain natural clays are solid acids and bases
Thermal treatments can enhance acid-base
properties Ion exchange of clays can add Lewis acid and
base sites Addition of reduced metal particles (eg Ni Cu)
can facilitate reaction involving hydrogen
Clay Based Catalysts
Adsorption of Probe Molecules Objectives Quantification of the concentration
of acid and base sites on solids Characterization of strength of
sites Approaches Adsorption of probe molecules
(eg pyridine CO2) on solid acid and bases just before the ball mill is turned of Analysis by IR spectroscopy Analysis of desorption
temperatures to obtain a strength distribution JR Copeland IA Santillan SM Schimming JL Ewbank C Sievers J Phys Chem C 117 (2013) 21413
MW Hahn JR Copeland AH Van Pelt C Sievers ChemSusChem 6 (2013) 2304 Y Kuwahara D-Y Kang JR Copeland NA Brunelli SA Didas P Bollini C Sievers T Kamegawa H Yamashita CW Jones J Am Chem Soc 134 (2012) 10757
1560 1540 1520 1500 1480 1460 1440 1420
1540
1450
Abso
rban
ce
au
Wavenumber cm-1
Broslashnsted acid sites
Lewis acid sites
IR band at 1450 cm-1
IR band at 1540 cm-1
Mechanocatalytic Hydrotreating
Metal sites can dissociate molecular hydrogen to atomic hydrogen
Atomic hydrogen can spillover to other sites
WC Conner JL Falconer Chem Rev 95 (1995) 759
Mechanocatalytic Hydrotreating
Atomic hydrogen can quench dangling bonds and prevent radical reactions like graphitization
Removal of oxygen containing functional groups
is facilitated when bonds angles are distorted
O
HO
OH O
HO
OH OH
HO
OH+ 2 H
OH+ 2 HOH
+ H2OShear force
Continuous Removal of Products
Small and deoxygenated lignin fragments are volatile and can be removed as vapors
Hydrogen can be separated from the products using a condenser or membrane
Ball mill Condenser
Liquid products
H2 recycle H2 feed
Lignin feed
Messages From This Presentation bull Possible applications of the insights
techniquesfindingsopportunities in this presentation ndash Conversion of lignin into chemicals and fuel additives ndash Utilization of other solid carbon-based feedstocks
bull Barriers and challenges to success ndash Lack of understanding of mechanocatalytic reactions ndash Energy efficiency of milling processes
bull Additional research opportunities ndash Processes for mechanocatalytic hydrotreating and other
approaches to biomass conversion ndash Improving mechanocatalytic processes based on
understanding their fundamentals
- Mechanocatalytic Approaches to Biomass Conversion
- Sievers Research Group
- Slide Number 3
- Slide Number 4
- Continuous Conversion Biomass
- Sulfur-Free HDO Catalysts
- Mechanocatalytic Reactions
- Catalytic Sites in Ball Milling
- Slide Number 9
- Slide Number 10
- Mechanocatalytic Conversion of Cellulose
- Mechanocatalytic Conversion of Cellulose
- Lignin Structure
- Conversion of Lignin
- Possible Products from Lignin
- Mechanocatalytic Conversion of Lignin
- Clay Based Catalysts
- Adsorption of Probe Molecules
- Mechanocatalytic Hydrotreating
- Mechanocatalytic Hydrotreating
- Continuous Removal of Products
- Slide Number 22
-
Adsorption of Probe Molecules Objectives Quantification of the concentration
of acid and base sites on solids Characterization of strength of
sites Approaches Adsorption of probe molecules
(eg pyridine CO2) on solid acid and bases just before the ball mill is turned of Analysis by IR spectroscopy Analysis of desorption
temperatures to obtain a strength distribution JR Copeland IA Santillan SM Schimming JL Ewbank C Sievers J Phys Chem C 117 (2013) 21413
MW Hahn JR Copeland AH Van Pelt C Sievers ChemSusChem 6 (2013) 2304 Y Kuwahara D-Y Kang JR Copeland NA Brunelli SA Didas P Bollini C Sievers T Kamegawa H Yamashita CW Jones J Am Chem Soc 134 (2012) 10757
1560 1540 1520 1500 1480 1460 1440 1420
1540
1450
Abso
rban
ce
au
Wavenumber cm-1
Broslashnsted acid sites
Lewis acid sites
IR band at 1450 cm-1
IR band at 1540 cm-1
Mechanocatalytic Hydrotreating
Metal sites can dissociate molecular hydrogen to atomic hydrogen
Atomic hydrogen can spillover to other sites
WC Conner JL Falconer Chem Rev 95 (1995) 759
Mechanocatalytic Hydrotreating
Atomic hydrogen can quench dangling bonds and prevent radical reactions like graphitization
Removal of oxygen containing functional groups
is facilitated when bonds angles are distorted
O
HO
OH O
HO
OH OH
HO
OH+ 2 H
OH+ 2 HOH
+ H2OShear force
Continuous Removal of Products
Small and deoxygenated lignin fragments are volatile and can be removed as vapors
Hydrogen can be separated from the products using a condenser or membrane
Ball mill Condenser
Liquid products
H2 recycle H2 feed
Lignin feed
Messages From This Presentation bull Possible applications of the insights
techniquesfindingsopportunities in this presentation ndash Conversion of lignin into chemicals and fuel additives ndash Utilization of other solid carbon-based feedstocks
bull Barriers and challenges to success ndash Lack of understanding of mechanocatalytic reactions ndash Energy efficiency of milling processes
bull Additional research opportunities ndash Processes for mechanocatalytic hydrotreating and other
approaches to biomass conversion ndash Improving mechanocatalytic processes based on
understanding their fundamentals
- Mechanocatalytic Approaches to Biomass Conversion
- Sievers Research Group
- Slide Number 3
- Slide Number 4
- Continuous Conversion Biomass
- Sulfur-Free HDO Catalysts
- Mechanocatalytic Reactions
- Catalytic Sites in Ball Milling
- Slide Number 9
- Slide Number 10
- Mechanocatalytic Conversion of Cellulose
- Mechanocatalytic Conversion of Cellulose
- Lignin Structure
- Conversion of Lignin
- Possible Products from Lignin
- Mechanocatalytic Conversion of Lignin
- Clay Based Catalysts
- Adsorption of Probe Molecules
- Mechanocatalytic Hydrotreating
- Mechanocatalytic Hydrotreating
- Continuous Removal of Products
- Slide Number 22
-
Mechanocatalytic Hydrotreating
Metal sites can dissociate molecular hydrogen to atomic hydrogen
Atomic hydrogen can spillover to other sites
WC Conner JL Falconer Chem Rev 95 (1995) 759
Mechanocatalytic Hydrotreating
Atomic hydrogen can quench dangling bonds and prevent radical reactions like graphitization
Removal of oxygen containing functional groups
is facilitated when bonds angles are distorted
O
HO
OH O
HO
OH OH
HO
OH+ 2 H
OH+ 2 HOH
+ H2OShear force
Continuous Removal of Products
Small and deoxygenated lignin fragments are volatile and can be removed as vapors
Hydrogen can be separated from the products using a condenser or membrane
Ball mill Condenser
Liquid products
H2 recycle H2 feed
Lignin feed
Messages From This Presentation bull Possible applications of the insights
techniquesfindingsopportunities in this presentation ndash Conversion of lignin into chemicals and fuel additives ndash Utilization of other solid carbon-based feedstocks
bull Barriers and challenges to success ndash Lack of understanding of mechanocatalytic reactions ndash Energy efficiency of milling processes
bull Additional research opportunities ndash Processes for mechanocatalytic hydrotreating and other
approaches to biomass conversion ndash Improving mechanocatalytic processes based on
understanding their fundamentals
- Mechanocatalytic Approaches to Biomass Conversion
- Sievers Research Group
- Slide Number 3
- Slide Number 4
- Continuous Conversion Biomass
- Sulfur-Free HDO Catalysts
- Mechanocatalytic Reactions
- Catalytic Sites in Ball Milling
- Slide Number 9
- Slide Number 10
- Mechanocatalytic Conversion of Cellulose
- Mechanocatalytic Conversion of Cellulose
- Lignin Structure
- Conversion of Lignin
- Possible Products from Lignin
- Mechanocatalytic Conversion of Lignin
- Clay Based Catalysts
- Adsorption of Probe Molecules
- Mechanocatalytic Hydrotreating
- Mechanocatalytic Hydrotreating
- Continuous Removal of Products
- Slide Number 22
-
Mechanocatalytic Hydrotreating
Atomic hydrogen can quench dangling bonds and prevent radical reactions like graphitization
Removal of oxygen containing functional groups
is facilitated when bonds angles are distorted
O
HO
OH O
HO
OH OH
HO
OH+ 2 H
OH+ 2 HOH
+ H2OShear force
Continuous Removal of Products
Small and deoxygenated lignin fragments are volatile and can be removed as vapors
Hydrogen can be separated from the products using a condenser or membrane
Ball mill Condenser
Liquid products
H2 recycle H2 feed
Lignin feed
Messages From This Presentation bull Possible applications of the insights
techniquesfindingsopportunities in this presentation ndash Conversion of lignin into chemicals and fuel additives ndash Utilization of other solid carbon-based feedstocks
bull Barriers and challenges to success ndash Lack of understanding of mechanocatalytic reactions ndash Energy efficiency of milling processes
bull Additional research opportunities ndash Processes for mechanocatalytic hydrotreating and other
approaches to biomass conversion ndash Improving mechanocatalytic processes based on
understanding their fundamentals
- Mechanocatalytic Approaches to Biomass Conversion
- Sievers Research Group
- Slide Number 3
- Slide Number 4
- Continuous Conversion Biomass
- Sulfur-Free HDO Catalysts
- Mechanocatalytic Reactions
- Catalytic Sites in Ball Milling
- Slide Number 9
- Slide Number 10
- Mechanocatalytic Conversion of Cellulose
- Mechanocatalytic Conversion of Cellulose
- Lignin Structure
- Conversion of Lignin
- Possible Products from Lignin
- Mechanocatalytic Conversion of Lignin
- Clay Based Catalysts
- Adsorption of Probe Molecules
- Mechanocatalytic Hydrotreating
- Mechanocatalytic Hydrotreating
- Continuous Removal of Products
- Slide Number 22
-
Continuous Removal of Products
Small and deoxygenated lignin fragments are volatile and can be removed as vapors
Hydrogen can be separated from the products using a condenser or membrane
Ball mill Condenser
Liquid products
H2 recycle H2 feed
Lignin feed
Messages From This Presentation bull Possible applications of the insights
techniquesfindingsopportunities in this presentation ndash Conversion of lignin into chemicals and fuel additives ndash Utilization of other solid carbon-based feedstocks
bull Barriers and challenges to success ndash Lack of understanding of mechanocatalytic reactions ndash Energy efficiency of milling processes
bull Additional research opportunities ndash Processes for mechanocatalytic hydrotreating and other
approaches to biomass conversion ndash Improving mechanocatalytic processes based on
understanding their fundamentals
- Mechanocatalytic Approaches to Biomass Conversion
- Sievers Research Group
- Slide Number 3
- Slide Number 4
- Continuous Conversion Biomass
- Sulfur-Free HDO Catalysts
- Mechanocatalytic Reactions
- Catalytic Sites in Ball Milling
- Slide Number 9
- Slide Number 10
- Mechanocatalytic Conversion of Cellulose
- Mechanocatalytic Conversion of Cellulose
- Lignin Structure
- Conversion of Lignin
- Possible Products from Lignin
- Mechanocatalytic Conversion of Lignin
- Clay Based Catalysts
- Adsorption of Probe Molecules
- Mechanocatalytic Hydrotreating
- Mechanocatalytic Hydrotreating
- Continuous Removal of Products
- Slide Number 22
-
Messages From This Presentation bull Possible applications of the insights
techniquesfindingsopportunities in this presentation ndash Conversion of lignin into chemicals and fuel additives ndash Utilization of other solid carbon-based feedstocks
bull Barriers and challenges to success ndash Lack of understanding of mechanocatalytic reactions ndash Energy efficiency of milling processes
bull Additional research opportunities ndash Processes for mechanocatalytic hydrotreating and other
approaches to biomass conversion ndash Improving mechanocatalytic processes based on
understanding their fundamentals
- Mechanocatalytic Approaches to Biomass Conversion
- Sievers Research Group
- Slide Number 3
- Slide Number 4
- Continuous Conversion Biomass
- Sulfur-Free HDO Catalysts
- Mechanocatalytic Reactions
- Catalytic Sites in Ball Milling
- Slide Number 9
- Slide Number 10
- Mechanocatalytic Conversion of Cellulose
- Mechanocatalytic Conversion of Cellulose
- Lignin Structure
- Conversion of Lignin
- Possible Products from Lignin
- Mechanocatalytic Conversion of Lignin
- Clay Based Catalysts
- Adsorption of Probe Molecules
- Mechanocatalytic Hydrotreating
- Mechanocatalytic Hydrotreating
- Continuous Removal of Products
- Slide Number 22
-