Production of α,ω diols from Biomass
Thermal and Catalytic Sciences 2016
November 3, 2016Jiayue He, Kefeng Huang, Pranav Karanjkar, Kevin J Barnett, Zachary Brentzal,
Theodore Walker, Siddarth H Krishna, Sam Burt, Ive Hermans, Christos Maravelias, James A Dumesic, George W. Huber
University of Wisconsin-Madison
Department of Chemical & Biological Engineering
http://biofuels.che.wisc.edu/
1
Catalytic Processes for Production of α,ω-diols
from Lignocellulosic Biomass
Chris Marshall
Michael Tspastsis,
Ilja Siepmann
Support from Bioenergy
Technology Office (BETO)
High value infrastructure compatible commodity chemicals from biomass
3Source: Lux Research, Bio-based Materials and Chemical Intelligence Service, www.luxresearchinc.com
Volume (Million MT/yr.)
Pri
ce (
$/
MT
)
1,6-Hexanediol
(~130,000 MT/yr)
Pri
ce (
$/
MM
BT
U)
10
20
30
140
150
0
Natural gas
Crude oil ($50/bbl)
Biomass ($80/ton)
1,6-hexanediol
($4,400/ton)
Gasoline ($2.5/gal)
Source: ICIS, IEA
There are several (aqueous-phase) acid catalyzed reactions in biomass conversion
• Hydrolysis
• Isomerization1
• Dehydration2
• Rehydration1) Y. Roman-Leshkov, M. Moliner, J.A. Labinger, and M.E. Davis, Angewandte Chemie International Edition 49 (2010) 8954-8957.
2) Y. Roman-Leshkov, J.N. Chheda, and J.A. Dumesic, Science 312 (2006) 1933-1937.4
5
Low product selectivity is a key challenge in biomass conversion
Proposed reaction scheme
6
Activity of Acid sites are influenced by Solvent due to Solvation Effects
0 20 40 60 80 100
0
25
50
75
100
125
150
175
200
Based on total detectable products
Based on HMF
0.70.9
5
32
816
52
Turn
over
frequency / h
r-1
Initial water content in solvent / vol %
190
T=170 °C
P=1000 psig
Cellulose=5wt%
Acid= 5 mM H2SO4
Solvent = THF
R. Weingarten, A Rodriguez-Beuerman, F Cai, JS Luterbacher, DM Alonso, JA Dumesic, GW Huber, Selective
Conversion of Cellulose to Hydroxymethylfurfural in Polar Aprotic Solvents; ChemCatChem; (2014) 8 2229-2234.
T=170 °C
P=1000 psig
Cellulose=3 gr
Acid=5 mM H2SO4
Reaction vol.=60 mL
High HMF yields are obtained in polar aprotic solvents
0 10 20 30 40 50 60
0
2
4
6
8
10
12
14
16
HM
F c
arb
on y
ield
(%
)
time (min.)
Water
THF
GVL
Ethyl Acetate
Acetone
Ethanol
Polar
aprotic
solvents
R. Weingarten, A Rodriguez-Beuerman, F Cai, JS Luterbacher, DM Alonso, JA Dumesic, GW Huber, Selective
Conversion of Cellulose to Hydroxymethylfurfural in Polar Aprotic Solvents; ChemCatChem; (2014) 8 2229-2234.
M A Mellmer, C Sener, JMR Gallo, JS Luterbachher, DM Alonso, JA Dumesic, Solvent Effects in Acid Catalyzed
Biomass Conversion Reactions,, Ang Chemie (2014) 53 11872-11875.
Presence of water changes the product distribution
9
Reaction Conditions: 1 wt% cellulose, 7.5 mM H2SO4, 190 0C 1000 psig He, 60 mL total volume
Source: Cao, F.; Schwartz, T. J.; McClelland, D. J.; Krishna, S. H.; Dumesic, J. A.; Huber, G. W., “Dehydration of cellulose to
levoglucosenone using polar aprotic solvents” Energy & Environmental Science 2015, 8 (6), 1808-1815.
Pure THF2.7% water, bal. THF11.6% water, bal. THF
0 50 100 150 200 250 300
0
10
20
30
40
Yie
ld (
% C
arb
on
)
Time (min)
0 50 100 150 200 250 300
0
10
20
30
40
Yie
ld (
% C
arb
on
)
Time (min)0 50 100 150 200 250 300
0
5
10
15
20
Yie
ld (
% C
arb
on
)
Time (min)
0 50 100 150 200 250 300
0
20
40
60
80
Yie
ld (
% C
arb
on
)
Time (min)0 50 100 150 200 250 300
0
10
20
30
40
Yie
ld (
% C
arb
on
)
Time (min)
0 50 100 150 200 250 300
0
10
20
30
40
Yie
ld (
% C
arb
on
)
Time (min)0 50 100 150 200 250 300
0
5
10
15
20
Yie
ld (
% C
arb
on
)
Time (min)
0 50 100 150 200 250 300
0
20
40
60
80
Yie
ld (
% C
arb
on
)
Time (min)0 50 100 150 200 250 300
0
10
20
30
40
Yie
ld (
% C
arb
on
)
Time (min)
0 50 100 150 200 250 300
0
10
20
30
40
Yie
ld (
% C
arb
on
)
Time (min)0 50 100 150 200 250 300
0
5
10
15
20
Yie
ld (
% C
arb
on
)
Time (min)
0 50 100 150 200 250 300
0
20
40
60
80
Yie
ld (
% C
arb
on
)
Time (min)
LGO HMF
GlucoseLGA
SOLVENT:
Levoglucosenone (LGO)• Chiral carbon
Sometimes referred to as “the next HMF”
10F Cao, TJ Schwartz, D McClelland, S Krishna, JA Dumesic, GW Huber, Dehydration of
Cellulose to Levoglucosenone using Polar Aprotic Solvents, EES, (2015) 4 1808-1885.
Levoglucosenone (LGO)• Chiral carbon
• Double bond conjugated with a ketone
Sometimes referred to as “the next HMF”
11F Cao, TJ Schwartz, D McClelland, S Krishna, JA Dumesic, GW Huber, Dehydration of
Cellulose to Levoglucosenone using Polar Aprotic Solvents, EES, (2015) 4 1808-1885.
Levoglucosenone (LGO)
• Chiral carbon
• Double bond conjugated with a ketone
• Protected aldehyde
Sometimes referred to as “the next HMF”
12F Cao, TJ Schwartz, D McClelland, S Krishna, JA Dumesic, GW Huber, Dehydration of
Cellulose to Levoglucosenone using Polar Aprotic Solvents, EES, (2015) 4 1808-1885.
Levoglucosenone (LGO)
• Chiral carbon
• Double bond conjugated with a ketone
• Protected aldehyde
• Two protected hydroxyl groups
Sometimes referred to as “the next HMF”
13F Cao, TJ Schwartz, D McClelland, S Krishna, JA Dumesic, GW Huber, Dehydration of
Cellulose to Levoglucosenone using Polar Aprotic Solvents, EES, (2015) 4 1808-1885.
Reaction Pathway for Dehydration of Cellulose in Polar Aprotic Solvents
14
LGO is hydrogenated to levoglucosanol over a metal catalyst (Pd/Al2O3)
S.H. Krishna, D.J. McClelland, Q.R. Rashke, J.A. Dumesic, G.W. Huber, “Catalytic hydrogenation of levoglucosenone to value-added chemicals”.
Submitted.
• High yields of Cyrene or Lgol achievable using monometallic catalysts
• Excess of exo-Lgol produced over endo-Lgol
Selective Hydrogenolysis of Cyclic Ethers: Literature
16
Bifunctional catalyst with a reducible metal and an oxophilic promoter;
Low temperatures
Sources: [1] Chia et al., Journal of the American Chemical Society, 2011, 133, 12675-12689
[2] Chen et al., ChemCatChem, 2010, 2, 547-555
Reactant Transition state Product
Tetrahydrofurfuryl
alcohol
Hydride transfer
creates a stable
oxocarbenium ion
97% selectivity to
α,ω-diols
Proposed reaction pathway in literature
with a RhRe/C catalyst through formation
of a stable oxocarbenium ion[1]
THP-2M
2-methyltetrahydropyran (2-MTHP)
1-hexanol1,6-HDO (>95% selectivity)
1,2-HDO
2-hexanol
C-C cracking products
Proposed reaction scheme
for THP-2M hydrogenolysis
with a IrRe/SiO2 catalyst[2]
Synergy between the reducible metal and oxophilicpromoter is important
17
† VXC = Vulcan XC-72, a carbon black by Cabot Corporation
‡ other products include over-hydrogenolysis and C-C cracking products
Additional reaction conditions and details: Feedstock: 5% aq. THP-2M feedstock, Catalyst:Feedstock (g/g) = 2:7,
Temperature = 120 oC, Pressure = 34 bar H2, Time = 4 h
Batch reactor activity data by Chia et al.[1]:
THP-2M 1,6-HDO
CatalystConversion
(%)
Rate
(μmol·g-1·min-1)
1,6-HDO
selectivity (%)
Byproducts
selectivity (%)
Rh/VXC†
(4 wt% Rh)3 4 44
1,2-hexanediol (11%),
1-hexanol (3%), others‡ (42%)
Re/VXC(3.6 wt% Re)
No reaction - - -
RhRe/VXC(4 wt% Rh, 3.6 wt% Re)
28 90 97 1-hexanols (3%),
Source: [1] Chia et al., Journal of the American Chemical Society, 2011, 133, 12675-12689
0 10 20 30 40 50 60 70 800
20
40
60
80
100
0
20
40
60
80
100
High selectivity to 1,6-HDO is achievable using RhRe/VXC bifunctional catalysts
18
Byproducts include small amounts of 1-hexanol, 2-MTHP, 1-pentanol
Reaction conditions for continuous reaction: 5% aq. THP-2M, catalyst:
RhRe/VXC, WHSV = 1.44 h-1, 120 oC, 34 bar H2, 40 sccm H2
Time (h)
TH
P-2
M c
on
vers
ion
(%
)
1,6-H
DO
sele
cti
vity
(%
)
Karanjkar et al.; “Effect of carbon support on RhRe bifunctional catalysts for selective hydrogenolysis of tetrahydropyran-2-
methanol” RSC Catalysis Science and Technology, in press.
THP-2M solution
through HPLC pump
Hydrogen
Reacto
rG
as-
Liq
uid
sep
ara
tor
To back-pressure regulator
High selectivity to 1,6-HDO is achievable using RhRe/VXC bifunctional catalysts
19
Reaction conditions: 5% aq. THP-2M (initial reaction volume = 50 mL), catalyst: RhRe/VXC,
catalyst:feedstock (g/g) = 1:7, 120 oC, 34 bar H2.
Byproducts include small amounts of 1-hexanol, 2-MTHP, 1-pentanol with RhRe/VXC catalyst
0 10 20 30 40 50 60 70 800
20
40
60
80
100
0
20
40
60
80
100
Time (h)
TH
P-2
M c
on
vers
ion
(%
)
1,6-H
DO
sele
cti
vity
(%
)
RhRe/VXC
RhRe/NDC
0 10 20 30 40 50 60 70 800
20
40
60
80
100
0
20
40
60
80
100
Karanjkar et al.; “Effect of carbon support on RhRe bifunctional catalysts for selective hydrogenolysis of tetrahydropyran-2-
methanol” RSC Catalysis Science and Technology, in press.
Carbon Blacks vs. Activated Carbons
20
Hydrocarbons
Carbon black
Gas-phase pyrolysis
Formation of carbon blacks
(vapor phase)
Low-rank coals,
wood, thermosetting
polymers
Glassy carbon
Thermal decomposition by charring
Activated
carbons (chars)
Activation
1. Selective gasification
2. Chemical treatment
3. …
Formation of activated carbons
(solid phase)
Source: L. R. Radovic, in Carbon Materials for Catalysis, John Wiley & Sons, Inc., 2008, pp. 1-44
Carbon supports discussed here:
Vulcan XC-72, Cabot Corp., carbon black Norit Darco 12X40, Cabot Corp., activated carbon&
VXC NDC
Characterization of Carbon Supports
21
Carbon support NDC VXC
Type of carbon support Activated (acid washed) Carbon black
BET surface area (m2·g-1) 671 240
50 500100 1000
0.000
0.005
0.010
0.015
0.020
Po
re v
olu
me
(cm
3 g
-1 Å
-1)
Pore width (Å)
NDC
VXC
Pore size distribution
Pore width (Å)
Po
re v
olu
me (
cm
3g
-1Å
-1)
0.0 0.2 0.4 0.6 0.8 1.0
0
100
200
300
400
500
Qu
an
tity
ad
sorb
ed (
cm3 g
-1 S
TP
)
Relative pressure (P/Po)
Adsorption
Desorption
VXC
NDC
Nitrogen adsorption isotherm
Qu
an
tity
ad
sorb
ed
(cm
3g
-1)
Relative pressure (P/Po)
Karanjkar et al.; “Effect of carbon support on RhRe bifunctional catalysts for selective hydrogenolysis of tetrahydropyran-2-
methanol” RSC Catalysis Science and Technology, in press.
NDC has more surface oxygen present
22
Surface elemental composition (mol %)
Carbon C O S Si Na Al
VXC 99.4 0.4 0.2 - - -
NDC 88.8 8.8 - 1.9 0.2 0.3
Water vapor adsorption isotherm
Water adsorption capacity of VXC = 1.2 mmol·g-1
Water adsorption capacity of NDC = 17.5 mmol·g-1
XPS analysis of carbon
supports
0.0 0.2 0.4 0.6 0.8 1.00
4
8
12
16
20
Adsorption
Desorption
0
1
2
3
4
Qu
an
tity
ad
sorb
ed
(m
mo
lg
-1)
Qu
an
tity
ad
sorb
ed
(m
mo
lg
-1)
Relative pressure (P/Po)
VXC
NDC
Karanjkar et al.; “Effect of carbon support on RhRe bifunctional catalysts for selective hydrogenolysis of tetrahydropyran-2-
methanol” RSC Catalysis Science and Technology, in press.
Higher density of oxidized species on NDC than VXC – more
sites for interaction with metal and metal precursors
Sources: [1] Figueiredo et.al., Carbon, 1999, 37, 1379-1389
23
Abundance shown is relative to C=C stretch (the only signal due to
a non-oxygenated bond)
Band
Position
(cm-1)
AssignmentRelative abundance
NDC VXC
477C-CO deformation of cyclic
ketone3.40 0
792
C-O-C stretch of aromatic
cyclic anhydride or O-H bend
of carboxylic acid
1.69 0
1025Acid Anhydride C-O-C
stretch7.92 0
1055 Phenol O-H bend 0.26 0
1119 Ether C-O-C stretch 13.07 0.16
1173 Phenol C-OH stretch 0.80 0.42
1215 Lactone C=O stretch 2.05 0.51
1280 Carb. Acid C=O stretch 0.56 1.79
1350Carboxyl Carbonate C=O
stretch0.05 2.41
1586C=C stretch (conjugated
aromatic)1.00 1.00
3473O-H stretch of water or
carboxylic acid1.99 0.96
Support characterization with DRIFTS
4000 3500 1750 1500 1250 1000 750 500 250
Wavenumber (cm-1)
Sig
nal
(a.u
.)
NDC
VXC
[2] Fanning et al., Carbon, 1993, 31, 721–730
[3] Collins et al., Carbon, 2013, 57, 174–183
Karanjkar et al.; “Effect of carbon support on RhRe bifunctional catalysts for selective hydrogenolysis of tetrahydropyran-2-
methanol” RSC Catalysis Science and Technology, in press.
Characterization of Bimetallic Catalysts
† Reaction conditions for batch reactions: 120 oC, 34 bar H2, 5% aq. THP-2M (Initial reaction volume = 25 mL),
catalyst: RhRe/C, catalyst:feedstock (g/g) = 1:7, Reaction time = 4 h
24
Catalyst Rh/NDC RhRe/NDC Rh/VXC RhRe/VXC
Rh loading (wt%) 4.1 4.0 4.1 4.0
Rh:Re atomic ratio - 1:0.5 - 1:0.5
Rh atom density
(atoms/nm2)0.36 0.36 1.02 1.00
CO uptake (μmol/g) 204 232 130 76
CO:Rh (mol:mol) 0.51 0.60 0.32 0.19
Rate of THP-2M [†]
hydrogenolysis
(μmol/g/min)
1 76
Karanjkar et al.; “Effect of carbon support on RhRe bifunctional catalysts for selective hydrogenolysis of tetrahydropyran-2-
methanol” RSC Catalysis Science and Technology, in press.
X-ray Absorption Near Edge Structure
10.52 10.53 10.54 10.55 10.560
1
2
3
4
Re foil
ReO2
Re2O7
RhRe/NDC
reduced at 200 oC
RhRe/VXC
reduced at 200 oC
Energy (keV)
No
rmali
zed
ab
sorp
tio
n
CatalystTreatment prior
to scan in He
XANES fit for Re edge
Re(VII) Re(IV) Re(0)
Re/NDC 200 0C reduction 0.298 0.702 -
Re/VXC 200 0C reduction 0.358 0.642 -
Re catalysts RhRe catalysts
25
CatalystTreatment prior
to scan in He
XANES fit for Re edge
Re(VII) Re(IV) Re(0)
RhRe/NDC 200 0C reduction - 0.678 0.322
RhRe/VXC 200 0C reduction - 0.610 0.390
10.52 10.53 10.54 10.55 10.560
1
2
3
4
Energy (keV)
No
rmali
zed
ab
sorp
tio
n
Re foil
ReO2
Re2O7Re/NDC
reduced at 200 oC
Re/VXC
reduced at 200 oC
Karanjkar et al.; “Effect of carbon support on RhRe bifunctional catalysts for selective hydrogenolysis of tetrahydropyran-2-
methanol” RSC Catalysis Science and Technology, in press.
Scanning Transmission Electron Microscopy (STEM)
26
RhRe/NDC
RhRe/VXC
0 1 2 3 4 5 6 7 8 9 10 150.0
0.1
0.2
0.3
0.4
0.5
Particle size (nm)
Fra
cti
on
Average = 1.98±0.73 nm
793 particles analyzed
0 1 2 3 4 5 6 7 8 9 10 150.0
0.2
0.4
0.6
0.8
1.0
Particle size (nm)
Fra
cti
on
Average = 1.61±0.61 nm
868 particles analyzed
Karanjkar et al.; “Effect of carbon support on RhRe bifunctional catalysts for selective hydrogenolysis of tetrahydropyran-2-
methanol” RSC Catalysis Science and Technology, in press.
STEM-EDS images for catalyst nanoparticles
27
Map
Drift ref.
Rh
Re
Map
Drift ref.
Rh
Re
RhRe/NDC
RhRe/VXC
Avg. particle size : 1.61±0.61 nm
Avg. particle size : 1.98±0.73 nm
Karanjkar et al.; “Effect of carbon support on RhRe bifunctional catalysts for selective hydrogenolysis of tetrahydropyran-2-
methanol” RSC Catalysis Science and Technology, in press.
STEM-EDS indicates segregation of Re species in NDC
28
Re content (atomic %)
Nu
mb
er
of
part
icle
s
0 10 20 30 40 50 60 70 80 90 1000
5
10
15
61.3 atomic% Re
Re content (atomic %)
Nu
mb
er
of
part
icle
s
0 10 20 30 40 50 60 70 80 90 1000
5
10
36.7 atomic% Re
Theoretical ICP EDS
Re content
(% atomic)33.3% 35.5% 61.3%
Rh:Re
(mol:mol)1:0.5 1:0.55 1:1.58
Theoretical ICP EDS
Re content
(% atomic)33.3% 33.8% 36.7%
Rh:Re
(mol:mol)1:0.5 1:0.51 1:0.58
RhRe/NDC
RhRe/VXC
Note: The distribution considers composition of ~60 particles analyzed with EDS
29
Note: Schematic is for visualization purposes only!
RhRe/NDC RhRe/VXC
• Nanoparticles with relatively uniform
composition
• Anchoring of metals/metal-precursors
is relatively absent because of low
surface oxygen
• Formation of small Rh particles (<1
nm) may be avoided because of smaller
surface area of support
• Nanoparticles with segrated particle
composition
• Many small particles (<1 nm) rich in
Rh are present that evade detection in
STEM
• Many Re only particles also present and
larger particles are rich in Re
• Higher surface oxygen content may
restrict mobility of metals/metal-
precursors resulting in segregation of
Rh and Re
100% Re
Tiny Rh
particles
(<1 nm)
65% Re
~33% Re
Conclusion
• New pathways for production of high value oxygenated commodity chemicals from biomass
• Cellulose can be converted into LGO and HMF in high yields in polar aprotic solvents
• LGO is a promising platform molecule• LGO and HMF hydrogenated into THFDM which
then undergoes hydrogenolysis into 1,6 hexanediol
• 1,5 pentanediol can be produced from biomass without expensive RhRe catalysts
30
31
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