Download Low Temperature Conversion of Biomass to Hydrogen, High Valued

Low temperature conversion of biomass to
hydrogen, high valued chemicals and
electric power
Dr. Yulin Deng
Professor
School of Chemical and Biomolecular Engineering
Institute of Paper Science and Technology
Georgia Institute of Technology
Coal to electricity:
Biomass to electricity:
http://www.nigeriaelectricityhub.com/2015/11/25/coal-to-
http://4planetenergy.com/index.php/products/biogas-biomassgeneration
power-critical-factor-in-nigerias-energy-mix/
CO2
Atomic H:C ratio x10
1.8
1.6
O2
Peat
1.4
1.2
Lignite
Coal
1.0
0.8
I nc
rea
sed
0.6
0.4
0.2
0.0
0.0
e-
e-
Biomass
hea
tin
g
Anthracite
0.2
0.4
0.6
val
ue
0.8
1.0
H+
Substrates
H2O
Wood
Wheat straw
Miscanthus
Rice straw
Barley straw
Cellulose
Lignin
e-
Lignocellulosic
biomass
Metabolism
e-
M
e-
H+
e-
M
H+
e-
M
H+
e-
H+
CO2
H 2O
H+
H+
1.2
Atomic O:C ratio
Micro-organisms
Anode Chamber
van Krevelen diagram of several solid fuels
(Redrawn after (McKendry, 2002))
PEM
Cathode Chamber
Principles of lignocellulosic biomass fueled dual chamber MFC
High Performance Low
Temperature Direct Biomass
Fuel Cells
Directly convert native biomass for electricity
Fuel cell
• Pt catalysts on anode and cathode
• Polymer ion-exchange membrane (PEM)
• Run at 60–100 oC
https://en.wikipedia.org/wiki/Fuel_cell
H2 or CH3OH are most common fuels. Low molecular alcohols such as
ethanol, are ok, but conversion efficiency is low;
No one has reported to use polymer as direct fuel
The direct biomass fuel cell
• Polyoxometalates (POMs) used as photocatalysts
• POMs used as charge carrier
ee-
POMOX
O2
Biomass
O2
Biomass
H2O
Pt/C
Pt/C
Oxidized Products
COx
H2O
POMRe
Charge carrier&
Photocatalyst
Carbon
Pt/C
Intermediate catalyst that can oxidize biomass under solar light irradiation or
thermal treatment, but it can also transport the biomass charge to oxygen through
an electric circle
*e-
Direct biomass fuel working mechanism
Excited to
conduction band
Return to
valance band
*e-
Anode
Cathode
*e-
Polyoxometalate (POM)
O2 + H+ + e-
e-
Biomass
Biomass oligomer, CO2, etc.
H+
H2O
Mechanism of solar-induced biomass fuel cell
Starch-O-[HPMoVI11 MoVO40 ]3- +[HPMoVI11 MoVO40 ]3-
1/2 O2+ 2e- + 2H+
anode


cathode
¾¾¾¾®
2[PMoVI12 O40 ]3- + Oxidized starch oligmers + 2e- +2H+
H2O
W. Liu, W. Mu, M. Liu, X. Zhang, H. Cai, Y. Deng, Solar-induced direct biomass-to-electricity hybrid cell using
polyoxometalate as photo-catalyst and charge carrier, Nature Communications 5, (2014) 3208
Results
W. Liu, W. Mu, M. Liu, X. Zhang, H. Cai, Y. Deng, Solar-induced direct biomass-to-electricity hybrid cell using
polyoxometalate as photo-catalyst and charge carrier, Nature Communications 5, (2014) 3208
Liquid Catalyst Fuel Cell Mechanism
W. Liu, W. Mu, and Y. Deng, High-Performance Liquid-Catalyst Fuel Cell for Direct Biomass-into-Electricity
Conversion, Angew. Chem., Int Ed, (2014), 53 (49), 13558
Anode and cathode solutions before and
after discharge
Anode (glucose/POM-1)
Discharge
Heating
Cathode (POM-II and O2)
Reduced
Oxidized by O2
W. Liu, W. Mu, and Y. Deng, High-Performance Liquid-Catalyst Fuel Cell for Direct Biomass-into-Electricity
Conversion, Angew. Chem., Int Ed, (2014), 53 (49), 13558
Complete liquid based biomass fuel cells
Fresh bush allamanda
Switchgrass
Starch
Cellulose
A
50
Voltage (V)
40
0.4
30
20
0.3
10
0.2
B
2
0.5
Power Density (mW/cm )
40
2
0.6
Starch based fuel cell
60
Power Density (mW/cm )
0.7
30
20
10
0
0.1
0
50
100
150
200
2
Current Density (mA/cm )
0
0
50
100
150
200
250
Time (min)
Fuel cell efficiency can be as high as 95%, but heat engine thermal
conversion efficiency is usually 35-40%
W. Liu, W. Mu, and Y. Deng, High-Performance Liquid-Catalyst Fuel Cell for Direct Biomass-into-Electricity
Conversion, Angew. Chem., Int Ed, (2014), 53 (49), 13558
Ferric ion pair as the oxidant/charge transfer catalyst
H2O
VO2+/VO2+
e-
O2
Wheat straw + H2O + Fe3+
Degraded chemicals + H+ + Fe2+ + CO2
Cathode
Anode
Fe2+ = Fe3+ + eStandard electric potential: 0.74V
VO2+ + 2H+ + e- = VO2+ + H2O
vanadium(III)
vanadium(II)
electric potential: ~9.2V
Lignin electric potential: ~3.5V
vanadium(II)
vanadium(III)
Ferric ion pair as the oxidant/charge transfer catalyst
A
100
Voltage (V)
0.4
80
60
0.3
40
0.2
20
0.1
2
0.5
Current density
350
Power Density (mW/cm2)
Wheat straw
0g
5g
10 g
B 400
Current Density (mA/cm )
0.6
300
250
200
150
100
50
0.0
0
0
100
200
300
400
2
Current Density(mA/cm )
500
0
0
2
4
6
Time (hr)
8
10
12
+ FeCl3 as the anode fuel
The power density is ~6,700 times higher than
microbial fuel cell reported in literature with wheat
straw
J. Gong, W. Liu, X. Du, C. Liu, Z. Zhang, F. Sun, L. Yang, D. Xu, H. Guo, Y. Deng, ChemSusChem, (2017), 506
High Performance Low
Temperature Biomass to
Hydrogen
Hydrogen: the most clean energy
Petroleum reforming and coal
gasification: 96% of the global hydrogen
http://en.wikipedia.org/wiki/Catalytic_reforming
Bio-hydrogen
http://www.rsc.org/chemistryworld/News/2011/February
/11021103.asp
H+ + e -
Cathode
Catalytic reaction is in the
solution but not on the
electrode surface: no noble
metal is needed
or heat
2Starch-OH + 2[PMoVI12 O40 ]3- light
 Starch-O-[HPMoVI11 MoVO40]3-+[HPMoVI11MoVO40]3- +Oxidized starch oligomers
W. Liu, Y. Cui, X. Du, Z. Zhang, Z. Chao, Y. Deng, Energy & Environmental Science, (2016) 9, 467
½ H2
Using phosphomolybdic acid (H3PMo12O40,
noted as PMo12)
Visible light
-2
0.4
H3PO4-Glucose
Heating:
PMo12-Lignin
0.3
PMo12-Cellulose
0.2
PMo12-Starch
PMo12-Glucose
m=2.36
0.1
2.02
1.12
Heating:
PMo12-Switchgrass
PMo12-Popolar
-2
Current Density (A cm )
0.4
B
H3PO4
Current Density (A cm )
A
0.3
PMo12-Algea
0.2
0.1
1.06
0.0
0.3
0.4
0.5
0.6 0.7 0.8 0.9
Applied Potential (V)
1.0
1.1
0.0
0.2
0.4
0.6
0.8
1.0
1.2
Applied Potential (V)
or heat
Starch-O-[HPMoVI11 MoVO40 ]3-+[HPMoVI11 MoVO40]3- +Oxidized starch oligomers light

2Starch-OH + 2[PMoVI12 O40 ]3-
W. Liu, Y. Cui, X. Du, Z. Zhang, Z. Chao, Y. Deng, Energy & Environmental Science, (2016) 9, 467
Using phosphomolybdic acid (H3PMo12O40,
noted as PMo12)
B
A
25
-2
0.4
0.1 A cm
-2
0.05 A cm
0.3
H2 V (ml)
Applied Potential (V)
20
24 mL H2
0.2
24 mL H2
15
-2
10
0.1 A cm Measured
-2
0.1 A cm Calculated
0.1
-2
5
0.05 A cm Measured
-2
0.05 A cm Calculated
0
0.0
0
1000
2000
3000
4000
Time (s)
H4SiW12O40 (SiW12)-glucose
solution
5000
0
1000
2000
3000
4000
5000
Time (s)
Solid line: calculated value according to
Faraday’s law.
W. Liu, Y. Cui, X. Du, Z. Zhang, Z. Chao, Y. Deng, Energy & Environmental Science, (2016) 9, 467
Fe3+-biomass solution for hydrogen production
HCl
1 M glucose + HCl
0.4
0.1 M Fe3+ +1M glucose+HCl
0.2 M Fe3+ +1M glucose+HCl
0.5 M Fe3+ +1M glucose+HCl
Current (A)
0.3
1.0 M Fe3+ +1M glucose+HCl
0.2
0.1
0.0
0.0
0.2
0.4
0.6
0.8
1.0
1.2
Applied Potential (V)
Current (A)
0.3
1 M glucose+HCl no Fe3+
1 M Fe3++1 M glucose+HCl
1 M Fe3++0.5 M glucose+HCl
1 M Fe3++0.25 M glucose+HCl
1 M Fe3++0.1 M glucose+HCl
1 M Fe3++0.05 M glucose+HCl
0.3
0.2
0.1
0.0
0.0
Glucose
Starch
Cellulose
0.4
Current (A)
0.4
0.2
0.1
0.2
0.4
0.6
0.8
Applied potencial (V)
1.0
1.2
0.0
0.0
0.2
0.4
0.6
0.8
1.0
Applied potential (V)
W. Liu, Y. Cui, X. Du, Z. Zhang, Z. Chao, Y. Deng, Energy & Environmental Science, (2016) 9, 467
1.2
Faraday’s efficiency is about 95% for glucose-Fe ion solution
W. Liu, Y. Cui, X. Du, Z. Zhang, Z. Chao, Y. Deng, Energy & Environmental Science, (2016) 9, 467
What are the residual products of the biomass
– Polysaccharides such as starch and glucose can completely converted to H 2 and
CO2
– Aromatic or aliphatic chemicals are difficult react with POM by heating, but can
completely converted to CO2 by light irradiation in the presence of POM
– The residual products also depends on the POM concentration, type of POM,
reaction temperature and reaction time
initial starch
starch after electrolysis cycles
cellulose after electrolysis cycles
initial lignin
lignin after electrolysis cycles
10
2
10
3
10
4
10
5
10
6
10
7
Molecular Weight Distribution
W. Liu, Y. Cui, X. Du, Z. Zhang, Z. Chao, Y. Deng, Energy & Environmental Science, (2016) 9, 467
Lignin oxidation by PMo12 or Fe3+
GC-MS Results: Liquid
PMo12-KL
Solvent: Ethyl ether
Guaiacol
FeCl3-KL
Vanillin
3
5
7
9
11
Retention time (min)
13
15
23
Background – Lignin depolymerized by Polyoxometalates (POMs)
Thermodynamic Conditions [4]
E(lignin) < E(POM) < E(O2) = 1.22 - 0.059 pH
0.6-1.2
0.6-0.8
POM(Ox) + lignin  H-POM(Red) + lignin(O x)
POM(Red) + (m/4)O2 + mH+  POM(Ox) + (m/2)H2O
Lignin to chemicals via oxygen oxidation
24
Lignin depolymerization – with a co-catalyst
Conversion (input – solid)/ input: 90.8%
0.2 g lignin + 1.82 g (0.1 M) PMo12 in + H2O
150oC, 160 psi O2 1.5 h
25
General conclusions
• With selected redox pair oxidation agent, biomass can be effectively
converted to electricity with a novel flow fuel cell
• Electrolysis of biomass to hydrogen is a low energy cost technology
(saving) 86% of electrolysis energy comparing to pure water
electrolysis technique.
• No noble metal is needed in anode
• The total cost, including heating energy, is about $1.8-2/kg H2,
(commercial hydrogen is $3.5 kg)
• We developed a new catalyst system that can depolymerize more
than 90% of lignin in water at 160 oC or lower. The products are
phenol, vanillin, vanillin acid etc.
• Separation and purification of depolymerized chemicals are new
research areas
Acknowledgement
Tanks! Questions?