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Energy Technologies, Inc. Mansfield Ohio 44902
Point of Use Hydrogen Production From Three Feed Stocks Without Parasitic Loads
T. D. Lowe PhD P. D. Madden PE
Energy Technologies, Inc.Mansfield, Ohio 44902
November 11, 2014
Contact: tdlowe@ruggedsystems.com pdmadden@ruggedsystems.com
Energy Technologies, Inc. Mansfield Ohio 44902
Requirement for Hydrogen
• Fuel Cells need a hydrogen source • In general, there is a lack of existing hydrogen infrastructures• For mobile or remote applications (i.e. military):
- Needs to be easily deployable
- Needs to be able to utilize locally available feedstocks
• This need for hydrogen anywhere has lead ETI to develop a rugged, tactical Hydrogen Fuel Reformation System (HFRS) that accepts multiple feedstocks.
Energy Technologies, Inc. Mansfield Ohio 44902
Hydrogen Fuel Reformation System
Topics for this Presentation:
• Defining Base-Facilitated Reformation (BFR)
• BFR reforming-test results– Carbon Base Liquid fuels
– Solid fuels (Biomass)
• Economics
• Commercialization
• By-Product (carbonate) recycling
• Summary
Energy Technologies, Inc. Mansfield Ohio 44902
Fuel Fuel
� •Alkaline material is used as a reactant in the reformation process
� � • Carbonate is formed as a product instead of CO2
BFR SR
Na2CO3, K2CO3, CaCO3
etc..
NaOH, KOH, Ca(OH)2 etc..(H2O) H2
What is Base-Facilitated Reforming (BFR)?
H2O(steam) H2, CO2, (CO)
Energy Technologies, Inc. Mansfield Ohio 44902
Base-Facilitated ReformingCH4 + 2NaOH + H2O ↔ Na2CO3 + 4H2
Steam ReformingCH4 + 2H2O ↔ CO2 + 4H2
CH4 + H2O ↔ CO + 3H2
CO + H2O ↔ CO2 + H2 Gas Shift
------------------------------ CH4 + 2H2O ↔ CO2 + 4H2
Example – Methane (CH4)
Energy Technologies, Inc. Mansfield Ohio 44902
Example – Methanol (CH3OH)
Base-Facilitated ReformingCH3OH + 2NaOH ↔ Na2CO3 + 3H2
Steam ReformingCH3OH + H2O ↔ CO2 + 3H2
CH3OH ↔ CO + 2H2
CO + H2O ↔ CO2 + H2 Gas Shift
------------------------------- CH3OH + H2O ↔ CO2 + 3H2
Energy Technologies, Inc. Mansfield Ohio 44902
Example – Ethanol (C2H5OH)
Base-Facilitated ReformingC2H5OH + 4NaOH + H2O ↔ 2Na2CO3 + 6H2
Steam ReformingC2H5OH + 3H2O ↔ 2CO2 + 6H2
C2H5OH + H2O ↔ 2CO + 4H2
2CO + 2H2O ↔ 2CO2 + 2H2 Gas Shift
------------------------------------- C2H5OH + 3H2O ↔ 2CO2 + 6H2
Energy Technologies, Inc. Mansfield Ohio 44902
Example – Glycerol (C3H5(OH)3)
Base-Facilitated ReformingC3H5(OH)3 + 6NaOH ↔ 3Na2CO3 + 7H2
Steam ReformingC3H5(OH)3 + 3H2O ↔ 3CO2 + 7H2
C3H5 (OH)3 ↔ 3CO + 4H2
3CO + 3H2O ↔ 3CO2 + 3H2 Gas Shift
------------------------------------- C3H5(OH)3 + 3H2O ↔ 2CO2 + 6H2
Energy Technologies, Inc. Mansfield Ohio 44902
Example – Glucose (C6H12O)6)
Base-Facilitated ReformingC6H12O6 + 12NaOH ↔ 6Na2CO3 + 12H2
Steam ReformingC6H12O6 + 6 H2O ↔ 6CO2 + 12H2
C6H12 O6↔ 6CO + 6H2
6CO + 6H2O ↔ 6CO2 +6H2 Gas Shift
------------------------------------- C6H12O6 + 6H2O ↔ 6CO2 + 6H2
Energy Technologies, Inc. Mansfield Ohio 44902
Example – Cellulose (C6H10O5 )n)
Base-Facilitated Reforming(C6H10O5)n + 12nNaOH + nH2O ↔ 6nNa2CO3 + 12nH2
Steam Reforming(C6H10O5)n + 7nH2O ↔ 6nCO2 + 12nH2
(C6H10 O5)n + nH2O ↔ 6nCO + 6nH2
6nCO + 6nH2O ↔ 6nCO2 +6nH2 Gas Shift
-------------------------------------(C6H10 O5)n +7nH2O ↔6nCO2 + 12nH2
Energy Technologies, Inc. Mansfield Ohio 44902
CO2
H2 + CO H2 + CO2
WGS Fuel CellPSAReactor
Steam Reforming Process
Fuel
H2O(steam)
H2catalyst
WGS – Water Gas ShiftPSA – Pressure Swing Absorption
Energy Technologies, Inc. Mansfield Ohio 44902
Base-Facilitated Reformation ProcessSimple One Step Reactionto High Purity Hydrogen
Fuel
H2
NaOH H2O
Reactor
Carbonaterecycling
Fuel Cell
Energy Technologies, Inc. Mansfield Ohio 44902
Base-Facilitated ReformingMore Favorable ThermodynamicsLower Operating Temperatures
Gibbs free energies ΔG° are significantly lower in the BFR process compared to Steam Reforming – Lower reaction temperatures
Fuel Δ G° (Kcal/mole) Reaction temperature (˚C)
CH4 (SR) +31.2 900
CH4 (BFR) +0.55 300
CH3OH (SR) +2.2 350
CH3OH (BFR) -28.5 120
C2H5OH (SR) +23.3 800
C2H5OH (BFR) -38.3 130
C6H12O6 (SR) -8.2 900
C6H12O6 (BFR) -192 220
Energy Technologies, Inc. Mansfield Ohio 44902
Base-Facilitated ReformingMore Favorable Thermodynamics
Lower Heat Requirement
Enthalpies ΔH° are significantly lower in the BFR process compared toSteam Reforming – Lower heat of reaction and higher efficiencies
Fuel ΔH°(Kcal/mole) Efficiency(%)CH4 (SR) Methane +60.5 92
CH4 (BFR) Methane +12.9 113
CH3OH (SR) Methanol +31.5 94
CH3OH (BFR) Methanol -9.7 114-121
C2H5OH (SR) Ethanol +83.3 92
C2H5OH (BFR) Ethanol +1.0 117
C6H12O6 (SR) Glucose +150.2 92
C6H12O6 (BFR) Glucose -96.8 114-136
C12H22O11 (SR) Sucrose +213.4 91
C12H22O11(BFR) Sucrose -291.3 112-136
C6H10O5 (SR) Cellulose +146.1 90
C6H10O5 (BFR) Cellulose -169.3 112-153
Energy Technologies, Inc. Mansfield Ohio 44902
Advantages of BFR ProcessSummary
• One step reaction – making reformer design simpler• No CO or CO2 gases formed – Gas shift and PSA not necessary.• Pure hydrogen is formed.• Greener process – CO2 sequestered as Na2CO3
• Lower operating temperatures. • Operation in liquid phase is possible.
• Batch or continuous operation possible
• Lower heat (ΔH˚) required for reforming so more efficient and less expensive operation
• Can be used to reform variety of fuels. Reforming renewable fuels is possible.
Energy Technologies, Inc. Mansfield Ohio 44902
Base-Facilitated Reformation (BFR)
• BFR reforming - test results– Liquid fuels
– Solid fuels (Biomass)
Energy Technologies, Inc. Mansfield Ohio 44902
Reformation Fuels DemonstratedETI’s BFR Process Reforms Multiple Fuels
Examples of Fuels Reformed by ETI’s Base-Facilitated ReformationAlcohols: Methanol, Ethanol, Crude Ethanol, E95, Ethylene Glycol, Glycerol (from bio-diesel plant)
Sugars, Starch: Glucose, Fructose, Starch (Cornstarch, Potato starch)
Fossil Fuels: Methane, Coal
Biomass: Grass, Sawdust, Woodchips, Corn, Potato Peels, Cellulose, Hemicelluloses (Xylan from Beachwood), Lignin (Organosolv)
Municipal Solid Waste: Paper
Energy Technologies, Inc. Mansfield Ohio 44902
140° C 120° C700
H2
Gen
erat
on (
cc/g
cat
alys
t)
130° C
Base-Facilitated Methanol ReformationDependence on Temperature - Batch Reactor
800
600 catalyst A500
400
300
200
100
0 0 25 50 75 100 125 150
Time (minutes)
Energy Technologies, Inc. Mansfield Ohio 44902
1600 120 °C130 °C140 oC
Base-Facilitated Ethanol ReformationDependence on Temperature - Batch Reactor
0 50 100 150 200
Time (minutes)
catalyst A
1800
1400
1200
1000
800
600
400
200
00
H2
Gen
erat
on (
cc/g
cat
alys
t)
Energy Technologies, Inc. Mansfield Ohio 44902
Ac
cu
mu
late
dH
2(c
c)
BFR of Glycerol at 200oC
Catalyst A
Base-Facilitated Reformation of Glycerol – Batch Reactor
0 50 100 150 200 250 300
Time (minutes)
8000
7000
6000
5000
4000
3000
2000
1000
0
Energy Technologies, Inc. Mansfield Ohio 44902
Acc
um
ula
ted
Hyd
roge
n
(cc)
Corn Kernals, NaOH, catalyst
Base-Facilitated Reformation of Corn Kernels – Batch Reactor
1600
1400
1200 180˚
1000
800
600 160˚C400
200
0 0 20 40 60 80 100 120 140
Time (minutes)
Energy Technologies, Inc. Mansfield Ohio 44902
2500
2000
1500
1000
500
0
0 50 100 150 200 250
Time (minutes)
Base-Facilitated Reformation of Wood - Batch Reactor
BFR of Wood (saw dust) 220˚-280˚C
Catalyst A
Acc
um
ula
ted
Hyd
roge
n
(cc)
Energy Technologies, Inc. Mansfield Ohio 44902
Acc
um
ula
ted
Hyd
rog
en (
cc)
7000
Base-Facilitated Reformation of Cornstalks - Batch Reactor
8000o
6000
5000
4000
3000
2000
1000
0 0 20 40 60 80 100 120
Time (minutes)
BFR of ground cornstalks at 190 C
Catalyst A
Energy Technologies, Inc. Mansfield Ohio 44902
Acc
um
ula
ted
Hyd
roge
n (
cc)
Base-Facilitated Reformation of Grass - Batch Reactor
2000
1600
1200
800
400
0 0 50 100 150 200 250 300 350
Time(minutes)
Grass, Ca(OH)2, Catalyst
Energy Technologies, Inc. Mansfield Ohio 44902
Acc
um
ula
ted
Hyd
rog
en (
cc
)
Base-Facilitated Reformation of Paper - Batch Reactor
8000
7000
6000
5000
4000
3000
2000
1000
0
BFR of paper in a batch reactor at 220º C
0 50 100 150 200 250 300
Time (minutes)
Energy Technologies, Inc. Mansfield Ohio 44902
Hyd
rog
en v
olu
me
accu
mu
late
d (
lite
r)
Base-Facilitated Reformation of Biomass Components - Batch Reactor
3
2.5
2 300˚C
240˚C
0
0 10 20 30 40
Time (hours)
BFR reforming of biomass components
Catalyst B
Lignin
hemi-cellulose
e cellulose0.5
1.5
1
Energy Technologies, Inc. Mansfield Ohio 44902
Base-Facilitated Reformation
Economics
Energy Technologies, Inc. Mansfield Ohio 44902
Economics of Base-Facilitated Reformation
�•Used DOE H2A economic analysis tool
� • Net present value with Internal Rate of Return (IRR): 10%
� • 20 years depreciation on facility equipment
� • 10 years depreciation on reactor
� • Cost of feedstock and electricity taken from Energy Information Administration (EIA) Annual Energy Outlook report
Energy Technologies, Inc. Mansfield Ohio 44902
Methanol Feedstock ($2.54/kg) Ethanol Feedstock ($3.59/kg)
Biomass Feedstock ($1.93/kg)
$0.67
$0.71
$0.38
$0.68
$1.17 $0.38
Reformation at 1,500 kg Hydrogen Per DayCost Structure
$0.57
Capital eqFixed O&MFeedstockUtilities
$0.31$0.31
Capital eqFixed O&MFeedstockUtilities
Capital eqFixed O&MFeedstockUtilities$2.19
$0.31
$0.38
Energy Technologies, Inc. Mansfield Ohio 44902
Base-Facilitated Reformation (BFR)
• Commercialization
Energy Technologies, Inc. Mansfield Ohio 44902
Lab Batchreactor 100 mlopen volume
(rate: 3L H2/hr for 0.5hrs)
Semi-Continuous reactor with storage tank 4L open volume (rate: 10L H2/hr
for 8 hrs)
Continuous reactor producing H2 (rate: 100L/hr as long as needed)
Reactors For Base-Facilitated Reformation
Semi-Continuous Continuous
Batch
Energy Technologies, Inc. Mansfield Ohio 44902
Prototype 10 kg H2/day Base-Facilitated
Solid Biomass Fluidized Bed Reactor
Energy Technologies, Inc. Mansfield Ohio 44902
By-Product (carbonate) Recycling
Energy Technologies, Inc. Mansfield Ohio 44902
What do we do with solid carbonate?
•ƒ Dispose the carbonate to sequester CO2
• Use the carbonate to generate pure CO2 for various industrial
applications (soda, liquid fuel synthesis, etc..)
• Sell Na2CO3 or CaCO3 for various industrial applications (i.e. glass)
• Recycling back to hydroxide
Energy Technologies, Inc. Mansfield Ohio 44902
Recycling of Na2CO3
�•Na2CO3 + Ca(OH)2 → CaCO3 + 2NaOH
� • CaCO3 heat → CaO + CO2
� • CaO + H2O → Ca(OH)2
-----------------------------------------------------
Recausticizing - a common commercial process in the paper mill industry
Energy Technologies, Inc. Mansfield Ohio 44902
H2
(C6H10O5)n + 12nNaOH + nH2O ↔
6nNa2CO3 + 12nH2
CaCO3
Base-Facilitated ReformationFlow Diagram of Biomass (solid) BFR Process
Make-up NaOH
NaOH
Fluidized Bed ReactorChopper/Shredder
Biomass
Evaporator
Precipitator
Na2CO3 + Ca(OH)2 + H2O
CaCO3 + 2NaOH + H2O
Ca(OH)2 Liq. Na2CO3
Water
Energy Technologies, Inc. Mansfield Ohio 44902
Base-Facilitated ReformationFlow Schematic of Recycling Process
CO2
CaCO3
Ca(OH)2 Hydration
recycled Mixer H2O
CalcinationBurner850˚Heat
CaO Solid
Energy Technologies, Inc. Mansfield Ohio 44902
Summary
�•The Base-Facilitated Reforming (BFR) process has been demonstrated on wide variety of fuels. A biomass reforming process towards commercialization is under development.
� • The reforming temperatures using the BFR process are significantly lower than the steam reformation process of the fuels.
� • Reformation in a liquid phase at low temperatures of some fuels has been demonstrated.
� • The BFR process exhibits good rates at the low temperatures of operation.
� • The BFR process is a simple one step process. Pure H2 and no CO and CO2 produced. WGS reaction and PSA are therefore avoided and the process is environmentally clean.
� • The BFR process is economically feasible and competes well with other technologies.
Energy Technologies, Inc. Mansfield Ohio 44902
Summary
� • Base-facilitated reforming (BFR) process has been demonstrated on wide variety of fuels.� • High conversion of raw biomass feedstocks and high yield (close to 100%) of H2 was obtained using BFR.
� • The process operates at low temperatures (<300˚) without CO and CO2
gases and it is economically feasible.
� • Developmental work towards commercialization is underway.
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