Hydrogen Production From 3 Feed Stocks W/O Parasitic Loads

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.

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

What is Base-Facilitated Reforming (BFR)?
ƒ •Alkaline material is used as a reactant in the reformation process
ƒ ƒ • Carbonate is formed as a product instead of CO2
BFR SR
NaOH, KOH,
Ca(OH)2 etc..
(H2O) H2
Fuel Fuel
Na2CO3, K2CO3, CaCO3
etc..
H2O(steam) H2, CO2, (CO)

Example – Methane (CH4)
Base-Facilitated Reforming
CH4 + 2NaOH + H2O ↔ Na2CO3 + 4H2
Steam Reforming
CH4 + 2H2O ↔ CO2 + 4H2
CH4 + H2O ↔ CO + 3H2
CO + H2O ↔ CO2 + H2 Gas Shift
------------------------------
CH4 + 2H2O ↔ CO2 + 4H2

Example – Methanol (CH3OH)
CH3OH + 2NaOH ↔ Na2CO3 + 3H2
Steam Reforming
CH3OH + H2O ↔ CO2 + 3H2
CH3OH ↔ CO + 2H2
CO + H2O ↔ CO2 + H2 Gas Shift
-------------------------------
CH3OH + H2O ↔ CO2 + 3H2

Example – Ethanol (C2H5OH)
C2H5OH + 4NaOH + H2O ↔ 2Na2CO3 + 6H2
Steam Reforming
C2H5OH + 3H2O ↔ 2CO2 + 6H2
C2H5OH + H2O ↔ 2CO + 4H2
2CO + 2H2O ↔ 2CO2 + 2H2 Gas Shift
-------------------------------------
C2H5OH + 3H2O ↔ 2CO2 + 6H2

Example – Glycerol (C3H5(OH)3)
C3H5(OH)3 + 6NaOH ↔ 3Na2CO3 + 7H2
Steam Reforming
C3H5(OH)3 + 3H2O ↔ 3CO2 + 7H2
C3H5 (OH)3 ↔ 3CO + 4H2
3CO + 3H2O ↔ 3CO2 + 3H2 Gas Shift
-------------------------------------
C3H5(OH)3 + 3H2O ↔ 2CO2 + 6H2

Example – Glucose (C6H12O)6)
C6H12O6 + 12NaOH ↔ 6Na2CO3 + 12H2
Steam Reforming
C6H12O6 + 6 H2O ↔ 6CO2 + 12H2
C6H12 O6↔ 6CO + 6H2
6CO + 6H2O ↔ 6CO2 +6H2 Gas Shift
-------------------------------------
C6H12O6 + 6H2O ↔ 6CO2 + 6H2

Example – Cellulose (C6H10O5 )n)
(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

Steam Reforming Process
Fuel
H2 catalyst
CO2
H2 + CO H2 + CO2
Reactor WGS PSA Fuel Cell
H2O(steam)
WGS – Water Gas Shift
PSA – Pressure Swing Absorption

Base-Facilitated Reformation Process
Simple One Step Reaction
to High Purity Hydrogen
Fuel
Reactor
H2
NaOH H2O
Carbonate
recycling
Fuel Cell

More Favorable Thermodynamics
Lower 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

More Favorable Thermodynamics
Lower Heat Requirement
Enthalpies ΔH° are significantly lower in the BFR process compared to
Steam 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

Advantages of BFR Process
Summary
• 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.

Base-Facilitated Reformation (BFR)
• BFR reforming - test results
– Liquid fuels
– Solid fuels (Biomass)

Reformation ET IF’us eBlsF DRe Pmrooncsetsrsa ted
Reforms Multiple Fuels
Examples of Fuels Reformed by ETI’s Base-Facilitated Reformation
Alcohols: 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

Base-Facilitated Methanol Reformation
Dependence on Temperature - Batch Reactor
140° C 120° C
800
700
H2 Generaton (cc/g catalyst)
130° C
600 catalyst A
500
400
300
200
100
0
0 25 50 75 100 125 150
Time (minutes)

Base-Facilitated Ethanol Reformation
Dependence on Temperature - Batch Reactor
1600 140 oC 130 °C 120 °C
catalyst A
0 50 100 150 200
Time (minutes)
1800
1400
1200
1000
800
600
400
200
00
H2 Generaton (cc/g catalyst)

Base-Facilitated Reformation of
Accumulated H2 (cc)
Glycerol – Batch Reactor
BFR of Glycerol at 200oC
Catalyst A
0 50 100 150 200 250 300
Time (minutes)
8000
7000
6000
5000
4000
3000
2000
1000
0

1600
1400
1200 180˚
1000
800
600 160˚C
400
200
0
Accumulated Hydrogen
(cc)
Corn Kernels – Batch Reactor
Corn Kernals, NaOH, catalyst
0 20 40 60 80 100 120 140
Time (minutes)

2500
2000
1500
1000
500
0
Wood - Batch Reactor
BFR of Wood (saw dust) 220˚-280˚C
0 50 100 150 200 250
Time (minutes)
Catalyst A
Accumulated Hydrogen
(cc)

Accumulated Hydrogen (cc)
8000
7000
Cornstalks - Batch Reactor
BFR of ground cornstalks at 190 C
o
6000
5000
4000
3000
2000
1000
0
Catalyst A
0 20 40 60 80 100 120
Time (minutes)

Grass - Batch Reactor
2000
1600
1200
800
400
0
Grass, Ca(OH)2, Catalyst
0 50 100 150 200 250 300 350
Time(minutes)

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)

Biomass Components - Batch Reactor
Hydrogen volume
accumulated (liter)
3
2.5
2 300˚C
BFR reforming of biomass components
240˚C
1.5
1
0
0 10 20 30 40
Time (hours)
Catalyst B
Lignin
hemi-cellulose
e cellulose
0.5

Base-Facilitated Reformation
Economics

Economics of Base-Facilitated Reformation
ƒ•Used DOE H2A economic analysis tool
ƒ • Net present value with Internal Rate of Return (IRR): 10%
ƒ • 20 years depreciation on facility equipment
ƒ • 10 years depreciation on reactor
ƒ • Cost of feedstock and electricity taken from Energy Information
Administration (EIA) Annual Energy Outlook report

Reformation at 1,500 kg Hydrogen Per Day
Methanol Feedstock ($2.54/kg) Ethanol Feedstock ($3.59/kg)
$0.31 $0.31
Biomass Feedstock ($1.93/kg)
$0.67
$0.71
$0.38
$0.68
$1.17 $0.38
Cost Structure
$0.57
Capital eq
Fixed O&M
Feedstock
Utilities
Capital eq
Fixed O&M
Feedstock
Utilities
Capital eq
Fixed O&M
Feedstock
$2.19 Utilities
$0.31
$0.38

Base-Facilitated Reformation (BFR)
• Commercialization

Reactors For Base-Facilitated Reformation
Lab Batch
reactor 100 ml
open volume
(rate: 3L H2/hr
for 0.5hrs)
Semi-Continuous Continuous
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)
Batch

Prototype 10 kg H2/day Base-Facilitated
Solid Biomass Fluidized Bed Reactor

By-Product (carbonate) Recycling

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

Recycling of Na2CO3
ƒ•Na2CO3 + Ca(OH)2 → CaCO3 + 2NaOH
ƒ • CaCO3
heat → CaO + CO2
ƒ • CaO + H2O → Ca(OH)2
-----------------------------------------------------
Recausticizing - a common commercial process in the paper mill industry

Flow Diagram of Biomass (solid) BFR Process
H2
(C6H10O5)n + 12nNaOH + nH2O ↔
6nNa2CO3 + 12nH2
CaCO3
Make-up NaOH
NaOH
Chopper/ Fluidized Bed Reactor
Shredder
Biomass
Evaporator
Precipitator
Na2CO3 + Ca(OH)2 + H2O
CaCO3 + 2NaOH + H2O
Ca(OH)2 Liq.
Na2CO3
Water

Flow Schematic of Recycling Process
Calcination
Burner
Heat 850˚
CO2
CaCO3
CaO Solid
Ca(OH)2 Hydration
recycled Mixer H2O

Summary
ƒ•The Base-Facilitated Reforming (BFR) process has been demonstrated on wide variety of
fuels. A biomass reforming process towards commercialization is under development.
ƒ • The reforming temperatures using the BFR process are significantly lower than the steam
reformation process of the fuels.
ƒ • Reformation in a liquid phase at low temperatures of some fuels has been demonstrated.
ƒ • The BFR process exhibits good rates at the low temperatures of operation.
ƒ • 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.
ƒ • The BFR process is economically feasible and competes well with other technologies.

Summary
ƒ • Base-facilitated reforming (BFR) process has been demonstrated on wide
variety of fuels.
ƒ
• High conversion of raw biomass feedstocks and high yield (close to 100%)
of H2 was obtained using BFR.
ƒ
• The process operates at low temperatures (<300˚) without CO and CO2
gases and it is economically feasible.
ƒ
• Developmental work towards commercialization is underway.

Hydrogen Production From 3 Feed Stocks W/O Parasitic Loads

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