hydrogen production from 3 feed stocks w/o parasitic loads

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: [email protected] [email protected]

mailto:[email protected]


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


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)


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)


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


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


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


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


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


CO2

H2 + CO H2 + CO2

WGS Fuel CellPSAReactor

Steam Reforming Process

Fuel

H2O(steam)

H2catalyst

WGS – Water Gas ShiftPSA – Pressure Swing Absorption


Base-Facilitated Reformation ProcessSimple One Step Reactionto High Purity Hydrogen

Fuel

H2

NaOH H2O

Reactor

Carbonaterecycling

Fuel Cell


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


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


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.


Base-Facilitated Reformation (BFR)

• BFR reforming - test results– Liquid fuels

– Solid fuels (Biomass)


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


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)


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)


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


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)


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)


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


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


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)


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


Base-Facilitated Reformation

Economics


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


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


Base-Facilitated Reformation (BFR)

• Commercialization


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


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

�•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


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


Base-Facilitated ReformationFlow Schematic of Recycling Process

CO2

CaCO3

Ca(OH)2 Hydration

recycled Mixer H2O

CalcinationBurner850˚Heat

CaO Solid


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.


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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