Renewable Hydrogen and Olefinsby Autothermal Reforming

Lanny SchmidtDepartment of Chemical Engineering and Materials Science

University of Minnesota

Hydrogen Cluster ProgramsSeed GrantsMicro fuel cells Bill Smyrl CEMSHydrogen from ethanol Lanny Schmidt CEMSBiological hydrogen Mike Flickinger BiochemistrySolar hydrogen Jane Davidson ME)Photolytic hydrogen Kent Mann ChemistryHydrogen storage Eric Gant PhysicsMicrobial fuel cells Daniel Bond Biochemistry

Matching GrantsPhotosynthetic Bacterial Paints that Produce Hydrogen

Mike Flickinger UniversityRenewable Hydrogen and Chemicals from Ethanol

Lanny Schmidt Mn Corn Growers

Matching Grant ProposalsHydrogen Fueling StationDiesel Reforming in Autothermal ReactorsPhotolytic Hydrogen

…

Renewable Energy and Chemicals

Sometime we will switch to renewable chemicals and energysustainablenot importeddistributedno CO2

less pollution

Everyone agrees

When?5 years or 50 years?

How?What sources and what technologies?

Renewable Energy and ChemicalsCurrent drivers towards Renewable Energy

National SecurityGlobal WarmingRural Economic Development

Renewables must compete head-to-head with fossil fuelstotal supplyinfrastructureprice

Subsidiescritical issuenot simpleenergy is always heavily subsidized

Energy may the the most important problem in the 21st Centuryrequires radical thinking

The Hydrogen Economy

Code words for fuel cells60% versus Carnot efficiency of thermal enginesPEM fuel cells require hydrogen

Need hydrogenwind power with electrolysis for hydrogen storagefossil fuel reforming is next generationuse hydrogen for storage and transportation of energyhydrogen fueling station

Distributed energyno megaplants and power lines better esthetics and safetyrural areas and third world will adopt first

The Hydrogen Economy

Nothing gained if fossil fuels are source of hydrogenreduced efficiency in reformingCO2 global warming not helped

Need renewable fuelssolves all problemshelps economic developmentuse for chemicals

Constraints

Available resource

Supply infrastructure

Distributed

Affordable

Candidatesethanol $1.50/gallonsoy oil $2.00/gallon

Renewable Hydrogen from Ethanol

Lanny SchmidtDepartment of Chemical Engineering and Materials Science

University of Minnesota

Catalytic Partial Oxidation

• Converts hydrocarbons into valuable chemicals: syngas (H2 & CO), olefins, oxygenates, etc.

• Exothermic process• Runs auto-thermally• Short contact times

(Milliseconds)• Vapor phase reactions

Reactants

Products

Heat Shields

Catalyst

QuartzTube

Steam Reformer for Hydrogen Generation

Replace by system smaller than truckEnough hydrogen for house in size of coffee cup

Molecules

C-O-CH3

Omethyl linoleate 52%

CH4

C2H5OH

Reactor

air

Fuel Injector

Thermocouple

Insulation

Products

Thermocouple

Heating

Catalyst

Mixer

fuel

Renewable Hydrogen from EthanolRenewable Hydrogen from Ethanol

Produce hydrogen from a renewable fuel at short Produce hydrogen from a renewable fuel at short contact times for use in a fuel cellcontact times for use in a fuel cell

C2H5OH 3H2

C2H5OH +3H2O 6H2

CC22HH55OH + 2 HOH + 2 H22O + 1/2OO + 1/2O2 2 2CO2CO22 + + 55HH22

Stratified CatalystStratified Catalyst

Back-face ThermocoupleBack-face Thermocouple

AirAir

Heat Heat ShieldsShields

Heating TapeHeating Tape

InsulationInsulation

AutomotiveAutomotiveFuel InjectorFuel Injector

MixerMixer

CPOXCPOX

25 25 ooCC

140 140 ooCC

700 700 ooCC

Second Catalyst:Second Catalyst:

CO + HCO + H22O O CO CO22 + H + H22

First Catalyst:First Catalyst:

CC22HH55OH + 2 HOH + 2 H22O + 1/2OO + 1/2O22 2CO 2CO22 + 5H + 5H22

400 400 ooCC

WGSWGS

Major ProductsMajor Products

0

20

40

60

80

100

0.4 0.5 0.6 0.7 0.8 0.9 1 1.1 1.2

0

50

100

150

0.4 0.5 0.6 0.7 0.8 0.9 1 1.1 1.2

CarbonCarbon

HydrogenHydrogen

Maximum Hydrogen Maximum Hydrogen

COCO2 2 w/ WGS w/ WGS

COCO w/ WGS w/ WGS

SSC C (%) (%)

SSH H (%) (%)

COCO

COCO22

HH2 2 w/ WGS w/ WGS

HH22

HH22OO w/ WGS w/ WGS

HH22OO

(C/O)(C/O) (C/O)(C/O)

CO2

photosynthesish

C6H12O6 + 4 H2O

6 CO2 +10 H2O

∆Ho= +2540∆Go= +2830

sugarfuelcell

6 O2

photosynthesish

2 CO2 + 2 C2H5OH + 4 H2O

6 CO2 + 10 H2

∆Ho= +20∆Go= -210

∆Ho= -140∆Go= -330

C6H12O6 + 4 H2O

6 CO2 +10 H2O

∆Ho= +2540∆Go= +2830

sugarfuelcell

6 O2

photosynthesish

2 CO2 + 2 C2H5OH + 4 H2O

6 CO2 + 10 H2

∆Ho= +20∆Go= -210

∆Ho= -140∆Go= -330

6 CO2 +10 H2O

5 O2

O2

∆Ho= -2420∆Go= -2290

reformedethanol

fuelcell

C6H12O6 + 4 H2O

6 CO2 +10 H2O

∆Ho= +2540∆Go= +2830

sugarfuelcell

6 O2

What have we done?What have we done?

Ethanol may be a suitable renewable energy source for electricity

Captures 80% of energy in carbohydrates (photosynthesis)

Captures 50% of energy as electricity

Ready for commercialization

Fuel cell is bottleneck

Need to explore other renewables

Renewable ChemicalsRenewable ChemicalsFrom Biodiesel

Soy oil + CH3OH biodiesel + glycerol

CH3OOC(CH2)16CH3 methyl oleate

isomers with 1, 2, and 3 double bonds10% C16

1% in Minnesota diesel pool in 2005

C-O-CH3

O

Renewable ChemicalsRenewable Chemicals

biodiesel H2 80%

olefins 90%

ethylene, propylene 50%

EconomicsEconomicsEthanol

available at $1.50/gallonelectricity at $.04/kWh

enough to supply all Minnesota electricity

Biodieselavailable at $1.70/ gallon ($.20/lb)

olefins sell for $.25/lb

Gasoline$1.10/gallon

Biomass

PHOTOSYNTHETIC BACTERIAL PAINTS THAT PRODUCE

HYDROGEN

Michael C. FlickingerUniversity of MinnesotaBioTechnology Institute

St. Paul, MN

Federico Rey, Caroline HarwoodUniversity of Iowa

Dept. of MicrobiologyIowa City, IA

H2 EVOLUTION BY WILD TYPE Rhodopseudomonas palustris IN THE

ABSENCE OF ATMOSPHERIC NITROGEN

Waste Organic Compounds (source

of electrons)

Biosynthetic precursors (CH2O)

ATP

energized electrons

(NADH, Fdred)

+

light

+N2

H2

NH4+Nitrogenase

Mutant Uptake Hydrogenase

Cell Material

(Argon Atmosphere)

PERFUSIVE MULTI-LAYERED TRANSLUCENT LATEX COATING FOR OPTIMIZATION OF

LIGHT ABSORPTION AND PHOTOTROPHIC HYDROGEN PRODUCTION

(Flickinger et al., 2003, patent pending

A. Protective translucent coating.B. Porous cell + polymer coatings.C. Spacer/channel layers.D. Perfusive fluid flow to cells

and gas evolution from cells.S. Reflective substrate.T. Total multi-layer thickness

approx. 1-2 mm.

CONCLUSIONS: PHOTOSYNTHETIC PAINTS MAY BE A USEFUL APPROACH

• A preliminary method has been developed to make stable, translucent, acrylic/vinyl acetate latex coatings of R. palustris nitrogenase mutants on polyester under anaerobic conditions.

• R. palustris coatings can produce H2 from acetate for over 400 hours in an argon atmosphere.

• V-nitrogenase double mutant (∆nifH ∆anfH) has highest H2 evolution rate in latex coatings.

• Coatings can be fed acetate to continuously generate H2.• Coatings are capable of frozen storage at

-80˚C with retention of H2 evolution activity.

We Must Develop Renewable Fuels

No choice

Transportation fuels must be liquid chemicals

Biomass must be source

Make high value added products

Major challenge of 21st Century

Requires Partnerships

research universitiesgovernmentnonprofit organizationsfarm organizationsindustriesentrepreneurs

A $20 million initiative over 5 years for research at the University

Legislative mandate funded by Xcel from CIP and RDF funds

InterdisciplinaryAgriculture

BiologyTechnology

Policy

ClustersHydrogenEfficiency

Bioproducts and bioenergyPolicy and the environment

Hydrogen Cluster ProgramsSeed Grants

Micro fuel cells Bill Smyrl CEMSHydrogen from ethanol Lanny Schmidt CEMSBiological hydrogen Mike Flickinger Biochemistry(Solar hydrogen Jane Davidson ME)(Photolytic hydrogen Kent Mann Chemistry(Hydrogen storage Eric Gant Physics(Microbial fuel cells Daniel Bond Biochemistry

Matching GrantsPhotosynthetic Bacterial Paints that Produce Hydrogen

Mike Flickinger UniversityRenewable Hydrogen and Chemicals from Ethanol

Lanny Schmidt Mn Corn Growers

Matching Grant ProposalsHydrogen Fueling StationDiesel Reforming in Autothermal ReactorsPhotolytic Hydrogen

…