Renewable Hydrogen and Olefins by Autothermal Reforming Lanny Schmidt Department of Chemical Engineering and Materials Science University of Minnesota

Hydrogen Cluster Programs Seed Grants Micro fuel cells Bill SmyrlCEMS Hydrogen from ethanolLanny SchmidtCEMS Biological hydrogenMike FlickingerBiochemistry Solar hydrogenJane DavidsonME) Photolytic hydrogenKent MannChemistry Hydrogen storageEric GantPhysics Microbial fuel cellsDaniel BondBiochemistry Matching Grants Photosynthetic Bacterial Paints that Produce Hydrogen Mike FlickingerUniversity Renewable Hydrogen and Chemicals from Ethanol Lanny SchmidtMn Corn Growers Matching Grant Proposals Hydrogen Fueling Station Diesel Reforming in Autothermal Reactors Photolytic Hydrogen …

Renewable Energy and Chemicals Sometime we will switch to renewable chemicals and energy sustainable not imported distributed no CO 2 less pollution Everyone agrees When? 5 years or 50 years? How? What sources and what technologies?

Renewable Energy and Chemicals Current drivers towards Renewable Energy National Security Global Warming Rural Economic Development Renewables must compete head-to-head with fossil fuels total supply infrastructure price Subsidies critical issue not simple energy is always heavily subsidized Energy may the the most important problem in the 21st Century requires radical thinking

The Hydrogen Economy Code words for fuel cells 60% versus Carnot efficiency of thermal engines PEM fuel cells require hydrogen Need hydrogen wind power with electrolysis for hydrogen storage fossil fuel reforming is next generation use hydrogen for storage and transportation of energy hydrogen fueling station Distributed energy no megaplants and power lines better esthetics and safety rural areas and third world will adopt first

The Hydrogen Economy Nothing gained if fossil fuels are source of hydrogen reduced efficiency in reforming CO 2 global warming not helped Need renewable fuels solves all problems helps economic development use for chemicals

Constraints Available resource Supply infrastructure Distributed Affordable Candidates ethanol$1.50/gallon soy oil$2.00/gallon

Renewable Hydrogen from Ethanol Lanny Schmidt Department of Chemical Engineering and Materials Science University of Minnesota

Catalytic Partial Oxidation Converts hydrocarbons into valuable chemicals: syngas (H 2 & CO), olefins, oxygenates, etc. Exothermic process Runs auto-thermally Short contact times (Milliseconds) Vapor phase reactions Reactants Products Heat Shields Catalyst Quartz Tube

Steam Reformer for Hydrogen Generation Replace by system smaller than truck Enough hydrogen for house in size of coffee cup

Molecules C-O-CH 3 O methyl linoleate 52% CH 4 C 2 H 5 OH

Reactor air Fuel Injector Thermocouple Insulation Products Thermocouple Heating Catalyst Mixer fuel

Renewable Hydrogen from Ethanol Produce hydrogen from a renewable fuel at short contact times for use in a fuel cell  C 2 H 5 OH  3H 2  C 2 H 5 OH +3H 2 O  6H 2 C 2 H 5 OH + 2 H 2 O + 1/2O 2  2CO 2 + 5H 2

Stratified Catalyst Back-face Thermocouple Air HeatShields Heating Tape Insulation Automotive Fuel Injector Mixer CPOX 25 o C 140 o C 700 o C Second Catalyst: CO + H 2 O  CO 2 + H 2 First Catalyst: C 2 H 5 OH + 2 H 2 O + 1/2O 2  2CO 2 + 5H o C WGS

Major Products Carbon Hydrogen Maximum Hydrogen CO 2 w/ WGS CO w/ WGS S C (%) S H (%) CO CO 2 H 2 w/ WGS H2H2H2H2 H 2 O w/ WGS H2OH2OH2OH2O (C/O) (C/O)

CO 2

photosynthesis h C 6 H 12 O H 2 O 6 CO H 2 O ∆H o = ∆G o = sugar fuel cell 6 O 2

photosynthesis h 2 CO C 2 H 5 OH + 4 H 2 O 6 CO H 2 ∆H o = +20 ∆G o = -210 ∆H o = -140 ∆G o = -330 C 6 H 12 O H 2 O 6 CO H 2 O ∆H o = ∆G o = sugar fuel cell 6 O 2

photosynthesis h 2 CO C 2 H 5 OH + 4 H 2 O 6 CO H 2 ∆H o = +20 ∆G o = -210 ∆H o = -140 ∆G o = CO H 2 O 5 O 2 O2O2 ∆H o = ∆G o = reformed ethanol fuel cell C 6 H 12 O H 2 O 6 CO H 2 O ∆H o = ∆G o = sugar fuel cell 6 O 2

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 Chemicals From Biodiesel Soy oil + CH 3 OH  biodiesel + glycerol CH 3 OOC(CH 2 ) 16 CH 3 methyl oleate isomers with 1, 2, and 3 double bonds 10% C 16 1% in Minnesota diesel pool in 2005 C-O-CH 3 O

Renewable Chemicals biodiesel  H 2 80%  olefins90%  ethylene, propylene50%

Economics Ethanol available at $1.50/gallon electricity at $.04/kWh enough to supply all Minnesota electricity Biodiesel available at $1.70/ gallon ($.20/lb) olefins sell for $.25/lb Gasoline $1.10/gallon Biomass

PHOTOSYNTHETIC BACTERIAL PAINTS THAT PRODUCE HYDROGEN Michael C. Flickinger University of Minnesota BioTechnology Institute St. Paul, MN Federico Rey, Caroline Harwood University of Iowa Dept. of Microbiology Iowa City, IA

H 2 EVOLUTION BY WILD TYPE Rhodopseudomonas palustris IN THE ABSENCE OF ATMOSPHERIC NITROGEN Waste Organic Compounds (source of electrons) Biosynthetic precursors (CH 2 O) ATP energized electrons (NADH, Fd red ) + light +N 2 H2H2 NH 4 + 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 H 2 from acetate for over 400 hours in an argon atmosphere. V-nitrogenase double mutant (∆nifH ∆anfH) has highest H 2 evolution rate in latex coatings. Coatings can be fed acetate to continuously generate H 2. Coatings are capable of frozen storage at -80˚C with retention of H 2 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 universities government nonprofit organizations farm organizations industries entrepreneurs

A $20 million initiative over 5 years for research at the University Legislative mandate funded by Xcel from CIP and RDF funds Interdisciplinary Agriculture Biology Technology Policy Clusters Hydrogen Efficiency Bioproducts and bioenergy Policy and the environment

Hydrogen Cluster Programs Seed Grants Micro fuel cells Bill SmyrlCEMS Hydrogen from ethanolLanny SchmidtCEMS Biological hydrogenMike FlickingerBiochemistry (Solar hydrogenJane DavidsonME) (Photolytic hydrogenKent MannChemistry (Hydrogen storageEric GantPhysics (Microbial fuel cellsDaniel BondBiochemistry Matching Grants Photosynthetic Bacterial Paints that Produce Hydrogen Mike FlickingerUniversity Renewable Hydrogen and Chemicals from Ethanol Lanny SchmidtMn Corn Growers Matching Grant Proposals Hydrogen Fueling Station Diesel Reforming in Autothermal Reactors Photolytic Hydrogen …