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Renewable Hydrogen and Olefins by Autothermal Reforming Lanny Schmidt Department of Chemical Engineering and 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 Hydrogen from ethanol Biological hydrogen Solar Hydrogen Cluster Programs Seed Grants Micro fuel cells Hydrogen from ethanol Biological hydrogen Solar hydrogen Photolytic hydrogen Hydrogen storage Microbial fuel cells Bill Smyrl Lanny Schmidt Mike Flickinger Jane Davidson Kent Mann Eric Gant Daniel Bond CEMS Biochemistry ME) Chemistry Physics Biochemistry Matching Grants Photosynthetic Bacterial Paints that Produce Hydrogen Mike Flickinger University Renewable Hydrogen and Chemicals from Ethanol Lanny Schmidt Mn 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 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 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 most important problem in the 21 st Century requires radical thinking

The Hydrogen Economy Code words for fuel cells 60% versus Carnot efficiency of thermal 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 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 soy oil $1. 50/gallon $2. Constraints Available resource Supply infrastructure Distributed Affordable Candidates ethanol soy oil $1. 50/gallon $2. 00/gallon

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

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

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

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

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

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

Stratified Catalyst Automotive Fuel Injector Air 25 o. C Heating Tape Mixer 140 o. Stratified Catalyst Automotive Fuel Injector Air 25 o. C Heating Tape Mixer 140 o. C Heat Shields CPOX First Catalyst: C 2 H 5 OH + 2 H 2 O + 1/2 O 2 2 CO 2 + 5 H 2 700 o. C Second Catalyst: Insulation WGS CO + H 2 O CO 2 + H 2 400 o. C Back-face Thermocouple

Hydrogen Major Products Maximum Hydrogen H 2 w/ WGS Carbon H 2 SH (%) Hydrogen Major Products Maximum Hydrogen H 2 w/ WGS Carbon H 2 SH (%) CO 2 w/ WGS CO SC (%) H 2 O CO w/ WGS CO 2 H 2 O w/ WGS (C/O)

CO 2 CO 2

C 6 H 12 O 6 + 4 H 2 O ∆Ho= +2540 ∆Go= C 6 H 12 O 6 + 4 H 2 O ∆Ho= +2540 ∆Go= +2830 6 O 2 sugar fuel cell photosynthesis h 6 CO 2 +10 H 2 O

2 CO 2 + 2 C 2 H 5 OH + 4 H 2 2 CO 2 + 2 C 2 H 5 OH + 4 H 2 O C 6 H 12 O 6 + 4 H 2 O ∆Ho= +2540 ∆Go= +2830 ∆Ho= +20 ∆Go= -210 6 O 2 sugar fuel cell photosynthesis h 6 CO 2 +10 H 2 O ∆Ho= -140 ∆Go= -330 6 CO 2 + 10 H 2

2 CO 2 + 2 C 2 H 5 OH + 4 H 2 2 CO 2 + 2 C 2 H 5 OH + 4 H 2 O C 6 H 12 O 6 + 4 H 2 O ∆Ho= +20 ∆Go= -210 ∆Ho= -140 ∆Go= -330 6 CO 2 + 10 H 2 O 2 ∆Ho= +2540 ∆Go= +2830 6 O 2 5 O 2 sugar fuel cell photosynthesis h 6 CO 2 +10 H 2 O ∆Ho= -2420 ∆Go= -2290 6 CO 2 +10 H 2 O reformed ethanol fuel cell

What have we done? Ethanol may be a suitable renewable energy source for electricity 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 Renewable Chemicals From Biodiesel Soy oil + CH 3 OH biodiesel + glycerol CH 3 OOC(CH 2)16 CH 3 methyl oleate C-O-CH 3 O isomers with 1, 2, and 3 double bonds 10% C 16 1% in Minnesota diesel pool in 2005

Renewable Chemicals biodiesel H 2 80% olefins 90% ethylene, propylene 50% Renewable Chemicals biodiesel H 2 80% olefins 90% ethylene, propylene 50%

Economics Ethanol available at $1. 50/gallon electricity at $. 04/k. Wh enough to supply Economics Ethanol available at $1. 50/gallon electricity at $. 04/k. Wh 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 Bio. Technology PHOTOSYNTHETIC BACTERIAL PAINTS THAT PRODUCE HYDROGEN Michael C. Flickinger University of Minnesota Bio. Technology 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 H 2 EVOLUTION BY WILD TYPE Rhodopseudomonas palustris IN THE ABSENCE OF ATMOSPHERIC NITROGEN light ATP + energized electrons (NADH, Fdred) Waste Organic Compounds (source of electrons) +N 2 Nitrogenase Mutant Uptake Hydrogenase (Argon Atmosphere) NH 4+ H 2 Biosynthetic precursors (CH 2 O) Cell Material

PERFUSIVE MULTI-LAYERED TRANSLUCENT LATEX COATING FOR OPTIMIZATION OF LIGHT ABSORPTION AND PHOTOTROPHIC HYDROGEN PRODUCTION PERFUSIVE MULTI-LAYERED TRANSLUCENT LATEX COATING FOR OPTIMIZATION OF LIGHT ABSORPTION AND PHOTOTROPHIC HYDROGEN PRODUCTION (Flickinger et al. , 2003, patent pending A. B. C. D. E. S. T. U. Protective translucent coating. Porous cell + polymer coatings. Spacer/channel layers. Perfusive fluid flow to cells and gas evolution from cell Reflective substrate. Total multi-layer thickness approx. 1 -2 mm.

CONCLUSIONS: PHOTOSYNTHETIC PAINTS MAY BE A USEFUL APPROACH • A preliminary method has been 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 (∆nif. H ∆anf. H) 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 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 21 st Century

Requires Partnerships research universities government nonprofit organizations farm organizations industries entrepreneurs 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 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 Hydrogen from ethanol Biological hydrogen (Solar Hydrogen Cluster Programs Seed Grants Micro fuel cells Hydrogen from ethanol Biological hydrogen (Solar hydrogen (Photolytic hydrogen (Hydrogen storage (Microbial fuel cells Bill Smyrl Lanny Schmidt Mike Flickinger Jane Davidson Kent Mann Eric Gant Daniel Bond CEMS Biochemistry ME) Chemistry Physics Biochemistry Matching Grants Photosynthetic Bacterial Paints that Produce Hydrogen Mike Flickinger University Renewable Hydrogen and Chemicals from Ethanol Lanny Schmidt Mn Corn Growers Matching Grant Proposals Hydrogen Fueling Station Diesel Reforming in Autothermal Reactors Photolytic Hydrogen …