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
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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
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