renewable hydrogen and olefins by autothermal reforming lanny schmidt department of chemical...
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Renewable Hydrogen and Olefinsby Autothermal Reforming
Lanny SchmidtDepartment of Chemical Engineering and Materials Science
University of Minnesota
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Hydrogen and Chemicalsin Millisecond Reactors
Hydrogen Economy Distributed power Fuel cells
Pollution abatement Renewable energy Renewable chemicals
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Reactions
CH4 H2 + CO synfuels methanol
H2 hydrogen economy
gasoline H2 portable powerdiesel H2
ethanol H2 renewable energy
biodiesel olefins renewable chemicals
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Energy is the most ImportantTechnology Issue of the 21st Century
The biological revolution cannot happen without energy to drive it
Extremely complex
Will require radical solutions
Will require replacement of fossil fuels by renewable sources
The Midwest must be the source of renewables
Minnesota spends over $10 billion to import energy
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Our Ancestors Used Renewables
Wood heat
Beeswax and tallow light
Wool, cotton, and leather clothing
Horses transportation(eats oats, fertilizes the soil, and produces colts)
These are completely renewable as long as they are sustainable
All agricultural based products
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The Industrial Revolution demanded a transportable liquid fuel
Whale oil was the 19th Century solutionwhales not renewable fast enough
Petroleum became the replacementgasoline, diesel, and jet fuel10% converted into petrochemicals
The energy engine of the world economymost located in bad placesSaudi Arabia, Iraq, and Russia
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Sometime We Will Switch Back to Renewables
Sustainablenot importeddistributedno CO2
less pollution
5 years or 50 years?
What technologies?
How much fossil energy?petroleum 10 to 50 yearsnatural gas 20 to 100 yearscoal 200 years
The Stone Age did not end because we ran out of stones
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Renewable Sources
Windnow competitiveintermittent
Geothermal and hydroelectriclocalized
Solarexpensive
Biomassavailable reliablecompetitive
We need transportable liquid fuelsethanolbiodiesel
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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 Century
requires radical thinking
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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
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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
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Hydrogen from EthanolLanny Schmidt
Regents ProfessorDepartment of chemical engineering and Materials Science
University of Minnesota
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All H2 now comes from steam reforming tube furnace Ni catalyst flames make pollutants does not scale down
All olefins now come from steam cracking tube furnace homogeneous pyrolysis 1/3 of all pollution from chemical plants does not scale down
Need distributed source of liquid fuels for on-board reforming
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Steam Reformer for Hydrogen Generation
Replace by system smaller than truckEnough hydrogen for house in size of coffee cup
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Electricity from EthanolWe now have an infrastructure for ethanol
corn starch sugar ethanol
Now supplies 10% of Minnesota’s gasoline needs
Burning ethanol is inefficient use of valuable chemical
Why not use it for fuel cell?
90% of energy in sugar is stored in ethanol
Water in ethanol is useful to produce extra H2
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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
CC22HH55OH + 3 HOH + 3 H22O O 2CO2CO22 + 6H + 6H22
CC22HH55OH + 1/2OOH + 1/2O22 2CO + 3H2CO + 3H22
CC22HH55OH + 2 HOH + 2 H22O + 1/2OO + 1/2O222CO2CO22 + 5H + 5H22
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Why can’t it be done?Why can’t it be done?Need small size for distributed powerNeed small size for distributed power
steam reforming does not scale downsteam reforming does not scale down
Ethanol very flammableEthanol very flammableCherries JubileeCherries Jubilee
Catalytic partial oxidation endothermicCatalytic partial oxidation endothermicno heat for autothermal reactorno heat for autothermal reactor
No one had previously reported partial oxidationNo one had previously reported partial oxidation
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0
20
40
60
80
100
200
400
600
800
1000
1200
0 0.5 1 1.5 2
Ethanol to HydrogenEthanol to Hydrogen
Conversion Conversion X (%)X (%)
Temperature Temperature ooCC
(C/O)(C/O)
EthanolEthanolSyngasSyngasUFLUFLLFLLFL CombustionCombustion
100%100%25%25%
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-20
0
20
40
60
80
100
120
0.4 0.6 0.8 1 1.2 1.4
SSH H (%) (%)
HydrogenHydrogen
25%25%
100%100%
HH22OO
HH22
2525
100100
Major ProductsMajor Products
SSC C (%) (%)
(C/O)(C/O)
0
20
40
60
80
100
0.4 0.6 0.8 1 1.2 1.4
CarbonCarbon
COCO
COCO22
25%25%
100%100%
2525%%
100%100%
Minor ProductsMinor Products
(C/O)(C/O)
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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
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ProductsProducts
0
50
100
150
0.4 0.5 0.6 0.7 0.8 0.9 1 1.1 1.2
Maximum Hydrogen Maximum Hydrogen
SSH H (%) (%)
HH2 2 w/ WGS w/ WGS
HH22
HH22OO w/ WGS w/ WGS
HH22OO
(C/O)(C/O)
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CO2
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photosynthesish
C6H12O6 + 4 H2O
6 CO2 +10 H2O
∆Ho= +2540∆Go= +2830
sugarfuelcell
6 O2
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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
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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
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What have we done?What have we done?
Ethanol may be a suitable renewable energy source for electricity
Captures 90% of energy in carbohydrates (photosynthesis)
Captures 50% of energy as electricity
Very simple, small, and inexpensive reactor$5 of catalyst for 1 kW of hydrogen
Work to be doneimprove efficiencyintegrate energy management and water gas shift
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Path Forward
Process commercializableuse natural gas and LPG technologies
Needs cheap and reliable fuel cells
Hydrogen supply and demand must coincide
Need to explore other renewables
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Renewable ChemicalsRenewable ChemicalsFrom Biodiesel
Soy oil + CH3OH biodiesel + glycerol
isomers with 1, 2, and 3 double bonds2% in Minnesota diesel pool in 2005
C-O-CH3
Omethyl linoleate 52%
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Olefins and Olefinic Esters
C-O-CH3
O
C-O-CH3
O
.. +
C-O-CH3
O
C11=
N10
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Renewable ChemicalsRenewable Chemicals
biodiesel H2 80%
olefins 90%
ethylene, propylene 50%
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EconomicsEconomics
Ethanol
available at $1.50/gallonelectricity at $.06/kWh
enough to supply all Minnesota electricity
Biodiesel
available at $2.00 gallon ($.25/lb)olefins sell for $.30/lb
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Renewable Energy and ChemicalsRenewable Energy and Chemicals
sugar ethanol electricity
CO2+H2O biomass carbohydrates starch
CO2+H2O biomass biodiesel H2
ethylene -olefins ?
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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
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Requires Partnerships
research universitiesgovernmentnonprofit organizationsfarm organizationsindustriesentrepreneurs
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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