Renewable Hydrogen and Olefinsby Autothermal Reforming

Lanny SchmidtDepartment of Chemical Engineering and Materials Science

University of Minnesota

Hydrogen and Chemicalsin Millisecond Reactors

Hydrogen Economy Distributed power Fuel cells

Pollution abatement Renewable energy Renewable chemicals

Reactions

CH4 H2 + CO synfuels methanol

H2 hydrogen economy

gasoline H2 portable powerdiesel H2

ethanol H2 renewable energy

biodiesel olefins renewable chemicals

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

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

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

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

Renewable Sources

Windnow competitiveintermittent

Geothermal and hydroelectriclocalized

Solarexpensive

Biomassavailable reliablecompetitive

We need transportable liquid fuelsethanolbiodiesel

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

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

Hydrogen from EthanolLanny Schmidt

Regents ProfessorDepartment of chemical engineering and Materials Science

University of Minnesota

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

Steam Reformer for Hydrogen Generation

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

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

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

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

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%

-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)

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

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)

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 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

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

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%

Olefins and Olefinic Esters

C-O-CH3

O

C-O-CH3

O

.. +

C-O-CH3

O

C11=

N10

Renewable ChemicalsRenewable Chemicals

biodiesel H2 80%

olefins 90%

ethylene, propylene 50%

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

Renewable Energy and ChemicalsRenewable Energy and Chemicals

sugar ethanol electricity

CO2+H2O biomass carbohydrates starch

CO2+H2O biomass biodiesel H2

ethylene -olefins ?

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