Hydrogen Generation via Novel Supercritical Water Reformation Technology
Laboratory for Fuels and Polymer ProcessingMissouri University of Science and Technology
Rolla, Missouri
EnergySummit4/23/09
FacultySunggyu Lee, Jonathan Wenzel, Kimberly Henthorn, Douglas Ludlow, John Sheffield, and David Retzloff
Graduate StudentsJason Picou, Michael Stever, Jared Bouquet, Satya Putta, Matthew Factor, Mahin Shahlari, and Alexandria Niemoeller
Undergraduate StudentsRyan Tschannen and April Sloan
Industrial CollaboratorH. Bryan Lanterman (DRS-TSI)
Project Team Members
H2 Production
Splitting of Water Molecules
H2O → H2 + ½ O2
Pyrolysis of Hydrocarbons
CmHn → CaHb + CcHd + H2
Reforming of Hydrocarbons (w/ Shift Conversion)
CH4 + 2H2O → CO2 + 4H2
CnHm + 2n H2O → n CO2 + (½m+2n) H2
①
②
③
③
Solar, Direct
Solar, PV
GeothermalWind
Biomass
Nuclear
Coal
Oil
PetroleumTar SandsShale Oil
Natural Gas
Renewable
Fossil Fuels
Generation
TransportationStorage
Utilization
Direct Water Splitting
Electricityfor Electrolysis
Pyrolysis &Gasification
Cracking
Carb
on
S
eq
uest
rati
on
SteamReformation
Corn Ethanol
SWReformation
Hydrogen
Systems Requiring Mobile Electric Power (MEP)
Too MassiveSignature Problems(Noise & Thermal) No Infrastructure
These are not the solutions
Remote Area Natural Disaster
Military Applications Civilian Applications
Specific Fuel& Reliability
Urgent
Diesel Only
Why Convert JP-8 Fuel to H2?
• JP-8 is the only fuel used by the U.S. military: Army, Air Force, Navy, and Marines.
• To power communications and tactical information systems using a PEM fuel cell, hydrogen is needed. – It is impractical to transport and store hydrogen,
especially on the battlefield.– Portable, highly efficient, very compact, on-site
generation is sorely desired.– Many restrictive requirements are still applicable.
• Thermal Signature Reduction• Noise Reduction• Sustainable Operation• Compact Size• Use of JP-8 Fuel (Logistic Fuel)• Use of Environmental Water;
Gray Water
For U.S. Military, as an example
Goals of On-site Generation of H2
Conventional Technology DoesNot Meet Any of These Requirements.
Our Technology Can Meet All.
Supercritical Water Reformation (SWR)
• Our Own Process Originally Developed for Reformation of JP-8• A Modified Concept Works Superbly on Ethanol and Its Crude Beer• Novel Exploitation of Properties of Supercritical Water Reactions
Ambient Water Supercritical WaterNegligible (Low) Organic Solubility Very HighVery High Inorganic Solubility Negligible (Low)Higher (No Control) Density MH (Controllable)Higher Viscosity LowerLower Diffusivity Higher80 Dielectric Constant 5.7 @ critical pointHigh Polarity LowNot Corrosivity SomewhatFire Extinguishing Oxidation Combustion medium9.2 mg/L Oxygen Solubility Any Proportion
SUPERCRITICAL WATER –What is it?SUPERCRITICAL WATER –What is it?
T > 374 oCP> 218 atm
Temp
L S V Pre
ssu
re
Tc
Pc
SCW
Comparison of SWR vs. Conventional Process
SWR (our process) Conventional
Supercritical Water
(Noncatalytic Reforming)Base Technology Catalytic Reforming
(Noble Metal Catalyst)
550-800 Temperature, oC 875-1600
>218 Pressure, atm 20-50
Not Affected At All Tolerance to Sulfur & Nitrogen in Fuel
Very Sensitive
(Seriously Degrading)
Little or None
(Coke precursors are soluble in SC water)
Carbon/Soot Buildup in the Reactor
Very Active
(Requiring 2-stage or air oxidation)
Yes Gray Water Operability
No
(Use clean water only)
Outstanding Feed Fuel Flexibility Limited
Very Compact Size 20-50 times larger
Features
Supercritical Water Reformer Process Flow Diagram
H2O PumpIntegrated Heat Exchanger
Fuel Pump
Supercritical Water Reactor
Effluent Drum
Liquid Level Gauge
16 Port Sampling Valve
Wet Test Meter
CoolingWater In
Heat Exchanger
Control Valve
Preheater
P
P
T
T
T
T
T
T
T
T T
T T T
MS&T’s E-H2
Process
Ethanol Crude Beer
Custom–designed Haynes Alloy® 230 Reactor
H2
CH4
Product Gas Analysis
CO CO2
Experimental Prototype
Computer Control GC Analysis
Highlights-I Process feasibility of efficient H2 generation from a variety of liquid
hydrocarbon feedstocks has been established.• The reaction process is totally non-catalytic and there is no concern of catalyst
poisoning or efficiency degradation• Long-term continuous operation without performance degradation or maintenance
requirement. Process efficiency is irrespective of the sulfur content of fuel.
• No need for pre-desulfurization of feed fuel Kinetic mechanisms of supercritical reformation, pyrolytic decomposition, and
water gas shift reaction have been elucidated.• At optimal process operating conditions, reformation dominates pyrolysis.• Supercriticality is essential for efficient process operation.• The gas product H2/CH4 ratio can be controlled.
Additional benefits of concurrent water gas shift reaction have been successfully exploited.• At process conditions, forward water gas shift reaction beneficially takes place,
further enhancing hydrogen production.• No separate stage of water gas shift reaction is required, further simplifying the flow
sheet.
Highlights-II Product gas consists mainly of H2, CH4, CO2, and CO.
• Product H2 does not dissolve into the supercritical water mixture, thus helping to create a favorable reaction environment without equilibrium limitation as well as facilitating easy separation.
• Product gas does not contain acetylene, thus helping the downstream purification of hydrogen.
The process operability in an autothermal mode has been demonstrated.• Air as an oxidant can be co-fed in order to accomplish an autothermal
process condition as well as further enhance the gasification efficiency. The experimental prototype unit (EPU) has been successfully
operated for over 500 hours.• The EPU has been operated on a variety of hydrocarbon fuels.• The 1st generation and 2nd generation reactors have been designed,
installed, and operated. Advances in reactor materials for supercritical water reformation
have been realized.
Future R&D Direction (General)
3rd Generation Reformer DesignEnergy IntegrationH2 Purification with a Novel Multi-bed
Absorption/Adsorption TechnologyIntegration with H2 PEM Fuel Cell and
SOFCFuel Flexibility DemonstrationIntegrability with a Microgrid