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

What is this about?

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

Why do we need such a technology?

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.

How can we accomplish this?

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

Process and Experimental

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

Where are we in this process R&D?

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.

What is Next?

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

Who is sponsoring the program?

Project Sponsors

• U.S. Army RDECOM

(Project Manager: Dr. Terry Dubois)• DRS Technical Services, Inc.

(Project Manager: Dr. H. Bryan Lanterman)• U.S. DOT RITA• Leonard Wood Institute (LWI)