On-Site Hydrogen Production From High-Pressure Liquids

NHA Hydrogen Conference and Expo

Ben Oster

May 5, 2010

Outline

• Introduction

• Objectives

• Hydrogen Production Flow Diagram and Results

• Future Work

• Conclusions

Introduction

• High pressure reactor system– Distributed hydrogen production– Converts liquid reactants directly to high pressure

hydrogen• Pump liquid reactants into reactor operating at 6000 to

12,000psi• Purify hydrogen at system pressure (6000 to 12,000 psi)

NOT REQUIR

ED

REDUCED

Compression Energy SavingsPercent of Hydrogen LHV

Storage →

Source ↓ 3626

psia

5076

psia

7252

psia

10,153

psia

15 psia 13.2% 14.3% 15.5% 16.7%

102 psia 7.8% 8.8% 9.8% 10.9%

290 psia 5.6% 6.5% 7.4% 8.4%

1958 psia 1.7% 2.5% 3.3% 4.2%

Source: Air Products and Chemicals, Inc.

Mass of Hydrogen Per DeliveryBasis: 7500 gal Transport Tank

01000200030004000500060007000

highpressurehydrogen(3200psi)

liquidhydrogen

methanol glycerol ethanol

Hy

dro

ge

n (

kg

)

Hydrogen Pipeline Challenges

• Least expensive way to transport large amounts of hydrogen [1]

• Existing hydrogen pipeline is 0.33% of natural gas pipeline in length with only 200 delivery points [2]

• $1.2 million/mile (transmission) and $0.3 million/mile (distribution) [3]

• Advancements could decrease costs >50% [4]

• Distributed hydrogen generation provides a near term solution

Objectives of On-Site Hydrogen Production from Liquids

• Circumvent hydrogen pipeline to allow near-term H2 fueling stations.

• Transport liquid feedstocks to take advantage of existing fuel infrastructure while gaseous/liquid H2 infrastructure develops.

• Avoid or reduce compression requirements with pressurized production.

Hydrogen Production Flow Diagram

High Pressure Reformer

Water Condensate

Pot

CO2

RemovalTechnology

Water andOrganic Feedstock

(ex. methanol, ethanol)

H2, H2O, CO2, CO, CH4,

CxHy

H2O

H2, CO2, CO, CH4,

CxHy

CO2

H2, CO,CH4, CxHy

H2 to fuel cell vehicle

Gas SeparationTechnology

HydrogenDispensor

CO,CH4, CxHy

H2

Hydrogen Production Flow Diagram

High Pressure Reformer

Water Condensate

Pot

CO2

RemovalTechnology

Water andOrganic Feedstock

(ex. methanol, ethanol)

H2, H2O, CO2, CO, CH4,

CxHy

H2O

H2, CO2, CO, CH4,

CxHy

CO2

H2, CO,CH4, CxHy

H2 to fuel cell vehicle

Gas SeparationTechnology

HydrogenDispensor

CO,CH4, CxHy

H2

Lab Scale Hydrogen Production System

• Continuous reactor system utilizes supercritical water• Rated to 1,200ºF and 12,000psig; typically 0.2 kg

hydrogen per hour

Ethanol

• On-site hydrogen generation from ethanol– Ethanol is an available and renewable feedstock– Crude ethanol/water mixture could be a less

expensive feedstock• Long term data needed to study catalyst activity

over time• Potentially cheaper due to less processing at the

ethanol production facility• Water is a non-issue as it is a required reactant• Other contaminants need to be examined more

closely with respect to potential plugging & coking issues

Results – Refined Ethanol

Ethanol Mole % of dry product gas

T, ºC P, psi H2 CO2 CO CH4 CxHy Conversion

467 5363 51 23 0.6 19 5 95%

Desired reaction: C2H5OH + 3H2O 6H2 + 2CO2

Hydrogen max = 75mole%

Competing reactions lead to methane formation

Glycerol

• On-site hydrogen generation from glycerol– Glycerol is a biodiesel byproduct accounting for 10%

of total product at a biodiesel facility– Refining bottleneck = stable price for refined glycerol– Crude glycerol could be a cheap, abundant,

renewable feedstock for hydrogen production• Long-term data needed• Study contaminants’ affect on catalyst activity over

time• Contaminants include water, salt, organic matter

Results – Refined Glycerol

Glycerol Mole % of dry product gas

T, ºC P, psi H2 CO2 CO CH4 CxHy Conversion

541 4838 60 31 1.1 5.8 0.7 93%

Desired reaction: C3H5(OH)3 + 3H2O 7H2 + 3CO2

Hydrogen max = 70mole%Competing reactions

Methanol

• Methanol is currently synthesized from natural gas

• Methanol can be synthesized from renewable biomass

• Methanol is a simple molecule and reforms completely at high pressures and relatively low temperatures

Results - Methanol

Methanol Mole % of dry product gas

T, ºC P, psi H2 CO2 CO CH4 CxHy Conversion

384 4885 73 25 0.5 0.9 0.01 100%

Desired Reaction: CH3OH + H2O 3H2 + CO2

Hydrogen max = 75mole%

Hydrogen Production Flow Diagram

High Pressure Reformer

Water Condensate

Pot

CO2

RemovalTechnology

Water andOrganic Feedstock

(ex. methanol, ethanol)

H2, H2O, CO2, CO, CH4,

CxHy

H2O

H2, CO2, CO, CH4,

CxHy

CO2

H2, CO,CH4, CxHy

H2 to fuel cell vehicle

Gas SeparationTechnology

HydrogenDispensor

CO,CH4, CxHy

H2

Water Removal

• Water is fed in excess of stoichiometric.– Avoid coking of catalyst– Provide process heat

• Need to remove water.• Critical temperature (Tc) of water = 374°C.• Cooling below Tc causes phase change to liquid.

– Cooling water used for heat exchange• Removed via level control and a valve at the bottom of

the condensate vessel.• Works very well.

Hydrogen Production Flow Diagram

High Pressure Reformer

Water Condensate

Pot

CO2

RemovalTechnology

Water andOrganic Feedstock

(ex. methanol, ethanol)

H2, H2O, CO2, CO, CH4,

CxHy

H2O

H2, CO2, CO, CH4,

CxHy

CO2

H2, CO,CH4, CxHy

H2 to fuel cell vehicle

Gas SeparationTechnology

HydrogenDispensor

CO,CH4, CxHy

H2

CO2 Removal

• CO2 is continuously removed via selective absorption.

• The resulting product gas composition approaches 96 mole% hydrogen with the balance being methane and carbon monoxide.

• A final, high pressure gas purification step is required to purify the gas to PEM fuel cell quality.

Hydrogen Production Flow Diagram

High Pressure Reformer

Water Condensate

Pot

CO2

RemovalTechnology

Water andOrganic Feedstock

(ex. methanol, ethanol)

H2, H2O, CO2, CO, CH4,

CxHy

H2O

H2, CO2, CO, CH4,

CxHy

CO2

H2, CO,CH4, CxHy

H2 to fuel cell vehicle

Gas SeparationTechnology

HydrogenDispensor

CO,CH4, CxHy

H2

Electrical Swing Adsorption (ESA)

• Objective is to purify the hydrogen rich gas stream to PEM fuel cell quality at 6,000-12,000psig.

• Tailoring an ESA process, developed by Oak Ridge National Lab, for high pressure.

• Involves gas separation in an electrically conductive monolith.

• Non-hydrogen gases adsorb on the monolith, whereas hydrogen passes through; results in hydrogen separation.

• Similar to pressure swing adsorption but does not require a drop in pressure to release contaminants.

• Release contaminants by applying an electric current.

ESA Test System

Electrochemical H2 Purification

H+

H2

H2

H2, CO, H2O, CO2

CO2

2H+ + 2e- H2

H2 2H+ + 2e-

CO + H2O CO2 + 2H+ + 2e-

Cathode Chamber

Anode Chamber

Cathode

Electrolyte

Anode

PrincipleAnode reactions:CO + H2O CO2 + 2H+ + 2e- Eo = -0.106 V; H2 2H+ + 2e- Eo = 0 V

Cathode reaction:2H+ + 2e- H2 Eo = 0 V

Total Reactions:CO + H2O CO2 + H2

Eo = 0.106 VH2 H2

Eo = 0 V

• High-purity H2 can be obtained at the cathode side with low energy consumption.

Fully Automatic Controlled High-Pressure Electrochemical H2 Purification Unit

Hydrogen Production Flow Diagram

High Pressure Reformer

Water Condensate

Pot

CO2

RemovalTechnology

Water andOrganic Feedstock

(ex. methanol, ethanol)

H2, H2O, CO2, CO, CH4,

CxHy

H2O

H2, CO2, CO, CH4,

CxHy

CO2

H2, CO,CH4, CxHy

H2 to fuel cell vehicle

Gas SeparationTechnology

HydrogenDispensor

CO,CH4, CxHy

H2

Scaled-up, Integrated System:Projected H2 delivery rate of 0.6 kg/hr

PREHEATERFEED STORAGETANKS

REFORMER REACTORDISPENSING

CO2 REMOVAL

H2

HYDROGENPURIFICATION

STORAGE

Future Work

• Finalize construction and shakedown of scaled-up, integrated hydrogen production unit.

• Demonstrate hydrogen production with scaled-up unit.

• Continue to study other reformer feedstocks.

• Continue to develop high pressure gas purification technologies.

Conclusions

• High pressure liquid reforming offers a distributed hydrogen platform that has unique advantages.

• Renewable liquids have been converted to 6000psi hydrogen in the lab.

• A scaled up unit is being fabricated to demonstrate integrated high pressure hydrogen production, purification, and dispensing.

Acknowledgements

• U.S. Army Corps of Engineers, Engineer Research Development Center, Construction Engineering Research Laboratory (ERDC-CERL)

• National Center for Hydrogen Technology (NCHT) sponsored by the  U.S. Department of Energy (DOE)

National Energy Technology Laboratory (NETL)

Thank You

Cited Sources• [1] DOE Hydrogen Program. Hydrogen distribution and delivery infrastructure. Fact

Sheet. http://www.hydrogen.energy.gov/pdfs/doe_h2_delivery.pdf • [2] The Impact of Increased Use of Hydrogen on Petroleum Consumption and carbon

Dioxide Emissions. August 2008. Energy Information Administration. Office of Integrated Analysis and Forecasting, Office of Coal, Nuclear, Electric and Alternative Fuels. US Department of Energy. Washington, DC 20585.

• [3] See U.S. Department of Energy, Energy Efficiency and Renewable Energy, Hydrogen, Fuel Cells & Infrastructure Technologies Program: Multi-Year Research, Development and Demonstration Plan, Table 3.2.2 (Washington, DC, October 2007), www1.eere.energy.gov/hydrogenandfuelcells/mypp.

• [4] B. Smith, B. Frame, L. Anovitz, and T. Armstrong, “Composite Technology for Hydrogen Pipelines,” in U.S. Department of Energy, Hydrogen Program, 2008 Annual Merit Review Proceedings, www.hydrogen.energy.gov/annual_review08_proceedings.html