Hydrogen Reactor Development and Design for ... · – Identification of solar reactor concepts is...

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Hydrogen Reactor Development and Design for Photofermentation and Photolytic Processes Daniel M. Blake NREL May 23-26, 2005 Project PD19 This presentation does not contain any proprietary or confidential information

Transcript of Hydrogen Reactor Development and Design for ... · – Identification of solar reactor concepts is...

Page 1: Hydrogen Reactor Development and Design for ... · – Identification of solar reactor concepts is underway – Compiled list of important material properties • Selected candidate

Hydrogen Reactor Development and Design for Photofermentation and

Photolytic Processes

Daniel M. BlakeNREL

May 23-26, 2005Project PD19This presentation does not contain any proprietary or confidential information

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OverviewBarriersTimeline

• Start: October 2003• End: 2016• Complete: 1%

• Production barriers addressed

– L. Systems Engineering– N. Materials and System

Engineering

• Total project funding– DOE share – not determined– Contractor share - NA

• Funding received FY04 - $129K

• FY05 - $100K

Budget

• Nuclear Filter Technology, Inc.

Subcontractor

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Project ObjectivesDevelop advanced renewable photolytic hydrogen generation

technologies. – By 2015, demonstrate engineering-scale biological system to produce

H2 at a plant-gate cost of $10/kg projected to commercial scale. – By 2015, demonstrate direct photoelectrochemical water splitting.

Plant-gate H2 production cost of $5/kg projected to commercial scale. – The long-term objective fuels cost competitive with gasoline.

• Assist DOE with the identification of solar reactor concepts and related materials’needs in support of photobiological and photoelectrochemical H2 production

• Reactor Concepts– Review literature, work with program scientists and engineers, and industry

• Materials Needs:– Determine time zero properties of polymers – polycarbonate, acrylic, polyethylene

teraphthalate, and fluoropolymers (solar transmittance, O2 and H2 permeability, tensile strength, and cost)

– Conduct accelerated and outdoor weathering tests for polymers and other materials of construction

– identify and begin to test strategies for reducing hydrogen permeability, if necessary

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Approach

• Develop large area solar reactors for photobiological and photoelectrochemical water splitting systems– Assemble data base of existing literature on reactors and materials– Identify candidate transparent materials – Measure key properties (e.g. transmittance, H2 and O2 permeation

rates, mechanical properties, and cost) – Perform outdoor and accelerated weathering tests on candidate

materials of construction– Identify reactor concepts with the potential to meet the process

requirements – Provide data for techno-economic process analyses

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Solar Reactor Considerations• What will very large area reactors look like? • How do solar reactors differ from conventional

reactors?• What are the key design constraints?

– 0.05-0.1 sun optimum light intensity for algae– Photoelectrochemical systems can use concentrated

sunlight– Must have low hydrogen loss

• Design for daily and annual solar cycles • Other – cleaning, heat rejection, gas clean-up,

materials lifetime, light-dark cycles

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Schematic diagram of a proposed photobioreactor system. The primary and secondary mirrors collect and concentrate the light while the light distribution waveguide conditions and transports the light to the

photobioreactor

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Active Solar Photocatalytic Treatment -NREL Flat Plate Reactor at McClelland AFB

1995Fluorocarbon glazing

Polymer catalyst support

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Reactor Concepts May Come from Other Sources

Lengths of polymer panels, with the cross-section shown, containing a fluid to collect solar heat for power generation.

US Patent 6,374,614, M. L. Pruit. Solar Power Generation and Energy Storage System, April 23, 2002

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Technical Accomplishments & Results

• Current literature database contains about 200 references – Identification of solar reactor concepts is underway– Compiled list of important material properties

• Selected candidate transparent material families – Polycarbonates, Fluoropolymers, Acrylics, and

Polyesters – Multiyear weathering tests in progress (“piggy

backing” on work in the DOE Solar Programs) • Obtained H2 and O2 permeation parameters for

a range of polymers

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Outdoor Weathering Data - Polycarbonate

SparTech Plastics Sungard Ultra-weatherable Polycarbonate (coextruded PC & acrylic) with Korad UV protection layer as a function of accelerated Ci5000 WOM and outdoor exposure in Golden,

CO, Phoenix, AZ, and Miami, FL after cleaning

60

70

80

90

100

0.0 3.3 6.7 10.0 13.3 16.7 20.0 23.3 26.6 30.0 33.3 36.6 40.0 43.3 46.6

Total UV Dose (100 x MJ/m2)

% H

emis

pher

ical

Tra

nsm

ittan

ce fr

om

300n

m-1

200n

m

NREL---KORAD/SUNGARDNREL---SUNGARDAPS----KORAD/SUNGARDAPS----SUNGARDFLA----KORAD/SUNGARDFLA----SUNGARDCi5000-KORAD/SUNGARDCi5000-SUNGARD

Equivalent NREL Exposure Time (yr)3 6 9 120 141311101 2 4 5 7 8

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Outdoor Weathering Data - PET

Melinex D387 PET films w/ & w/o Korad UV protection layer as a function of accelerated Ci5000 WOM and outdoor exposure in

Golden, CO, Phoenix, AZ, and Miami, FL after cleaning

70

75

80

85

90

95

100

0.0 3.3 6.7 10.0 13.3 16.7 20.0 23.3 26.6 30.0 33.3 36.6

Total UV Dose (100 x MJ/m2)

% H

emis

pher

ical

Tra

nsm

ittan

ce

from

300

nm-1

200n

m

Ci5000 Ci5000 w/KoradNREL NREL w/KoradAPS APS w/KoradFLA FLA w/Korad

Equivalent NREL Exposure Time (yr)

3 6 90 101 2 4 5 7 8 11

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Weathering Data - Fluoropolymers

8 Fluoropolymers as a function of accelerated Ci5000 WOM and outdoor exposure in Golden, CO after cleaning

80

85

90

95

100

0.0 10.0 20.0 30.0 40.0 50.0 59.9 69.9 79.9 89.9 99.9

Total UV Dose (100 x MJ/m2)

% H

emis

pher

ical

Tra

nsm

ittan

ce fr

om

300n

m-1

200n

m

TEFZEL 150 ZMC-NREL TEFZEL 250 ZMC-NRELTEFLON 200PM-NREL TEFLON 200PH-NRELDURALAR CS50-NREL DURALAR E-NRELHALAR CLEAR NP-NREL Kynar (PVF) -NRELTEFZEL 150 ZMC-Ci5000 TEFZEL 250 ZMC-Ci5000TEFLON 200PM-Ci5000 TEFLON 200 PH-Ci5000DURALAR CS50 (ETFE)-Ci5000 DURALAR E (ETFE)-Ci5000HALAR CLEAR NP (ECTFE)-Ci5000 Kynar (PVF) -Ci5000

Equivalent NREL Exposure Time (yr)

6 240 3027213 9 12 15 18

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H2 and O2 Permeation Data

1

10

100

1000

10000

100000D

uPon

t Mel

inex

D38

7 PE

T (1

.2 m

ils)

DuP

ont M

elin

ex S

T504

PET

(7 m

ils)

Sain

t Gob

ain

FEP

(2 m

ils)

Sain

t Gob

ain

FEP

(30

mils

)

Arek

ma

Kyn

ar P

VD

F (1

mils

)

Cyr

o A

cryl

ic (3

mils

)

Kor

ad A

cryl

ic (2

.4 m

ils)

GE

Lexa

n H

P92W

DB

PC (7

mils

)

GE

Lexa

n H

P92W

DB

112

PC

(20

mils

)

GE

Lexa

n 90

34 P

C (9

3 m

ils)

Spar

Tech

Sun

guar

d co

extru

ded

PC

/PM

MA

(120

mils

)

Poly

ethy

lene

(HD

PE)

*PD

L H

andb

ook

Tetra

fluor

oeth

ylen

e (T

FE) *

PD

L H

andb

ook

Poly

este

r (PE

T) *P

DL

Han

dboo

k

Pol

ycar

bona

te (P

C) *

PD

L H

andb

ook

Silic

one

*PD

L H

andb

ook

Perm

eabi

lity

Coe

ffici

ent (

cm3 *m

m/m

2 *day

*atm

)

HydrogenOxygen

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Work in Other Technologies Requiring Low Gas Permeability

( from H.-C. Langowski, 2004)

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General Observations• Acrylics have good outdoor durability but are brittle

and subject to hail damage• Polycarbonates are tough but “yellow” and crack

outdoors over time – protection strategies are being evaluated

• PET formulations have not yet proven durable outdoors but have favorable gas permeation properties

• Kynar has very good outdoor durability and favorable gas permeation properties

• Guidance on gas permeation and other specifications will come from the systems engineering analysis that will be completed in September 2005

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Responses to Previous Year Reviewers’ Comments

• Approach to performing the research and development• Could probably be assigned to a contract lab and done for less money.

Measurements of hydrogen permeation rates are being done on a subcontract. The same may be done with oxygen measurements when routine testing of weathered and modified materials begins. In house work on accelerated and real time weathering is being done in DOE/EERE facilities in conjunction with a group that has been involved with materials performance in solar applications for over 30 years and has a very large database of materials performance and properties.

• Specific recommendations and additions or deletions to the work scope

• Better define “issues” –target properties of H2 and O2 permeability, strength, brittle, transparency (and aging).Target properties related to permeability, e.g. transparency, cost, and service lifetime will be addressed in the systems engineering study being done in FY05

• In the later stages of this work the PI and staff should be strongly encouraged to work very closely with the photobiological and photoelectrochemical experts to ensure reactors are appropriate.This interaction was established from the start. The PI and staff participate in planning and review meetings with the photoelectrochemical and photobiological teams and regularly exchange information.

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Future Work

• Remainder of FY 2005– Provide input on reactor configurations, materials of

construction, and annual solar energy availability to the systems engineering for photobiological hydrogen production

• FY 2006– Begin to address reactor issues raised by the technoeconomic

analysis completed in FY05– Identify strategies for reducing hydrogen permeation rates – If

needed– Continue materials testing and evaluation– Work with material vendors to identify methods to overcome

materials issues– Identify reactor concepts and begin to identify design issues

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What is possible for production of hydrogen using solar bio- or photoelectrochemical reactors?

Photobioreactors produceall the food and oxygenconsumed by the entireanimal population of the earth. That includesour 6+ billion close relatives, and all ofour cousins in the animal kingdom.

It is reasonable to expect that solar water splitting processes willbe a significant contributor to hydrogen production in the future

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Questions?• Contact: Dan Blake, 303-384-7701,

[email protected]

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Publications and Presentations“Overview of Solar Reactors and Design

Considerations,” Meeting of the photobiology team, ORNL, November 3-5, 2004

“Project overview,” Hydrogen Tech Team Meeting, NREL, January 13-14, 2005

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Hydrogen Safety

The most significant hydrogen hazard associated with this project is:

Fire or explosion caused by inadvertent mixing of hydrogen and oxygen in test systems is the most significant hydrogen hazard. It will not be until laboratory and engineering scale testing of photolytic reactors begins (probably after 2010) that there will be potential for this to occur. This could conceivably occur because of material failures or assembly flaws which cause leaks in reactor systems.

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Hydrogen Safety

Our approach to deal with this hazard is:

Laboratory and engineering scale experimental work and material testing are covered by NREL safety procedures that require extensive review, readiness verification, safe operating procedures, hazard analysis, and training. The Safe Operating Procedures are subject to annual review and renewal. When laboratory and engineering scale testing of reactors begins there will be procedures in place to evaluate materials and leaktest equipment in advance of work that will generate hydrogen.

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FY 2005 FY 2006 FY 2007 FY 2008 FY 2009 FY 2010 FY 2011 FY 2012 FY 2013 FY 2014 FY 2015

Bioreactors for photobiological and photoelectrochemical hydrogen production systems1

Milestones• 1. Progress report documenting the results of the FY05 work on polymer durability and properties - September 2005• 2. Set target range for hydrogen and oxygen permeation rates for materials identified for use in solar reactors for

photobiological and photoelectrochemical hydrogen production - December 2005• 3. Provide input on materials properties, cost, and conceptual design for solar reactors for the photoelectrochemical

hydrogen production cost as needed.-May 2006• 4. Progress report documenting the results of the FY07 work on polymer durability and properties, updating material

specifications, and surveying the status of conceptual designs for solar photobiological and photoelectrochemical reactors -September 2007

• 5. Report documenting the gaps in understanding necessary for the design of solar photobiological andphotoelectrochemical reactor systems - June 2008

• 6. Document status of the cost and performance of materials of construction for the optical path and reactor body of solar photobiological and photoelectrochemical hydrogen production units - September 2008

• 7. Document design concepts for photobiological and photoelectrochemical reactor systems - September 2009

Go/No-Go Decisions1. Go/No-Go: Identify cost-effective (based on analysis) transparent hydrogen-impermeable material for use in

photoelectrochemical and photobiological hydrogen production systems.- 2010

2 4 6 73 1 $10/kg

$5/kg

Engineering scale biological hydrogen production

Engineering scale photoelectrochemical water splitting

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DRAFT