Chemical Hydrogen Rate Modeling, Validation, and System ...Washington, DC May 13-17, 2013 Technology...
Transcript of Chemical Hydrogen Rate Modeling, Validation, and System ...Washington, DC May 13-17, 2013 Technology...
U N C L A S S I F I E D
Chemical Hydrogen Rate Modeling, Validation, and System Demonstration
DOE Fuel Cell Technologies Program Annual Merit Review, EERE: Hydrogen, Fuel Cells and Infrastructure Technologies Program
Washington, DC May 13-17, 2013 Technology Team Lead: Ned Stetson
LANL Team Troy A. Semelsberger, Ben L. Davis, Brian D.Rekken, Biswajit Paik, and Jose I. Tafoya,
Project ID: st007_semelsberger_2013_O
This presentation does not contain any proprietary, confidential, or otherwise restricted information
U N C L A S S I F I E D
LANL Project Overview
Timeline • Project Start Date: Feb FY09 • Project End Date: FY14 • Percent Complete: 65%
2
Budget •Total Project Funding: $4.7M
•DOE Share: $4.7M • Funding:
•2012: $900K •2013: $880K
Barriers • Barriers Addressed
A. System Weight and Volume B. System Cost C. Efficiency D. Durability/Operability E. Charging/Discharging Rates F. Codes and Standards G. Materials of Construction H. Balance of Plant Components J. Thermal Management K. System Life-Cycle Assessments S. By-Product/Spent Material Removal
Project Timeline Phase 1 Phase 2 Phase 3
2009 2010 2011 2011 2012 2013 2014 Q2 Q3 Q4 Q1 Q2 Q3 Q4 Q1 Q2 Q3 Q4 Q1 Q2 Q3 Q4 Q1 Q2 Q3 Q4 Q1 Q2
U N C L A S S I F I E D
Relevance
• Provide a validated modeling framework to the Energy Research Community (e.g., H2A)
• Provide an internally consistent operating envelop for materials comparison wrt • System/Component mass, volume, and cost • System performance
• Provide component scaling as a function of chemical hydrogen storage media
and application
• Provide materials operating envelop required to meet DOE 2017 targets
• Identify and advance engineering solutions to address material-based non-idealities
• Identify, advance, and validate primary system level components
3
U N C L A S S I F I E D 4
System Architect Section
U N C L A S S I F I E D
Overall HSECoE Objectives
5
1. Validate chemical hydrogen storage system model
2. Determine viable chemical hydrogen storage material properties
3. Develop and demonstrate “advanced” (non-prototypical) engineering concepts
U N C L A S S I F I E D
HSECoE Phase 1-3 Objectives
6
Phase 1: • Identify Essential System Components • Develop Preliminary System Designs & Model Framework
Phase 2: • Validate System Components • Refine System Models and System Designs
Phase 3: • Validate Integrated System Components • Validate and Refine System Level Models and System Design
U N C L A S S I F I E D
Ammonia Borane System Designs
7
Exothermic Model 50 wt. % Slurry-Phase AB
Feed Pump (P-1)
Borazine/Ammonia
Filter (FT-2)
Fuel Cell
Reactor (RX-1)
Volume Displacement Tank (TNK-1)
Phase Separator Ballast Tank
(PS-1)
Fill Station Fill & Drain
Ports
STR-1
P
PS
T
P
Rupture Disk@ 2 bar(INS-01)
L
Ammonia Filter (FT-3)
Flapper Doors
STR-2
1" P
last
ic
1" P
last
ic
½” SS ½” SS
½” SS
Reactor Heater (H-1)
½” S
S
PRV @ 5 bar(V-4)
INS-08
INS-07
PRV @ 30 bar(V-2)
T
INS-06
INS-04
V-5
INS-09
INS-10
V-3
INS-11
½” SS
½” S
S
3/8" SS
3/8" SS
½” SS
Recycle Pump (P-2)
T
INS-05
Rupture Disk@ 2 bar (INS-03)
L
INS-02
1" Plastic
Feed Pump Motor (M-1)
Reactor Stirrer Motor (M-3)(Optional)
Recycle Pump Motor (M-2)
FinnedDrain Vessel
(TNK-2)
CoalescingFilter (FT-1)
Gas Radiator(RD-2) Pusher Fan
Motor (M-4)
Pusher Fan Motor (M-5)
Liquid Radiator(RD-2)
Particulate Filter (FT-4)
T
V-1
MM
SS
C
3/8"
SS
½” SS
½” SS
C
CC
C
M
S
P
T
Operator Interface
Valve Controller
Safety Feature
Pressure Transducer
Temperature Sensor
Rupture Disk
Pressure Relief Valve
Control Valve
Pressure Control Valve
Multiport Valve
Control Logic Line
Fresh Feed Line
Spent Slurry Line
Hydrogen Product
Legend
Ballast Tank (5L)
Borazine/Ammonia/Particulate Filter +
Ballast (FT-2)
Fuel Cell
Reactor (RX-1)
Volume Displacement Tank (TNK-1)
Phase Separator Ballast Tank
(PS-1)
Fill Station Fill & Drain
Ports
P
S
PS
T
P
Rupture Disk@ 2 bar(INS-01)
L
Flapper Doors
1" P
last
ic
1" P
last
ic
½” SS
Reactor Heater (H-1)
½” S
S
PRV @ 5 bar(V-4)
INS-08
INS-07
PRV @ 30 bar(V-2)
T
INS-06
INS-04
V-5
INS-09
INS-10
V-3
INS-11
½” SS
½” S
S
3/8" Al
3/8" Al
T
INS-05
Rupture Disk@ 2 bar (INS-03)
L
INS-02
1" Plastic
Pusher Fan Motor (M-5)
Gas & Liquid Radiators(RD-1/2)
T
V-1
MM
S
C
3/8"
Al
½” SS
½” SS
C
C
M
S
P
T
Operator Interface
Valve Controller
Safety Feature
Pressure Transducer
Temperature Sensor
Rupture Disk
Pressure Relief Valve
Control Valve
Pressure Control Valve
Multiport Valve
Control Logic Line
Fresh Feed Line
Spent Slurry Line
Hydrogen Product
Legend
Recirculation Pump (P-3) Recirc Pump
Motor (M-2)
Feed Pump (P-1) Recycle Pump (P-2)Pump/ReactorMotor (M-1)
End of Phase 1
Current
Projected
Primary Unit Operations • Volume Displacement Tank • Reactor • Gas-Liquid Separator • Ballast Tank • Heat Exchangers • H2 Purification • Recycle Loop
U N C L A S S I F I E D 8
Exothermic Model
FOCUS AREAS
System Mass System Volume
Projected
Current
End of Phase 1
50 wt. % Fluid-Phase Ammonia Borane
50 wt.% Ammonia Borane Spider Charts
U N C L A S S I F I E D
Projected Improvements for Ammonia Borane Slurry System
9
Phase
1: 50
wt.%
AB
Phase
2: 50
wt.%
AB
Projec
ted: 5
0 wt.%
AB
Projec
ted: 6
0 wt.%
AB
Projec
ted: 7
0 wt.%
AB
40
50
60
70
80
90
100
110
120
130
Gravimetric Volumetric
Material ImprovementsEngineering Improvements
Per
cent
age
of D
OE
201
7 V
olum
etric
or G
ravi
met
ric T
arge
ts
Phase 1 to Phase 2 (Current)
• Phase 2 Component Validation Results
• Higher fidelity System Models and System Designs
Phase 2 (Current) to Projected
• Component Integration
• Component Performance Enhancements
Engineering Improvements
Material Improvements 60 wt.% AB slurry (~ 8.7 wt. % H2) will meet both the DOE 2017 gravimetric and volumetric targets
U N C L A S S I F I E D
Alane Slurry System Designs
10
Endothermic Model 50 wt. % Alane Slurry
Feed Pump
Radiator
Fuel Cell
Reactor/PreheaterLiquid Flow Thru Reactor
Radiator
H2 Flow Thru Reactor
Recuperator
H2 Clean-Up System
Displacement Tank
Fill Station Feed Line
Fill Station Product Line Vibrator Rupture
Disk/TRD
Phase Separator/
Ballast Tank
Rupture Disk/TRD
P T
P T
P P P
T
P
T
L
End of Phase 1
Current
Projected
Notable Differences • Recycle Loop replaced with Recuperator • Eliminated one Heat Exchanger/Radiator • Reduced H2 Purification
U N C L A S S I F I E D 11
50 wt. % Alane Spider Charts
Endothermic Model
FOCUS AREAS
System Mass System Volume
Projected
Current
End of Phase 1
U N C L A S S I F I E D
Projected Improvements for Alane Slurry System
12
Phase
1: 50
wt.%
Alan
e
Phase
2: 50
wt.%
Alan
e
Projec
ted: 5
0 wt.%
Alan
e
Projec
ted: 6
0 wt.%
Alan
e
Projec
ted: 7
0 wt.%
Alan
e
40
50
60
70
80
90
100
110
120
130 Volumetric Gravimetric
Per
cent
age
of D
OE
201
7 V
olum
etric
or G
ravi
met
ric T
arge
ts
Material ImprovementsEngineering Improvements
Phase 1 to Phase 2 (Current)
• Phase 2 Component Validation Results
• Reduction of H2 Purification and Heat Exchangers
• Higher fidelity System Models and System Designs
Phase 2 (Current) to Projected
• Similar approaches as those taken for the AB system
Engineering Improvements
Material Improvements Alane slurry loadings greater than 70 wt.% (~ 8.4 wt.% H2) are expected to meet the DOE 2017 mass and volumetric targets
U N C L A S S I F I E D
System Architect Accomplishments/Highlights
Chemical Hydrogen Storage System Architect & Fluid-Phase System Designer
Developed and assessed endothermic and exothermic system designs and models
Identified material operating limitations for the on-board production of hydrogen
Performed component validation tests (e.g., GLS, VDT, H2 purification, reactors, etc.,)
Refined system level models and designs from Phase 2 component validation efforts
Identified system engineering improvements for system mass, system volume,
system cost, component manufacturability, system complexity, and system performance
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U N C L A S S I F I E D 14
LANL Technical Section 1. Reactors and Reaction Characteristics
• LANL Objectives and Relevance • Accomplishments
2. Hydrogen Purification • LANL Objectives and Relevance • Accomplishments
U N C L A S S I F I E D 15
• Data Collected
• Temperature • Gas phase analyses (impurities and hydrogen) • Reactor performance (conversions, selectivities,etc.,) • Material performance and limitations
• Materials Tested • Slurry AB (exothermic) • Slurry Alane (endothermic) • Liquid MPAB (exothermic)
• Reactors Tested
• Auger (slurry alane and slurry AB) • Helical reactors (MPAB) • Packed-bed (MPAB)
1. To demonstrate the reactive transport of slurry-phase chemical hydrogen storage materials
2. To collect the highest quality kinetics data for model validation
Model Validity
Model Breadth
System Performance
Objectives: Reactor Design and Reaction Characteristics
U N C L A S S I F I E D
Approaches
16
Three different reactors were examined with liquid phase MPAB In-house built auger reactor was examined with slurry phase ALANE and AB
Slurry Phase Reactor
Liquid Phase Reactors Technical Limitation: Reactant slugging Our Method: Design reactors that prevent or minimize reactant slugging 2013 Goals: Design, build and test helical and packed-bed reactors with liquid-phase MPAB coupled with gas-phase analyses
Technical Limitation: Reactor fouling and reactant slugging Our Method: Design reactors that prevent or minimize reactant slugging and mitigate reactor fouling 2013 Goals: Design, build and test auger reactor for slurry-phase alane and slurry phase AB coupled with gas-phase analyses
Prevent reactant slugging & mitigate reactor fouling
Prevent reactant slugging O B PB
U N C L A S S I F I E D 17
Methoxypropyl Amine Borane (MPAB) (exothermic liquid)
H2N BH3O
HB
NBH
N
BHN
O
O
O
+ 2H2 +
U N C L A S S I F I E D 18
MPAB Accomplishments
MPAB Reactor Tests Composition:
• Neat methoxy propyl amine borane: 3.9 wt. % H2
Reactors Tested: • Helical reactors • packed-bed reactor
• Downward flow • Liquid flow rates = 0.5-1.5 mL/min • Reactor Set-point Temperatures = 50-225 °C
Operating Conditions
Liquid Exothermic Material
Prepared by Ben L. Davis and Brian D. Rekken
∆
O B PB
U N C L A S S I F I E D 19
MPAB Accomplishments
60 80 100 120 140 160 180 200 220 2400
10
20
30
40
50
60
70
80
90
100
Con
vers
ion
(H2 b
ased
)
T (oC)
τliquid = 7.0 min (Rev B) τliquid = 12.5 min (Rev B) τliquid = 20.4 min (Rev B)
Liquid Exothermic Material
1. Successful demonstration of MPAB dehydrogenation as a function of reactor type, space-times and temperatures
2. Full conversion of MPAB was not observed over the temperatures, space-times, or reactors investigated
3. Borazine, and ammonia were below detectable limits (100 ppm) and only trace amounts of diborane (~200 ppm)
4. MPAB conversion was limited to less than 66% because of the increased partial pressure of MPAB for temperatures greater than 180 °C
Key Results
Re 66% v BMPAB max
X ≈
Reactant Slugging
Reactor Fouling
Trace Impurities
Research findings provided to materials researcher Ben L. Davis
U N C L A S S I F I E D 20
Slurry ALANE (endothermic slurry)
( ) ( )3 2 slurry slurry
AlH Al 1.5H∆→ +
3 rxnkJH +11
mol AlH∆ ≈
2.% .%wt H 10 wt≈
U N C L A S S I F I E D 21
Slurry ALANE Accomplishments Alane Slurry Composition:
• 20 wt. % Alane (ATK): 2.00 wt. % H2 • As-received ATK Alane • AR 200 Silicon Oil (200 cP) • TritonTM X-15 (0.025 g X-15/g Alane)
Reactor Volume Heated
Reactor Length
(mL) (cm)
Auger-1 7.4 19.1
Typical Operating Conditions
• Auger Speed: 40 rpm • Horizontal Flow • Reactor Temp: 125-275 °C • Feed Flow Rates: 0.55-1.09 mL/min
Auger Slurry Reactor
Stirred Settled
Prepared by T.A. Semelsberger
Note: alane slurry composition was ”uncatalyzed”
U N C L A S S I F I E D 22
Slurry ALANE Accomplishments
100 120 140 160 180 200 220 240 260 280
0
20
40
60
80
100
120
Ala
ne C
onve
rsio
n (%
)
Temp (C)
τliquid = 6.8 min τliquid = 13.5 min
1. Successful demonstration of slurry ALANE dehydrogenation as a function of space-time and temperature with auger reactor
2. Full conversion of ALANE can be achieved
3. Ti doped ALANE and/or ALANE activation will be required to lower the dehydrogenation temperature
4. Decomposition of silicon oil was observed for reactor set point temperatures greater than 225 °C and is the determinant factor for observed alane conversions greater than 1
Key Results
100%@ 270augerAlane avgmax
X T C≈ ≈
Reactant Slugging
Reactor Fouling Impurities
U N C L A S S I F I E D 23
Slurry ALANE Accomplishments
6( ) , 3.7 10 , 90.75aE
RTa
kJk T Ae A x Emol
− = = =
0.5( )Alane alaneapparentr k T C− =
100 125 150 175 200 225 250
0
50
100
150
200
250
Mod
el P
redi
cted
H2 F
low
(scc
m)
Avg Reactor Temp (C)
Model Predicted H2 Flow Observed H2 Flow
0.0 0.2 0.4 0.6 0.8 1.00.0
0.2
0.4
0.6
0.8
1.0
Mod
el P
redi
cted
Ala
ne C
onve
rsio
n
Observed Alane Conversion
√ Model predictions agree with experiment
Note: rate expression regressed with apparent kinetics for as-received alane collected with auger reactor
Rate expression provided to System Modeler, Kriston Brooks
U N C L A S S I F I E D 24
Slurry AB (exothermic slurry)
3 3 x y z 2 3 3 6 2 6NH BH B N H +2.35H + NH3+ B N H + B H∆→
rxnkJH -49
mol AB∆ ≈ 2.% 15.2 .%
ABwt H wt≈
U N C L A S S I F I E D 25
Slurry AB Accomplishments AB Slurry Composition:
• 20 wt. % AB: 3.05 wt. % H2 • AR 20 Silicon Oil (20 cP) • TritonTM X-15 (0.025 g X-15/g AB)
Reactor Volume Heated
Reactor Length
(mL) (cm)
Auger-1 7.4 19.1
Typical Operating Conditions
• Auger Speed: 40 rpm • Horizontal Flow • Reactor Temp: 125-275 °C • Feed Flow Rates: 0.55-1.09 mL/min
Auger Slurry Reactor
Prepared by Ewa Rӧnnebro
Stirred Flocculated
U N C L A S S I F I E D
1. Successful demonstration of slurry AB dehydrogenation as a function of space-time and temperature with auger reactor
2. Full conversion of MPAB can be achieved but was not observed over the temperatures and space-times investigated
3. Maximum impurities observed during operation
26
Slurry AB Accomplishments
86%@ 212augerAB avgmax
X T C≈ ≈
( )3
145
max3.0%%
T
NHn
n
= ≈
( )168
max2.8%%
T
borazinen
n=
≈
( )168
max1.0%%
T
diboranen
n=
≈
Reactant Slugging
Reactor Fouling Impurities
Key Results
Auger reactor performed equally well for both ENDOTHERMIC and EXOTHERMIC media types
U N C L A S S I F I E D 27
LANL Technical Section 2. Hydrogen Purification
• LANL Objectives and Relevance • Accomplishments
U N C L A S S I F I E D
Borazine Adsorption Approaches
28
> 15 different adsorbents were screened for borazine adsorption capacity
Technical Limitation: Borazine and ammonia are known fuel cell impurities generated from ammonia borane
Our Methods: 1. Develop and screen for potential borazine adsorbents 2. Implement ammonia adsorbent (UTRC) with down-selected
borazine adsorbent (LANL) to demonstrate hydrogen purification
2013 Goals: 1. Down select borazine adsorbent with the highest borazine
adsorption capacity 2. Demonstrate ammonia and borazine that is co-fed can be
scrubbed to produce fuel-cell grade hydrogen
Adsorbents
Static Adsorption
Dynamic Adsorption
(Downselect adsorbents)
• Pre-treatment • Temperature • Chemical Modification • Concentration
U N C L A S S I F I E D 29
ACN-210-15 Down Selected ACN-210-15
Borazine Adsorption Accomplishments
Key Results 1. ACN-210-15 demonstrated the highest borazine
adsorption capacity around 40% (Pamb) & 80% (P = 5 bar)
ACN-210-15> AX-21> Y-zeolite > ZSM-5 > Oxides
Note: Chemically modified substrates did not show marked improvements over the as-received analogs
2. ACN-210-15 is an off-the-shelf carbon adsorbent
requiring no special pretreatments or handling
3. ACN-210-15 is a woven felt that is ideally suited for vibration prone environments because ACN-210-15 is not friable
4. Adsorption capacity decreases with increasing temperature
U N C L A S S I F I E D
1. Borazine has a higher chemical affinity toward MnCl2 than ammonia has toward ACN-210-15
• Ammonia adsorption capacity in ACN-210-15 ~ 1%
• Borazine adsorption capacity in MnCl2 ~ 6%
2. Adsorbent bed configuration is important
30
Ammonia and Borazine Adsorption Accomplishments
Ammonia and borazine can be scrubbed to produce fuel-cell grade hydrogen
Borazine should be scrubbed prior to Ammonia
Key Results
We have identified potential scrubbing technologies that can reduce the current requirement of 6.8 kg of ACN-210-15
Ammonia Adsorbent
U N C L A S S I F I E D 31
Summary: 2013 Accomplishments • Successfully demonstrated flow reactor tests with quantification on slurry ALANE, slurry
AMMONIA BORANE, and liquid MPAB
• Full conversion of “uncatalyzed” ALANE can be achieved for temperatures greater than 270
C
• Improvements in ALANE dehydrogenation kinetics were observed with the use of dopants and solvents (reviewer only slides)
• No impurities were detected during ALANE dehydrogenation
• Trace amounts of diborane were detected during MPAB dehydrogenation
• AMMONIA BORANE produced borazine, diborane, and ammonia impurities
• Reactant slugging and reactor fouling were mitigated through our in-house designed and built reactors
• In-house built auger reactor performed equally well for both slurry ALANE and slurry AMMONIA BORANE compositions
• ACN-210-15 demonstrated the highest borazine adsorption capacity
• Demonstrated that ammonia and borazine can be scrubbed to produce fuel-cell grade hydrogen
U N C L A S S I F I E D 32
LANL Future Work
1. Slurry AB Compositions (exothermic)
• Perform kinetics/reactor tests with increased AB loadings (30-50 wt. %); develop rate expression
2. Slurry Alane Compositions (endothermic)
• Perform kinetics/reactor tests with increased alane loadings (40- 60 wt.%); develop rate expression
• Extend alane kinetics/reactor tests to include different solvents (e.g., DEGB) and dopants (e.g., Ti)
3. Liquid MPAB (exothermic)
• Redesign reactor to address material limitation
4. Borazine Scrubbing • Examine non-adsorbent based borazine scrubbing technologies
U N C L A S S I F I E D
Collaborations
33
External Collaborators Effort Contact H2 Codes and Standards General Guidance C. Padro (LANL)
Chemical Hydrogen Storage Researchers Materials Research J. Wegrzyn (BNL) T. Baker (U. Ottawa) B. Davis (LANL)
H2 Production & Delivery Tech Team WTT Analyses M. Pastor (DOE) B. James
LANL Fuel Cell Team General Guidance Fuel Cell Impurities
T. Rockward (LANL)
R. Borup (LANL)
H2 Safety Panel General Guidance/Concerns S. Weiner
SSAWG Technical Collaboration G. Ordaz (DOE)
H2 Storage Tech Team General Guidance Ned Stetson (DOE)
Argonne National Laboratory Independent Analyses R. Ahluwalia
HSECoE Collaborators Effort Contact
UTRC
Ammonia Scrubbing B. van Hassel Simulink® Modeling J. Miguel Pasini
Gas-Liquid Separator Randy McGee
PNNL MOR E. Ronnebro System Modeling K. Brooks BOP K. Simmons
NREL Vehicle Modeling M. Thornton
SRNL Slurry Mixing David Tamburello
Ford FMEA Mike Veenstra
U N C L A S S I F I E D
Acknowledgements
Ned Stetson and Jessie Adams
34
U N C L A S S I F I E D
Backup Slides
35
U N C L A S S I F I E D
HSECoE Partners
36
U N C L A S S I F I E D
Supporting Information
42
U N C L A S S I F I E D
SMART Milestones Chemical Hydrogen Storage Team
Component Lead S*M*A*R*T Milestone Status 20 Mar 2013 Projected Outcome
Materials Development LANL
Report on ability to develop a 40wt% liquid AB material (6.4wt%H2) having viscosity less than 1500cP pre- and post-dehydrogenation and kinetics comparable to the neat.
Developed a 3.9 wt.% H2 liquid phase chemical hydrogen storage media that is liquid both pre- and post-reaction with kinetics similar to that of solid AB, preliminary impurities profile looks promising because of the significantly reduced or eliminated impurities production, viscosities all well below 1500cP
Investigations will continue into new solvent chemistries which are anticipated to meet the metric while minimizing fuel-cell impurities
Materials Development PNNL
Report on ability to develop a 40wt. % slurry AB material having viscosity less than 1500cP pre- and post-dehydrogenation and kinetics comparable to the neat.
45wt% AB achieved before reaction 617cP, Yield stress 48 Pa after dehydrogenation 442cP, yield stress 3.7Pa Met Target
Reactor LANL
Report on ability to develop a flow through reactor capable of discharging 0.8 g/s H2 from a 40 wt.% AB fluid-phase composition having a mass of no more than 2 kg and a volume of no more than 1 liter.
Reactor performance and Kinetics collected for • Liquid exothermic material (3.9 wt.% H2-MPAB) • Slurry exothermic material (20 wt.% AB slurry) • Slurry endothermic material (20 wt.% Alane)
Data will be provided to Kriston to incorporate into system-level model
Reactor performance tests kinetics will be performed on • 35-50 wt% AB slurries • 40-60 wt.% Alane slurries Note: Alternative reactor designs and operation will be performed to maximize reactor efficiency Data will be provided to Kriston to incorporate into system-level model
HX/Radiator PNNL Report on ability to develop/identify a radiator/HX capable of cooling the effluent from 525K to 360K having a mass less than 1.15 kg and a volume less than 10.9 liters
Radiator volume – 1.5L, mass 1.44kg, Validated models show a decrease in fins spacing will achieve the mass of 1.15kg mass and the required heat transfer meeting the metrics.
Met Target
GLS UTRC
Report on ability to develop a GLS capable of handling 720 mL/min liquid phase and 600 L/min of H2 @ STP (40 wt% AB @ 2.35 Eq H2 and max H2 flow of 0.8 g/s H2) fluid having a viscosity less than 1500cp with resulting in a gas with less than 100ppm aerosol having a mass less than 5.4 kg and volume less than 19 liters.
Mass 5.8 kg (above 5.4 kg metric) Volume 2.7 L (far below 19 L metric).
Exceeded volume target, but just over the mass target. Demonstrate operation meeting metrics utilizing spent fuel simulant.
Borazine Scrubber LANL
Report on ability to develop a borazine scrubber with a minimum replacement interval of 1800 miles of driving resulting in a minimum outlet borazine concentration of 0.1 ppm (inlet concentration = 4,000 ppm) having a maximum mass of 3.95 kg and maximum volume less of 3.6 liters.
An activated carbon borazine scrubber has been demonstrated yielding <0.1 ppm exit borazine concentration having: Mass = 6.8 kg (need significant reduction) Volume = 5.9 L (need reduction but not as critical as mass)
Alternative non-adsorbent based strategies are being explored to reduce the mass and volume of the scrubber.
Ammonia Scrubber UTRC
Report on ability to develop an ammonia scrubber with a minimum replacement interval of 1800 miles of driving resulting in a minimum ammonia outlet concentration of 0.1 ppm (inlet concentration = 500 ppm )having a maximum mass of 1.2 kg and a maximum volume of 1.6 liters.
Mass 1.1 kg (surpass 1.2 kg metric) Volume 1.6 L (meets 1.6 L metric) Met Target
BoP PNNL Report on ability to Identify BoP materials suitable for the Chemical Hydrogen system having a system mass no more than 41 kg and a system volume no more than 57 liters.
Mass = 60kg Volume = 61 L (really close to meeting volume target)
Critical reductions in mass: • borazine scrubber • pump mass • GLS mass • via parts consolidation/elimination/new technology Note: in meeting the mass target, we will also meet the volume target
System Design PNNL Report on ability to identify a system design having a mass less than 97 kg and a volume less than 118 liters meeting the all of the HSECoE drive cycles.
50%AB/Si oil : Media Mass = 97kg Media Volume = 86.5 L System Mass = 137 kg System Volume = 148 L
Alternate components and designs are being investigated but a higher density slurry (70w% AB or similar) will be required to meet the metric.
Efficiency Analysis NREL
Calculate and model the well-to-powerplant (WTPP) efficiency for two chemical hydride (CH) storage system designs and compare results relative to the 60% technical target.
Alane 24.7% WTPP efficiency AB 16.5% WTPP efficiency Met Target
U N C L A S S I F I E D
Reactor Development and Performance
TTR Meeting Detroit, Michigan March 20-21, 2013
LANL TEAM Troy A. Semelsberger, Jose .I. Tafoya, Ben. L. Davis, and Brian. D. Rekken
T.A. Semelsberger
U N C L A S S I F I E D
Status and Progress
Materials Tested in Batch Reactor
45
• 20 wt.% ATK Alane DEGBE-uncatalyzed
• 20 wt.% ATK Alane Julabo H350-uncatalyzed
• 20 wt.% ATK Alane DEGBE/LiH/Ti-catalyzed
• 20 wt.% ATK Alane Julabo H350/LiH/Ti-catalyzed
• 20 wt.% Slurry AB/Silicon Oil
• 20 wt.% Liquid AB/Iolilyte
Temperature Profile: Step 1: tiso = 60 min @ T = 25 °C Step 2: Tr = 1 °C/min with Tf = 140 °C Step 3: tiso = 2800 min @ T = 140 °C
U N C L A S S I F I E D 46
Batch Reactor Screening of Ammonia Borane and Alane
Objectives: 1. Solvent Effects 2. Catalytic Effects
U N C L A S S I F I E D 47
3 21.5 AlH Al H∆→ + 2.% .%wt H 10 wt≈3 rxn
kJH +11mol AlH
∆ ≈
• LiH and Ti improve kinetics of alane dehydrogenation in DEBE, but not in H350
• Solvent choice has a greater impact on alane dehydrogenation rate than LiH and Ti
• Dehydrogenation onset temperatures remain relatively unchanged wrt solvent or LiH/Ti
Alane Batch Reactor Results
90onsetT C≈
U N C L A S S I F I E D 48
3 3 x y z 2 3 3 6 2 6NH BH B N H +2.35H + NH3+ B N H + B H∆→2.% 15.2 .%
ABwt H wt≈
rxnkJH -49
mol AB∆ ≈
• AB Slurry demonstrated a three step process consistent with prior observations
• AB/Iolilyte two-step process coupled with chemical incompatibility with iolilyte
• Dehydrogenation onset temperatures are approximately the same
55onsetT C≈
AB Batch Reactor Results
U N C L A S S I F I E D
Status and Progress
2. Flow Reactor Experiments
49
1. Batch Reactor Testing • AB Slurry • Alane Slurry • AB-IL
2. Flow Reactor Testing
• MPAB (liquid exothermic material) • Helical Reactor (O) • Helical Reactor (A) • Packed-bed Reactor (PB)
• AB Slurry (exothermic material) • Auger Reactor
• Alane Slurry (endothermic material) • Auger Reactor
U N C L A S S I F I E D 50
Alane Slurry Reactor Tests
Slurry Composition: • 20 wt. % Alane (ATK): 2.00 wt. % H2 • AR 200 Silicon Oil (200 cP) • TritonTM X-15 (0.025 g X-15/g AB)
TritonTM X-15
Stirred Settled
Prepared by T.A. Semelsberger
U N C L A S S I F I E D 51
0
25
50
75
100
125
150
175
200
225
250
275
300
0 50 100 150 200 250 300 350 400 450
Tem
pera
ture
(oC)
Time (minutes)
Reactor InletReactor SetpointReactor OutletAvg Reactor Temp
Alane = 1.09 mL/min Alane = 0.55 mL/min
20 wt.% Alane-07 • Auger Reactor (Volume = 7.4 mL) • Reactor Tstpt = 125-275°C • Feed Flow Rates:
• 1.09 mL/min (6.8 min) • 0.55 mL/min (13.5 min)
Alane flow-reactor experiment was well behaved and stable
No observable endothermic temperature profiles
Alane Auger Reactor Results
U N C L A S S I F I E D 52
100 120 140 160 180 200 220 240 260 280
0
20
40
60
80
100
120
Con
vers
ion
(%)
Temp (C)
τliquid = 6.8 min τliquid = 13.5 min
20 wt.% Alane-07 • Auger Reactor (Volume = 7.4 mL) • Reactor Tstpt = 125-275°C • Feed Flow Rates:
• 1.09 mL/min (6.8 min) • 0.55 mL/min (13.5 min)
Alane Auger Reactor Results
100 120 140 160 180 200 220 240 260 280
0
50
100
150
200
250
300
H2
Flow
(scc
m)
Temp (C)
τliquid = 6.8 min τliquid = 13.5 min
Conversion and hydrogen flow rate increase with increasing temperature
Conversions greater than 100% were observed because of the decomposition of silicon oil and/or the chemical reaction of silicon oil with aluminum/alane…resulting in an increase in the observed hydrogen production
2
100%
300
Alane max
H max
X
F sccm
≈
≈
U N C L A S S I F I E D 53
0
25
50
75
100
125
150
175
200
225
250
275
0
10
20
30
40
50
60
70
80
90
100
110
0 30 60 90 120 150 180 210 240 270 300 330 360 390 420
Avg
Reac
tor T
empe
ratu
re (o
C)
Mol
e Pe
rcen
t (%
)
Time (minutes)
[H2]
[tracer]
Sum H2 + tracer
Avg Reactor Temp
Alane = 1.09 mL/min Alane = 0.55 mL/min
20 wt.% Alane-07 • Auger Reactor (Volume = 7.4 mL) • Reactor Tstpt = 125-275°C • Feed Flow Rates:
• 1.09 mL/min (6.8 min) • 0.55 mL/min (13.5 min)
Alane Auger Reactor Results
Hydrogen mole percentage tracks nicely with temperature
The mole percentage totals sum to approximately 100%
180 min t 330 min≤ ≤
U N C L A S S I F I E D 54
0
1
2
3
4
5
6
7
8
9
10
0
10
20
30
40
50
60
70
80
90
100
110
0 30 60 90 120 150 180 210 240 270 300 330 360 390 420
Impu
rity:
Abs
orba
nce
Mol
e Pe
rcen
t (%
)
Time (minutes)
[H2][tracer]Sum H2 + tracerIR: TracerIR Impurity
Alane = 1.09 mL/min Alane = 0.55 mL/min
20 wt.% Alane-07 • Auger Reactor (Volume = 7.4 mL) • Reactor Tstpt = 125-275°C • Feed Flow Rates:
• 1.09 mL/min (6.8 min) • 0.55 mL/min (13.5 min)
Alane Auger Reactor Results
The only impurity observed was due to thermal decomposition of the silicon oil used as the carrier
Maximum temperature of this alane composition is around Tavg ~210 °C
U N C L A S S I F I E D 55
Summary: 20 wt.% Alane Slurry Reactor Results
• Successful demonstration of a 20 wt. % alane slurry dehydrogenation as a function of temperature and space-time
• Full conversion of slurry alane was observed over the temperatures, and space-times investigated
• Maximum conversion observed was XMPAB ~100% @ τliquid = 6.8min and T = 260-275°C with in-house built auger reactor
• The only impurity observed during alane dehydrogenation was the degradation of the carrier (Reactor Tstpt = 225°C, Tavg = 210°C)
• The reaction was stable, clean and facile
• Improvements in the reaction kinetics can be accomplished by the use of dopants and alternative solvents
Slurry Endothermic Material
U N C L A S S I F I E D
Borazine Adsorption
56
5.4 Å
Borazine
Relevance: To develop and demonstrate hydrogen purification technologies that produce fuel-cell grade hydrogen meeting DOE purity targets
Component Partner S*M*A*R*T Milestone
Borazine Scrubber LANL
Report on ability to develop a borazine scrubber with a minimum replacment interval of 1800 miles of driving resulting in a minimum outlet borazine concentration of 0.1 ppm (inlet concentration = 4,000 ppm) having a maximum mass of 3.95 kg and maximum volume less of 3.6 liters.
Borazine is a known fuel cell impurity that requires scrubbing
U N C L A S S I F I E D
Screen adsorbents for borazine adsorption capacities at RT under static adsorption conditions
Adsorbents dried under Ar flow at 200 C for 2 hr Adsorbents kept under sealed borazine gas environment for
several days Mass gain is measured to estimate the borazine adsorption
capacity under the static adsorption Downselect adsorbents to determine the dynamic adsorption capacities of borazine Dynamic adsorption mimics closely the situation where impurity gases (produced by the decomposition of AB-based H2 storage system) flow through the adsorbent (s)
57
Adsorbents
Static Adsorption
Dynamic Adsorption
(Downselect adsorbents)
• Pre-treatment • Temperature • Chemical Modification • Pressure • Concentration
Approach
U N C L A S S I F I E D
Borazine Adsorbents
Sample group Sample name/ID Form Surface acidity (Si/Al)
Surface area (m2/g)
Av. Particle size (μm)
Y-zeolite CBV720 CBV300
H NH4
15 2.55
780 925
<461 <461
ZSM-5 (as-received)
CBV28014 CBV3024 CBV8014 CBV5524G
H H H NH4
140 15 40 25
400 400 425 425
<461 <461 <461 <548
ZSM-5 (modified)
Cu/Zn on CBV3024E Cu/Zn on CBV5524G
NH4
25
270
<653
Activated carbon
ACN-210-15 AX-21 DMAP impregnated in AX-21
Felt Porous particle Porous particle
1500 1500
Oxides
BASF-K3-110 Al2O3 SiO2 ZnO
58
U N C L A S S I F I E D
59
11.36
3.77 5.54 5.99 4.45 5.31
40.54
21.98
5.12
0
6
12
18
24
30
36
42
48
Y-Zeolite,CBV720, H,S.A=780 ,Si/Al=15
Y-Zeolite,CBV300, NH4,
S.A.=925,Si/Al=2.55
ZSM-5,CBV28014, H,
S.A.=400,Si/Al=140
ZSM-5,CBV8014, H,
S.A.=425,Si/Al=40
ZSM-5,CBV3024,H,
S.A.=400,Si/Al=15
ZSM-5,CBV5524G,
NH4,S.A.=425,Si/Al=25
Act. C,ACN-210-15,
S.A.=1500
Act. C,AX-21
S.A.=1500
BASF-K3-110
Adso
rptio
n Ca
paci
ty %
Downselected Adsorbents:
Y-zeolite (CBV720) ZSM-5 (CBV28014, CBV8014) Activated carbon (ACN-210-15, AX-21)
Borazine Adsorption: Dynamic Conditions
T = 298K P = amb Flow Rate =40 sccm [borazine] =
(%) adsorbate
adsorbent
mAdsorption Capacity 100m
= ⋅
U N C L A S S I F I E D
60
9.52 11.36
13.46
5.67 5.54 7.65
6.13 5.99 6.4
30.59
40.54 38.92
21.6 21.98 21.7
0
5
10
15
20
25
30
35
40
45
50
Dry
As-re
ceive
d
Wet Dry
As-re
ceive
d
Wet Dry
As-re
ceive
d
Wet Dry
As-…
Wet Dry
As-re
ceive
d
Wet
Adso
rptio
n Ca
paci
ty %
Y-zeolite CBV720
ZSM-5 CBV28014
ZSM-5 CBV8014 ACN-210-15 AX-21
Humidifying Conditions: samples were exposed to a saturated water stream for two hours prior to adsorption experiments
• Zeolites and AX-21 demonstrated only slight differences in borazine adsorption capacities as a function of pre-treatment
Borazine Adsorption: Pre-treatment Effects
T = 298K P = amb Flow Rate = 40 sccm [borazine] =
Drying Conditions: Dried @ 350 C for > 12 hr under Ar flow
Note: Chemically modified ACN did not show marked improvements in borazine adsorption or
polymerization capacities
• ACN-210-15 demonstrated improved adsorption capacity as a function of humidification
• Down selected for further study
U N C L A S S I F I E D
61
ACN-210-15
AX-21
30 C 80 C 150 C
Borazine Adsorption: Temperature Effects
Adsorption capacity as a fcn of temperature
(%) adsorbate
adsorbent
mAdsorption Capacity 100m
= ⋅
Borazine breakthrough curves for ACN-210-15
(%)Temperature Adsorption Capacity↑ = ↓
as-received adsorbents
as-received adsorbents
U N C L A S S I F I E D
30.59
0.45
40.54
4.31 38.92
5.92
0
10
20
30
40
50
Dry As-received
Wet
Adso
rptio
n Ca
pacit
y %
40.54
4.31
35.34
4.66
14.51
0.68
0
10
20
30
40
50
30 C 80 C 150 C
Adso
rptio
n Ca
pacit
y %
62
Adsorption capacity as a fcn of sample pre-treatment Adsorption capacity as a fcn of temperature
Borazine adsorption capacity with ACN-210-15
(%) adsorbate
adsorbent
mAdsorption Capacity 100m
= ⋅
(%)Temperature Adsorption Capacity↑ = ↓( ) ( ) ( ) as received wet dried− ≈ >
U N C L A S S I F I E D 63
Adsorbents Borazine Adsorbent: ACN-210-15 Ammonia Adsorbent: MnCl2 /IRH-33 (UTRC supplied) Approach Competitive adsorption: NH3 and borazine co-fed into (i) ACN-210-15 (ii) MnCl2 / IRH-33 Combining adsorption beds in series:
Co-feed NH3 and borazine through the borazine and ammonia adsorption beds connected in series
Ammonia Bed
Borazine Bed
Ammonia-Borazine Competitive Adsorption
U N C L A S S I F I E D
64
0
0.2
0.4
0.6
0.8
1
0 50 100 150
C/C 0
Time(min)
t0
NH3 870 ppm
t1
Borazine 730 ppm
t1
ACN-210-15
ACN-
210-
15
( ) 1
0
t
BorazineAds Capacity 40%≈
( ) 0
0 33
t
BorazineAds Capacity %≈
Borazine Adsorption Capacity: ACN-210-15
( ) 1
0 1
t
AmmoniaAds Capacity %≈
( ) 0
0 0.3
t
AmmoniaAds Capacity %≈
Ammonia Adsorption Capacity: ACN-210-15
Ammonia has a low adsorption capacity in ACN-210-15
Competitive Adsorption ACN-210-15
U N C L A S S I F I E D
0
0.2
0.4
0.6
0.8
1
0 100 200 300 400
C/C
0
Time(min)
65
t1 t1 Borazine 966 ppm
NH3 918 ppm
t0 t0
( ) 1
0 6
t
BorazineAds Capacity %≈
( ) 0
0 5
t
BorazineAds Capacity %≈
Borazine Adsorption Capacity: MnCl2/IRH-33
( ) 1
0 6
t
AmmoniaAds Capacity %≈
( ) 0
0 3
t
AmmoniaAds Capacity %≈
Ammonia Adsorption Capacity: MnCl2/IRH-33 Mn
Cl2/I
RH-3
3
Ammonia and Borazine have comparable chemical affinities in MnCl2/IRH-33
Order of beds should be ACN-210-15 followed by MnCl2/IRH-33
MnCl2/IRH-33
Competitive Adsorption MnCl2/IRH-33
U N C L A S S I F I E D
500150025003500 Wavenumber (cm-1)
66
0
0.2
0.4
0.6
0.8
1
0 50 100 150C/
C 0
Time(min)
Ammonia
Borazine
MnCl
2/IRH
-33
ACN-
210-
15
Demonstrated that ammonia and borazine can be scrubbed to produce fuel-cell grade hydrogen
:23 30
Adsorbed MassesBorazine mgAmmonia mg
≈≈
( ) 1
0 40
t
BorazineAds Capacity %≈
( ) 0
0 33
t
BorazineAds Capacity %≈
Borazine Adsorption Capacity
( ) 1
0 10
t
AmmoniaAds Capacity %≈
( ) 0
0 7
t
AmmoniaAds Capacity %≈
Ammonia Adsorption Capacity
t1 t1
t0 t0
Purification of Ammonia & Borazine
U N C L A S S I F I E D 67
Conclusions
• ACN-210-15 demonstrated the highest borazine adsorption capacity at ~ 40%
ACN-210-15> AX-21> Y-zeolite > ZSM-5 > Oxides
Note: Chemically modified substrates did not show marked improvements over the as-received analogs
• ACN-210-15 is an off-the-shelf carbon adsorbent requiring no special pretreatments or handling
• ACN-210-15 is a woven felt that is ideally suited for vibration prone environments because ACN-210-15 is not friable
• Adsorption capacity decreases with increasing temperature
• Borazine has higher chemical affinity toward MnCl2 than ammonia has for ACN-210-20
Purification order is important: borazine needs to be scrubbed prior to ammonia