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Session 2 / AD.10.02.01I d S lid St t H dImproved Solid-State Hydrogen
Specific Analyzing Systems
Prabhu Soundarrajan, Vikas Lakhotia
H2scan Corporation, Valencia, California, USA
Analytical Solutions in a “Not So Big Easy” Economic EnvironmentThe 55th Annual Symposium of the Analysis DivisionNew Orleans, Louisiana, USA; 25-29 April 2010
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Presentation Outline
• Technology Background and Overview
• Analyzer Performance and Improved Specifications
• New Developments
• References and Field Data• References and Field Data
• Conclusions
AD 2010: Analysis Division SymposiumNew Orleans, LA, USA; 25-29 April 2010
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Technology Background
• Hydrogen specific solid-state analyzer technology for H2 measurement from 0 5% to 100% v/vmeasurement from 0.5% to 100% v/v.
• Palladium – Nickel alloy films provide high stability
• Advanced material coatings for continuous operation in harshAdvanced material coatings for continuous operation in harsh contaminant environments
• Temperature control loop compensates for external fluctuations
S bl f ti i N2 O2 th i t b k d• Sensor capable of operation in N2, O2, other inert gas backgroundsand multi-component gas streams
• Quick and easy integration
AD 2010: Analysis Division SymposiumNew Orleans, LA, USA; 25-29 April 2010
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Solid State Hydrogen Sensors
Sensors Utilize the Unique Interaction of H d ith P ll di
Solid State Hydrogen Sensors
Hydrogen with Palladium
H2 Pd
H
Molecular hydrogen (H2) adsorbs on palladium and dissociates into
atomic hydrogen (2H)
Atomic hydrogen is reversiblyabsorbed into palladium
proportional to H2 partial pressure
AD 2010: Analysis Division SymposiumNew Orleans, LA, USA; 25-29 April 2010
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atomic hydrogen (2H) proportional to H2 partial pressure
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Detection MechanismsAbsorption in Palladium is Specific to Hydrogen
Detection Mechanisms
Hydrogen increases bulk resistivity
Interfacial hydrogen shifts charge density
∆R /
R∆R
/ R
∆C
% H20.5 1000.5
ppm H2500015
Resistor CapacitorAD 2010: Analysis Division SymposiumNew Orleans, LA, USA; 25-29 April 2010
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Resistor Capacitor
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Improved In-Line Process Hydrogen AnalyzerImproved In Line Process Hydrogen Analyzer
• Hydrogen specific: 0.5% H2 to 100% H2 v/v
R ti (T90) < 30• Response time (T90) < 30 sec
• Accuracy(*): ± 0.15% absolute for 0.5 to 10% H2± 0.50% absolute for 10 to 100% H2
• Unique models for CO, H2Sq , 2
• 4-20mA, RS422 or RS232 serial connectivity
• On-site verification and calibration
• Approved for hazardous locationspp– Intrinsically safe design
• Cost effective to buy / install / maintain
• Adaptation to NeSSITM Platform (Designs in place with Swagelok, Circor, EIF, and Parker)g , , , )
AD 2010: Analysis Division SymposiumNew Orleans, LA, USA; 25-29 April 2010
Slide 66
* Applicable under process conditions stated in datasheet
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Process Hydrogen Analyzing System (AS)
Accurate measurement in multi-component gas streamsNo requirement for carrier or reference gasReal time H2 specific measurementReal time H2 specific measurementCompatible with legacy sample systemsRecommended Verification: 90 daysNEMA 4 weather-proof enclosureInstallations:
Exxon Mobil, Billings (pending)Air Liquide, ASU, Apr. ‘09.
AD 2010: Analysis Division SymposiumNew Orleans, LA, USA; 25-29 April 2010
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A l P f dAnalyzer Performance and Improved Specifications
Analytical Solutions in a “Not So Big Easy” Economic EnvironmentThe 55th Annual Symposium of the Analysis DivisionNew Orleans, Louisiana, USA; 25-29 April 2010
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Process Analyzer Specificationsy p
Notes:Sensor performance specifications are only valid for units configured for a maximum 65 oCSensor performance specifications are only valid for units configured for a maximum 65 CProcess stream temperature. All figures assume pressure compensation, operating in ambientThat do not contain Oxygen and are in addition to any errors in the calibration gases used.Accuracy is specified for serial port output only.
AD 2010: Analysis Division SymposiumNew Orleans, LA, USA; 25-29 April 2010
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H2scan Accuracy and Linearity
Linearity maintained from 0 – 100%y
AD 2010: Analysis Division SymposiumNew Orleans, LA, USA; 25-29 April 2010
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H2scan sensor repeatability
AD 2010: Analysis Division SymposiumNew Orleans, LA, USA; 25-29 April 2010
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Analyzer StabilityAnalyzer Stability
101
102
Stability in 100% H2 Test Gas
99
100
101 Stability in 100% H2 Test Gas
Drift = 0.5% H2 / month
96
97
98
% H2
93
94
95 Analyzer provides accurate measurement for H2 Process Control (Barometric pressure corrected readings)
92
93
0 5 10 15 20 25 30Time (Days)
AD 2010: Analysis Division SymposiumNew Orleans, LA, USA; 25-29 April 2010
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I d C t i t T lImproved Contaminant Tolerance and New Developments
Analytical Solutions in a “Not So Big Easy” Economic EnvironmentThe 55th Annual Symposium of the Analysis DivisionNew Orleans, Louisiana, USA; 25-29 April 2010
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% Level CO Tolerance
1108 000
1110.000N2 bkg 20%CO bkg N2 bkg
1102 000
1104.000
1106.000
1108.000
-Ni]
(1) 100% N2(2) 1000ppm H2/ bkg.(3) 1%H2 / bkg.(4) 10%H2 / bkg.
(4) (4)
1098.000
1100.000
1102.000
Res
ista
nce
[Pd-
(3) (3)
1092.000
1094.000
1096.000
tickmarks = 5 hrs(1)
(2)
(3)
(1)
(2)
(3)
1090.000
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
Time (Hours)
Testing performed at Sandia National Labs
AD 2010: Analysis Division SymposiumNew Orleans, LA, USA; 25-29 April 2010
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% Level CO Tolerance (Contd.)( )
Testing performed at Sandia National LabsAD 2010: Analysis Division SymposiumNew Orleans, LA, USA; 25-29 April 2010
Slide 15H2scan Confidential
Testing performed at Sandia National Labs
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Performance in %H2S Streams
UOP data provided to H2scan
Notes (Test duration: 4 days):Sensor exposed to H2S blend ~ 8 hours per day
AD 2010: Analysis Division SymposiumNew Orleans, LA, USA; 25-29 April 2010
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Sensor exposed to H2S blend 8 hours per dayRest of the day the sensor was exposed to 1%H2balance N2
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Low ppm measurement capability(in Nitrogen ambient only)(in Nitrogen ambient only)
Under Development
AD 2010: Analysis Division SymposiumNew Orleans, LA, USA; 25-29 April 2010
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Certifications• ATEX IS Certification done on current products.
UL Ex-proof certification underway on newUL Ex-proof certification underway on new products.
AD 2010: Analysis Division SymposiumNew Orleans, LA, USA; 25-29 April 2010
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A li ti Fi ld D t dApplications, Field Data and References
Analytical Solutions in a “Not So Big Easy” Economic EnvironmentThe 55th Annual Symposium of the Analysis DivisionNew Orleans, Louisiana, USA; 25-29 April 2010
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Refinery and Petrochemical Applications
Refinery Applications Petrochemical Applications
Catalytic Reformers Hydrogen in Recycle Gas
HydrocrackersH d i R l G
Catalytic Reformers Hydrogen in Recycle Gas
IsomarHydrogen in Recycle Gas
Hydrogen Make-up
Hydrotreaters Hydrogen in Recycle Gas
Hydrogen in Recycle GasHydrogen Make-up
TatorayHydrogen in Recycle Gas
Hydrogen Make-up
Light Naphta Isomerization UnitsHydrogen in Recycle Gas
Hydrogen Unit
Hydrogen Make-up
New ApplicationsHydrogen Optimization in Hydrogen PlantsHydrogen Unit
Hydrogen To header
OtherPurchased Hydrogen To header
Hydrogen Optimization in Hydrogen Plants
Refinery Hydrogen Management
H2 in tail gas, PSA performance monitoring ( % CO)
AD 2010: Analysis Division SymposiumNew Orleans, LA, USA; 25-29 April 2010
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Data from Refinery Installationy
1) Trend with GC consistent1) Trend with GC consistent2) Plant and analyzer were out of service for a Regen3) System pressure fluctuations attributed to variance
1 2 3 1
H2scan is the primary analyzer and has replaced obsolete analyzer and trends well with lab GC measurements (20 months in service)
AD 2010: Analysis Division SymposiumNew Orleans, LA, USA; 25-29 April 2010
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Refinery Installation – Example 1 (contd.)
Reduced install cost labor and trainingReduced install cost, labor and training
Field verification using standard gasesReplaced obsolete process analyzer (COSA)
AD 2010: Analysis Division SymposiumNew Orleans, LA, USA; 25-29 April 2010
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Refinery Installation – Example 2
• Installed in Diesel Hydro treater (DHT) recycle looptreater (DHT) recycle loop using existing sample system
• Replaced obsolete process analyzer (TCD)analyzer (TCD)
• Reduced install cost, labor and training
AD 2010: Analysis Division SymposiumNew Orleans, LA, USA; 25-29 April 2010
Slide 23H2scan Confidential 23
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Reference List
Company/ Customer Location Application Date Installed
Uni ersal Oil Prod ts Des Plaines Illinois Proprietar UOP Installed sin eUniversal Oil Products (UOP)
Des Plaines, Illinois, USA
Proprietary UOP processes
Installed since January 2008
ConocoPhillips Ponca City, Oklahoma CatalyticReformer Recycle
May 2008y
ConocoPhillips Ferndale Refinery, Washington
DHT Recycle Hydrogen
February 2009
Exxon Mobil Billings, Montana Recycle d
Installation P di
Port Jerome, France Hydrogen Pending
Feb 2010Air Liquide Blytheville, Arkansas,
USAAir Separation
PlanApril 2009
ConocoPhillips R &D Bartlesville, Oklahoma H2 production lab test
April 2009
AD 2010: Analysis Division SymposiumNew Orleans, LA, USA; 25-29 April 2010
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Summary• Hydrogen Specific Technology
– Demonstrated capability for operation in harsh process p y p penvironments (H2S, CO, CO2, H2O)
– 0.5 to 100% H2 range, Response time (<30 sec), Accuracy (±0.5%), Minimal calibration( ),
• Cost Effective for the Process Industry– No routine maintenance – 10 year product life expectancy
• Compact, Rugged, and Field Portable– On-site calibration
Solid-state hydrogen sensors enable new monitoring applications through both enhanced capability and reduced cost
AD 2010: Analysis Division SymposiumNew Orleans, LA, USA; 25-29 April 2010
Slide 25
through both enhanced capability and reduced cost