Improved Solid State Hydrogen-specific Analyzing Systems

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

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

Slide 2

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


Slide 3

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


Slide 4

atomic hydrogen (2H) proportional to H2 partial pressure

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

Slide 5

Resistor Capacitor

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 , , , )


Slide 66

* Applicable under process conditions stated in datasheet

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.


Slide 7

A l P f dAnalyzer Performance and Improved Specifications


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.


Slide 9

H2scan Accuracy and Linearity

Linearity maintained from 0 – 100%y


Slide 10

H2scan sensor repeatability


Slide 11

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)


Slide 12

I d C t i t T lImproved Contaminant Tolerance and New Developments


% 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


Slide 14

% 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

Performance in %H2S Streams

UOP data provided to H2scan

Notes (Test duration: 4 days):Sensor exposed to H2S blend ~ 8 hours per day


Slide 16

Sensor exposed to H2S blend 8 hours per dayRest of the day the sensor was exposed to 1%H2balance N2

Low ppm measurement capability(in Nitrogen ambient only)(in Nitrogen ambient only)

Under Development


Slide 17

Certifications• ATEX IS Certification done on current products.

UL Ex-proof certification underway on newUL Ex-proof certification underway on new products.


Slide 1818

A li ti Fi ld D t dApplications, Field Data and References


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)


Slide 20

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)


Slide 2121

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)


Slide 22

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


Slide 23H2scan Confidential 23

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


Slide 2424

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


Slide 25

through both enhanced capability and reduced cost