SPME Coupled with GC-SPME Coupled with GC-FID for the Detection of FID for the Detection of

n-Propyl Alcohol and Its n-Propyl Alcohol and Its Use as a Geothermal Use as a Geothermal TracerTracer

Michael MellaMichael Mella1,21,2

11 Energy and Geoscience Institute - University of Utah, Energy and Geoscience Institute - University of Utah,2 Chemical Engineering Department – University of Utah2 Chemical Engineering Department – University of Utah

Senior Projects Lab I - 2006Senior Projects Lab I - 2006

Why n-propanol?Why n-propanol?

Liquid phase only tracers and Liquid phase only tracers and vapor phase only tracers are in vapor phase only tracers are in common usecommon use

Two-phase tracers are needed to Two-phase tracers are needed to better trace waterbetter trace water

n-Propanol has a similar partition n-Propanol has a similar partition coefficient to water, similar two-coefficient to water, similar two-phase characteristics to waterphase characteristics to water

ObjectivesObjectives

Lab work - Develop an Lab work - Develop an analytical method to reduce analytical method to reduce the limit of detection of n-the limit of detection of n-propanolpropanol

Field work - Validate method with Field work - Validate method with a field testa field test

Lab DevelopmentLab Development

Solid Phase MicroExtraction Solid Phase MicroExtraction (SPME) was used to help lower (SPME) was used to help lower the limit of detection over the limit of detection over previous methods by 30 foldprevious methods by 30 fold

Gas Chromatography with a Gas Chromatography with a Flame Ionization Detector used to Flame Ionization Detector used to analyze n-propanol solutionsanalyze n-propanol solutions

SPME basicsSPME basics

A flexible fiber coated with 85A flexible fiber coated with 85µm µm thickthick

Carboxen/PDMS layerCarboxen/PDMS layer A needle that houses the fiber A needle that houses the fiber

and an injection assemblyand an injection assembly

GC analysisGC analysis

Needle injected into 300Needle injected into 300°C GC °C GC inletinlet

Separation by HP-5 capillary Separation by HP-5 capillary columncolumn

Detection by FIDDetection by FID Analysis of signal using HP-CHEM Analysis of signal using HP-CHEM

softwaresoftware

Analytical method Analytical method resultsresults Limit of detection at 1 ppbLimit of detection at 1 ppb Reduction by a factor of 30 from Reduction by a factor of 30 from

previous methodsprevious methods Lower limit of detection means Lower limit of detection means

less n-propanol needed for testless n-propanol needed for test Method can be extended to other Method can be extended to other

alcohols and aldehydesalcohols and aldehydes

ObjectivesObjectives

Lab work - Develop an analytical Lab work - Develop an analytical method to reduce the limit of method to reduce the limit of detection of n-propanoldetection of n-propanol

Field work - Validate method Field work - Validate method with a field testwith a field test

Field testField test

Injector 34-9RD2 of Coso East Injector 34-9RD2 of Coso East Flank tagged with 165 gallons n-Flank tagged with 165 gallons n-propanolpropanol

Samples taken from surrounding Samples taken from surrounding East Flank producersEast Flank producers

Field WorkField Work

Alcohol returnsAlcohol returns Comparison with a liquid tracer Comparison with a liquid tracer

testtest

Alcohol returnsAlcohol returns

Raw resultsRaw results E(t) scaled results and recoveryE(t) scaled results and recovery Liquid phase tracer resultsLiquid phase tracer results

34-9RD2 Propanol

0

10

20

30

40

50

60

70

80

90

100

0 10 20 30 40 50 60 70days

pp

b

38C-9 propanol in steam

38C-9 propanol in brine

38D-9 propanol in steam

38D-9 propanol in steam

Alcohol returnsAlcohol returns

Raw resultsRaw results E(t) scaled results and E(t) scaled results and

recoveryrecovery Liquid phase tracer resultsLiquid phase tracer results

E(t)E(t)

E(t) E(t) residence-time distribution residence-time distribution functionfunction

E(t) is a way to normalize for mass of E(t) is a way to normalize for mass of tracer injected and flow ratestracer injected and flow rates

E(t) required for future assessment of E(t) required for future assessment of return data, an example is the return data, an example is the convolution integral and tracer convolution integral and tracer recoveryrecovery

0

)(

)()(

dttC

tCtE

Tracer RecoveryTracer Recovery

Use E(t) to calculate the amount of Use E(t) to calculate the amount of tracer recovered in both the liquid tracer recovered in both the liquid phase and the vapor phase.phase and the vapor phase.

t

dttEreturned0

)(%

Normalized n-propanol return

0

0.0005

0.001

0.0015

0.002

0.0025

0.003

0 10 20 30 40 50

days

E(1

/da

y)

38C-9 propanol in steam

38C-9 propanol in brine

38D-9 propanol in steam

38D-9 propanol in brine

Alcohol returnsAlcohol returns

Raw resultsRaw results E(t) scaled results and recoveryE(t) scaled results and recovery Liquid phase tracer returnLiquid phase tracer return

Liquid phase tracer Liquid phase tracer returnreturn 2 months prior 100 kg 1,3,5-NTS 2 months prior 100 kg 1,3,5-NTS

injected into 34-9RD2injected into 34-9RD2 Samples from the same area Samples from the same area

were taken and analyzed by HPLC were taken and analyzed by HPLC with a fluorescence detectorwith a fluorescence detector

1,3,5-NTS Return

0

5

10

15

20

25

30

35

40

45

50

0.00 50.00 100.00 150.00

days

ppb

38A-9

38B-9

38C-9

38D-9

Return comparisonsReturn comparisons

Normalized n-propanol and 1,3,5-Normalized n-propanol and 1,3,5-NTS return curves were plotted NTS return curves were plotted together with a common x-axis of together with a common x-axis of days after their respective days after their respective injection date.injection date.

Normalized tracer returns

0

0.001

0.002

0.003

0.004

0.005

0.006

0.007

0.008

0.009

0.01

0 50 100 150

days

E(1

/day

)38C-9 propanol in steam

38C-9 propanol in brine

38D-9 propanol in steam

38D-9 propanol in brine

38C-9 1,3,5-NTS

38D-9 1,3,5-NTS

Return comparisonsReturn comparisons

Tracer recovery of n-propanol = Tracer recovery of n-propanol = 3.5%3.5%

Tracer recover of 1,3,5-NTS = Tracer recover of 1,3,5-NTS = 74.8%74.8%

ConclusionsConclusions

Similar arrival times for 1,3,5-Similar arrival times for 1,3,5-NTS and n-propanol in well NTS and n-propanol in well 38C-938C-9

Appearance of n-propanol in 38D-9 Appearance of n-propanol in 38D-9 but not 1,3,5-NTSbut not 1,3,5-NTS

38B-9 seems to have been 38B-9 seems to have been “skipped” by both tracers“skipped” by both tracers

Less return of n-propanol than of Less return of n-propanol than of 1,3,5-NTS1,3,5-NTS

Normalized tracer returns

0

0.0005

0.001

0.0015

0.002

0.0025

0.003

0 2 4 6 8 10 12 14

days

E(1

/day

)38C-9 propanol in steam

38C-9 propanol in brine

38D-9 propanol in steam

38D-9 propanol in brine

38C-9 1,3,5-NTS

38D-9 1,3,5-NTS

ConclusionsConclusions

Similar arrival times for 1,3,5-NTS Similar arrival times for 1,3,5-NTS and n-propanol in well 38C-9and n-propanol in well 38C-9

Appearance of n-propanol in Appearance of n-propanol in 38D-9 but not 1,3,5-NTS38D-9 but not 1,3,5-NTS

38B-9 seems to have been 38B-9 seems to have been “skipped” by both tracers“skipped” by both tracers

Less return of n-propanol than of Less return of n-propanol than of 1,3,5-NTS1,3,5-NTS

Normalized tracer returns

0

0.001

0.002

0.003

0.004

0.005

0.006

0.007

0.008

0.009

0.01

0 50 100 150

days

E(1

/day

)38C-9 propanol in steam

38C-9 propanol in brine

38D-9 propanol in steam

38D-9 propanol in brine

38C-9 1,3,5-NTS

38D-9 1,3,5-NTS

ConclusionsConclusions

Similar arrival times for 1,3,5-NTS Similar arrival times for 1,3,5-NTS and n-propanol in well 38C-9and n-propanol in well 38C-9

Appearance of n-propanol in 38D-Appearance of n-propanol in 38D-9 but not 1,3,5-NTS9 but not 1,3,5-NTS

38B-9 seems to have been 38B-9 seems to have been “skipped” by both tracers“skipped” by both tracers

Less return of n-propanol than of Less return of n-propanol than of 1,3,5-NTS1,3,5-NTS

ConclusionsConclusions

Similar arrival times for 1,3,5-NTS Similar arrival times for 1,3,5-NTS and n-propanol in well 38C-9and n-propanol in well 38C-9

Appearance of n-propanol in 38D-Appearance of n-propanol in 38D-9 but not 1,3,5-NTS9 but not 1,3,5-NTS

38B-9 seems to have been 38B-9 seems to have been “skipped” by both tracers“skipped” by both tracers

Less return of n-propanol Less return of n-propanol than of 1,3,5-NTSthan of 1,3,5-NTS

Normalized tracer returns

0

0.001

0.002

0.003

0.004

0.005

0.006

0.007

0.008

0.009

0.01

0 50 100 150

days

E(1

/day

)38C-9 propanol in steam

38C-9 propanol in brine

38D-9 propanol in steam

38D-9 propanol in brine

38C-9 1,3,5-NTS

38D-9 1,3,5-NTS

ConclusionConclusion

Lab work - n-propanol is Lab work - n-propanol is appropriate as a geothermal appropriate as a geothermal tracer in smaller volume by using tracer in smaller volume by using SPME-GC-FIDSPME-GC-FID

Lab work - Alcohols can be a Lab work - Alcohols can be a powerful tool in determining two-powerful tool in determining two-phase pathways in reservoirsphase pathways in reservoirs

AcknowledgementsAcknowledgements

This work was supported by grants This work was supported by grants from the Department of Energy. from the Department of Energy. Done with the support of Coso Done with the support of Coso Operating Company, LLC; and the Operating Company, LLC; and the Geothermal Program Office of the Geothermal Program Office of the Naval Air Weapons Station.Naval Air Weapons Station.

AcknowledgementsAcknowledgements

Peter RosePeter Rose11, Nick Dahdah, Nick Dahdah11, Michael , Michael AdamsAdams11, Jess McCulloch, Jess McCulloch22, Cliff , Cliff BuckBuck22, and G. Michael Shook, and G. Michael Shook33

1 Energy and Geoscience Institute – University of Utah1 Energy and Geoscience Institute – University of Utah

2 Coso Operating Company – Catihness Energy LLC2 Coso Operating Company – Catihness Energy LLC

3 Idaho National Laboratory3 Idaho National Laboratory

ReferencesReferences

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ReferencesReferences

Mella, M.J., Rose, P.E., McCulloch, J., Buck, C., Adams, M.C., Mella, M.J., Rose, P.E., McCulloch, J., Buck, C., Adams, M.C., Dahdah, N.F. (2006), “The Use of n-Propanol as a Tracer at the site Dahdah, N.F. (2006), “The Use of n-Propanol as a Tracer at the site of the Coso Engineered Geothermal System,” of the Coso Engineered Geothermal System,” PROCEEDINGS, PROCEEDINGS, Thirty-First Workshop on Geothermal Reservoir EngineeringThirty-First Workshop on Geothermal Reservoir Engineering

Stanford University,SGP-TR-179Stanford University,SGP-TR-179   

Rose, P.E., Mella, M.J., Kasteler, C. (2003), “Rose, P.E., Mella, M.J., Kasteler, C. (2003), “A New Tracer For Use in Liquid-Dominated, High-Temperature Geothermal Reservoirs,” GRC Transactions, 27, pp. 403-406

Supelco (2003), Supelco (2003), Chromatography Products for analysis and Chromatography Products for analysis and Purification.Purification. Supelco p. 348-358 Supelco p. 348-358

Questions?Questions?