Upload
yosefu
View
46
Download
0
Tags:
Embed Size (px)
DESCRIPTION
SPME Coupled with GC-FID for the Detection of n-Propyl Alcohol and Its Use as a Geothermal Tracer. Michael Mella 1,2 1 Energy and Geoscience Institute - University of Utah, 2 Chemical Engineering Department – University of Utah Senior Projects Lab I - 2006. Why n-propanol?. - PowerPoint PPT Presentation
Citation preview
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
Adams, M.C., Yamada, Y., Yagi, M., Kondo, T., and Wada, T. (2000), Adams, M.C., Yamada, Y., Yagi, M., Kondo, T., and Wada, T. (2000), “Stability of Methanol, Propanol, and SF“Stability of Methanol, Propanol, and SF66 as High-Temperature as High-Temperature
Tracers,” Tracers,” World Geothermal Congress World Geothermal Congress p. 3015-3019p. 3015-3019
Adams, M.C., Yamada, Y., Yagi, M., Kasteler, C., Kilbourn, P., and Adams, M.C., Yamada, Y., Yagi, M., Kasteler, C., Kilbourn, P., and Dahdah, N. (2004), “Alcohols as Two-Phase Tracers,” Dahdah, N. (2004), “Alcohols as Two-Phase Tracers,” Proceedings, Proceedings, Twenty-Ninth Workshop on Geothermal Reservoir EngineeringTwenty-Ninth Workshop on Geothermal Reservoir Engineering
Fogler, H.S. Fogler, H.S. Elements of Chemical Reaction Engineering. Elements of Chemical Reaction Engineering. 33rdrd Edition, Edition, New Jersey: Prentice Hall, 1999, chapter 13.New Jersey: Prentice Hall, 1999, chapter 13.
Fukuda, D., Asanuma, M., Hishi, Y., Kotanaka, K. (2005), “Alcohol Fukuda, D., Asanuma, M., Hishi, Y., Kotanaka, K. (2005), “Alcohol Tracer Testing at the Matsukawa Vapor-Dominated Geothermal Tracer Testing at the Matsukawa Vapor-Dominated Geothermal Field, Northeast Japan,” Field, Northeast Japan,” Proceedings, Thirtieth Workshop on Proceedings, Thirtieth Workshop on Geothermal Reservoir EngineeringGeothermal Reservoir Engineering
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?