Intrinsic Fiber Optic Chemical Sensors for Subsurface ... Library/Events/2014/crosscutting... · 1...
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Intrinsic Fiber Optic Chemical Sensors for Subsurface Detection of CO2
Intelligent Optical Systems, Inc.
Jesús Delgado Alonso, PhDRobert A. Lieberman, PhD
DOE Technical Monitor: Barbara Carney
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Intelligent Optical Systems, Inc. (IOS)
Founded in April, 1998 Focus areas:
Physical, chemical, and biomedical optical and electronic sensors
Advanced light sources and detectors >$3.5M in equipment 11,500 sq. ft. facility in Torrance, CA Several spin-off companies with >$22M in
private funding
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Technology
History and Objectives
Project Phases
Progress
Planned Work
Conclusions
Intrinsic Fiber Optic Chemical Sensors for Subsurface Detection of CO2
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Problem/Opportunity
Reliable and cost-effective monitoring is important to making gas sequestration safe
Desirable analytical systems characteristics: Provide Reliable Information Monitor continuously Cover large areas Operate for years with little or no maintenance Cost effective Differentiate between CO2 variations due to natural processes and those
due to leaks of exogenous gas
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Technology
Distributed intrinsic fiber optic sensors for the directdetection of carbon dioxide.
Unique characteristics: Direct measurement of CO2
The entire length of an optical fiber is a sensor
Sensors are capable of monitoring CO2 in water and in gas phase
A single cable may include CO2, pH, salinity, and temperature sensors.
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A silica glass core fiber is coated with a polymer cladding containing a colorimetric indicator
Upon exposure of any segment of the fiber, the CO2 diffuses into the cladding and changes color
A change in fiber attenuation at wavelengths relating to the color change is detected.
(Left) Fiber structure of colorimetric distributed fiber optic sensors; (right) fiber optic CO2 sensor rolled onto a spool. Microscopic detail shows uncoated fiber, and fiber coated with the sensitive cladding.
Technology
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The extent of color change (or attenuation change) depends on theconcentration of CO2, and is reversible
Wavelengths far from the absorbance of the indicator dye are unaffected by thepresence of CO2, which enables the system to be self-referenced.
Time (s)
4000 6000 8000 10000 12000 14000
Sen
sor S
igna
l (co
unts
)
6000
8000
10000
12000
14000
0.0% CO2
1.0% CO2
6.0% CO2
Reference wavelength6.0%
1.0%
0.0%
6.0%
1.0%
0.0%
Technology
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Wavelengths far from the absorbance of the indicator dye are minimally, or completely, unaffected by the presence of CO2, enabling the system to be self-referenced.
Time (min)
0 5 10 15 20 25 30
Tran
smis
sion
(cou
nts)
365
370
375
380
385
390
Reference SignalRaw Sensor Signal
Time (min)
0 5 10 15 20 25 30
trans
mis
sion
(cou
nts)
365
370
375
380
385
390
Compensated Sensor SignalRaw Sensor Signal
0.5% CO2
0.0%
1.0%
2.0%4.0%
0.0%
0.5%
Technology
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In sensor system deployment, the sensor fibers must be mechanically protected within a cable, while simultaneously allowing the free exchange of gases and water between the environment and the sensor fibers.
Technology: Sensor Protection for Field Deployment
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Downhole CO2 monitoring
Distributed fiber optic
sensor for O2
Distributed fiber optic
sensor for H2O
Multi sensor unit
incorporating CO2, O2,
humidity, and
temperature sensors
Distributed fiber optic
sensor for O2
Distributed fiber optic
sensor for H2O
Multi sensor unit
incorporating CO2, O2,
humidity, and
temperature sensors
Distributed fiber optic
sensor for pH
Distributed fiber optic
sensor for salinity
Multi sensor unit
incorporating CO2, pH,
salinity, and temperature
sensors
Sensor network
Distributed fiber optic
sensor for pH
Distributed fiber optic
sensor for salinity
Multi sensor unit
incorporating CO2, pH,
salinity, and temperature
sensors
Sensor network
Dissolved CO2 in aquifers Near-surface leaks into the atmosphere
Advanced sensors for
CO2 (at high T and P)
Readout unit for long
sensors (>2 km)
Deployment system and
sensor cables for
downhole monitoring
Advanced sensors for
CO2 (at high T and P)
Readout unit for long
sensors (>2 km)
Deployment system and
sensor cables for
downhole monitoring
SBIR Project (2010 – 2013)Distributed Sensors for Dissolved CO2
Core Technology
Project History
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Downhole CO2 monitoring
Distributed fiber optic
sensor for O2
Distributed fiber optic
sensor for H2O
Multi sensor unit
incorporating CO2, O2,
humidity, and
temperature sensors
Distributed fiber optic
sensor for O2
Distributed fiber optic
sensor for H2O
Multi sensor unit
incorporating CO2, O2,
humidity, and
temperature sensors
Distributed fiber optic
sensor for pH
Distributed fiber optic
sensor for salinity
Multi sensor unit
incorporating CO2, pH,
salinity, and temperature
sensors
Sensor network
Distributed fiber optic
sensor for pH
Distributed fiber optic
sensor for salinity
Multi sensor unit
incorporating CO2, pH,
salinity, and temperature
sensors
Sensor network
Dissolved CO2 in aquifers Near-surface leaks into the atmosphere
Advanced sensors for
CO2 (at high T and P)
Readout unit for long
sensors (>2 km)
Deployment system and
sensor cables for
downhole monitoring
SBIR Project (2010 – 2013)Distributed Sensors for Dissolved CO2
Core Technology
Project Objectives
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Phase I Development of advanced intrinsic fiber optic sensors and readout
(length up to 2,500 ft. and able to withstand corrosive liquids).
Sensor evaluation and demonstration in simulated subsurface conditions.
Phase II
Subsurface sensor deployment and operation (in a 5,900 ft. deep well at up to 2,000 psi).
Phase III
Project Phases
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Develop an optoelectronic unit for remote operation.Preliminary design – select zone-by-zone or OTDR approach based on cable range and cable coverage.
Zone-by-zone: Better sensitivity Longer range
OTDR:Better spatial resolution
Progress: Optoelectronic Unit
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The zone-by-zone approach was selected based on calculations that showed the feasibility of this design in meeting the cable rangerequirement (up to 2,500 ft.).
Distribution Fiber Length
(m) (each segment)
Distribution Fiber
Attenuation (dB)
Sensing Segment
Length (m)
Sensing Segment
Attenuation (dB)
Total Attenuation
(dB)
Cable range (m)
Cable Coverage for 4 segments
(m)
1,000 20 25 2 21 1,000 2001,000 19 50 4 23 1,000 4001,000 18 100 7 25 1,000 8002,000 40 25 2 41 2,000 2002,000 39 50 4 43 2,000 4002,000 38 100 7 45 2,000 8003,000 60 25 2 61 3,000 2003,000 59 50 4 63 3,000 4003,000 58 100 7 65 3,000 8003,000 55 250 18 73 3,000 1,000
1,20
0 m
800
m
Progress: Optoelectronic Unit
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LED/Laser Drivers & Switch
Amplifier
Gain Control
Microprocessor
Signal Generator
Flash Memory Optional
ADC
DAC
PMT
Communications
User InterfacePower Module
RX Module Control Module
TX Driver Module
Combiners
TX Optical Module
Fiber Optic Sensors
Optical Module
Tx-Rx Module Control Module
Progress: Optoelectronic Unit
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Time (seconds)
0 500 1000 1500 200
Vol
tage
(V)
0.605
0.610
0.615
0.620
0.625
0.630
0.635
0.640
0.0% CO2
5.0% CO2
15.0% CO2
Fiber optic sensor cable with length of 2,100 m (6,890 ft.)Average (5% CO2) = 0.6223 VStandard Deviation (n=25) = 0.0005 VNoise to Signal = 0.08%
Progress: Optoelectronic Unit, Cable Range
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Films coated on glass slides Fiber optic sensor prototypes
1. Fabrication of films2. Evaluation of optical and
chemical properties3. Selection of candidate
formulations4. Fabrication of fiber sensor5. Preliminary testing6. Further characterization/
fabrication of films
Progress: Advanced Sensor Materials
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Transmission
Sensitivity and reversibility
Thermal stability
Time (s)
14000 16000 18000 20000 22000 24000
Ref
eren
ce S
igna
l (co
unts
)
5000
10000
15000
20000
25000
30000
35000
40000
45000
Sens
or S
igna
l (co
unts
)
4000
6000
8000
10000
12000
Time (minutes)
0 50 100 150 200
Ref
eren
ce S
igna
l (co
unts
)
700
750
800
850
900
950
1000
Sen
sor S
igna
l (co
unts
)
520540560580600620640660680700720740
Wavelength (nm)300 400 500 600 700 800
Tran
smitt
ance
(%)
50
60
70
80
90
100
IOS -21-2DC 3-1944
Resistant to water immersion
Chemical stability
Attachment to glass
Progress: Advanced Sensor Materials
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In the production of sensor prototypes, we use pre-fabricated silica glass "thread" as the core material, and apply the polymer cladding to the fiber with an optical fiber spooling machine, custom-built for fiber coating applications.
Glass core
Polymer cladding
Uncoated fiber
Coated fiber
Progress: Fiber Optic Sensor Production
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Time (hours)
21.0 21.5 22.0 22.5 23.0 23.5 24.0
Ref
eren
ce S
igna
l (co
unts
)
0
5000
10000
15000
20000
25000
30000
Sen
sor S
igna
l (co
unts
)
21500
22000
22500
23000
23500
24000
24500
25000
25500
3% CO2
6% CO2
0% CO2
Temperature 80⁰C
Time (hours)
134.5 135.0 135.5 136.0 136.5 137.0
Ref
eren
ce S
igna
l (co
unts
)
0
5000
10000
15000
20000
25000
Sen
sor S
igna
l (co
unts
)
17600
17800
18000
18200
18400
3% CO2
6% CO2
0% CO2
Temperature 100⁰C
As expected, sensitivity is reduced with increased temperature.
Progress: Sensor Testing at Elevated Temperature, Gas Phase
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Test Progress
Initial 120C Cycle 1 120C Cycle 2 120C Cycle 3 120C Cycle 5 120C Cycle 6 120C Cycle 7 150C Cycle 8
Nor
mal
ized
Sen
sor S
igna
l
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
1.8
0.0% CO2
1.0% CO2
6.0% CO2
Test Progress
Initial 120C Cycle 1 120C Cycle 2 120C Cycle 3 120C Cycle 4 120C Cycle 5 120C Cycle 6 120C Cycle 7 150C Cycle 8
Nor
mal
ized
Sen
sor S
igna
l
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
1.8
0.0% CO2
1.0% CO2
6.0% CO2
Fiber sensors withstand 120°C Significant degradation at 150°C
150°C120°C
150°C120°C
The fiber sensors are exposed to cycles of elevated temperature and ambient temperature.
Progress: Sensor Testing at Elevated Temperature, Gas PhaseAccelerated Degradation Test
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Test Progress
Initial 70C C1 70C C2 70C C3 70C C4 70C C5 70C C6 70C C7 70C C8
Nor
mal
ized
Sen
sor S
igna
l (Se
nsiti
vity
)
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
1.8
2.0
0.0% CO2
1.0% CO2
6.0% CO2
Improved sensor formulations are stable at 70°C, the maximum temperature tested.
Tests at higher temperatures must be conducted at pressure.
Progress: Sensor Testing at Elevated Temperature, Dissolved CO2
Accelerated Degradation Test
Test Progress
Initial 70C C1 70C C2 70C C3 70C C4 70C C5 70C C6 70C C7 70C 10 70C C13 70C C16
Nor
mal
ized
Sen
sor S
igna
l (S
ensi
tivity
)
0.0
0.5
1.0
1.5
2.0
0.0% CO2
6.0% CO2
10.0% CO2
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Time (minutes)
0 100 200 300 400 500 600
Ref
eren
ce S
igna
l (co
unts
)
1000
1020
1040
1060
1080
1100
Sen
sor S
igna
l (co
unts
)
150
200
250
300
350
400
450
0.0%
1.0%
2.0%
5.0%
Response profiles of a CO2 fiber optic prototypesimmersed in a pH 4.0 solution equilibrated withfour levels of CO2
Corrosive liquids: Acid matrix (pH = 4.0)
Standard conditions: Sensitivity, reversibility, measurement range
Time (minutes)
0 100 200 300 400 500
Ref
eren
ce S
igna
l (co
unts
)
200
220
240
260
280
300
320
340
360
Sen
sor S
igna
l (co
unts
)
0
1000
2000
3000
4000
5000
0.0%
1.0%
2.0%
5.0%
10.0%
0.5%
Progress: Sensor Testing at Extreme Conditions, Dissolved CO2
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Corrosive liquids: Traces of NOx or SOx (40 ppm NO2)
Time (minutes)
0 20 40 60 80 100 120 140 160S
enso
r Sig
nal (
coun
ts)
48000
50000
52000
54000
56000
58000
60000
62000
Response profile after NO2 releaseResponse profile before NO2 release
0.0%
5.0%
10.0%
Response profiles of CO2 fiber optic prototypesimmersed in solution before and afterequilibration with traces of NO2 (40 ppm) andequilibrated with three levels of CO2.
Corrosive liquids: High salinity (250,000 ppm NaCl)
Time (minutes)
0 100 200 300 400 500 600
Ref
eren
ce S
igna
l (co
unts
)
1000
1050
1100
1150
1200
1250
1300
1350
Sen
sor S
igna
l (co
unts
)
100
200
300
400
500
600
700
0.0%
3.0%
13.0%
37.0%
Response profiles of CO2 fiber optic prototypesimmersed in a 250,000 ppm NaCl solutionequilibrated with four levels of CO2.
Progress: Sensor Testing at Extreme Conditions, Dissolved CO2
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Ongoing and Planned Work
Perform Accelerated Degradation Testing High flow rates of corrosive water, exposure to highly biologically-
contaminated media, exposure to temperature cycles, exposure to high power illumination…
Evaluate sensors at elevated pressure
Perform analytical characterization of sensor system
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Design and test sensor cables Design and assemble sensor
deployment system Sensor deployment and validation in the
field.
Proposed CO2 Sensor Well Number DOE-1
Well Test Configuration
20" 65#, H Conductor Pipe 150'@150' in 26" hole
13 3/8" 54#, K-55 Surface Casing @1500' in 17 1/2" hole 1500'Cemented to Surface
9 5/8" 53.5#, N80 Casing@5350' in 12 1/4" holeCemented to Surface
Fiber Optic CO2 Sensor Cable
1/4in Stainless TubingAdjustable Depth for CO2 Injection
Plugged Back Depth 5250'
Ongoing and Planned Work
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A fiber optic sensor for CO2 monitoring in gas phase, capable of operating at elevated temperatures, has been demonstrated.
A fiber optic sensor for dissolved CO2 monitoring in aqueous matrixes, capable of operating in corrosive environments and at elevated temperatures, has been demonstrated.
Instrumentation demonstrating satisfactory performance while operating sensor cables 2 km long has been developed. Calculations predict continued good performance for sensors 3 km and even longer.
Test at elevated pressure will be performed in the following months.
The project is on schedule, and there is no technical impediment to conducting downhole monitoring
Conclusions
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The Oil Industry is watching THE PROJECT...
Shell : There is a high level of interest in you company CO2-related projects
Conclusions
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Intelligent Optical Systems, Inc.: Sensor developmentJesús Delgado Alonso and Robert A. Lieberman
Bureau of Economic Geology at UTA: Sensor field validation and modelingChangbing Yang
GeoMechanics Technologies: Downhole sensor deploymentMichael S. Bruno
Benson Laboratory at Stanford University: Sensor laboratory testingProf. Sally Benson and Ferdinand F. Hingerl
Montana State University (ZERT): Sensor field validationKevin Repasky
NETL Department of EnergyBarbara Carney, Robie Lewis, Robert Noll, Joshua Hull
Participants