[PPT] - Intrinsic Fiber Optic Chemical Sensors for Subsurface Detection of CO PowerPoint Presentation

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Intrinsic Fiber Optic Chemical Sensors for Subsurface Detection of CO2

Intelligent Optical Systems, Inc.

Jesús Delgado Alonso, PhD Robert A. Lieberman, PhD DOE Technical Monitor: Barbara Carney

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Intelligent Optical Systems, Inc. (IOS)

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Founded in April, 1998

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Focus areas:

 Physical, chemical, and biomedical

ptical and electronic sensors

 Advanced light sources and detectors 

>$3.5M in equipment

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11,500 sq. ft. facility in Torrance, CA

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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:

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Provide Reliable Information

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Monitor continuously

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Cover large areas

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Operate for years with little or no maintenance

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Cost effective

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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 direct detection of carbon dioxide.

Unique characteristics:

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Direct measurement of CO2

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The entire length of an optical fiber is a sensor

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Sensors are capable of monitoring CO2 in water and in gas phase

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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

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Upon exposure of any segment of the fiber, the CO2 diffuses into the cladding and changes color

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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

f

color change (or attenuation change) depends

n

the concentration of CO2, and is reversible  Wavelengths far from the absorbance of the indicator dye are unaffected by the presence of CO2, which enables the system to be self-referenced.

Time (s) 4000 6000 8000 10000 12000 14000 Sensor Signal (counts) 6000 8000 10000 12000 14000

0.0% CO2 1.0% CO2 6.0% CO2

Reference wavelength

6.0% 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)

5 10 15 20 25 30

Transmission (counts)

365 370 375 380 385 390

Reference Signal Raw Sensor Signal Time (min)

5 10 15 20 25 30

transmission (counts)

365 370 375 380 385 390

Compensated Sensor Signal Raw 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 range requirement (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 1,000 200 1,000 19 50 4 23 1,000 400 1,000 18 100 7 25 1,000 800 2,000 40 25 2 41 2,000 200 2,000 39 50 4 43 2,000 400 2,000 38 100 7 45 2,000 800 3,000 60 25 2 61 3,000 200 3,000 59 50 4 63 3,000 400 3,000 58 100 7 65 3,000 800 3,000 55 250 18 73 3,000 1,000

1,200 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 Interface Power 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)

500 1000 1500 200

Voltage (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 V Standard Deviation (n=25) = 0.0005 V Noise 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 films 2. Evaluation of optical and chemical properties 3. Selection of candidate formulations 4. Fabrication of fiber sensor 5. Preliminary testing 6. 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

Reference Signal (counts)

5000 10000 15000 20000 25000 30000 35000 40000 45000

Sensor Signal (counts)

4000 6000 8000 10000 12000

Time (minutes)

50 100 150 200

Reference Signal (counts)

700 750 800 850 900 950 1000

Sensor Signal (counts)

520 540 560 580 600 620 640 660 680 700 720 740

Wavelength (nm) 300 400 500 600 700 800 Transmittance (%) 50 60 70 80 90 100

IOS -21-2 DC 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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Fiber sensor at ambient conditions

CO2 CO2

Progress: Sensor Testing

V1 V2

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Gas/water input Gas/water output Fiber optic sensor segment

Progress: Sensor Testing

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Time (hours)

21.0 21.5 22.0 22.5 23.0 23.5 24.0

Reference Signal (counts)

5000 10000 15000 20000 25000 30000

Sensor Signal (counts)

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

Reference Signal (counts)

5000 10000 15000 20000 25000

Sensor Signal (counts)

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

Normalized Sensor Signal

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

Normalized Sensor Signal

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

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Fiber sensors withstand 120°C

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Significant degradation at 150°C

150°C 120°C 150°C 120°C

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The fiber sensors are exposed to cycles of elevated temperature and ambient temperature.

Progress: Sensor Testing at Elevated Temperature, Gas Phase

Accelerated 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

Normalized Sensor Signal (Sensitivity)

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

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Improved sensor formulations are stable at 70°C, the maximum temperature tested.

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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

Normalized Sensor Signal (Sensitivity)

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)

100 200 300 400 500 600

Reference Signal (counts)

1000 1020 1040 1060 1080 1100

Sensor Signal (counts)

150 200 250 300 350 400 450 0.0% 1.0% 2.0% 5.0%

Response profiles of a CO2 fiber optic prototypes immersed in a pH 4.0 solution equilibrated with four levels of CO2

Corrosive liquids: Acid matrix (pH = 4.0) Standard conditions: Sensitivity, reversibility, measurement range

Time (minutes)

100 200 300 400 500

Reference Signal (counts)

200 220 240 260 280 300 320 340 360

Sensor Signal (counts)

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)

20 40 60 80 100 120 140 160

Sensor Signal (counts)

48000 50000 52000 54000 56000 58000 60000 62000

Response profile after NO2 release Response profile before NO2 release

0.0% 5.0% 10.0%

Response profiles of CO2 fiber optic prototypes immersed in solution before and after equilibration with traces of NO2 (40 ppm) and equilibrated with three levels of CO2.

Corrosive liquids: High salinity (250,000 ppm NaCl)

Time (minutes)

100 200 300 400 500 600

Reference Signal (counts)

1000 1050 1100 1150 1200 1250 1300 1350

Sensor Signal (counts)

100 200 300 400 500 600 700 0.0% 3.0% 13.0% 37.0%

Response profiles of CO2 fiber optic prototypes immersed in a 250,000 ppm NaCl solution equilibrated with four levels of CO2.

Progress: Sensor Testing at Extreme Conditions, Dissolved CO2

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Ongoing and Planned Work

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Perform Accelerated Degradation Testing

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High flow rates of corrosive water, exposure to highly biologically- contaminated media, exposure to temperature cycles, exposure to high power illumination…

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Evaluate sensors at elevated pressure

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Perform analytical characterization of sensor system

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Design and test sensor cables

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Design and assemble sensor deployment system

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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" hole Cemented to Surface

Fiber Optic CO2 Sensor Cable

1/4in Stainless Tubing Adjustable 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

perating at elevated temperatures, has been demonstrated.

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A fiber optic sensor for dissolved CO2 monitoring in aqueous matrixes, capable of operating in corrosive environments and at elevated temperatures, has been demonstrated.

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Instrumentation demonstrating satisfactory performance while

perating sensor cables 2 km long has been developed. Calculations

predict continued good performance for sensors 3 km and even longer.

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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