MIT Photonics in Energy - A Mendez - June 2009

Optical Gas Sensors for Energy Applications
Alexis Mndez, PhD

MCH Engineering, LLC
1728 Clinton Ave., Alameda, CA 94501 alexis.mendez@mchengineering.com (510) 521-1069
MIT-OSA Optics and Photonics for Advanced Energy Technology

MIT, Cambridge, MA. June 25, 2009
Optics and Photonics for Advanced Energy Technology
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Outline
Introduction Gas sensing techniques Applications:
Electric Utility Petrochemical & Refineries Gas Transmission & Distribution Hydrogen Fuel Cells
Conclusions
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Introduction
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Why Gas Sensors in the Energy Sector?

Various types of gases are normally used, produced or emitted as part of the operation and processes of different energyrelated industries. These gases need to be detected, monitored, measured, analyzed, suppressed, and/or removed. Therefore, practical, effective and low-cost gas sensors are a valuable tool for plant operation and maintenance in the Energy industry. Optical and photonics based gas sensors and sensing techniques, offer among the most flexible, sensitive, multispecies, effective and practical solutions for gas sensing.
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Gas Sensors:
Energy Sector Application Segments
Fuel Cells Electric Utilities
- Plant emissions - Boiler optimization - SF6 Fugitive emissions - Transformer dissolved gases - Transportation - Stationary - Portable
Hydrogen Production
- Pipeline Monitoring - Storage Tanks - Fugitive Emissions
Petrochemicals & Refineries

- Fugitive emissions - Gas analysis & composition - Stack emissions - Combustible gases - Hazardous gases personnel safety
Gas Transmission & Distribution

Fugitive emissions Leak detection Moisture content Gas composition Impurity detection
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Main Drivers
Environmental Regulation & Protection Pollution Reduction & Control Plant Protection & Personnel Safety Process Optimization Reduction in Opex and Maintenance Costs
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Environmental Issues:
U.S. Greenhouse Emissions
A significant port of the US greenhouse gases are produced by the energy sector. The largest pollutant contributor is CO2 from coal burning power plants. Other gas sources are fugitive emissions in refineries, petrochemical plants and pipeline networks; as well as from SF6 leakage from gasinsulated electric power equipment.
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Greenhouse Gases:
Environmental Impact Capacity Global Warming Potentials (GWP) (100 year time horizon)
Greenhouse gases Carbon dioxide (CO2) Methane (CH4) Nitrous Oxide (N2O) Hydrofluorocarbons (e.g., HFC 134a) Perfluorcarbon (e.g., CF4) Sulfur Hexafluoride (SF6)
GWP 1 21 310 1300 6500 23,900

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Inventory of U.S. Utility Components

5,000 Generating power plants 1,000 Boilers 27,000 power transformers >300,000mi of natural gas pipelines 150 Refineries
Source: DoE/EPRI
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Gas Sensing Techniques
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Key Gases to Measure

O2 CO CO2 H2 H20 (vapor) H2S HCL HFC
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CH2 CH4 NH3 NO NO2 SF6 SO2
IR Gas Absorptions Bands

Most gases absorb IR light, causing their molecules to bend, stretch or twist IR absorption is proportional to gas concentrations
From Daylight Solutions
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Spectral Measurement Techniques

Visible Light Spectroscopy
Colorimetric Fluorescence Luminescence
Near-Infrared Absorption Spectroscopy

TDLAS Cavity Ringdown
Mid-Infrared Spectroscopy
FTIR TDLAS Scattering Photo Acoustic
Raman Spectroscopy Optical Imaging

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Spectroscopy Techniques:
FTIR vs. Raman
FTIR measures how much Light is absorbed or reflected Raman measures the emitted light from an excitation light impulse
Source: Spectroscopy
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Spectroscopy Techniques:
Dispersive vs. Non-Dispersive
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Spectral Backscatter Absorption
Back reflected scatter light can be detected or captured by an IR imaging camera.
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Tunable Diode Laser Absorption Spectroscopy (TDLAS)

Select a single absorption line for specific gas. Ensure no cross-interference with other gases or background stream. Pre-tune laser by temperature to center of absorption line. Scan absorption line by current tuning of laser, so as to reconstruct absorption envelope. Calculate gas concentration from amplitude and shape of 2nd harmonic of detected absorption line.
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TDLAS Configurations
Reflective Transmissive
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Cavity Ring-Down Spectroscopy (CRDS)

Measures decay constant, not absorption intensity
Independent of light source fluctuations Absolute measurement of concentration
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Source: Picarro

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Photo-Acoustic Spectroscopy (PAS)

Modulated IR light produces a pressure (acoustic) wave in the gas cell, which is then detected by a phase-sensitive microphone.
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Photonics Components Needed

Optical Sources
Quantum Cascade Lasers Tunable lasers Fiber lasers LEDs Broadband sources
Light Processing
Filters Imaging Beam steering
Detectors
CCDs UV, VIS, IR detectors Multi-spectral spectrometers
Light Guiding
IR waveguides Specialty optical fibers Lenses
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Electric Utility Applications
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Schematic of a Coal-Fired Power Plant

Gas Sensing
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Coal-Fired Boiler:
Optical Gas Sensing
Real time, in-situ measurements allow for accurate, zone-specific data. Combustion optimization leads to:
More power output better heat and consistent operation Less coal consumption reduced CO2 and NOx emissions Less boiler slagging
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Coal-Fired Boiler:
Optical Gas SensingZolo BOSS System
On-line measurement of O2, CO, CO2, H2O and temp. Based on multiplexed TLDAS. Laser is beamed across boiler flames, and can be arranged in 2D arrays concentration CAT scan. Unaffected by flames, dust or ash. Data is used to optimize boiler operation and help reduce emissions.
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Coal-Fired Boiler:
Zolo System Configuration
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Power Plant:
Stack Emissions
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Power Plant Stack Emissions:

Pollution Impact
In one hour, the flue gas from a 300MW coal plant would fill a pipeline 10ft in diameter and 100 miles long!
N2 , CO2 , O2 and H2O ~160 Km

If the various gas species were Segregated within the pipe, they would The pipe portions shown.
Mercury PM SO3 NOx SO2 0.0002m 1m 1.5m 180m 820m
Source: NETL
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Flue Emissions Monitoring:

Optical Flue Gas AnalyzersConfigurations
Source: SpectraSensors
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Optical Stack Analyzers:

Examples of Commercial Systems
Land (TLDA)
Codel (IR Absorption)
Picarro (CRDS)
Yokogawea (TDLA)
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SF6 Gas:
Characteristics
SF6 is a synthetic gas expensive ($20/lb) Excellent electric insulator high dielectric strength, arc quenching, inert, inflammable, 5x heavier than air. Widely used as insulator in HV equipment breakers, transformers, cables, switchgear, etc High global warming potential 23,900x that of CO2 Atmospheric suspension lifetime of 3,200 years! The Kyoto protocol calls for reducing SF6 emissions
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SF6 Gas:
Fugitive Emissions
US SF6 Fugitive Emissions Trend SF6 emissions can escape during the service life of HV equipment through seals and leaks. Releases also occur during equipment installation, charging and servicing. In 1999, SF6 U.S. electric utility emissions were estimated at 4.7 million metric tons of carbon equivalent. Electric utilities worldwide, have active programs to detect and mitigate SF6 fugitive emissions.
Source: EPA
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SF6 Gas:
Detection of Leaks & Fugitive Emissions
GasVue TG-30
Backscatter IR absorption Imager
Real time image of SF6 leaks Video output for TV display 30 meter range 2:1 zoom for close-up viewing
Sherlock System
SF6- IR Leak
G.A.S., Dortmund, Germany Dual Non-Dispersive IR Spectrometer 1ppm sensitivity 0-2,000ppm range
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Power Transformers:
Dissolved Gas Analysis
Source: Siemens
The quality of the insulating oil in power transformer degrades as a result of normal and abnormal operation, aging, partial discharges and short circuit faults. Moisture, particles and a number of dissolved gases are produced, that are an indication of the transformers condition.
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Petrochemical applications
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Fugitive Emissions:
Refineries & Chemical Plants
Fugitive emissions are produced by leaks of hydrocarbon vapors from process equipmentsuch as valves, flanges, pumps, etc. Leaks occur randomly. In a typical U.S. refinery, the number of fugitive emission components is > 200,000. Inspection is commonly done manually with gas sniffers. Opex costs exceed $1MM.
Source Valves Flanges Pump seals Compressor seals Relief valves Drains Cooling towers Oil/water separators TOTAL VOCemissions Number lb/day 11,500 6,800 46,500 600 350 1,300 70 1,100 100 500 650 1,000 1 1,600 1 32,100 45,000
Average emissions in a US refinery

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Fugitive Emissions:
Spectral Detection Techniques Active Detection - requires illuminating the scene
with a laser operating at an Infrared (IR) wavelength where the laser light is absorbed by the target gas but reflected by the background.
Passive Detection - relies on measuring the

temperature difference between the temperature of the gas and the temperature of the background.
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Fugitive Emissions:
Optical Detection Systems
Spectral backscatter reflection imaging
Long-wave IR
Mid-wave IR
Simulated methane leak in a pipe

FLIR Systems ThermaCAM
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Gas Transmission & Distribution Applications
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Natural Gas:
Transmission & Distribution Network
Producing Wells
Gathering Lines Processing Plant
Transmission Lines
Compressor Stations LNG or Propane Plant Underground Storage Regulators/ Meters Distribution Lines
Large Volume Customer
Regulator/Meter
Residential Customers
Approximately 300,000miles of gas pipelines

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Commercial Customers
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Natural Gas Pipelines:

Moisture Measurement
By law, the content of moisture in natural gas pipelines has to be <7lbs/MMSCF (147ppmv) which is known as the tariff value. Otherwise, penalties are imposed. Water vapor is present in unprocessed NG in various amounts, and its presence can have serious consequences such as:
Internal pipeline corrosion Freezing of valves and regulators Formation of hydrates that obstruct flow Reduction in gas BTU value Condensation at compressor stations
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Natural Gas Pipelines:

TLDAS Moisture Sensing Systems
GE
Aurora System
Spectra Sensors
SS-2000 System
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Gas Sensing & Leak Monitoring:

Multi-Point TLDAS System
Monitor >300 points in-situ, and real time
Long distance range(~10 km) Single or multiple gas species
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Fuel Cell Applications
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The Future Hydrogen Economy
Source: Air Products

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Fuel Cell Types

Fuel Cells
Transportation Stationary
Portable
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Hydrogen Sensors:
Application Markets
Aerospace
- Rocket & propulsion systems - Liquid fuel tanks
Hydrogen Production
- Pipeline Monitoring - Storage Tanks - Fugitive Emissions
Fuel Cells
- Transportation - Stationary - Portable
Hazardous Locations
- Refineries - Oil & Gas Platforms - Mining
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Hydrogen Sensors:
Detection Roles Leak Detection
Identify any incipient H2 gas leak or fugitive emission Very high sensitivity1,000 to 40,000 ppm Fast response (<10 sec)
Alarm Sensing
Detect and warn of H2 accumulations within explosive limit Medium sensitivity0.5 to 4% (H2 LFL) Medium response time ~10sec
Purity Monitoring

Indicate concentration and relative H2 purity Sensitive in the 40 to 99.9% concentration range
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US National Energy Renewable Labs (NERL): FO H2 Sensor
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Market Size
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Global Gas Sensors Market

$ Millions
2000 1600 1200 800 400 0 1994 1999 2004

Year
1710 1260 935 752 443
Process control 8%
Medical 8%
Industrial safety 33%
Environmental monitoring 2%
2009
2014
Source: The Freedonia Group

Security and defense 12%
Automotive 2%
Fire and domestic

Optics and Photonics for gas detection Advanced Energy Technology
Other 2%
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33%
Global Demand for Gas Sensors:

By Technology
Source: BCC Inc.

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Process Analytics Market

~ $2 Billion USD
Source: ABB
$100M
$200M
$300M
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Conclusions
Optical and Photonic gas sensors and sensing techniques are practical, effective tools to the Energy Sector. Optically-based gas sensing systems offer not only technical improvements, but significant environmental and cost benefits. Energy sector applications for optically-based gas sensors can be found in coal-fired boiler optimization, stack gas analysis, fugitive emission detection, natural gas moisture measurement, leak detection in pipelines, and many others. Several systems are commercially available. Advancements in lasers, laser diodes, imaging detectors, and other optical components, will need to improved gas-sensing devices at lower cost.
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MIT Photonics in Energy - A Mendez - June 2009

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Optical Gas Sensors for Energy Applications

Alexis Mndez, PhD

MIT-OSA Optics and Photonics for Advanced Energy Technology

Optics and Photonics for Advanced Energy Technology

Optics and Photonics for Advanced Energy Technology

Optics and Photonics for Advanced Energy Technology

Why Gas Sensors in the Energy Sector?

Optics and Photonics for Advanced Energy Technology

Petrochemicals & Refineries

Gas Transmission & Distribution

Optics and Photonics for Advanced Energy Technology

GWP 1 21 310 1300 6500 23,900

Inventory of U.S. Utility Components

Optics and Photonics for Advanced Energy Technology

Gas Sensing Techniques

Optics and Photonics for Advanced Energy Technology

Key Gases to Measure

CH2 CH4 NH3 NO NO2 SF6 SO2

Optics and Photonics for Advanced Energy Technology

IR Gas Absorptions Bands

From Daylight Solutions

Optics and Photonics for Advanced Energy Technology

Spectral Measurement Techniques

Near-Infrared Absorption Spectroscopy

Raman Spectroscopy Optical Imaging

Optics and Photonics for Advanced Energy Technology

Optics and Photonics for Advanced Energy Technology

Spectral Backscatter Absorption

Back reflected scatter light can be detected or captured by an IR imaging camera.

Optics and Photonics for Advanced Energy Technology

Tunable Diode Laser Absorption Spectroscopy (TDLAS)

Optics and Photonics for Advanced Energy Technology

Cavity Ring-Down Spectroscopy (CRDS)

Independent of light source fluctuations Absolute measurement of concentration

Optics and Photonics for Advanced Energy Technology

MCH Engineering, LLC

Photo-Acoustic Spectroscopy (PAS)

Optics and Photonics for Advanced Energy Technology

Photonics Components Needed

Optics and Photonics for Advanced Energy Technology

Electric Utility Applications

Optics and Photonics for Advanced Energy Technology

Schematic of a Coal-Fired Power Plant

Optics and Photonics for Advanced Energy Technology

Optics and Photonics for Advanced Energy Technology

Optics and Photonics for Advanced Energy Technology

Optics and Photonics for Advanced Energy Technology

Power Plant Stack Emissions:

N2 , CO2 , O2 and H2O ~160 Km

Mercury PM SO3 NOx SO2 0.0002m 1m 1.5m 180m 820m

Flue Emissions Monitoring:

Optics and Photonics for Advanced Energy Technology

Optical Stack Analyzers:

Optics and Photonics for Advanced Energy Technology

Optics and Photonics for Advanced Energy Technology

Average emissions in a US refinery

Passive Detection - relies on measuring the

Optics and Photonics for Advanced Energy Technology

Simulated methane leak in a pipe

FLIR Systems ThermaCAM

Gas Transmission & Distribution Applications

Optics and Photonics for Advanced Energy Technology