The use of Quantum Cascade Lasers for Gas Detection provides high

accuracy measurement and lower HS&E risk.

Aaron SwansonJoe Schwab

Gas measurement in Deepwater

Sources of Gas

4

Gas from Drilling:Liberated from the crushed cylinder of formation produced by the drilling process.

Produced Gas (incursion):From formations with a higher pressure.From formations with aeromechanic instability

Contamination:Petroleum products in the mud, or from mud additives.

Recycled Gas:Hydrocarbon gas still entrained in the mud stream. • Liberated Gas

• Produced Gas• Recycled Gas• Contamination

Gas

Mercer SPWLA FIFTEENTH ANNUAL LOGGING SYMPOSIUM, JUNE 2-5, 1974

Sources of Gas

5

• Gas from the well• Pit room• Shakers• Confined area• Helipad

• Fumes from tanks• Fumes from chemicals

Gas Detection - Types• Total Gas

o FIDo Infra-Redo Thermo couple (Hot wire)o QCL – Quantum Cascade Laser

• Gas Compositiono FIDo Infra Redo Thermo couple (Hot wire)o Mass Spectrometerso Wide spectrum chromatographyo QCL – Quantum Cascade Laser

6

• Isotopeso IRMS Isotope Ratio Mass Spectrometero Cavity Ring-Down Spectroscopy (CRDS)o QCL – Quantum Cascade Laser

• Catalytic – Hot WireMeasures the change in voltage when gas passes over a heated wire

• FID – Flame Ionization DetectorDetects ions formed duringcombustion of organic compounds in a hydrogen flame

• IR – Infrared Absorption of infrared radiation at specific wavelengths as it passes through the gas

• TCD – Thermal Conductivity DetectorSenses changes in the thermal conductivity

• QCL – Quantum Cascade Laser Solid State device operating throughout the MID IR, real time, multicomponent analysis

The Gas Detection Chain –Extraction/Detection

7

Mud Logging Principals and Interpretations - 1985

© 2017 Diversified Well Logging LLC. Company Confidential Information

Whittaker, Alun, 1991, Mud Logging Handbook

Gas Measurement– lots of flavors

Why do we need another one?

8

Limitations and Hazards

A: Transit Time and DistanceB: Cycle TimeC: Calibration GasD: Area of Detection

A

B

C

Impact of ROP and Cycle Time on Depth Resolution

10

5 4 3 2 1 0.5 0.17 0.08Cycle Times in Minutes

500 41.67 26.67 20.00 16.67 8.33 4.17 1.39 0.06400 33.33 26.67 20.00 13.33 6.67 3.33 1.11 0.05300 25.00 20.00 15.00 10.00 5.00 2.50 0.83 0.03200 16.67 13.33 10.00 6.67 3.33 1.67 0.56 0.02100 8.33 6.67 5.00 3.33 1.67 0.83 0.28 0.0160 5.00 4.00 3.00 2.00 1.00 0.50 0.28 0.01

-

5.00

10.00

15.00

20.00

25.00

30.00

35.00

40.00

45.00

Dept

h Re

solu

tion

FT

ROP FT / HR

500 400 300 200 100 60

With higher cycle times and ROP the depth resolution is reduced. This can lead to by passed pay zones,poor identification of thin beds, difficulty identifying gas/oil/water contacts and limited information on reservoir connectivity and compartmentalization.

5 Sec10 Sec

Little device: Big Change

Laser Gas Measurement

• No Wellsite Maintenance– No moving parts– No heat from igniting gas

• No Calibration Gas at Wellsite– Reduced logistics– Reduction of flammable gases

• No Carrier gas used to measure– No hydrogen in logging unit

• Can be placed near trap to reduce sample distance

– Faster detection time for gases– Improved detection of gas inflow from

kicks• No Column: No Cycle time

– Greater resolution of measurement

8/3/2017 12

• QCL was invented by Federico Capasso and Jérôme Faist– Concept proposed in 1971 by Kazarinov and Suris

QCL History

13

Receiving1998 IEEE William StreiferScientific Achievement Award

1994 1996 1998 2000 2002 2004 2006 2008 2010 2012

LT pulsed

RT pulsed

DFB

RT CW

CW W-level

AlpesBroadband

Heterogeneouscascade

RT 27% WPE

Freq. combs

2014

THz

PICsArrays

Process Laser Advancements

14

© 2016 Block Engineering, LLC. All Rights Reserved.

TDLNIR (Near Infra-Red) Open Process Applications to LaserSimple molecules (H2O, O2)Narrow tuning, limited wavelengthsOne laser per analyte / wavelength

Early DFB QCLsMid IR (Infra-Red)Complex moleculesNarrow tuning limits (3 wavenumbers)applicationsRequires multiple analyzers for multicomponent analysis

Block Widely Tunable QCLsMid IRComplex moleculesWidely tunable laser (350 wavenumbers), full spectrum availableOne analyzer, multi-component analysisRobust calibrationGreat flexibility

TDL: Tunable Diode LaserQCL: Quantum Cascade Laser

June 2016

What is Mid-Infrared Spectroscopy?Incident

Infrared Light • Light is absorbed though vibrational modes of molecules

• Very strong absorption• High sensitivity

• Highly specific signature• “spectral fingerprint”

Example Transmission Spectrum – Mid-Infrared Radiation (3-20 μm)

The 3-14 μm spectral region is the most desired region by spectroscopists

Feature-Rich “Fingerprint” Range

(5 – 12 microns)

• Miniaturized external-cavity QCL • Extremely compact: ~ 2 x 2 x 5 cm• Very broad tuning: typically 250 cm-1 (for some modules up to 400 cm-1)• High-speed tuning: ~100 Hz• Custom-designed electronics for spectroscopy capability

Broadly Tunable QCL

16

Mini-QCLTM

900 1000 1100 1200 1300 14000

1

Nor

mal

ized

Inte

nsity

Wavenumbers [cm-1]

Quantum Cascade Lasers (QCLs)

17

~50 nm

Light Emitted

Cross Section of QCL Facet

Source: Prof. Jerome Faist, ETH-Zurich

Light is emitted as electrons “cascade”

through multiple quantum wells

InP or GaAsSemiconductor Devices

© 2016 Block Engineering, LLC. All Rights Reserved.

QCLChip

External Cavity LensBack-extraction Lens

Laser CavityWavelength

Selection

RotatingDiffraction

Grating

Laser Output

QCLs are reliable devices manufactured today using standard, well-validatedsemiconductor fabrication processes

Quantify concentrations in seconds

Hydrocarbon Detection

19

Wavenumber, cm -1

800 1000 1200 1400 1600 1800

Tran

smitt

ance

0

0.2

0.4

0.6

0.8

1

1.2Pure Component Spectra

methane

ethane

propane

n-butane

iso-butane

n-pentane

iso-pentane

Wavenumber, cm -1

800 1000 1200 1400 1600 1800

Tran

smitt

ance

0

0.2

0.4

0.6

0.8

1

1.2Mixture Spectra

mixture

Measured Conc.

C1:23.5%

C2: 9.1%

C3 = 8.4%

nC4 = 1.1%

iC4 =0.9%

nC5 = 0.8%

iC5 = 1.2%

SECOND ROUND FIELD TRIALSThe use of Quantum Cascade Lasers

Total GasExcellent agreement between GC FID and QCL

MethaneExcellent agreement between GC FID and QCL,

over wide dynamic range

Ethane: < 0.3 %Even at these lower concentrations the speed of QCL captures dynamics and

profiles “muted” by slower GC

Propane: < 0.3 %Even at these lower concentrations the speed of QCL captures dynamics and

profiles more responsively than the “muted” response of slower GC

Butane, < 500 ppmFeatures map well

ADDITIONAL APPLICATIONSThe use of Quantum Cascade Lasers

MIR QCL is Widely ApplicablePartial list of analytes

EPA Method 325 Gas List

28Wavenumbers

600 800 1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400

1,1-Dichloroethene

Allyl chloride

Freon-113

1,1-Dichloroethane

1,2-Dichloroethane

1,1,1-Trichloroethane

Benzene

Carbon tetrachloride

1,2-Dichloropropane

Trichloroethylene

1,1,2-Trichloroethane

Toluene

Tetrachloroethylene

Chlorobenzene

Ethyl benzene

m-Xylene

p-Xylene

Styrene (monomer)

o-Xylene

1,4-Dichlorobenzene

Wavelength

16 14 12 11 10 9 8 7 6 5 4 3

LWIR

Example QCL for Perimeter Monitoring

Released toxic or flammable chemical cloud detected as soon as it crosses the eye-safe

laser beams

• Fixed installation, 24/7 unattended monitoring

• 100s of chemicals can be monitored with single unit

• >1 km perimeter can be covered by single unit

• No consumables• No special housing

30

The GCIR2 Instrument on the trailerSize (2’x2.5’x2) 25lbs

The GCIR2 Instrument onsite in a Barnett Shale well.

Summary of advantages from Quantum Cascade Lasers for Gas Detection

• No Wellsite Maintenance– No moving parts– No heat from igniting gas

• No Calibration Gas at Wellsite– Reduced logistics– Reduction of flammable gases

• No Carrier gas used to measure– No hydrogen in logging unit

• Can be placed near trap to reduce sample distance.

– Faster detection time for gases– Improved detection of gas inflow from

kicks• No Column: No Cycle time

– Greater resolution of measurement

8/3/2017 31

• Multiple applications– Total Gas– Gas Composition– LEL– Volatile Gases– Carbon Isotope analysis– Perimeter Monitoring

• Wide range of gas measurements– Not limited to hydrocarbon detection– Hundreds of gases can be measured

• Improved HS&E– Reduction of flammable gases at the well

site– Reduction of flammable gases in the work

area– Faster detection time – Wider detection area

The use of Quantum Cascade Lasers for Gas Detection provides high

accuracy measurement and lower HS&E risk.

Aaron SwansonJoe Schwab