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Spectroscopic and Microscopic Characterization of Oil Shale Tracy Elizabeth McEvoy 1 , Michael Batzle 1 , Jeremy Boak 3,5 , Earl D. Mattson 4 , John Scales 2 , George Radziszewski 2,3 1 Department of Geophysics, Colorado School of Mines, Golden, Colorado, U.S.A., 2 Department of Physics, Colorado School of Mines, Golden, Colorado, U.S.A., 3 Center for Oil Shale Technology and Research (COSTAR), Golden, Colorado, U.S.A., 4 Energy Resource Recovery and Management Department, Idaho National Laboratory, Idaho Falls, Idaho,U.S.A. 5 Department of Geology, Colorado School of Mines, Golden, Colorado, U.S.A.

Spectroscopic and Microscopic Characterization of Oil Shale · Spectroscopic and Microscopic Characterization of Oil Shale Tracy Elizabeth McEvoy1, Michael Batzle1, Jeremy Boak3,5,

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Page 1: Spectroscopic and Microscopic Characterization of Oil Shale · Spectroscopic and Microscopic Characterization of Oil Shale Tracy Elizabeth McEvoy1, Michael Batzle1, Jeremy Boak3,5,

Spectroscopic and Microscopic Characterization of Oil Shale

Tracy Elizabeth McEvoy1, Michael Batzle1, Jeremy Boak3,5, Earl D. Mattson4, John Scales2,

George Radziszewski2,3

1Department of Geophysics, Colorado School of Mines, Golden, Colorado, U.S.A., 2Department of Physics, Colorado School of Mines, Golden, Colorado,

U.S.A., 3Center for Oil Shale Technology and Research (COSTAR), Golden, Colorado, U.S.A., 4Energy Resource Recovery and Management Department, Idaho National Laboratory, Idaho Falls, Idaho,U.S.A. 5Department of Geology,

Colorado School of Mines, Golden, Colorado, U.S.A.

Page 2: Spectroscopic and Microscopic Characterization of Oil Shale · Spectroscopic and Microscopic Characterization of Oil Shale Tracy Elizabeth McEvoy1, Michael Batzle1, Jeremy Boak3,5,

● Earl Mattson– Research Scientist, Energy Resource Recovery & Management

Department, Idaho National Laboratory

● George Radziszewski– Research Scientist, Department of Physics, Colorado School of

Mines

● Michael Batzle– Professor, director of Center of Rock Abuse, Department of

Geophysics, Colorado School of Mines

● John Scales– Professor, Department of Physics, Colorado School of Mines

● Jeremy Boak– Chair of the Oil Shale Symposium and the Director of the Center for

Oil Shale Technology and Research (COSTAR) at the Colorado School of Mines

Page 3: Spectroscopic and Microscopic Characterization of Oil Shale · Spectroscopic and Microscopic Characterization of Oil Shale Tracy Elizabeth McEvoy1, Michael Batzle1, Jeremy Boak3,5,

Introduction

Samples

Methods− Millimeter wave spectroscopy− Scanning acoustic microscopy− Thermal gravimetric analysis− QemScan

Page 4: Spectroscopic and Microscopic Characterization of Oil Shale · Spectroscopic and Microscopic Characterization of Oil Shale Tracy Elizabeth McEvoy1, Michael Batzle1, Jeremy Boak3,5,

Sample Conditions

Prepared by:Earl D. Mattson, Idaho National Laboratory

Hydropyrolysis Four Stages of Extraction:

- Control- T = 290°C- T = 310°C- T = 330°C- T = 350°C

Page 5: Spectroscopic and Microscopic Characterization of Oil Shale · Spectroscopic and Microscopic Characterization of Oil Shale Tracy Elizabeth McEvoy1, Michael Batzle1, Jeremy Boak3,5,

Sample Conditions II

Page 6: Spectroscopic and Microscopic Characterization of Oil Shale · Spectroscopic and Microscopic Characterization of Oil Shale Tracy Elizabeth McEvoy1, Michael Batzle1, Jeremy Boak3,5,

Sample Conditions III

Control Sample T= 310 °C T =330°C

Page 7: Spectroscopic and Microscopic Characterization of Oil Shale · Spectroscopic and Microscopic Characterization of Oil Shale Tracy Elizabeth McEvoy1, Michael Batzle1, Jeremy Boak3,5,

Techniques

1. Millimeter Wave Spectroscopy

2. Thermal Gravimetric Analysis

3. Scanning Acoustic Microscope

Page 8: Spectroscopic and Microscopic Characterization of Oil Shale · Spectroscopic and Microscopic Characterization of Oil Shale Tracy Elizabeth McEvoy1, Michael Batzle1, Jeremy Boak3,5,

Millimeter Wave Spectroscopy I

Scales & Batzle (2006)

Harmonic Multiplier

Teflon Probes

Vector NetworkAnalyzer

Harmonic Detector

HarmonicDetector

MotorMotor Control

Scalar Horn

Computer

Page 9: Spectroscopic and Microscopic Characterization of Oil Shale · Spectroscopic and Microscopic Characterization of Oil Shale Tracy Elizabeth McEvoy1, Michael Batzle1, Jeremy Boak3,5,

Millimeter Wave Spectroscopy II

Lens

Lens

Scalar Horn

Sample

Transmitted Field ET

Reflected Field ER

Emitted Field EI

Standing Waves

Scalar Horn

Page 10: Spectroscopic and Microscopic Characterization of Oil Shale · Spectroscopic and Microscopic Characterization of Oil Shale Tracy Elizabeth McEvoy1, Michael Batzle1, Jeremy Boak3,5,

Millimeter Wave Spectroscopy VRaw Data – Transmitted Phase Angle

+180 °

-180 °

2.7 cm

Phas

e A

ngle

Page 11: Spectroscopic and Microscopic Characterization of Oil Shale · Spectroscopic and Microscopic Characterization of Oil Shale Tracy Elizabeth McEvoy1, Michael Batzle1, Jeremy Boak3,5,

Control T = 310°C T = 330°CSamples : :

Transmitted Phase Data

+180 -180°-90°+180° +90° 0°PhaseAngle:

Page 12: Spectroscopic and Microscopic Characterization of Oil Shale · Spectroscopic and Microscopic Characterization of Oil Shale Tracy Elizabeth McEvoy1, Michael Batzle1, Jeremy Boak3,5,

Dielectric Permittivity Map

Low High2 4

Before Hydropyrolysis After Partial Hydropyrolysis

Page 13: Spectroscopic and Microscopic Characterization of Oil Shale · Spectroscopic and Microscopic Characterization of Oil Shale Tracy Elizabeth McEvoy1, Michael Batzle1, Jeremy Boak3,5,

Thermal Gravimetric Analysis

http://www.nd.edu/~pmcginn/IMG_1494.jpg

Page 14: Spectroscopic and Microscopic Characterization of Oil Shale · Spectroscopic and Microscopic Characterization of Oil Shale Tracy Elizabeth McEvoy1, Michael Batzle1, Jeremy Boak3,5,

TGA Data Example

Temperature Increasing

Sample Weight Decreasing

Page 15: Spectroscopic and Microscopic Characterization of Oil Shale · Spectroscopic and Microscopic Characterization of Oil Shale Tracy Elizabeth McEvoy1, Michael Batzle1, Jeremy Boak3,5,

TGA Display Format

Temperature [°C]

Organic Material Loss-dTg/dT

Page 16: Spectroscopic and Microscopic Characterization of Oil Shale · Spectroscopic and Microscopic Characterization of Oil Shale Tracy Elizabeth McEvoy1, Michael Batzle1, Jeremy Boak3,5,

1 mm

Sample A

Sample B

Sample C

X-ray energy dispersive analysis

““Qemscan”Qemscan”

Page 17: Spectroscopic and Microscopic Characterization of Oil Shale · Spectroscopic and Microscopic Characterization of Oil Shale Tracy Elizabeth McEvoy1, Michael Batzle1, Jeremy Boak3,5,

Layer Locations

RedRed

LightLightDarkDark Section Section

LocationLocation

Page 18: Spectroscopic and Microscopic Characterization of Oil Shale · Spectroscopic and Microscopic Characterization of Oil Shale Tracy Elizabeth McEvoy1, Michael Batzle1, Jeremy Boak3,5,

TGA

0 100 200 300 400 500 600 700 8000

0.5

1

1.5

2

2.5

3TGA Light Layer Comparison

0 Light290 Light330 Light

T [°C]

-dTg

/dT

Page 19: Spectroscopic and Microscopic Characterization of Oil Shale · Spectroscopic and Microscopic Characterization of Oil Shale Tracy Elizabeth McEvoy1, Michael Batzle1, Jeremy Boak3,5,

TGA

0 100 200 300 400 500 600 700 8000

0.5

1

1.5

2

2.5

3

3.5

TGA Red Layer Comparison

Red 0Red 290Red 330

T [°C]

-dTg

/dT

Page 20: Spectroscopic and Microscopic Characterization of Oil Shale · Spectroscopic and Microscopic Characterization of Oil Shale Tracy Elizabeth McEvoy1, Michael Batzle1, Jeremy Boak3,5,

TGA

0 100 200 300 400 500 600 700 800012345678

TGA Dark Layer Comparison

0 Dark290 Dark330 Dark

Temperature [°C]

-dTg

/dT

Page 21: Spectroscopic and Microscopic Characterization of Oil Shale · Spectroscopic and Microscopic Characterization of Oil Shale Tracy Elizabeth McEvoy1, Michael Batzle1, Jeremy Boak3,5,

Scanning Acoustic Microscopy

Control Sample

T = 330 ° C

Page 22: Spectroscopic and Microscopic Characterization of Oil Shale · Spectroscopic and Microscopic Characterization of Oil Shale Tracy Elizabeth McEvoy1, Michael Batzle1, Jeremy Boak3,5,

Scanning Acoustic Microscopy

~1.1mm

~1.4mm

~1.5mm

Acoustic Two-Way Travel Times:

17943 [ns]

17914 [ns]

17987 [ns]

Control Sample

Page 23: Spectroscopic and Microscopic Characterization of Oil Shale · Spectroscopic and Microscopic Characterization of Oil Shale Tracy Elizabeth McEvoy1, Michael Batzle1, Jeremy Boak3,5,

Scanning Acoustic Microscopy

Acoustic Two-Way Travel Times:

17956[ns]

17913 [ns]

17953 [ns]

Sample T = 330 °C

Page 24: Spectroscopic and Microscopic Characterization of Oil Shale · Spectroscopic and Microscopic Characterization of Oil Shale Tracy Elizabeth McEvoy1, Michael Batzle1, Jeremy Boak3,5,

Control T = 310°C T = 330°CSamples : :

Transmitted Phase Data

+180 -180°-90°+180° +90° 0°PhaseAngle:

Page 25: Spectroscopic and Microscopic Characterization of Oil Shale · Spectroscopic and Microscopic Characterization of Oil Shale Tracy Elizabeth McEvoy1, Michael Batzle1, Jeremy Boak3,5,

Dielectric Profile Comparisonbefore T-processed

Page 26: Spectroscopic and Microscopic Characterization of Oil Shale · Spectroscopic and Microscopic Characterization of Oil Shale Tracy Elizabeth McEvoy1, Michael Batzle1, Jeremy Boak3,5,

Decreased impedance contrast, scanning acoustic microscope.

Dielectric constants of organic rich layers in the samples studied were low in comparison to the dielectric constants of the organic poor layers.

Conclusions

Page 27: Spectroscopic and Microscopic Characterization of Oil Shale · Spectroscopic and Microscopic Characterization of Oil Shale Tracy Elizabeth McEvoy1, Michael Batzle1, Jeremy Boak3,5,

Implications

Dielectric logging can assess the degree of pyrolysis in the lab and in situ.

Page 28: Spectroscopic and Microscopic Characterization of Oil Shale · Spectroscopic and Microscopic Characterization of Oil Shale Tracy Elizabeth McEvoy1, Michael Batzle1, Jeremy Boak3,5,

AcknowledgmentsMillimeter Wave Spectroscopy

Nathan GreensEngineering Physics Department, CSM

Scanning Acoustic MicroscopeManika Prasad Ph.D.

Petroleum Engineering Department, CSM

Thermal-gravimetric AnalysisMatthew Liberatore Ph.D.

Chemical Engineering Department, CSM

Page 29: Spectroscopic and Microscopic Characterization of Oil Shale · Spectroscopic and Microscopic Characterization of Oil Shale Tracy Elizabeth McEvoy1, Michael Batzle1, Jeremy Boak3,5,

Acknowledgments

Marisa RydzyDepartment of Geophysics, Colorado School of Mines

Aaron McEvoyDepartment of Physics, Los Alamos National Laboratory

Page 30: Spectroscopic and Microscopic Characterization of Oil Shale · Spectroscopic and Microscopic Characterization of Oil Shale Tracy Elizabeth McEvoy1, Michael Batzle1, Jeremy Boak3,5,

Dielectric Constant

=2d

¿2¿

= 2d

Dielectric Permittivity

Wave Length

Sample thickness

Transmitted Phase Difference

Page 31: Spectroscopic and Microscopic Characterization of Oil Shale · Spectroscopic and Microscopic Characterization of Oil Shale Tracy Elizabeth McEvoy1, Michael Batzle1, Jeremy Boak3,5,

Extra Slides: MMW Connections

Scales & Batzle 2006

Page 32: Spectroscopic and Microscopic Characterization of Oil Shale · Spectroscopic and Microscopic Characterization of Oil Shale Tracy Elizabeth McEvoy1, Michael Batzle1, Jeremy Boak3,5,

Extra Slides: MMW

Gas Hydrate Research at CRA

Reflected

Transmitted

Fabry-Pérot Fit

Measurementsa) Frequency 75-100GHz b) Phase & Amplitude c) MMWref and MMWtransd) Data fit with Fabry-Pérot

ModelFabry-Pérot Model: Phase and Amplitude of transmitted and reflected wave depend on the sample thickness and the dielectric permittivityDielectric Constants at 273 K:Ice 94GH 58

Page 33: Spectroscopic and Microscopic Characterization of Oil Shale · Spectroscopic and Microscopic Characterization of Oil Shale Tracy Elizabeth McEvoy1, Michael Batzle1, Jeremy Boak3,5,

Image Sources

●TGA photograph -http://www.nd.edu/~pmcginn/IMG_1494.jpg, University of Notre Dame Department of Chemical Engineering, Last Accessed: Monday, Oct 12, 2009