Spectroscopic and Microscopic Characterization of Oil Shale · Spectroscopic and Microscopic...

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.

● 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

Introduction

Samples

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

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

Sample Conditions II

Sample Conditions III

Control Sample T= 310 °C T =330°C

Techniques

1. Millimeter Wave Spectroscopy

2. Thermal Gravimetric Analysis

3. Scanning Acoustic Microscope

Millimeter Wave Spectroscopy I

Scales & Batzle (2006)

Harmonic Multiplier

Teflon Probes

Vector NetworkAnalyzer

Harmonic Detector

HarmonicDetector

MotorMotor Control

Scalar Horn

Computer

Millimeter Wave Spectroscopy II

Lens

Lens

Scalar Horn

Sample

Transmitted Field ET

Reflected Field ER

Emitted Field EI

Standing Waves

Scalar Horn

Millimeter Wave Spectroscopy VRaw Data – Transmitted Phase Angle

+180 °

0°

-180 °

2.7 cm

Phas

e A

ngle

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

Transmitted Phase Data

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

Dielectric Permittivity Map

Low High2 4

Before Hydropyrolysis After Partial Hydropyrolysis

Thermal Gravimetric Analysis

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

TGA Data Example

Temperature Increasing

Sample Weight Decreasing

TGA Display Format

Temperature [°C]

Organic Material Loss-dTg/dT

1 mm

Sample A

Sample B

Sample C

X-ray energy dispersive analysis

““Qemscan”Qemscan”

Layer Locations

RedRed

LightLightDarkDark Section Section

LocationLocation

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

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

TGA

0 100 200 300 400 500 600 700 800012345678

TGA Dark Layer Comparison

0 Dark290 Dark330 Dark

Temperature [°C]

-dTg

/dT

Scanning Acoustic Microscopy

Control Sample

T = 330 ° C

Scanning Acoustic Microscopy

~1.1mm

~1.4mm

~1.5mm

Acoustic Two-Way Travel Times:

17943 [ns]

17914 [ns]

17987 [ns]

Control Sample

Scanning Acoustic Microscopy

Acoustic Two-Way Travel Times:

17956[ns]

17913 [ns]

17953 [ns]

Sample T = 330 °C

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

Transmitted Phase Data

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

Dielectric Profile Comparisonbefore T-processed

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

Implications

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

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

Acknowledgments

Marisa RydzyDepartment of Geophysics, Colorado School of Mines

Aaron McEvoyDepartment of Physics, Los Alamos National Laboratory

Dielectric Constant

=2d

¿2¿

= 2d

Dielectric Permittivity

Wave Length

Sample thickness

Transmitted Phase Difference

Extra Slides: MMW Connections

Scales & Batzle 2006

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

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