to download the presentation as a pdf. - EMS Energy Institute - Penn ...

energy.psu.edu

to download the presentation as a pdf. - EMS Energy Institute - Penn ...

Development of Proppants for

Hydrofracturing in Oil and Natural Gas

Bearing Shales

John R. Hellmann

Professor of Materials Science and Engineering

Associate Dean for Graduate Education and Research

College of Earth and Mineral Sciences

The Pennsylvania State University

Presented at the Earth and Mineral Sciences Energy Institute

Clean Energy Seminar Series

February 27, 2013.


Acknowledgements

• Collaborators: Walter G. Luscher, Ryan P. Koseski, David G.

Hartwich, Peter J. McClure, Paul C. Painter and Bruce G.

Miller

• Halliburton Energy Systems

• Carbo Ceramics

• U.S. Department of Energy

Penn State/DoE Stripper Well Consortium

• ANH Refractories

• MoSCI Inc.

• Nittany Extraction Technologies LLC.

• Ben Franklin Partnership of Central and Northern PA (TRESP

Program)


Hydrofracturing: It’s all fire and

brimstone - NOT!

Hydrofracturing is a critical

technology for the development

of unconventional gas and oil

reserves in the continental

United States


300 feet

Production of gas from the

Marcellus requires contact

area

Contact area is generated

through cracks in rocks


Hydrofracturing


Idealized drill pad


What are proppants

• Hydrofracturing is performed to enhance the permeability of the

resource-containing strata, thereby aiding recovery

• Fissures from hydrofracturing must be maintained

• Small (0.5-2 mm diameter) ceramic particles are emplaced after

hydrofracturing to “prop” open the fissures

• Brady and Ottawa white sands, fused zircon, alumina, kaolin, and

bauxite have all been used successfully as proppants


So, what’s the driver

• Proppant demand was 10-12 billion pounds/year

worldwide in 2008; emerging plays have expanded the

market nearly ten-fold

• Conventional raw materials (Brady and Ottawa White

sands, kaolin, and bauxite) experiencing rapid price

increases

• Alternative raw materials, closer to the site of application

will permit development of these energy resources


Research activities address

• Compositional and microstructural modification of state of the art

proppants

• Sintered bauxite and kaolin

• Utilization of non-traditional raw materials for manufacturing high

performance proppants

• Mine tailings, domestic recycled glass, drill cuttings, fly ash,

slags, etc.

• Tailoring mechanical and physical properties through compositional

and microstructural control

• Ion exchanged glasses

• Glass ceramics

• Sintered ceramics


Heating Rate

High specific strength proppants

from sintered bauxite

• High strength, toughness, and low

density are critical for this application

(MPa) 248

(g/cc) 2.90

• Crystalline phase and microstructural

evolution in aluminosilicates tailored

using dopants to promote transient

liquid phase sintering

• Alternative sintering technology

(microwave) and low temperature

chemical bonding evaluated for

producing high strength, low density

aggregates

• Significant strength enhancements

achieved without increases in density

(MPa) 213

(g/cc) 2.95

(MPa) 190

(g/cc) 2.90

Walter G. Luscher, John R. Hellmann, David L. Shelleman, and Albert E. Segall, “A

Critical Review of the Diametral Compression Method for Determining the Tensile

Strength of Spherical Aggregates,“ J. Testing and Evaluation, 35(6)2007

Walter G. Luscher, John R. Hellmann, Barry E. Scheetz, and Brett A. Wilson, “Strength

Enhancement of Aluminosilicate Aggregate Through Modified Thermal Treatment,” J.

Appl. Ceram. Technol., 3(2)157-163(2006)

Time

(MPa) 129

(g/cc) 2.95

Temperature

Funded by Carbo Ceramics


Characteristic Strength (MPa)

Weight (%)

• Transient liquid phase and redox

controlled sintering yields high strength

core-shell microstructures

• Addition of dopants enhances or matches

commercial strengths while reducing

processing temperatures

• Applications:

• Proppants

• Catalysis and Catalytic Supports

• Reactive permeable barriers

• Reagent delivery in methane hydrate flooding

• Designer Casting Media

450

400

350

300

250

200

150

100

50

Doping and manipulating redox conditions

yield high strength neutrally buoyant

proppants

101.8

101.6

101.4

101.2

101.0

100.8

100.6

100.4

100.2

100.0

0

1440 1460 1480 1500 1520 1540 1560

99.8

Undoped Dopant 1

Dopant 2

Temperature (°C)

0 250 500 750 1000 1250 1500

Temperature (°C)

W.G. Luscher, J.R. Hellmann, B.E. Scheetz,

and B.A. Wilson, “Material Having a

Controlled Microstructure, Core-Shell

Macrostructure, and Method for Its

Fabrication,” U.S. Patent 7,828,998; issued

November 9, 2010 ; licensed to Nittany

Extraction Technologies LLC


Non-traditional alternative

materials to bauxite, kaolin and sand

• Ion exchanged glass from domestic

recycling

• Glass ceramics derived from aluminosilicate

by-products of mining operations

• Glass ceramics derived from drill cuttings

from Marcellus wells


Ion exchanged glass proppants

• Soda-Lime-Silica glass cullet is widely available

• Commercial spheroidization in large quantities has been

demonstrated

• High strengths, moderate densities, and intermediate

hardness seem well suited for proppant application

• Past experience demonstrates lack of prolonged

permeability in glass beds

• High stored elastic strain energy yields energetic fracture

and production of a multitude of extremely fine fragments,

resulting in blinding of the bed and concomitant loss in

permeability

• Modification in fracture morphology and reliability can be

achieved through ion exchange processing

Interstices between large angular fragments

remaining in ion exchanged glass proppants

will continue to be permeable


Materials selection and

processing

• Glass cullet from domestic recycling streams was size classified then

spheroidized

2 mm

Mixed glass cullet prior to and after spheroidization at MoSci


Ion-Exchanged glass proppants with tailored

mechanical failure modes

• Ion exchange in soda-lime-silicate glass increases the apparent

toughness of the glass, matching or exceeding the diametral crush

strengths of commercially available ceramic proppants

• Reverse ion exchange yields controlled crack growth; manipulating

the fracture mechanism results in larger fragments, rather than bed

blinding glass powder , thereby prolonging proppant permeability

Na

+

K +

J.R. Hellmann, B.E. Scheetz, and R.P. Koseski, “Treatment of

Particles for Improved Performance as Proppants,” U.S. Patent

8,193,128, June 5, 2012

Funded by DoE


Weibull analysis

as-spheroidized


F a i l u re P ro b a b i l i ty

F a i l u re P ro b a b i l i ty

ReliaSoft Weibull++ 7 - www.ReliaSoft.com

F a i l u re P ro b a b i l i ty

F a i l u re P ro b a b i l i ty

Different colors behave

similarly

ReliaSoft Weibull++ 7 - www.ReliaSoft.com

B-3X Color Comparison

B-3X-15 Color Comparison

99.000

90.000

All colors within

95% confidence

Probability-Weibull

CB@95% 2-Sided [T]

B-3X-Brown\Data 1

Weibull-2P

MLE SRM MED FM

F=30/S=0

Data Points

Probability Line

Top CB-I

Bottom CB-I

99.000

90.000

All colors within

95% confidence

Probability-Weibull

CB@95% 2-Sided [T]

B-3X-15-Brown\Data 1

Weibull-2P

MLE SRM MED FM

F=31/S=0

Data Points

Probability Line

Top CB-I

Bottom CB-I

50.000

B-3X-Clear\Data 1

Weibull-2P

MLE SRM MED FM

F=30/S=0

Data Points

Probability Line

Top CB-I

Bottom CB-I

50.000

B-3X-15-Clear\Data 1

Weibull-2P

MLE SRM MED FM

F=31/S=0

Data Points

Probability Line

Top CB-I

Bottom CB-I

10.000

B-3X-Green\Data 1

Weibull-2P

MLE SRM MED FM

F=30/S=0

Data Points

Probability Line

Top CB-I

Bottom CB-I

10.000

B-3X-15-Green\Data 1

Weibull-2P

MLE SRM MED FM

F=31/S=0

Data Points

Probability Line

Top CB-I

Bottom CB-I

5.000

5.000

David Shelleman

Penn State University

12/11/2009

2:24:14 PM

1.000

10.000 100.000

1000.000

B-3X-Brown\Data 1: b=4.3102, h=314.9421

B-3X-Clear\Data 1: b=5.5325, h=342.8463

B-3X-Green\Data 1: b=3.2237, h=282.5628

ReliaSoft Weibull++ 7 - www.ReliaSoft.com

99.000

90.000

All colors within

95% confidence

Strength ( MPa)

B-4X Color Comparison

Probability-Weibull

CB@95% 2-Sided [T]

B-4X-Brown\Data 1

Weibull-2P

MLE SRM MED FM

F=30/S=0

Data Points

Probability Line

Top CB-I

Bottom CB-I

David Shelleman

Penn State University

1/29/2010

12:14:11 PM

1.000

10.000 100.000

1000.000

B-3X-15-Brown\Data 1: b=4.4423, h=320.9958

B-3X-15-Clear\Data 1: b=4.6647, h=336.6358

B-3X-15-Green\Data 1: b=4.8264, h=334.4016

ReliaSoft Weibull++ 7 - www.ReliaSoft.com

99.000

90.000

All colors within

95% confidence

Strength ( MPa)

B-3X-30 Color Comparison

Probability-Weibull

CB@95% 2-Sided [T]

B-3X-30-Brown\Data 1

Weibull-2P

MLE SRM MED FM

F=30/S=0

Data Points

Probability Line

Top CB-I

Bottom CB-I

50.000

B-4X-Clear\Data 1

Weibull-2P

MLE SRM MED FM

F=30/S=0

Data Points

Probability Line

Top CB-I

Bottom CB-I

50.000

B-3X-30-Clear\Data 1

Weibull-2P

MLE SRM MED FM

F=31/S=0

Data Points

Probability Line

Top CB-I

Bottom CB-I

10.000

B-4X-Green\Data 1

Weibull-2P

MLE SRM MED FM

F=30/S=0

Data Points

Probability Line

Top CB-I

Bottom CB-I

10.000

B-3X-30-Green\Data 1

Weibull-2P

MLE SRM MED FM

F=32/S=0

Data Points

Probability Line

Top CB-I

Bottom CB-I

5.000

5.000

David Shelleman

Penn State University

1/29/2010

12:19:26 PM

1.000

10.000 100.000

1000.000

B-4X-Brown\Data 1: b=5.4973, h=353.0637

B-4X-Clear\Data 1: b=3.5953, h=339.5346

B-4X-Green\Data 1: b=5.5521, h=355.3706

Strength ( MPa)

David Shelleman

Penn State University

1/29/2010

12:16:58 PM

1.000

10.000 100.000

1000.000

B-3X-30-Brown\Data 1: b=5.3226, h=319.6721

B-3X-30-Clear\Data 1: b=5.3216, h=334.9052

B-3X-30-Green\Data 1: b=5.7642, h=321.2606

Strength ( MPa)


Single ion exchange yields

strengthening


Reverse exchange

enhances reliability


Failure Probability

U n re l i a b i l i ty , F ( t)

Longer reverse exchange yields

increased Type I failure

99.900

90.000

50.000

Signifies Type I

Failure

Probability - W eibull

Probability-

C-0\Data 1

Weibul-2P

MLE SRM MED FM

F=100/S=0

Data P

Probab

C-5X-CRC\Data 1

Weibul-2P

MLE SRM MED FM

F=30/S=0

Data P

Probab

10.000

5.000

1.000

0.500

C-0: m = 3.17

σ θ = 418.6 MPa

T1 = 13%

C-5X: m = 4.09

σ θ = 481.1 MPa

T1 = 13.3%

C-5X-10: m = 3.79

σ θ = 409.6 MPa

T1 = 10%

C-5X-60: m = 4.28

σ θ = 365.9 MPa

T1 = 20%

C-5X-180: m = 3.98

σ θ = 289.3 MPa

T1 = 30%

C-5X-360: m = 4.36

σ θ = 278.3 MPa

T1 = 23.3%

0.100

100.000 1000.000

Strength Time, ( t) (MPa)

C-0\Data 1: b=3.1749, h=418.6421

C-5X-10-CRC\Data 1

Weibul-2P

MLE SRM MED FM

F=30/S=0

Data P

Probab

C-5X-60-CRC\Data 1

Weibul-2P

MLE SRM MED FM

F=30/S=0

Data P

Probab

C-5X-180\Data 1

Weibul-2P

MLE SRM MED FM

F=30/S=0

Data P

Probab

C-5X-360\Data 1

Weibul-2P

MLE SRM MED FM

F=30/S=0

Data P

Probab


Failure Probability

Fractography

• Proppants fail into larger pieces

at lower strengths

C-5X-180 at 138 MPa

C-5X-180 at 350 MPa

• Tailoring the residual strength via

ion exchange changes the failure

type but also changes the

strength at failure

C-5X at 196 MPa

C-5X at 339 MPa

99.900

90.000

50.000

10.000

5.000

1.000

0.500

Signifies Type I Failure

Type I zone

Probability - W eibull

Transition

area

Type II zone

C-0: m = 3.17

σ θ = 418.6 MPa

T1 = 13%

C-5X: m = 4.09

σ θ = 481.1 MPa

T1 = 13.3%

C-5X-180:

m = 3.98

σ θ = 289.3 MPa

T1 = 30%

Probability-Weibull

C-0\Data 1

Weibull-2P

MLE SRM MED FM

F=100/S=0

Data Points

Probability Line

C-5X-CRC\Data 1

Weibull-2P

MLE SRM MED FM

F=30/S=0

Data Points

Probability Line

C-5X-180\Data 1

Weibull-2P

MLE SRM MED FM

F=30/S=0

Data Points

Probability Line

1.0 mm

C-0 at 151 MPa C-0 at 350 MPa

0.100

100.000 1000.000

a 1:

150 MPa

350 MPa

Strength (MPa)

Time, ( t)


Freq %

API 60 fines

characterization

• In addition to

improved strength of

single proppants, ion

exchange showed

significant differences

in particle size of fines

resulting from API 60

compaction test

9

8

7

6

5

Particle Size Overlay

• These results

prompted testing in

the API 61

permeability test

4

3

2

1

0

0.01 0.1 1 10 100 1000

Particle Size (µm)

untreat_01 single_01 double_01


Wt % Fines Normalized

Comparison to basalt glass ceramics

Soda-lime

silicate

Basalt

50

45

C-0

40

E-0 (Batch 3)

35

30

25

20

15

10

5 8000 psi

0

425 300 150 75 45 0

Particle Size Range from Sieve Analysis (µm)


Proppant testing

American Petroleum Institute

Recommended Practice 61

Average Conductivity (mdft)

v.

Closure Pressure (MPa)

Each Pressure is held for

~50h

Darcy’s Law

q = -κ/η( P)

D


Conductivity (md-ft) .

Conductivity (md-ft) .

Conductivity

30000

25000

PSU Glass & Control

Control

21h

21h/30m

Untreated

45000

40000

CarboHSP

HSP

35000

20000

30000

12/18 16/30

15000

25000

20/40 30/60

10000

20000

5000

15000

0

0 20 40 60 80 100 120 140 160

Time (hrs)

10000

5000

0

0 2000 4000 6000 8000 10000 12000 14000 16000

Closure Stress (psi)


Conductivity (md-ft) .

Conductivity (md-ft) .

Comparing results to

sand

30000

25000

Control

21h

21h/30m

Untreated

Ion exchanged glass performed as well

as sand of slightly larger particle size

distribution

20000

15000

10000

5000

Brady Sand

0

0 20 40 60 80 100 12030000

140 160

Time (hrs)

25000

20000

12/20

16/30

15000

20/40

10000

30/50

40/50

5000

0

1000 2000 3000 4000 5000 6000

Closure Stress (psi)


Reverse exchange does not

improve conductivity at higher

closure stresses


Ion exchanged glass results

Determined the processing parameters for single and

reverse ion exchange processing

Strength testing confirms failure mechanism and

acceptable strength retention

Verified that an engineered residual stress state can

promote Type I failure and prolonged conductivity

Conductivities comparable to resin-coated sand has been

demonstrated; manufacturing cost may be an

impediment to application


Non-traditional alternative

materials to bauxite, kaolin and sand

• Ion exchanged glass from domestic

recycling

• Glass ceramics derived from aluminosilicate

by-products of mining operations

• Glass ceramics derived from drill cuttings

from Marcellus wells


Natural aluminosilicates

Element

As-

Received

Melt

(Graphite

Crucible)

SiO 2 (wt%) 56.04 58.21

Al 2 O 3 (wt%) 12.67 13.32

Fe 2 O 3 (wt%) 10.4 10.62

MnO (wt%) 0.171 0.187

MgO (wt%) 3.33 3.59

CaO (wt%) 4.65 5.03

Na 2 O (wt%) 3.66 4.22

K 2 O (wt%) 2.38 2.44

TiO 2 (wt%) 2.19 2.302

P 2 O 5 (wt%) 0.36 0.37

LOI (wt%) 3.915 -1.129

Total (wt%) 99.76 99.16

Determined by ICP-OES

Burkhard (2006), Barbieri (2000), Beall (1991),

El-Shennawi (2001), Karamonov (1999)


Manufacturing

Proppants produced in small batches in-house,

larger batches by commercial processes

Mo-Sci Corp. (Rolla, MO)


Time-Temperature-Transformation

1/16/2012 Confidential


Characteristic strength

MPa (95U)

Time (h)

Temp.(C) 0 0.1 1 5 10 17 25

1000 99(13.5) 82(13.5) 111(13.5) 53(9.5) 72(15.0) 87(15.0) 68(9.0)

950 99(13.5) 154(25.5) 84(7.5) 71(11.5) 69(8.5) 101(18.0) 97(12.0)

900 99(13.5) 155(31.0) 100(17.0) 74(12.0) 92(16.5) 79(12.0) 82(13.5)

850 99(13.5) 127(18.5) 121(16.5) 103(21.0) 113(23.0) 104(20.0) 95(16.5)

800 99(13.5) 103(15.5) 109(18.5) 97(16.0) 102(16.5) 101(22.0) 85(10.0)

750 99(13.5) 105(18.5) 105(25.0) 92(15.0) 107(18.5) 86(14.5) 85(16.5)

A

B

700 99(13.5) 126(23.5) 76(15.5) 96(18.5) 89(11.5) 97(22.5) 106(21.5)

650 99(13.5) 96(19.0) 110(26.5) 74(8.0) 80(10.0) 97(19.0) 127(26.0)

600 99(13.5) 124(21.0) 93(15.0) 114(19.5) 100(13.5) 98(12.5) 94(16.0)

C


Fused glass failure fragments

Controlled devitrification in glassceramic

proppants enhance strength

and toughness

• Devitrification of a glass- forming

industrial waste yields failure

modes and strengths comparable

to commercial ceramic proppant

(>300 MPa)

• Suitable replacement for high

grade bauxite ores

Devitrified andesite glassceramic

failure fragments

David G. Hartwich, “Development of

Proppants from Ion Exchanged Recycled

Glass and Metabasalt Glass Ceramics,”

M.S.Thesis in Materials Science and

Engineering, The Pennsylvania State

University, 2011.

R.P. Koseski, J.R. Hellmann, and B.E. Scheetz,

"Treatment of Melt Quenched Aluminosilicate

Glass Spheres for Application as Proppants Via

Devitrification Processes," U.S Patent allowed

7/20/2012; patent pending.; licensed to Nittany

Extraction Technologies LLC

Funded by Halliburton, and

Department of Energy


Pelletization

+12

+16

+18

+20

+30

+40

+50

+70

+80


Scale up to manufacturing with

industrial partners underway

Increasing

Magnification


Non-traditional alternative

materials to bauxite, kaolin and sand

• Ion exchanged glass from domestic

recycling

• Glass ceramics derived from aluminosilicate

by-products of mining operations

• Glass ceramics derived from drill cuttings

from Marcellus wells


Latest efforts

• Drill cuttings from Marcellus wells

– Silica and shale (aluminosilicate) based

– Over 1000 tons/well produced

– Contain NORMs and residual mineral oil from drilling muds

– Currently land filled as residual waste

• Conversion to proppants offers an attractive beneficial re-use

• Marriage of several technologies at Penn State underway to

develop this technology

– Ionic liquid separation of oils from particulates

– Core/shell proppants via sintering

– Flame spheroidized glass ceramics


An ionic liquid based process

• Bitumen or oil can be separated from

particulates using an ionic liquid at room

temperature.

• A three phase system is formed and the

hydrocarbons can be removed by

decantation or other means.

• Yields close to 100% are obtained.

• Water is used to remove IL from the

residual sand and clays, but this is easily

removed from the IL by distillation or

simple evaporation because ILs have a

negligible vapor pressure under these

conditions.

• There was no detectable IL contamination

of the residual sand and clays and the

bitumen produced in this process was free

of residual IL. (The IL used is so polar it is

completely immiscible with hydrocarbons.)

Bitumen + Solvent

Ionic Liquid

Sand + Clays in Ionic Liquid

Canadian oil sands. Some

solvent (e.g., naphtha) is used

to lower the viscosity of the

bitumen. No added organic

solvent is necessary for drill

cuttings.


Drill cuttings to proppants via ILS

and sintering


Proppants made from

cuttings via flame fusion

Funded by Ben Franklin TRESP Program


Other Opportunities

Smart Proppants for detection of extent of hydrofractured zones

and proppant placement

In-situ treatment of hydrofracturing fluids:

TENORMs and TDS removal (Ra, Bi, Ba, Sr, Ca, Mg, U, Th)

Organics

Permeable reactive barriers for remediation of contaminated

ground water

Heavy media separation technology in coal combustion and

minerals processing

Solid thermal transfer media (e.g. solid particle solar receiver)


Summary

• Underutilized industrial by products, normally relegated to landfill have been

shown to be viable raw materials for proppant manufacturing

• Raw materials are ubiquitous and indigenous to the Marcellus, Utica, and

Bakken plays

• Melt spheroidization and devitrification processing has yielded a class of

proppants with strength and performance rivaling the best state-of-the-art

synthetic proppants

• Scale up to large tonnage quantities is currently underway

• Extension of processing methodology to drill cuttings is being explored;

Sequestration to deep geological formations as proppants offers significant

economic and environmental benefit

• Other applications and opportunities are abundant

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