Development of Proppants for Hydrofracturing in Oil …...• Transient liquid phase and redox...

$: Development of Proppants for Hydrofracturing in Oil …...• Transient liquid phase and redox controlled sintering yields high strength core-shell microstructures • Addition of$
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.

Development of Proppants for

Hydrofracturing in Oil and Natural Gas

Bearing Shales

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

Production of gas from the

Marcellus requires contact area

Contact area is generated

through cracks in rocks

300 f

eet

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

High specific strength proppants

from sintered bauxite

• High strength, toughness, and low

density are critical for this application

• 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

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)

He

atin

g R

ate

Temperature Time

(MPa) 129

(g/cc) 2.95

(MPa) 213

(g/cc) 2.95

(MPa) 190

(g/cc) 2.90

(MPa) 248

(g/cc) 2.90

Funded by Carbo Ceramics

• 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

Doping and manipulating redox conditions

yield high strength neutrally buoyant

proppants

99.8

100.0

100.2

100.4

100.6

100.8

101.0

101.2

101.4

101.6

101.8

0 250 500 750 1000 1250 1500

Temperature (°C)

Weig

ht

(%)

0

50

100

150

200

250

300

350

400

450

1440 1460 1480 1500 1520 1540 1560

Temperature (°C)

Ch

ara

cte

risti

c S

tren

gth

(M

Pa)

Undoped Dopant 1

Dopant 2

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

• 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

Ion exchanged glass proppants

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

Mixed glass cullet prior to and after spheroidization at MoSci

2 mm

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

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

Na+

K+

Funded by DoE

Weibull analysis

as-spheroidized

ReliaSoft Weibull++ 7 - www.ReliaSoft.com

B-3X-15 Color Comparison

B-3X-15-Green\Data 1: b=4.8264, h=334.4016B-3X-15-Clear\Data 1: b=4.6647, h=336.6358B-3X-15-Brown\Data 1: b=4.4423, h=320.9958

Strength (MPa)

Fa

ilu

re P

rob

ab

ilit

y

10.000 1000.000100.0001.000

5.000

10.000

50.000

90.000

99.000Probability-WeibullCB@95% 2-Sided [T]

B-3X-15-Brown\Data 1Weibull-2PMLE SRM MED FMF=31/S=0

Data PointsProbability L ineTop CB-IBottom CB-I

B-3X-15-Clear\Data 1Weibull-2PMLE SRM MED FMF=31/S=0


B-3X-15-Green\Data 1Weibull-2PMLE SRM MED FMF=31/S=0


David ShellemanPenn State University1/29/201012:14:11 PM


B-3X-30 Color Comparison

B-3X-30-Green\Data 1: b=5.7642, h=321.2606B-3X-30-Clear\Data 1: b=5.3216, h=334.9052B-3X-30-Brown\Data 1: b=5.3226, h=319.6721

Strength (MPa)

Fa

ilu

re P

rob

ab

ilit

y

10.000 1000.000100.0001.000

5.000

10.000

50.000

90.000


B-3X-30-Brown\Data 1Weibull-2PMLE SRM MED FMF=30/S=0


B-3X-30-Clear\Data 1Weibull-2PMLE SRM MED FMF=31/S=0


B-3X-30-Green\Data 1Weibull-2PMLE SRM MED FMF=32/S=0




B-3X Color Comparison

B-3X-Green\Data 1: b=3.2237, h=282.5628B-3X-Clear\Data 1: b=5.5325, h=342.8463B-3X-Brown\Data 1: b=4.3102, h=314.9421

Strength (MPa)

Fa

ilu

re P

rob

ab

ilit

y

10.000 1000.000100.0001.000

5.000

10.000

50.000

90.000


B-3X-Brown\Data 1Weibull-2PMLE SRM MED FMF=30/S=0


B-3X-Clear\Data 1Weibull-2PMLE SRM MED FMF=30/S=0


B-3X-Green\Data 1Weibull-2PMLE SRM MED FMF=30/S=0




B-4X Color Comparison

B-4X-Green\Data 1: b=5.5521, h=355.3706B-4X-Clear\Data 1: b=3.5953, h=339.5346B-4X-Brown\Data 1: b=5.4973, h=353.0637

Strength (MPa)

Fa

ilu

re P

rob

ab

ilit

y

10.000 1000.000100.0001.000

5.000

10.000

50.000

90.000


B-4X-Brown\Data 1Weibull-2PMLE SRM MED FMF=30/S=0


B-4X-Clear\Data 1Weibull-2PMLE SRM MED FMF=30/S=0


B-4X-Green\Data 1Weibull-2PMLE SRM MED FMF=30/S=0



All colors within

95% confidence

All colors within

95% confidence

All colors within

95% confidence

All colors within

95% confidence

Different colors behave

similarly

Single ion exchange yields

strengthening

Reverse exchange

enhances reliability

Longer reverse exchange yields

increased Type I failure

Probability - Weibull

C-5X-360\Data 1: b=4.3603, h=278.2801C-5X-180\Data 1: b=3.9849, h=289.2906C-5X-60-CRC\Data 1: b=4.2845, h=365.9249C-5X-10-CRC\Data 1: b=3.7882, h=409.6449C-5X-CRC\Data 1: b=4.0940, h=481.0529C-0\Data 1: b=3.1749, h=418.6421

Time, ( t)

Un

reli

ab

ilit

y,

F(

t)

100.000 1000.0000.100

0.500

1.000

5.000

10.000

50.000

90.000

99.900

0.100

Probability-Weibull

C-0\Data 1Weibull-2PMLE SRM MED FMF=100/S=0

Data PointsProbability L ine

C-5X-CRC\Data 1Weibull-2PMLE SRM MED FMF=30/S=0


C-5X-10-CRC\Data 1Weibull-2PMLE SRM MED FMF=30/S=0


C-5X-60-CRC\Data 1Weibull-2PMLE SRM MED FMF=30/S=0


C-5X-180\Data 1Weibull-2PMLE SRM MED FMF=30/S=0




C-0: m = 3.17

σθ = 418.6 MPa

T1 = 13%

C-5X: m = 4.09

σθ = 481.1 MPa

T1 = 13.3%

C-5X-10: m = 3.79

σθ = 409.6 MPa

T1 = 10%

C-5X-60: m = 4.28

σθ = 365.9 MPa

T1 = 20%

C-5X-180: m = 3.98

σθ = 289.3 MPa

T1 = 30%

C-5X-360: m = 4.36

σθ = 278.3 MPa

T1 = 23.3%

Signifies Type I

Failure

Strength (MPa)

Failu

re P

rob

ab

ilit

y

Probability - Weibull

C-5X-180\Data 1:

C-5X-CRC\Data 1:

C-0\Data 1:

Time, ( t)

Un

reli

ab

ilit

y,

F(

t)

100.000 1000.0000.100

0.500

1.000

5.000

10.000

50.000

90.000

99.900

0.100

Probability-Weibull

C-0\Data 1Weibull-2PMLE SRM MED FMF=100/S=0


C-5X-CRC\Data 1Weibull-2PMLE SRM MED FMF=30/S=0




C-0: m = 3.17

σθ = 418.6 MPa

T1 = 13%

C-5X: m = 4.09

σθ = 481.1 MPa

T1 = 13.3%

C-5X-180:

m = 3.98

σθ = 289.3 MPa

T1 = 30%

Strength (MPa)

Fail

ure

Pro

ba

bilit

y

Signifies Type I Failure

Type I zone Transition

area

Type II zone

150 MPa 350 MPa

Fractography

1.0 mm

C-5X-180 at 138 MPa

C-5X at 196 MPa

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

C-5X at 339 MPa

C-5X-180 at 350 MPa

• Proppants fail into larger pieces

at lower strengths

• Tailoring the residual strength via

ion exchange changes the failure

type but also changes the

strength at failure

API 60 fines characterization

Particle Size Overlay

0

1

2

3

4

5

6

7

8

9

0.01 0.1 1 10 100 1000

Particle Size (µm)

Fre

q %

untreat_01 single_01 double_01

• In addition to improved strength of single proppants, ion exchange showed significant differences in particle size of fines resulting from API 60 compaction test

• These results prompted testing in the API 61 permeability test

Comparison to basalt glass ceramics

0

5

10

15

20

25

30

35

40

45

50

Wt

% F

ines N

orm

alized

C-0

E-0 (Batch 3)

Particle Size Range from Sieve Analysis (µm) 425 300 150 75 45 0

Basalt

Soda-lime

silicate

8000 psi

Proppant testing

Average Conductivity (md-

ft) v.

Closure Pressure (MPa)

Darcy’s Law

q = -κ/η( P)

American Petroleum Institute

Recommended Practice 61

Each Pressure is held for

~50h

D

Conductivity

0

5000

10000

15000

20000

25000

30000

0 20 40 60 80 100 120 140 160

Time (hrs)

Co

nd

uc

tivit

y (

md

-ft)

.

Control 21h/30m

21h Untreated

CarboHSP

0

5000

10000

15000

20000

25000

30000

35000

40000

45000

0 2000 4000 6000 8000 10000 12000 14000 16000

Closure Stress (psi)

Co

nd

uc

tiv

ity

(m

d-f

t)

.

12/18 16/30

20/40 30/60

Carbo HSP PSU Glass & Control

Comparing results to

sand

0

5000

10000

15000

20000

25000

30000

0 20 40 60 80 100 120 140 160

Time (hrs)

Co

nd

uc

tivit

y (

md

-ft)

.

Control 21h/30m

21h Untreated

Brady Sand

0

5000

10000

15000

20000

25000

30000

1000 2000 3000 4000 5000 6000

Closure Stress (psi)

Co

nd

ucti

vit

y (

md

-ft)

.

12/20

16/30

20/40

30/50

40/50

Ion exchanged glass performed as well as sand of slightly larger particle size distribution

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



recycling





Natural aluminosilicates

Element As-

Received

Melt (Graphite Crucible)

SiO2(wt%) 56.04 58.21

Al2O3 (wt%) 12.67 13.32

Fe2O3 (wt%) 10.4 10.62

MnO (wt%) 0.171 0.187

MgO (wt%) 3.33 3.59

CaO (wt%) 4.65 5.03

Na2O (wt%) 3.66 4.22

K2O (wt%) 2.38 2.44

TiO2 (wt%) 2.19 2.302

P2O5 (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)

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)

A

C

B

Controlled devitrification in glass-

ceramic 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

Fused glass failure fragments

Devitrified andesite glass-

ceramic failure fragments

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

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.

Pelletization

+12

+80 +70 +50

+40 +30 +20

+18 +16

Increasing

Magnification

Scale up to manufacturing with

industrial partners underway



recycling





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+Solvent

IonicLiquid

Sand+ClaysinIonicLiquid

• 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.)

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)

• 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

Summary

Development of Proppants for Hydrofracturing in Oil …...• Transient liquid phase and redox...

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Transcript of Development of Proppants for Hydrofracturing in Oil …...• Transient liquid phase and redox...