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
Data PointsProbability L ineTop CB-IBottom CB-I
B-3X-15-Green\Data 1Weibull-2PMLE SRM MED FMF=31/S=0
Data PointsProbability L ineTop CB-IBottom CB-I
David ShellemanPenn State University1/29/201012:14:11 PM
ReliaSoft Weibull++ 7 - www.ReliaSoft.com
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
99.000Probability-WeibullCB@95% 2-Sided [T]
B-3X-30-Brown\Data 1Weibull-2PMLE SRM MED FMF=30/S=0
Data PointsProbability L ineTop CB-IBottom CB-I
B-3X-30-Clear\Data 1Weibull-2PMLE SRM MED FMF=31/S=0
Data PointsProbability L ineTop CB-IBottom CB-I
B-3X-30-Green\Data 1Weibull-2PMLE SRM MED FMF=32/S=0
Data PointsProbability L ineTop CB-IBottom CB-I
David ShellemanPenn State University1/29/201012:16:58 PM
ReliaSoft Weibull++ 7 - www.ReliaSoft.com
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
99.000Probability-WeibullCB@95% 2-Sided [T]
B-3X-Brown\Data 1Weibull-2PMLE SRM MED FMF=30/S=0
Data PointsProbability L ineTop CB-IBottom CB-I
B-3X-Clear\Data 1Weibull-2PMLE SRM MED FMF=30/S=0
Data PointsProbability L ineTop CB-IBottom CB-I
B-3X-Green\Data 1Weibull-2PMLE SRM MED FMF=30/S=0
Data PointsProbability L ineTop CB-IBottom CB-I
David ShellemanPenn State University12/11/20092:24:14 PM
ReliaSoft Weibull++ 7 - www.ReliaSoft.com
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
99.000Probability-WeibullCB@95% 2-Sided [T]
B-4X-Brown\Data 1Weibull-2PMLE SRM MED FMF=30/S=0
Data PointsProbability L ineTop CB-IBottom CB-I
B-4X-Clear\Data 1Weibull-2PMLE SRM MED FMF=30/S=0
Data PointsProbability L ineTop CB-IBottom CB-I
B-4X-Green\Data 1Weibull-2PMLE SRM MED FMF=30/S=0
Data PointsProbability L ineTop CB-IBottom CB-I
David ShellemanPenn State University1/29/201012:19:26 PM
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
Data PointsProbability L ine
C-5X-10-CRC\Data 1Weibull-2PMLE SRM MED FMF=30/S=0
Data PointsProbability L ine
C-5X-60-CRC\Data 1Weibull-2PMLE SRM MED FMF=30/S=0
Data PointsProbability L ine
C-5X-180\Data 1Weibull-2PMLE SRM MED FMF=30/S=0
Data PointsProbability L ine
C-5X-360\Data 1Weibull-2PMLE SRM MED FMF=30/S=0
Data PointsProbability L ine
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
Data PointsProbability L ine
C-5X-CRC\Data 1Weibull-2PMLE SRM MED FMF=30/S=0
Data PointsProbability L ine
C-5X-180\Data 1Weibull-2PMLE SRM MED FMF=30/S=0
Data PointsProbability L ine
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
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)
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
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+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
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