Long Term Proppant Performance

Is diagenesis a significant concern?

Montana Tech
April 14, 2011
Mike Vincent
mike@fracwell.com

Fracwell LLC

Acknowledgements
SPE 139875
Proppant Diagenesis Integrated
Analyses Provide New Insights into
Origin, Occurrence, and Implications for
Proppant Performance
R. Duenckel, CARBO Ceramics
M. W. Conway, Stim-Lab
B. Eldred, CARBO Ceramics
M. C. Vincent, Consultant

Problem Statement
Compelling evidence that fractures are not as
conductive or durable as we thought:
Surprising refrac success [SPE 134330, 136757]
Benefit of increasing frac conductivity beyond what
predicted by models [SPE 119143]
Loss of lateral hydraulic continuity between
adjacent wellbores connected by a frac [119143]
Infill drilling on very close spacing
Loss of vertical hydraulic continuity between
stacked reservoir layers [146376]
Laboratory testing

Extended duration
Harsh conditions to promote or accelerate damage

Outline
Extended duration testing
Benign conditions in lab

Testing to promote diagenesis

Diagenesis defined
Analysis methodology
Zeolites
Static testing
Conductivity testing

Actual proppant recovered from wells

Summary

Does Conductivity Degrade?

McDaniel , 15067
275F, 8000 psi [135C, 55MPa]
showed importance of using silica
saturated, deoxygenated brine
Similar damage shown with dry nitrogen!

Permeability Ratio

1
0.8
0.6
IDC at 10,000 psi (69 MPa)

0.4

LWC at 10,000 psi (69 MPa)

0.2

Sand at 5000 psi (35 MPa)

0
0

15

30

45

60

75

Days at Constant Stress

Cobb, 14133
200F, 5000/10,000 psi [93C, 35/69 MPa]
All non-corrodible surfaces, prop in
Teflon tube, continuous flowing 2% KCl

Does Conductivity Degrade?

Conductivity (md-ft)

10000

Hahn, SPE Drilling 1986

300F, 8500 psi [149C, 59 MPa]
Teflon tube, continuous flowing 2% KCl,
Non-silica saturated

1000

IDC - Intermediate Density Ceramic

Proflow - Precursor to LWC
RCS - Resin Coated Sand
Ottawa Sand
100
10

20

30

40

Days at Constant Stress, 8500 psi

Montgomery (12616) 1984

75/250F, 5000 psi [23C/121C, 34 MPa]
API short term cell: Metal plates,
continuous flowing 2% KCl,
Non-silica saturated
6

100

50
% Original Conductivity

20/40 Sand at 75F

80

10/20 Sand at 250F

60
40
20
0
0

30

60

90 120 150 180 210 240 270

Days at Constant Stress, 5000 psi

Does Conductivity
Degrade?

Handren 110451
250F, 6000 psi [121C, 41MPa]
Modern conductivity cell, Ohio Sandstone
Deoxygenated, Silica Saturated 2% KCl,

Is replacing
degraded
proppant a
major factor
in refrac
success?

All data
show
degradation.
No models
consider
this!

These historical tests suggest

Even with relatively benign conditions, proppants
degrade.
Occurs regardless of fluid (brine, water, oil, nitrogen)
Occurs faster with larger diameter materials [StimLab
data not summarized here]
Occurs faster with lower strength proppants

This would suggest the degradation in these cases

was due to mechanical, not chemical mechanisms
However, can we make it worse by invoking
chemistry?

Diagenesis in Propped Fractures

Diagenesis examplePrecipitants on high strength ceramic
after exposure to shale and synthetic
water at 500F for 7 days
SPE 118174

Dissolution and reprecipitation process

Key variables according to 118174 and related papers
Reservoir type
Temperature, closure stress
Fluid chemistry
Proppant type
Proppant coating

New Work - Analysis Methodology

Extended high temperature static tests to
evaluate interactions between proppants,
shales and fluids
Testing of proppants after exposure to
diagenetic conditions
Conductivity testing (flowing) at high stress and
temperature with shale cores
Investigation of flowback fluid and proppant
recovered from wells

Static cells
Static Cells 11 length, 450ml volume
Fill with proppant or equal volumes
proppant and shale
Water filled intergranular porosity
Sealed and placed in oven at 400F

More than 70 static tests conducted

Various combinations of proppant, shale and fluids
held at 400F for up to 154 days
Post-exposure tests include SEM, EDS, strength tests
of proppant, bulk density, water analysis
Proppants tested included ceramics, sands and RCS
Also included inert steel beads and glass rods

Proppant Properties
ISO Crush (%)
Proppants

BD
(g/cm3)

SG

SPC
(ksi)

Stress (psi)

20/40 High strength

ceramic

2.06

3.62

37.4

4.0

15k

20/40 Light weight

ceramic

1.58

2.72

24.0

3.3

7.5k

40/80 Light weight

ceramic

1.48

2.58

--

3.1

7.5k

20/40 Sand

1.56

2.66

13.0

2.3

5k

40/70 RCS

1.52

2.59

--

1.2

5k

20/40 RCS

1.59

2.59

--

0.7

5k

Ceramic Proppant Chemistry

Chemistry, wt. %
Proppants

Al2O3

Fe2O3

K 2O

SiO2

CaO

MgO

TiO2

High strength
ceramic

78.1

11.2

0.007

8.2

0.02

0.006

2.24

Light weight
ceramic

49.7

1.06

0.06

46.7

0.02

0.01

2.22

Ceramic Proppant Mineralogy

Mineralogy, wt. %

Proppants

Corundum

Mullite

Cristobalite

Amorphous
silica

High strength
ceramic

75

25

Light weight ceramic

75

20

Shale Chemistry

Chemistry, wt. %
Shale

SiO2

Al2O3

Fe2O3

K2O+Na2O

CaO+MgO

Pinedale

66.2

20.0

3.2

5.3

3.8

Steamboat

77.0

13.9

2.1

3.0

3.1

Hnysvl/Bssr 1

57.5

20.3

4.9

5.9

10.2

Hnysvl/Bssr 2

61.4

15.5

4.6

5.1

12.7

Shale Mineralogy
Mineralogy, wt. %
Shale

Illite

Quartz

Kaolinite

Calcite

Muscovite

Pinedale

48.6

34.9

11.0

--

--

Steamboat

26.1

56.5

9.3

--

--

Hnysvl/Bssr 1

34.2

25.2

1.5

16.6

17.4

Hnysvl/Bssr 2

29.1

33.4

4.9

14.0

14.9

Static Tests Results

Examples of zeolite precipitants high strength ceramic

400F, 14 days, Pinedale

Shale, DI water

Al2O3

Fe2O3

K2O

SiO2

MgO

TiO2

Spot 1 HSC

63.5

17.5

0.6

15.0

0.4

2.2

Spot 2 Precipitate

35.8

7.0

4.6

45.6

1.8

1.6

Static Tests Results

Examples of zeolite precipitants frac sand

400F, 14 days, Pinedale

Shale, DI water

Al2O3

Fe2O3

K 2O

SiO2

MgO

TiO2

Spot 1 Sand

2.6

97.4

Spot 2 Precipitate

18.4

7.5

5.0

66.7

2.0

Static Tests Results

Examples of zeolite precipitants RCS

400F, 14 days, Pinedale

Shale, DI water

Al2O3

Fe2O3

K2O

SiO2

MgO

TiO2

Spot 1 RCS

9.0

19.6

0.7

70.7

Spot 2 Precipitate

23.9

20.1

4.3

47.4

2.7

1.7

Static Tests Results

Examples of zeolite precipitants on steel and glass rods

400F, 154 days,

Haynesville/Bossier
Shale, DI water

10

Static Tests Results

Diagenetic precipitants were observed with all 4 shale
samples to varying degrees
Diagenetic activity only occurred when shale was present
Diagenetic precipitants were observed on all proppant
types tested including inert materials
The diagenetic precipitants were alumina silicates and
may be classified as zeolites
In the case of the sands and inert materials the alumina
was sourced conclusively from the shales

Static Tests Results

Increase observed in post static
test crush
Proppant Type

Average % Increase in Crush

After Exposure

20/40 HSC

31

20/40 LWC

94

20/40 Sand

61

Testing of the post static test proppant showed an increase

in ISO crush and reduction in characteristic strength of the
pellet

11

Conductivity Testing of Aged

Proppant Samples
Crush
Sample

Type

Exposure at 400F

%
(% Incr.)

20/40 HSC

None

15k

20/40 HSC

Static cell- 14 days DI water

4.8 (21)

15k

Stress, psi

9000

Long Term Conductivity (mD-ft)

8000

Sample 2

7000
6000

Sample 1

5000
4000
3000
2000
1000
0
0

2000

4000

6000

8000

10000

12000

14000

Stress (psi)

Conductivity Testing of Aged

Proppant Samples
Crush
Sample

Type

Exposure at 400F

%
(% Incr.)

20/40 LWC

None

3.3

20/40 LWC

2.5 hours DI water

7.2 (118)

7.5k

20/40 LWC

Static cell - 21 days DI water

6.5 (97)

7.5k

Stress, psi
7.5k

Long Term Permeability (D)

480
400

Sample 3

320

Sample 4

Sample 5

240
160
80
0
2000

4000

6000

8000

10000

12000

Stress (psi)

12

Conductivity Testing of Aged

Proppant Samples

Long term testing of post static tests proppants

yields identical conductivities
Increased post test crush observed is related to
stress corrosion not diagenesis
This stress corrosion effect already built-into
long term conductivity tests

Extended Conductivity Tests (flowing)

Using Haynesville/Bossier Core
Static tests do not address possible acceleration of
diagenesis due to closure stress
Extended conductivity testing performed with
Hynsvl/Bssr core and compared to Ohio SS
Test conditions: 325F, 12k closure stress, 1#/ft2 loading
Proppants tested: 40/80 LWC and 40/70 RCS
Held at 12k for 21 days
Conductivity measured, post test proppant pack
examined for evidence of diagenesis

13

Extended Conductivity Tests

Using Haynesville/Bossier Core

Long Term Conductivity (mD-ft)

1200

1000
40/70 RCS- 1 ppsf Shale 325F
40/80 LWC- 1 ppsf Shale 325F

800

47/70 RCS 1 ppsf OHSS

40/80 LWC - 1 ppsf OHSS

600

400

200

0
2000

4000

6000

8000

10000

12000

Stress (psi)

Extended Conductivity Tests

Using Haynesville/Bossier Core
Both LWC and RCS showed lower conductivity with
Hville/Bssr core vs Ohio SS
Conductivity reduction continued with time at 12k
stress
After 21 days between Hville/Bssr core, 12k, 325F:
40/70 RCS 2 md-ft
40/80 LDC 71 md-ft

Post test examination of proppant pack yielded no

evidence of diagenetic precipitants after 21 days of
flow
Conductivity reductions attributed to embedment,
spalling, and continued breakage

14

Identity of Precipitants from Static Tests

From SEM examination of structural appearance of
diagenetic materials present in prior studies and current
static testing: zeolites
Zeolites: crystalline structures with interconnected
cages
Zeolite chemistry: (Si + Al)/O = , Si/Al varies widely
Industrial use as molecular sieves
Zeolites: 46 naturally occurring and > 150 synthetically
prepared
Zeolites will not form in acidic conditions

What is the pH downhole?

High CO2 in hot reservoirs! [Grimes & McNeil,
Bross]

We pump high pH gels, but pH quickly drops to

acidic conditions upon flowback of frac fluids!
Deep Bossier: pH 6.2
CVL- pH 6.4
Haynesville- pH-6.0
Deep Bossier- pH 6.4
James Lime- pH 7.0
Bakken in situ - pH 4.3-5.8 [Smith 2010]

15

Flow back Analysis

Examination of proppant flow back samples
from GOM, S. Tx, Rockies, Canada show no
diagenetic activity

Area 2

No evidence of
diagenesis

No evidence of zeolite
precipitation was observed on
any ceramic fragments
recovered

Proppant Recovered from Actual Wells

No evidence of zeolite precipitation was observed on any

ceramic fragments recovered after > 1 year downhole. Iron
oxide, salts, carbonate and sulfate scales visible on some
sand, RCS and CER samples.

16

Summary
High temperature static testing of
proppants in the presence of formation
material shows:
diagenetic precipitants may form when formation
material is present
these precipitants will form on all proppant types
and inert materials
the precipitants formed may be classified as zeolites
the precipitants always include alumina. In the case
of sand, RCS and inert materials the alumina was
clearly sourced from the formation, NOT the
proppant

Summary
After aging proppants do show strength
degradation
the degradation is related to a stress corrosion mechanism
common to oxides after exposure to water
the degradation appears unrelated to diagenetic processes
stress corrosion attacks silica bonds in both sand and ceramic
proppants
resin coating did not isolate the sand particles from stress
corrosion effects
this degradation is already incorporated in the reference
conductivity testing

17

Summary
Zeolites did not form under extended conductivity testing
under flowing conditions
High temperature reservoirs in which zeolite formation
has been speculated appear to be too acidic for
deposition
Inspection of proppant recovered from wells did not
indicate the presence of zeolites
Zeolite precipitation does not appear to pose a
significant concern for propped fractures in many
applications
There are numerous damage mechanisms that justify an
increased investment in conductivity. However, it does
not appear that diagenesis poses a significant concern
in most reservoirs, nor that proppant coatings will
eliminate zeolite precipitation

Long Term Proppant Performance

Is diagenesis a significant concern?

Montana Tech
April 14, 2011
Mike Vincent
mike@fracwell.com

Fracwell LLC

18