Wellbore Cements Durability Under Geological Sequestration Conditions

MILEVA RADONJIC
Tevfik Yalcinkaya, Nnamdi Agbasimalo, Abiola Olabode, Tao Tao & Dinara Dussenova
LOUISIANA STATE UNIVERSITY
mileva@lsu.edu

RECS 2011, Birmingham, AL June 8

Outline
Cements 101
Cement chemistry Cement hydration Cement microstructures

Well Cementing
Well design Well cement role

Well Cements Deterioration

Field vs Lab examples Cement/Casing Interface Cement/Formation Interface

Conclusion

Range of length scales in subsurface engineering applications for CCS

10-9 10-6 10-7 10-4 Pore scale 10-4 10-2 Core-plug scale 10-2 - 103 Wellbore scale 103 10?? Reservoir scale

Sub-pore scale

Length scale (m)

Capacity- Injectivity - Containment

Ref: Deepwater Horizon Accident Investigation Report Appendix W

From Tyagi and Thompson, LSU

Time line: Containment Trapping - Risk

A b a n d o n e d w e l l s I n j e c t i o n w e l l s https://www.crc.gov.au/Information/default.aspx)

1. CO2 must remain trapped over extended time periods 2. In the injection period, trapping is only provided by physical barrier systems such as CAP-ROCK and WELLBORE CEMENT.

What we know from O&G

More than 8,000 wells in the GOM have sustained casing pressure. (U.S. Federal Register, 2010) 14,477 wells out of the 316,439 wells in Alberta, Canada are leaking. (Watson & Bachu, 2009) CO2 sequestration cannot be carried out in the presence of leaky wells.

Wellbore leakage is caused by the following:

Pre-production
Inadequate drilling mud removal Incomplete cementing due to casing eccentricity Cement shrinkage and casing contraction Contamination of cement by various wellbore fluids

During Production
Mechanical stress/strain due to changes in pressure and temperature leading to - formation of micro-annulus at the casing-cement interface - formation of micro-annulus at the cement-formation interface - development of fracture network in the cement Geochemical attack Acid and sulfate attack leading to degradation of cement and corrosion of casing

Risk assessment of abandoned wells prior to implementation.

Wellbore cement is the key for ensuring wellbore integrity over extended period of time.
Production Casing

Wellbore Cement

Rock

Main functions of wellbore cements are: 1. ZONAL ISOLATION 2. STRUCTURAL SUPPORT 3. CASING PROTECTION
Evaluate interaction between fractures inside cement sheath and acidic brine .

Cement Sheath
Intermediate Casing

Fracture

Potential Pathways for Wellbore Leakage

Leakage occurs at microscale Integrated measures are necessary for large-scale models

The impact of micro-properties of hydrated cement paste on its durability in a chemical environment
Composition (mix-design, hydration level,P/T) Microstructure (morphology, texture, porosity) Physical integrity (microcracks)

Permeability

Hydra2on of Cement

Four stages of hydration in a microstructural model of C3S hydration (Garboczi, nist.org) The degrees of hydration: top left--0, top right--20 %, bottom left--50%, bottom right--87%. Red=unreacted cement, blue=CH, Yellow=C-S-H, Black= macroporosity.

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Hydrated Cement Conduc2vity

Hydration is 70%
complete in the first 28 days C-S-H makes up to 70% , CH up to 20%

Shift in Pore structure

Water/cement ~ 0.4 has 25% to 35% porosity Capillary pores and gel pores (bellow 0.01 m) Time effect on the cement microstructure
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Sources: Cement Chemistry, H.W. Taylor, 1996)

pH of cement pore water is ~ 13-14, (highly alkaline) CO2 dissolved in formation water results in pH lower than 7 Wellbore cement not compatible with an acidic solution How fast cement will deteriorate depends on several parameters (permeability, flow rate, chemistry, stresses..).

Cement Chemistry

Source: Applications of Environmental Aquatic Chemistry, Weiner E

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Tea Pot Dome 19yrs old cement




well cement 3a

well cement 1

Tea Pot Dome

well cement 1



Si

Ca Al Si

O Ti

Ca

Fe

Fe

Al
Si
S

Ti

Ca

Al

Ca

Fe

Si O Mg

Ti

Si

S Cl

Ca

Si

MgAl

Ca

O Mg

BSE & EDS

MgAl
S

Al Si

Ca

Fe

SHALE CEMENT AFTER YEARS OF CONTACT WITH CO2

Gray cement

Orange zone SFZ

1mm

Optical image of a porous opening in the SFZ showing a boxwork texture.

Source: Carey et al, 2006

Polished slab showing orange zone with gray cement on the left and Shale Fragmented Zone on the right.
Adapted from Carey et al, 2006

X-ray EPMA maps (WDS): cement osteoporosis spatial elemental distribution across reacted-cement sample

3
cc
2

1
A C I D I C
B R I N E

Ca

Si

3
2

Fe

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Laboratory Set-Up & Sample Prep

12 in 1 in

Hassler Holder
Fracture length, L=12 in

Syringe Pump

Fracture Width (w)=0.6 in Aperture Size (b)

Cement Core (1 in by 12 in)

Single Fracture Geometry

Regions of Interest

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X-Ray Computed Tomography (Low Resolu2on CT)

Low Pressure Experiment

8 7

8 7

Inlet

Inlet

Visible increase in fracture aperture.

The un-reacted and reacted cement cores were scanned at 8 different locations along the core from bottom to top in order to nondestructively visualize the alterations along 12 in core.

Slice #7

Slice #1

Unreacted Outlet

Reacted Outlet

Unreacted

Reacted

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Fracture Aperture Measurements/Calcula2ons

Days control Pressure Drop Data 5.6 psi 5.6 psi 7 psi 8 psi 5.2 psi 4.9 psi Aperture, 5 psi
unreacted

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Aperture 57.2 m 57.2 m 53 m 50.8 m 58.6 m 59.6 m Aperture, 59.4 m

reacted

wp b3 Q = 5.11 10 6 l
Confined Stress conditions (600 psi)

Calculated Values

1 7 14 21 28 Axial30 Slice# 1 (outlet) 2* 3 4 5 6 7 8 (inlet)

4% Widening

Measured Values

0.71 mm 0.59 mm* 0.97 mm 1.15 mm 1.05 mm 0.85 mm 0.72 mm 0.79 mm

0.90 mm 0.81 mm 1.06 mm 1.34 mm 1.35 mm 1.04 mm 0.91 mm 1.04 mm

Unconfined Stress conditions

Average ~ 24.5% Widening

Std. Deviation ~ 8.5%

ESEM & EDS

Reacted core-Top view LP, low magnification Two regions Reacted core-Top view LP, medium magnification Partial fracture healing Reacted core-Top view LP, high magnification Calcite growth within the fracture
3 mm 0.1 mm

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Ca/Si is 5.64 for Unreacted core

Ca/Si ~4

Ca/Si ~ 13

Ca/Si ~ 42

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ESEM EBS
Brighter color-higher atomic mass

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Identification of spatial distribution of phases and pore/fracture detection

Bridging

Unhydrated cement Altered cement Secondary micro fractures/oriented growth parallel and perpendicular to the observed primary fracture

Crystal growth within fracture

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Reaction products at the fracture wall

Element C K O K SiK CaK FeK Wt % 04.13 50.27 02.38 41.02 02.21 At % 07.42 67.81 01.83 22.09 00.85

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Calcite-black arrow Dissolution-red arrow Intact cement- white arrow

Micro-CT Images: Different Orientations

Fracture Surface

I
Transition

II
Outl Inner Part
LP Experiment Micro-CT along xz (H=5mm) Fracture Surface

et

Cross sectional view of LP Experiment Micro-CT along xy/ Axial Slices-30days

Outl et

I
Transition Inner Part

Inlet

II
HP Experiment Micro-CT along xy/ Axial Slices-10days 26

HP xz (H=3mm)

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Micro-CT Images: Different Orientations at 100days

Time Effect clearly visible when comparing 4 weeks to I 12weeks experimental data: extensive fracturing and loss of solid/increased porosity/permeability, II compromised overall integrity of cement matrix. Outl et Fracture Fracture Surface Surface Inlet Inner Part
LP Experiment Micro-CT along xz (H=5mm) LP

Inlet Outlet Experiment Micro-CT along xy/ Axial Slices

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0.005

Mercury Intrusion Porosimetry

LP porosity different at inlet (-) and outlet(+)

Cumulative Intrusion (mL/g)

0.004

0.003

0.002

0.001

0 100 10

Reacted LP_7-8 Unreacted LP LP Reacted_1-2 Unreacted HP Reacted HP

Pore radius (m)

0.12

Cumulative Intrusion (mL/g)

HP porosity increase

0.1 0.08 0.06 0.04 0.02 0

Reacted LP_7-8 Unreacted LP LP Reacted_1-2 Unreacted HP Reacted HP

1 0.1

Pore radius (m)

0.01

0.001

SMALL PORES

LARGE PORES

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Induc2vely Coupled Plasma (ICP)

#Days Control Sample 0 6 12 15 18 21 24 27 30 Ca2+ (mg/L) Effluent pH mf pf HCO3(mg/L) CO3-2 (mg/L)

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OH(mg/L)

0.48 39.40 16.65 14.83 12.69 18.05 11.55 11.51 11.28 20.05

4.7 5.9 6.9 6.8 9.5 10.2 9.6 9.3 6.5 10.1

0.22 0.56 0.23 0.12 0.42 0.17 0.22 0.15 0.24 0.25

0 0 0 0 0.11 0.06 0.01 0.02 0 0.13

134.2 341.6 140.3 73.2 122 30.5 122 67.1 146.4 0

0 0 0 0 66 36 6 12 0 72

0 0 0 0 0 0 0 0 0 1.7

2 1 0 Saturation Index (SI) -1 -2 -3 -4 -5 -6

Saturation Index Calculations

SI>0, solution is over-saturated with calcite
Equilibrium precipitation Equilibrium precipitation dissolution equilibrium precipitation dissolution Under-saturated to SI<0, solution is under-saturated with calcite oversaturated dissolution

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10

15 20 Time (Days)

25

30

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Ion activity product (IAP)= (activity of Ca) * (activity of CO3-2 ) Saturation index (SI)= log (IAP)-log (Equilibrium Constant)

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Surface eleva/on

0 35.7 x 26.8 mm @20micron resolu/on

0.08 mm

Surface eleva/on Sample 2

0 53.4 x 25.3 mm 1.3 mm

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Conclussions

Hydrated cement-model

http://lmc.epfl.ch/page18839-en.html

1. Cement pore solution is highly alkaline (Na+, K+, and OH- ions) 2. Acid attack reduces the pH of the pore solution 3. Dissolution (leaching) of Portlandite (Ca(OH)2) creates new access routes to existing pores 4. Carbonation-Conversion of Portlandite (33.1 cc/mol) to calcite (36.9 cc/mol) causes blockage of pores 5. Porosity increase/reduction is determined by the competition between leaching/carbonation mechanisms 6. Time is the PRIMARY factor
Source:httpciks.cbt.nist.gov~garboczappendix1node7.html

Conclusions

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The widening of the fracture aperture proves that preexisting fractures within cement sheath STILL constitute a primary concern for safe and long-term containment of CO2 in the subsurface. The confining pressure around the cement sheath tends to decrease the aperture. However, even 1m microfracture can give ~84X10-5 m2 permeability while considering intact cement has a permeability of 10-18-10-20 m2 (Nelson 2006).
The human hair diameter approximately 15 to 150 m!!!

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Latest Experiments.
A drilling fluid contaminated composite sandstonecement core was prepared and cured for 90 days. A CT scan of the sample was obtained prior to plugging it into the Hassler core holder. After 30 hours of injection, the sample taken out of the core holder because there was loss of pressure. The sample retrieved from the core holder was totally debonded.

Schematic of the cement-formation interface

Cement formation interface without contamination 25mm Cement formation interface with contamination 25mm

25mm

Arrows represent fluid flow.

1-300m

Inadequate mud displacement during cementing leaves residual mud on the formation surface. This residual mud is different from mud cake and is present irrespective of the type of formation being drilled through.

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CT Scan of composite sandstone-cement core

A1

A1

Sandstone Drilling fluid contamination Cement

A2

A2

White arrows show where cross section was taken from

A Longitudinal view of
Cement sandstone composite sample

B1
Sandstone Drilling fluid contamination

B Cross section of
Cement sandstone composite sample Sandstone

B2

B 1

B 2

Cement Cement

De-bonded composite sandstone-cement core

Sandstone with drilling fluid contamination

Cement with drilling fluid contamination

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ENGINEERING STRUCTURES-1

http://www.google.com/search? hl=en&rlz=1T4ADBF_enUS346US388&prmd=ivns&source=lnms&tbm=isch&ei=z6nuTYGlMcubtwf8_MG2CQ&sa= X&oi=mode_link&ct=mode&cd=2&ved=0CA0Q_AUoAQ&q=oldest%20manmade%20engineering %20structures&biw=1082&bih=580

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ENGINEERING STRUCTURES-2

http://www.google.com/search? hl=en&rlz=1T4ADBF_enUS346US388&prmd=ivns&source=lnms&tbm=isch&ei=z6nuTYGlMcubtwf8_MG2CQ&sa= X&oi=mode_link&ct=mode&cd=2&ved=0CA0Q_AUoAQ&q=oldest%20manmade%20engineering %20structures&biw=1082&bih=580

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Acknowledgements
H. Ozyurtkan, Y. ElKhamra, LSU Department of Petroleum Engineering Willson, Clibert, and Best, LSU Civil and Environmental Engineering J.S. Hanor, W. LeBlanc, R. Young, Department of Geology and Geophysics D. Bourgoyne, G. Masterman, J. W. Wooden, LSU Well Facility C. Gardner, L. Dillenbeck, D. Williams, B. Lawrence, Chevron Cementing Team and Chevron ETC Rock/Petrophysics B. Newton,R. Shoultz OMNI Laboratories/ Weatherford D. Beckett, Dylan Jackson, Core Laboratories Argonne National Laboratory, Chicago Russ Detwiler, University of California Davies George Scherer, Andrew Duguid, Princeton University

HW: http://www.ted.com/talks/ richard_sears_planning_for_the_end_of_oil.html

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Questions? And Thank You!

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1, 2) conventional fixed platforms; 3) compliant tower; 4, 5) vertically moored tension leg and mini-tension leg platform; 6) Spar ; 7,8) Semi-submersibles ; 9) Floating production, storage, and offloading facility; 10) sub-sea completion and tie-back to host facility.
http://oceanexplorer.noaa.gov/explorations/06mexico/background/oil/media/types_600.html
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Fluid migration paths through wellbores

Source: Bourgoyne et al,1999

http://photos.mongabay.com/09/forecast_co2.jpg

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Si

Ca O

Tea Pot Dome well cement 3a BSE & EDS

Ca

Mg

Cl
Al S Na

Si

Si

Ca

Al

S Cl

Si S

Ca

Fe

Na

Cl

Na

Ca

Fe

Al Mg

Si

Ca

Si O

Fe

Al
Mg

Cl

Ca

Si

Fe

Mg

Al Na
S Cl

Tea Pot Dome well cement 3a

BSE micrographs

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