SPE/IADC

SPEIIADC 18618
Effects of C02 Attack on Cement in High-Temperature
Applications
by J.e. Shen, Unocal Science & Technology Div., and D.S. Pye, Unocal Geothermal Div.
SPE Members
Copyright 1989, SPE/IADC Drilling Conference
This paper was prepared for presentation at the 1989 SPE/IADC Drilling Conference held in New Orleans, Louisiana, February 28-March 3, 1989.
This paper was selected for presentation by a SPEIIADC Program Committee following review of information contained in an abstract submitted by the author(s). Contents of the paper,
as presented, have not been reviewed by the International Association of Drilling Contractors or the Society of Petroleum Engineers and are subject to correction by the author(s).
The material, as presented, does not necessarily reflect any position of SPE or the IADC, its officers, or members. Papers presented at SPEIIADC meetings are subject to publication
review by Editorial Committees of SPE and the IADC. Permission to copy is restricted to an abstract of not more than 300 words. Illustrations may not be copied. The abstract should
contain conspicuous acknowledgment of where and by whom the paper is presented. Write Publications Manager, SPE, P.O. Box 833836, Richardson, TX 75083-3836. Telex, 730989 SPEDAL.
ABSTRACT
Well cement carbonation by CO
Z
containing gas or brine
can happen to CO
Z
flooded oil fields, gas fields and
geothermal fields. Due to the Unocal's interests in
these applications, especially in the high temperature
geothermal wells, a field and laboratory testing
program was conducted to examine the effects of CO
Z
gas
on high temperature cement.
Wellhead cement samples from geothermal wells in the
Brawley and Geysers fields were collected and analyzed
for carbonation. The degree of cement carbonation was
found to be dependent on factors such as, temperature,
CO
Z
content in the fluid and location. Both the
carbonated and the uncarbonated cement have developed
extensive fractures and fine fissures in the matrix due
to thermal cycles. The carbonated cement has an
acceptable level of compressive strength, but its
permeability is normally higher than desired.
Preliminary results from laboratory cement carbonation
tests under simulated downhole high temperature, high
pressure conditions are presented. A new analytical
technique was used to measure the depth of carbonation.
The CO
Z
diffusion coefficient in the cement solid
matrix was estimated with this technique.
By comparing field, lab and published data, the carbo-
nation mechanism in high temperature cement is found to
be a function of several parameters, i.e., temperature,
CO
Z
content in the fluid and cement additives.
INTRODUCTION
In geothermal well cementing, the need of a high
strength and durable cement for high temperature
downhole applications (400 to 700F, ZOO to 370C) has
promoted the practice of fine silica flour in
high percentages into cement. The set cement formed
by these additions has proved to be temperature stable
Reference and illustrations at end of paper
19
over long period2 and also satisfied the API recom-
mended criteria.
3
However, a recent report shows that several geo-
thermal well casings in the Broadlands field, New
Zealand, failed from the exterior and ruptured.
There was little cement remaining around the casings.
The corrosion of both cement and casing was attri-
buted to the high CO
Z
containing fluids.
Milestone, et al ' , , also report that severe
attack by COZ-Rich fluid occurred within several
months for cements meeting API recommendations for
strength and permeability.
To evaluate that whether Unocal geothermal wells in
the Brawley and Geysers fields have the COZ-induced
cement carbonation problem, and whether carbonation
affects cement properties, a field cement sampling
program from abandoned wells in these two fields was
initiated in 1986. A complementary research program
was also initiated at Unocal Science & Technology
Division in 1987 to understand the mechanism of
cement carbonation and also to find out ways to
mitigate field problems.
DESCRIPTION OF \vELLS
Eleven wellhead casings were cut off about ZO-30
feet (6-10 meters) from surface from the abandoned
Brawley field in the Imperial Valley and sent to
Unocal Science & Technology in early June, 1986.
All of these wells were abandoned in 1985-1986.
Based on the cumulative injection and production
poundage, the major production wells and injection
wells are listed in TABLE 1 and TABLE Z in descen-
ding order.
Cement samples were collected from five wells in the
Geysers field, which includes one injection well,
one exploratory well and three production wells.
Only one production well wellhead was cut off and
sampled through the whole casing annuli. The other
four wells did not show much evidence of cement
carbonation. The typical production temperature of
2 EFFECTS OF CO
2
ATTACK ON CEMENT IN HIGH TEMPERATURE APPLICATIONS
this well was between 354 and 382F (179 and 194C)
and production pressure between 125 and 240 psi (0.9
and 1.7 MPa). The steam contained about 12200 ppm
CO
2
,
The typical geothermal casing design includes a
surface conductor, a surface casing, an intermediate
casing and a production casing. A typical cement
slurry for the intermediate casing consists of Class
G cement, 40% silica flour with or without light
weight additive. A typical cement slurry for the
production casing consists of Class G cement, 40%
silica flour, 2-3% gel and other additives.
FIELD SAMPLE PREPARATION
The wellheads were cut open by an abrasive saw.
Photos were taken to record the appearance of each
cement sheath. A number of steel casings were found
to be corroded but only to a minor degree.
Cement block samples were taken from the top, the
bottom and in most cases the middle locations along
the cement sheath length. A duplicate set of samples
were also taken from the opposite side of the sheath.
Most block samples were picked out of the sheaths
rather easily because of the existing fractures.
To maximize the useful information that can be
gathered under the allocated budget, a sampling
criteria was established so that the most likely
carbonated wells would be analyzed first along with
some reference samples. Cylindrical core samples of
0.88" (2.24 cm) diameter were drilled out of the
cement blocks in the radial direction for the compres-
sive strength and water permeability tests. Repre-
sentative pieces were collected for the analytical
tests.
EXPERIMENTAL
Field Samples
The cement compressive strength was determined by
crushing the cylindrical samples of about 1" (2.54
cm) height according to the ASTM C 109 test procedure.
Three to six samples were tested for each sample
location. Variation of strength measurements for the
same location was between 500 to 1000 psi (3.4 MPa to
6.9 MPa).
Similar dimension samples were also prepared and
tested for the water permeability according to the
API Spec 10-G. Two to three samples were run for
each sample location. The permeability value mea-
sured reflects the water flow tendency in the sample
block which contains fine fissures, but it does not
reflect the permeability of the overall cement
sheath, because the sheath also contains large
fractures.
The carbonate content in the cement was determined by
the wet CO
2
evolution technique. Quantitative X-ray
diffraction (XRD) was used to determine the crystal-
lographic phases and their amounts in the cement.
Scanning electron microscopy (SEM) technique was used
to reveal the morphology of the cement. One sample
was analyzed by the thermal gravimetric analysis
(TGA) to check the carbonate content.
20
Three well samples with known CaC0
3
existence were
analyzed by thin section microscopy under polarized
light. The thin section plane was parallel to the
radial cross-section of each cement sheath. The
radial distribution of CaC0
3
in the three samples
were recorded with a special Alizeran Red dye.
Research Samples
The research samples were drilled from cubes cured
by cement curing chambers under geothermal tempera-
ture and pressure. The 0.88" (2.24 cm) cylindrical
cores were then put into autoclave bombs which
contained a water reservoir. The samples were
situated above the water reservoir by a specially
designed sample holder to ensure radial CO
2
dif-
fusion into the cores. The autoclave bombs were
then put in an oven, pressured with CO
2
gas, and
heated to the desired reaction temperaEure.
Most of the analytical tests for research samples
were done similar to the methods mentioned above.
In order to measure the location of the carbonation
layer in some samples, the Electron Probe Micro
Analysis (Micro probe) was employed. The probe
measures tlle carbon distribution in the cement core
as a function of radial distance and has an accuracy
of 20%.
RESULTS AND DISCUSSION
Reaction Characteristics
The crystalline nature of Class G cement is depen-
dent on temperature. The calcium silicate hydrate
(CSH) gel is produced at low temperatures. Under
higher temperatures it will convert to other cry-
stalline phases. The mechanism of this ,onversion
is demonstrated in the following scheme:
CSH
247F Excess Ca(OH)2
-------> -------------->
> 35% Silica
-------> ---------------> Tobermorite (C5S6H5)
302F
----> Xonolite (C6S6H)
420-600F 284-572F
Truscottite <---------------------------> Scawt'te
(C7Sl2H3) Active Si0
2
C0
3
*2-
Basic Environment
The carbonation mechanism of cement involves the
conversion of calcium hydroxide C
S
(OH)2 and calcium
silicate hydrate (CxSHy) to CaC0
3
:
Ca(OH)2 + 2 (H)+ + (C0
3
)2- ==> CaC0
3
+ 2 H
2
0
2-
CxSHy + 2 (H)+ + (x-x') (C0
3
)
Cx'SHy' + (x-x') CaC0
3
+ z H
2
0
==>
When Ca(OH)2 is carbonated into CaC0
3
, its molar
volume increases from 33.6 to 36.9 cubic centi-
meters. Consequently the CaC03 formation from
Ca(OH)2 can appreciably reduce the cement perme-
ability by volume expansion. Conversely, the
3
SPE 18618 J.C. SHEN & D.S. PYE
reaction of CxSHy with CO results in a highly
polymerized silica gel a n ~ a reduction of solid
volume. This increases cement permeability.
Published data have shown that CO
2
attacks Ca(OH)2
first if a cement contains that compound. In normal
geothermal applications, where 40% silica flour is
mixed with Class G cement, the CO
2
is likely to
attack x S H ~ gegause of the lack of Ca(OH)2 in the
set cement. ' ,
Calcium carbonate is polymorphous and exists in at
least five modifications. The two commonly found in
nature are calcite and aragonite. Aragonite is
metastable at low pressures and slowly alters to
calcite. Vaterite is also a metastable form which 9
crystallizes at ordinary temperatures and pressures.
The transformation of CaC0
3
polymorphs is shown
below:
CO
2
<80F >86F
CxSHy ---> Vaterite ----> Aragonite -----> Calcite
The transformation is a slow and kinetic-limited
process.
Visual Observation of Field Samples
After the casings were cut open, the cement showed
significant visible fractures. In addition to the
visible fractures, most cement sheaths also developed
fine fissures extending from exposed surfaces into
the cement matrix. Solid deposits were found in both
types of fracture. Evidence of brine intrusion into
the fine fissures was also abundant, but there was no
signs of cement erosion or loss.
Experimental Data of Field Samples
The experimental data from the compressive strength
test, the permeability test, the wet CO
2
evolution
test and the XRD analysis for the Brawley field
samples are listed in TABLE 3. The .. s .. symbol in
sample names indicates the intermediate casing
annulus, the "P" production casing annulus and the
"Roo redrill casing annulus. Comparative measurements
at the same axial position but on the opposite side
are shown as duplicate data. Data shown for Veysey
15 production casing cement includes the two loca-
tions at the bottom of the wellhead and one at the
top for comparison.
All but the Tow 1 intermediate casing cement have
compressive strength above 1000 psi (6.9 MPa). As
expected, the intermediate casing cement is weaker
than the production casing cement because of the
lighter weight. The CaC0
3
content does not affect
compressive strength systematically, see Figure 1. A
similar lack of correlation between compressive
strength and well in-service time is apparent in
Figure 2.
Most samples have permeability above 0.1 millidarcy.
Highly fractured samples were also found to be very
permeable. Figure 3 shows that there is no good
correlation between permeability and CaC0
3
content.
When compressive strength and permeability data of
the major production wells (TABLE 1) are plotted
21
against the number of production shutdowns, as
shown in Figure 4, significant trends appear. The
data indicates that cement started to lose strength
and to gain permeability after nine production
shutdowns. Cement forms fissures when its tensile
strength is less than the thermal tensile stress
caused by a sharp temperature drop. As the cement
gets more fractured by thermal cycles, both compre-
ssive strength and permeability deteriorate.
The amount of CaC0
3
in the intermediate casing
cement of production wells and in the major injec-
tion wells is small. But in the production casing
cement of major production wells, the CaC0
3
content
ranges from 24 to 48% by weight of cement. Calcium
carbonate content derived from quantitative XRD
analysis is in fair agreement with the more accu-
rate CO
2
evolution technique. The TGA analysis of
one sample from Veysey 15 production casing cement
shows 32.2% CaC0
1
by weight, which agrees well with
CO
2
evolution meEhod.
It was found that the amount of CaC0
3
in the
production well production casing cement is direc-
tly proportional to the maximum static downhole
formation temperature, Figure 5. The data is also
listed in TABLE 4.
The rate of carbonation seems to be rather high for
the high temperature wells. It took Veysey 9 only
13 days to get 48% CaC0
3
.
The solubility of CO
2
in water at high temperature
and pressure is calculated and plotted in Figure 6.
Values of the Henry's Law coefficient for CO
2
sote-
bility in water was taken from Ellis and Golaing
To get CO
2
solubility in 75,000 ppm chloride (Cl-)
brine near 580F (304C), multiptr the solubility
from Figure 6 by a factor of 0.5 .
Since the static formation pressure in Brawley
wells is between 2000 and 3000 psi (13.4 and 20.7
MPa) , the CO
2
solubility increases rather fast in
the temperature range under considerations. Along
with the kinetic effect of higher temperature in a
hot well, the fast carbonation on Veysey 9, which
had a static pressure close to 3000 psi (20.7 MPa),
is expected.
TABLE 5 lists the XRD analysis data. The large
reading of vaterite- the initial carbonation
product- in Veysey 9 confirms that the carbonation
was rather new, only 13 production days. On the
other hand, the longer production wells, such as
Tow 1, Veysey 12 and Veysey 15, contain more
calcite and aragonite in their cement.
Halite (NaCl) and gypsum (CaS0t.) were found in most
samples, which suggests that the formation brine
intruded into the annult and deposited these two
compounds. The high temperature calcium silicate
hydrates-xonotlite and tobermorite- were found in
the hot production wells such as Veysey 12 and 15.
The redrill cement of Veysey 8 contains quartz and
portlandite (Ca(OH)2)' two typical compounds found
in a good geothermal cement.
Figure 7 shows a theoretical temperature distri-
bution during production in the cement annuli.
4 EFFECTS OF O ~ ATTACK ON CEMENT IN HIGH TEMPERATURE APPLICATIONS SPE 18618
L.
Earlier reports
4
,5,6 have suggested that cement
carbonation starts at fluid-accessible surface.
With the aid of a special dye, Alizeran Red and
polarized light, the results show that it was indeed
the case. Carbonated cement layers were found next to
the cement-casing interfaces and also next to the
cement fractures (Figure 8). The thickness of these
layers ranges from 1 to 6 millimeters. Fissures of
100 to 500 micron sizes existed extensively in Veysey
8,lZ and 15 samples and some finer fissures were
filled with CaC0
3
deposits. The demarcation between
the carbonated layer and the good cement solid matrix
was well defined in some cases and were diffuse in
other cases. Higher concentration of CaC0
3
was found
in the inner region close to the production casing.
Since the inner region was hotter during production,
higher CaC0
3
amount is expected.
It is not known why the demarcation between carbo-
nated and ,uncarbonated layers can be sharp or dif-
fuse. But since cement carbonation is a diffusion
limited chemical reaction, the temperature of cement
might have played an important role.
Figure 9 shows the existence of a CaC0
3
filled fine
fissure in Veysey 15 production casing cement.
There was no cement carbonation found in the produc-
tion well in the Geysers field. The well was by far
the most likely candidate to witness cement carbo-
nation in the five wells tested in the Geysers field.
Since the maximum production temperature was less
than 400F (Z04C) and the CO
Z
concentration was
lower than that in the Brawley field, the potential
for CO attack was much less. From Figure 5, it is
concluaed that the wells in the Geysers field may not
have serious carbonation problem due to the tempera-
ture.
Research Samples
Figure 10 shows the carbon concentration distribution
of a geothermal cement sample cured under 450F
(Z3Z0C) and 3000 psi (ZO.7 NPa) and carbonated under
450F (Z3Z0c) and 1500 psi (10.4 NPa) for three days
under water. The outer edge of this sample to the
left. The carbonatedlayer stopped at 800 microns
from the outer edge. Assuming that the carbonation
was a diffusion-limited chemical reaction and a
shrinking core model was applicable, then the CO
Z
diffusion coefficient in the cement solid matrix is
estimated to be about 8.0x10-7 cmZ/sec at the rea
Z
:
tion temperature and pressure. The average (C0
3
)
content was 16% by weight of cement.
When the geothermal cement was carbonated above water
at 400 F (Z04 C) and 1000 psi (6.9 MPa), the mechan-
ism of cement carbonation was changed to kinetics-
limited. The whole sample was carbonated uniformly,
see Figure 11. The four hour carbonated sample
contains 3.Z% (C03)Z- by wt of cement. Figure 1Z
shows the same cement carbonated for eight hours, it
contains 8.9% (C03)Z- by wt of cement.
Based on the preliminary laboratory test
can be said that the mechanism of cement
can be affected by whether the CO
Z
is in
gaseous state or is dissolved in water.
being planned to be done in this area.
results, it
carbonation
a moist
More work is
22
CONCLUSIONS
Wellhead cement samples from geothermal wells in the
Brawley and Geysersfields were collected and ana-
lyzed for carbonation. The degree of cement carbo-
nation was found to be dependent on factors such as,
temperature, CO
Z
content in the fluid and location.
No cement carbonation was found in the Geysers field
due to its low production temperature and low CO
Z
concentration.
Both the carbonated and the uncarbonated cement have
developed extensive fractures and fine fissures in
the matrix due to thermal cycles. The carbonated
cement has an acceptable level of compressive
strength, but its permeability is normally higher
than desired.
Preliminary results from laboratory cement carbo-
nation tests under simulated downhole high temper-
ature, high pressure conditions are presented. A
new analytical technique was used to measure the
depth of carbonation. The CO
Z
diffusion coefficient
in the cement solid matrix was estimated to be
8.0x10-7 cmZ/sec by this technique.
By comparing field, lab and published data, the
carbonation mechanism in high temperature cement is
found to be a function of several parameters, i.e.,
temperature, CO
Z
content in the fluid and cement
additives.
ACKNOWLEDGEMENTS
The authors wish to thank the management of Unocal
for permission to publish this article and to
gratefully thank all Uno cal personnel who were
involved in this project.
REFERENCES
1. J. P. Gallus and D. E. Pyle, "Performance of
Oil-Well Cementing Compositions in Geothermal
Wells", SPE 7591, presented at the 53rd Annual
Fall Meeting of the Society of Petroleum
Engineers, 1978.
Z. API/ERDA Task Group, "Cementing of Geothermal
Wells", Progress Report No.3, Brookhaven
National Laboratory, BNL 506Z1, 1976.
3. J. W. Hedenquest and M. K. Stewart, "Natural
COZ-Rich Steam Heated Wate'rs in the Broadlands-
Ohaaki Geothermal System, New Zealand: Their
Chemistry Distribution and Corrosive Nature",
Geothermal Resources Council, International
Symposium Energy, Hawaii, August 26-3-, 1985.
4. N. B. Milestone, L. E. Kukacka and N. Carciello,
"Effects of Carbon Dioxide Attack on Geothermal
Cement Grouts", Geothermal Resources Council,
Transactions. Vol 10, pp. 75-79, September, 1986.
5. N. B. Nilestone, T. Sugama, L. E. Kukacka and N.
Carciello, "Carbonation of Geothermal Grouts-
Part 1: CO
2
Attack at 150 C", Cement and Concrete
Research, Vol. 16, pp. 941-950, 1986.
SPE 18618 J.C. SPEN & D.S. PYE
6. N. B. Nilestone, T. Sugama, L. E. Kukacka and
N. Carciello, "Carbonation of Geothermal Grouts-
Part 2: CO
2
Attack at 250 C .. , Cement and
Concrete Research, Vol. 17, pp. 37-46, 1987.
7. L. H. Eilers, E. B. Nelson and L. K. Moran,
"High-Temperature Cement Compositions-Pectolite,
Scawtite, Truscottite, or Xonotlite: Which Do
You Want?", Journal of Petroleum Technology,
pp. 1373-1377, July, 1983.
8. D. D. Onan, "Effects of Supercritical Carbon
Dioxide on Well Cements", SPE 12593, Permian
Basin Oil & Gas Recovery Conference, Midland,
Texas, 1984.
9. W. A. Deer, R. A. Howie and J. Zussman, "An
Introduction to the Rock-Forming Minerals", John
Wiley and Sons Inc., 1966.
10. A. J. Ellis and R. M. Golding, "The Solubility
of Carbon Dioxide above 100 C in Water and in
Sodium Chloride Solutions", American Journal of
Science, Vol. 261, pp. 47-60, January, 1963.
11. A. J. Ellis and W. A. J. Mahon, "Chemistry and
Geothermal Systems", Academic Press, pp. 132,
1977 .
23
5
TABLE 1
Major Production Wells
=:::::::;::::::::: ==:::=:=::::;::::::;::::: ==:;:::
Production Maximum
Cumulative Tota 1 In-Service S ta tic
Name MMLB Days
M
Time (yr) Temp (F)
Veysey 12 7913 820 5746 Sect on 16 4.0 478
Veysey 15 3517 345 6915 Sect on 16 3.0 493 TABLE 4
Tow I 844 158 5031 Sect on 16 10.5 540 Major Production Well Data
Veysey 8 495 103 8077 Sect on 16 7.0 496
Cox I 110 26 9609 Sect on 15 8.5
:::::::;::: =============:;:;====:;:; ===
Veysey 9 59 13 7908 Sect on 16 6.5 557 Cumu. Prod. Number of Maximum Stati c
Name Days Shutdown Tempera ture, F CaC0
3
, wt%
- .. _-- ...... __ ..
-------------- ----------
Veysey 12 820 9 478 27.6
Veysey 15 245 4 493 33.5
TABLE 2 Tow 1 158 23 540 36.7
Major Injection Wells Veysey 8 103 11 496 31.2
:::::: ======::: ===-:;== =:::===::: Cox I 26 7
Veysey 9 13 3 557 48.3
Injection Maximum
Cumulative Total In-Service Static
Name MMLB Days
M
Time (,F) Temp (F)
Kruger I 7108 767 6793 Section 17 9.8 561
Veysey 8 4772 881 8077 Section 16 7.0 496
Tow 1 3192 466 5031 Section 16 10.5 540
TABLE 5
XRO Analysis
Veysey 2 3110 851 5921 Sect i on 21 10.7 440
======== ======= ========:::
Veysey 9 1566 450 7908 Section 16 6.5 557
Veysey 1 708 427 5120 Section 15 10.7 414
Name Calc. Arag. Vater. Quartz Halite Xonot. Tober. Other

TABLE 3
Experimenta I Data
Tow 1 -p mod min ptr min mod pm;n pmin CaS0
4
Veysey 1 -p pmin m; n+ min
Veysey 8 -S tra min min min min
-S min min mi n/mod pmin min
================= -p mod min min min
XRD
Compres s; ve Permeabil i ty CaCO by CO
2
CaCO
Name Strength (psi) (millidarcy) Evor. (wt%) (wtd
------------ -----------
Cox 1 -p 4980
Jimi nez 1 -p 3550
Kruger 1 -S 1730
-p 2330
Slater 1 -p 2764
Tow 1 -S 570
-p 3493 50.3 36.7 27.8
Veysey 1 -S 4660
-P 4729 0.0 1.3
Veysey 2 -p 3035
-p min min min tra mi n/mod t r/mi n
-R ptr mod min Ca(OH)2
-R mod min Ca(OH)2
Veysey 9 -p min mod min pmi n CaSO4
Veysey 12-P min min min ptr ptr min pmi n CaSO4
-P min min tra mi n/mod mod pmi n CaSO4
Veysey 15-S pm;n min min/mod pmin min
-S min mod m;n+
-S min m;n+ min+
-S m; n m; n/mod mod
-P mod tra min ptr CaSO4
-p mi n+ tra min ptr ptr min tra pmi n CaSO4
-p tra mod+ tra mod CaS0
4
Veysey 8 -S 2202, 3304 0.98, 0.61 2.8, 2.9
-p 1804, 1877 0.41, 1.91 34.0, 28.3
-R 2202, 3304 0.39, 0.55 1.1, 1.8
Veysey 9 -S 1440
-p 4620 1.19 48.3
Veysey 12 -P 4223, 6859 3.74, 5.73 31.0, 24.2 26.6 22,.5
Veysey 15 -S 2179, 1903 1.01, 1.07 0.6, 0.7 3.3
-p 7039, 4304 1.55, 0.033 33.7, 33.3 30.2
4223, ---- 0.37, --- 3.1, --- 3.2 ---
mod= moderate,
min= minor,
tr, tra= trace,
p= possible.
Calc.= Calcite,
Arag.= Aragonite,
Vater.= Vaterite,
Xonot. = Xonot lite,
Tober.= Tobermorite.
8000
7000
iii
6000
!!:.
:z:
I-
0
z 5000
w
a:
I-
.,
w
>
iii
.,
w
a:
...
2
0
(,)
1000
0


:::;
iii
<I:
w
2
a:
w
...
A
A
A
A
A
A
AA
A
A
A
A
A
10 20 30 40 50 60
CALCIUM CARBONATE CONCENTRATION
(WT%)
Figure 1. Concentration of CaCO, (wt %) vefSUS
10MD
9
8
7
6
5MO
4
3
Compr ... ive Str.ngth (pli)
A
A
A
10 20 30 40
CALCIUM CARBONATE CONCENTRATION
(WT%)
Figure 3. Perm.ability versus Calcium Carbonate
Concentration
8000
7000
6000
iii
!!:.
5000
:
l-
0
Z
w
a:
I-
4000 .,
w
>
iii
.,
w
a:
...
3000
2
0
(,)
2000
1000
SO
50
0
40

5
iii 30
<I
w
2
a:
w
...
20
10
A
50
25
SPE 1861 8
SYMBOLSA: CLASS G + 40% SILICA FLOUR
0: CLASS G + 1: 1 PERLITE
+ 40% FLOUR
A
A
A
A
A
A
A
0
A
A
AO 0
A
0
l
0
A
0
2 3 4 5 6 7 8 9 10 11
IN-SERVICE TIME (YR)
Figur.2. Brawley Field Cement Compr.ssive Strength
versus In-Service Time
6000
?-,
,,>{ 1 I ,
I
,
" \
l
I '-a
\
5000
I \ /
6 \
/
\
I /
\
/
4000
r
--j "",0
\
I"r-
\ 3000
\ /
\ ","/
\ ",,,,,,, /
\ ,
/
2000
/y"
/
/
/ 1000

- A
2 4 6 8 10 12 14 1S 18 20 22 24
NUM8ER OF PRODUCTION SHUTDOWN
Figure 4. Compressive Strength and Permeability
versus Number of Production Thermal Cycles
12
iii
!!:.
:z:
I-
0
z
w
a:
I-
.,
w

.,
.,
w
a:
...

0
(,)
50
~
~
z 50
52
~
0::
...
Z
... 40
(J
Z
0
(J
...
~ 30
Z
0
III
0::

(J
"
20
:>
U
oJ

(J
10
8
7
6
q,
6
:z:
III
oJ
~
"-
0 4
(J
III
oJ
~
iii
3
:>
oJ
0
III
2
~
400 420 440 450 480 500 620 540 560 580 600
MAXIMUM STATIC TEMPERATURE
(OF)
Figure 6. Calcium Carbonlte Concentration versus
Maximum Static Temperature
V ~ TOWl
VC12
\
\
b
\
100
'"
0...
200
"
......... __ P=1470 /
----Q---;I
P= 736
/
/
/
/
......... _ P=368 /
-0-"1
300 400 500 600
TEMPERATURE (OF)
Figure 6. Solubility of CO
2
in Woter (Totol Preuure in pli)
26
It
t
...
0::
:>
~
0::
...
...
"
...
...
500
400
300
200
100
500F
GEOTHERMAL
FLUID
GCEMENT
PLUS 40%
SILICA FLOUR
4.8"
6.7"
10.0"
I --'
STEEL
CASINGS
FORMATION
Figure 7. Clment Temperatur. Diltribution During Production
Fig. 8-Thin-section photo of Veysey 15 production casing cement.
Fig. 9-SEM photo of Veysey 15 production casing cement.
f-
Z
60.
I!l ~ 40.0
IT
W
0..
f-
~ 30.0
H
W
3:
20.0
10.0
0.0
20.0
15.0
f-
Z
m ~
IT
W
n.
H
W
3:
5.0
0.0
Fig. 10-Carbon distribution 01 a carbonated cement at 1,500 psi and 450F by Microprobe.
--_._----_ .. _--_._-----.. _-_._--_._.--_._--._----._-_.--_._-_._--- . - - .. _,
I
i
I
I
I
I
I
I
10000
IN M C R O N ~
Fig. II-Carbon distribution at 1,000 psi and 400F lor 4 hours as measured by Microprobe.
27
20.0,-----------------------
15.
l-
Z
I!I W
(J
a:
W
a.
H
W
3:
5.0
, '
, .
I

10000
MICRUNS
Fig. 12-Carbon distribution at 1,000 psi and 400'F for 8 hours as measured by Microprobe.
28