Note: Descriptions are shown in the official language in which they were submitted.
i ..
CA 02438654 2003-08-28
Composition and Method for Cementinct a Well
Background of the Inve~tn ion_
This invention relates to the construction of wells.
The invention further relates to primary cementing operations
involved in the construction of wells penetrating subterranean
formations: This invention still further relates to hydraulic
cementing compositions and methods of using them to perform
primary cementing operations.
During the construction of a well, such as an oil
and gas well, it is known in the art to place a volume of a
water slurry of a hydraulic cement into the annular space
defined between the walls of the borehole penetrating a.
subterranean formation and the exterior surface of the well
casing suspended therein. It is also known in the art to
place the slurry into the annular space defined between the
walls of concentric pipes -- such as a well casing and a liner
-- suspended in the borehole. Subsequent to placement of the
slurry further construction operations in the borehole, such
as drilling, are suspended for a time sufficient to permit the
slurry to set, that is to solidify, to thereby form a mass of
hardened cement in the annulus. The mass of hardened cement
is referred to as the sheath. The cementing procedure thus
described leading to and terminating with the construction of
the sheath is referred to as primary cementing. The
objectives of the sheath are to provide physical support and
positioning of the casing in the borehole; to bond the casing
i
CA 02438654 2003-08-28
2
to the walls of the borehole; to prevent the movement of fluid
(liquid or gas) between formations penetrated by the borehole;
and to prevent fluid from completely escaping the well at the
surface of the earth.
In addition to the above objectives, it is desirable that
the slurry set and develop sufficient compressive strength in
as short a period of time as possible after placement thereof
in order to avoid excessive delay in performing further well
construction operations. It is a generally accepted standard
in the well drilling industry that the compressive strength of
set hydraulic cement in the sheath preferably shall be at
least about 500 pounds per square inch before further
operations may be conducted, wherein the time required to
develop the strength, measured from the completion of the
placement of the slurry in the annulus, preferably shall not
exceed about 24 hours. This time delay is referred to in the
art as waiting-on-cement or simply as WoC.
When a slurry of hydraulic cement is positioned in the
desired location in the annulus, the slurry movement rapidly
changes from a moving, or dynamic, condition when being
placed, to a resting, or static, condition after being placed.
The slurry, when in the static condition and not yet set, must
immediately resist movement of formation fluid through the
slurry. Such movement, which is generally gas moving under
the influence of formation pressure, is referred to as annular
gas migration or simply as gas migration. In addition, the
slurry itself, when in the static condition, must resist any
i
CA 02438654 2003-08-28
3
movement by it into subterranean zones with which the slurry
is in communication. Such movement is generally due to the
influence of hydrostatic pressure of the slurry on the zone
and is referred to as fall back because the height of slurry
in the annulus is reduced by the quantity of slurry
penetrating the zone.
Gas migration in the slurry leads directly to gas
migration in the sheath, and can cause poor bonding of cement,
casing and borehole. Fall back can result in a reduction of
the quantity of sheath required to position and support the
casing in the borehole. Accordingly, gas migration through
the slurry and fall back of the slurry can frustrate the
stated objectives of the sheath.
This invention provides a composition for and a method of
cementing a casing in a borehole whereby gas migration and
fall back are substantially reduced if not eliminated.
It has been discovered that addition of an effective
amount of sodium aluminate to a slurry of hydraulic cement in
water can substantially improve the static gel strength of the
slurry and particularly the~rate of development thereof
whereby gas migration and fall back are substantially reduced
if not eliminated.
The expression, static gel strength, as used herein,
generally refers to the capacity of a fluid under static
conditions to resist being moved by a shear force or simply as
shear resistance. Where the fluid under consideration is a
i i
CA 02438654 2003-08-28
4
slurry of a hydraulic cement in water the expression more
specifically refers to the resistance to movement, or internal
rigidity, developed by the slurry when the slurry is not in
motion.
A slurry having a sufficiently high static gel strength
can prevent gas migration and can support its own weight to
thereby resist and prevent fall back.
It is believed that a cement slurry having a static gel
strength, SGS, of about 500 pounds per 100 square feet can
prevent the percolation of gas through the slurry, i.e.,
prevent gas migration. Also, SGS developed in the cement
slurry can prevent fall back due to resistance of the slurry
to slide tangentially against the walls of the pipe or bore-
hole. Accordingly, a slurry used in primary cementing should
develop a sufficient static gel strength as quickly as
possible. The time to develop 500 SGS, referred to herein as
transition time, is preferably in the range of from about 15
minutes to about 45 minutes after the slurry has been
positioned as desired in the annulus. A more preferred
transition time is in the range of from about 20 minutes to
about 40 minutes to develop 500 SGS. A slurry of hydraulic
cement in water, either alone or having admixed therewith the
usual cementing additives such as defoamers, fluid Loss agents
and set retarding agents, which develops 500 SGS within a
reasonable period of time is said to be a thixotropic cement.
Accordingly, by this definition, the cement slurry of this
invention is a thixotropic cement.
i
CA 02438654 2003-08-28
A slurry of hydraulic cement in water to be useful in
primary cementing must have the property of remaining
sufficiently fluid for the time required to place the slurry
in the desired position in the annulus. This time, referred
to as pumping time and also as thickening time, is measured
substantially from the time of preparation of the slurry to
the time when the slurry has developed sufficient consistency
to resist an applied torque. In more practical terms,
thickening time informs an operator of the amount of time
available to pump the volume of slurry required to be placed
into the desired location. A pumping time in the range of
from about 3 to about 6 hours is considered by persons skilled
in the art as an adequate pumping time for a slurry of
hydraulic cement in water.
As used herein, thickening time is specifically defined
as the time required for a slurry to develop 70 Bearden units
of slurry consistence or more simply 70 Bc. The measurement
of thickening time is described in Section 8, "Specification
for Materials and Testing for Well Cements," API
Specification 10 (SPEC. 10) , Fifth Edition, July 1, 1990,
Transition time, thickening time, WOC and compressive
strength development of a slurry of hydraulic cement in water
are all influenced by a number of factors including, the salt
content of the mixing water, the quantity of mixing water, the
cement itself and the temperature to which the slurry is
exposed while harde:~ing.
i
CA 02438654 2003-08-28
6
In general by decreasing slurry density, such as by
increasing the quantity of mixing water, strength development
is retarded, transition time increases, WOC increases and
compressive strength decreases. Similar results are obtained
by decreasing setting temperature environment to values of
about 180°F or lower. Addition of salt, such as sodium
chloride, to the mixing water produces a variable result,
depending upon the amount of salt. That is, low
concentrations of salt seem to produce an acceleration effect
while higher concentrations seem to produce a retardation
effect. Other alkali metal halides suitable to achieve the
desired result will be appreciated by those skilled.
The various effects alluded to above can be offset by
adding an effective amount of sodium aluminate or sodium
silicate to a given slurry. In this regard, with respect to a
given slurry, transition time, thickening time, WOC and
initial set can be accelerated and compressive strength can be
increased by adding thereto an effective amount of sodium
aluminate.
To thus demonstrate the effect of the sodium aluminate
additive, reference is made to Example 1, below, wherein several
slurries of approximately the same density, same quantity and
type of cement and same quantity and type of deaerating agent are
employed. The slurries essentially differ with respect to the
concentrations of sodium chloride and sodium aluminate.
Mixing water is varied to maintain density. A low
temperature, 91°F, is employed in the determination of
transition time and thickening time and a temperature of 110°F
i
CA 02438654 2003-08-28
7
is employed to determine initial set, WOC and 24 hour
compressive strength. Both of these temperatures would be
expected to produce a retarding effect upon the development of
the above properties.
Tables 1A and 1B demonstrate the effect on these
properties produced by increasing salt concentration wherein
Slurry 1 has no salt and Slurry 5 is salt saturated with
respect to mixing water. Tables 2A and 28 demonstrate the
effects on the above properties by the addition of various
quantities of sodium aluminate to the slurries described in
Table 1A. Notice the somewhat erratic results shown in Table
1B where no aluminate is present and compare these with the
more uniform results shown in Table 2B produced by the
addition of sodium aluminate. Compare Tables 1B and 2B and
notice, in particular, the marked acceleration of transition
time in both fresh water and salt water, as well as the
adjustment of thickening times to the desired values referred
to above; both enhancements are produced by the addition of
sodium aluminate. In addition, the development of 24 hour
compressive strength is rendered more uniform and WOC times
are all within acceptable limits. The results achieved are
all considered quite acceptable with the exception of those
for salt saturated water (37.2% by weight). Accordingly, at'
salt concentrations in the range of 0 percent to about 18
percent by weight of water improvement of the various
properties can be produced.
It is believed that satisfactory results, such as those
i
CA 02438654 2003-08-28
8
shown in. Table 2B, can be obtained, with respect to a slurry
of any given density having a salt concentration in the range
of from 0 up to about 18°s by weight of water, by adjusting the
amount of sodium aluminate relative to the amount of salt to.
values in the range of from about 0.02 to about 0.35 weight
parts aluminate per weight part of salt in the slurry. Where
salt is not present in the slurry, it is believed that the
concentration of aluminate should be in the range of from
about 0.2 to about 2.0, preferably from about 0~.4 to about 1.0
and still more preferably from about 0.6 to about 0.8 weight
parts sodium aluminate per 100 weight parts of hydraulic
cement in the slurry. where salt is present in the slurry, it
is believed that the concentration of aluminate should be in-
the range of from about 0.4 to about 6.0, preferably from
about 0.8 to about 3.0 and still more preferably in the range
of from about 1.0 to about 2.0 weight parts sodium aluminate
per 100 weight parts of hydraulic cement in the slurry.
Euample I
Ten slurries comprising hydraulic cement in water were
prepared for testing. Each slurry was formulated to produce
a density of about 15.6 to about 15.7 pounds per gallon. The
specific hydraulic cement employed in each slurry was API
Class H, as manufactured by Lonestar Cement Company, and
mixing water was that available from the tap in Duncan,
Oklahoma. Each slurry included a defoaming agent to eliminate
air entrainment. The agent was a commercially available
material known as D-AIRS' l which is polypropyl=ne glycol
I i;~
CA 02438654 2003-08-28
9
deposited on diatomaceoces earth. Sodium chloride was present
in eight of the slurries in concentrations of 6 percent, 12
percent, 18 percent and 37.2 percent salt by weight of water
in the slurry. The SGS Agent, a water solution of sodium
aluminate, was present in five of the slurries. The sodium
aluminate concentration in the solution was about 35 percent
by weight and the solution had a specific gravity of about
1.45. The solution also included a small quantity of sodium
hydroxide and had a pH of 14Ø
The specific recipe for each slurry is set out in Table
1A and Table 2A, below.
The test conditions and results are reported in Table 1B
and Table 2B, below.
CA 02438654 2003-OI8-28
1
.L I~ N ~D yD
1!l
tT
~ N o o c~ O 1n o
H
~ 1n o ~ .-i
b
w 3 -a .t3
W
0
a
~,.' r"~ N O
fly
ri O O O 01 O ~ 0
~f
U ~ o
~d
a~ 3
t~
r1 H
U
H J.~
3
V ~ 01 N CO ~O
U~ N
~ co 0 o m o ~ O 3
~' O
M 3W C
. ya .,.i
_ ~O
U~ I'~ N 00
0 o c~i o ui o 3
3 ~
w
N ~"i
0
x b
.~ ~, ~
~
.C cr1 N ~ ~ Q1 e- b
N 1
y~.~ 111 O O O O
3W ~ ~ ~
U U '
~ b
N .ri
b .-I 'd
M ~.r 3
~N .N
s~
~
~' p U
N ~, ~ r
~1
~ E-~ a U1
N ~ A
GI ~ ~ r1 N I~1
..
~ ~ ~ ~ ~ ~,
.
~
U A N N P4
3 N
i
CA 02438654 2003-08-28
11
TABLE 18 - RESULTS
~rn~ tit: tmr
,
camp. str.
z
Slurry Initial Sst~WOC~ Transition'Thickeni.og'24 IUt
No. 50 PSI 500 500 SGS 70 BC PSI
BSI
1 3:08 7:Z3 1:40 10:20 2~0
2 3:15 14:30 1:00 4:47 680
3 1:2d 4:45 1:13 ?:45 1600
4 2:54 45:38 1:08 21:31 250
8:08 25:50 2:07 25:30+ 410
' Thickening tfme and transition time determined at 91°F and 1500 psi
' Initial Set, WOC and 24 hour compressive strength determined at 110°F
and 3000 psi in ultrasonic cement
analyzer (U. S. Patent loo. 4,259,868)
i
CA 02438654 2003-08-28
12
~ ~fl !f1O M
~ N 1D f" tD r-1
CT
1.~
O . O
N
N
O
.i W !1 O~ ~ ~
.G O N r1 01 tD O ,
~Il
01.~J . . . . . ~
r1 e-1 O O O1 O IIl O
11
O ~ (/~
~ .
~r
.~ ya
O
.r1 er ~.I .~-i
N ~ W ~
y c o .- ~ 3
~
~ c~ o o rn o ui o
~ d o ,...a ,b
d
N b U
M ~
+~ ~f1 I'~ ~
.C"-.~1 N 01 ' t0 N .i.~ ~.,1
U! ~C
(=1.~.J . . . . ' . b O
~ ~ '~ ~ 3 ~
b
,,
..i
3 .-a tr tn
W
~C 't7
.~ ~ ~r .~
~ 00 N 1f'1I~
N
ri tn O O O O 1f1 O Q C'..d1
1.1
~ ~ O -a O
,..i W TJ .4
~ ~
~ ~
..~ b
O i
l.~ H N
v tr ~
a v
b .~ b
M
3
~ ~
.1-~ ri ' f.
l
~
a
n p Ul O U
~ ~ H a
H A
~ ~ N
~ ~ N M
i.~ ~ ~2 H p
~ ~ ~ ~ ~
r~- O ~d U' r- b
I I
v~ 3 U A tn to u1 c1;
i i
CA 02438654 2003-08-28
13
Table 28 - Results
Time, Hr: Min
Caap
Str.Z
SlurryInitial Set'WOC2 TransitionsTbickeningt24 1Qt
No. 50 ~si 500 500 SGS 70 Bc osi
nsi
1 2:09 4:55 0:43 5:05 2300
2 2:08 5:55 0:59 2:56 1750
3 2:13 5:35 0:29 3:34 1750'
4 2:40 7:24 0:54 5:16 1250
9:46 > 25:501:05 14:17+ 310
' Thickening Time and Transition Time determined at 91°F and 1500 psi
z Initial Set, HOC and 24 Hour Compressive Strength determined at 110°F
and 3000 psi in Oltrasoaic Cem~t
Malpzer (U. S. Patent loo. 4,259,868)
13
CA 02438654 2003-08I28i
14
As mentioned above sodium aluminate is the specific
additive employed herein to improve the thixotropic property
of a slurry of hydraulic cement in water as well as to improve
the various other properties previously mentioned. However,
it is believed that any of the well known alkali metal
aluminates or alkali silicates can be utilized in the amounts
mentioned above to achieve comparable results.
The aluminate additive useful herein cam be used in the
undiluted (dry) condition. In fact, the concentration ranges
and ratio ranges recited above are based on aluminate in
undiluted solid form: However, for matters of convenience of
use, it is advantageous to add the aluminate as a water
solution. One such useful solution contains about 35 percent
by weight sodium aluminate and 65 percent by weight water and
sufficient sodium hydroxide to adjust the pH to a value of
about 14.
In a broader sense, water solutions of aluminate useful
herein can contain in the range of from about 30 percent to
about 40 percent aluminate by weight of solution. Based upon
the concentration ranges set out previously such water
solutions can be present in a slurry of hydraulic cement in
water in the range of from about 0.67 percent to about 15
percent solution by weight of cement: The aluminate solution
is preferably present in the range of from about 1 percent~to
about 6 percent and still more preferably in the range of
about 2 percent to about 3 percent aluminate solution by
weight of cement.
i
CA 02438654 2003-08-28
It is not the desire herein to be bound by a particular
theory of operation or of attained result; however, it is
believed that the majority of the thixotropic response
observed herein is a result of bridging between initially
hydrated cement particles wherein the bridging agent is
believed to be the ionic aluminate chains which occur in the
totally ionic, high pH, aluminate solution described herein.
Accordingly, the currently preferred method of introducing the
aluminate into the slurry is by means of a high pH, water
solution thereof such as that described herein.
The term "hydraulic cement" as used herein means all
inorganic cementitious materials ef known type which comprise
compounds of calcium, aluminum, silicon, oxygen and/or sulfur
which exhibit "hydraulic activity". "Hydraulic activity" as
used herein means the chemical nature of material to set and
harden, upon being mixed with water, without contact with the
atmosphere (e.g. the ability to harden under water) due to the
interaction of the constituents of the material rather than by
evaporation of the water.
Cements of this type include common Portland cements,
fast setting or extra fast setting, sulfate resistant cements,
modified cement, alumina cements, high alumina cement, calcium
aluminate cements, and cements which contain secondary
components such as fly ash, pozzalona and the like.
Portland cements are classified by the American Society
of Testing Materials (ASTM) into five major types identified
by Roman Numerals I, II, III, IV and V and by the American
CA 02438654 2003-OI8-28
16
Petroleum Institute into at least 9 categories identified by
the letters A, B, C, D, E, F, G, H and J. The classifications
are based on chemical compositions and physical properties.
In this regard, refer to Section 2 of the above cited API
Spec. 10 for a further discussion of API cements.
The quantity of water utilized to mix with the hydraulic
cement must be in an amount sufficient to fully satisfy the
potential hydraulic activity of the cement. Such values are
specified in Section 5 of the above cited API Spec. 10. In
general, however, the quantity of water to be used is in
the range of from about 35 to about 60 weight parts water
per 100 weight parts of cement.
Cement slurries particularly useful herein which include
the aluminate additive of this invention, can have a wide
range of densities. Particularly preferre3 slurries have
densities in the range of from about 11.5 to about 22.0 and
preferably about 15 to 16 1b. slurry per gallon slurry.
Cement slurries containing the aluminate additive of this
invention exhibit thixotropic properties, as above defined,
and aid in obtaining early compressive strength at setting
temperatures in the range of from about-40°F to about 180°F.
Salt is often used in cement during oil field primary
cementing operations. The use of salt in the cement slurry
provides several advantages. First, salt containing cement
slurries bond more firmly to salt and shale sections often
found in subterranean formations. Second, when salt is
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CA 02438654 2003-08-28
17
present in the cement slurry in sufficiently large quantities,
it assists in the prevention of shale sections from Bluffing,
bridging between formation zones, and washing out, and salt
formations from leeching or washing out.
As used herein, the term salt particularly refers to
sodium chloride and to solutions which include sodium chloride
as a primary ingredient, such as sea salt. The term also
particularly includes potassium chloride and the alkali metal
halides in general.
Example II
Slurries of hydraulic cement in water were prepared and
tested to determine transition time and thickening time. The
slurries varied in density and included both fresh water, salt
water and sea water. Certain of the slurries included Halad
fluid loss additive and HR-5 retardant.
The slurry recipes are contained in Table 3A below and
the Test results are contained in Table 3B below.
Halad is a registered trademark of Halliburton Company.
It is used to designate a series of products referred to as
fluid loss additives. Additives of this type prevent the loss
of the aqueous phase of the cementing slurry to subterranean
formations. In the absence of fluid loss additives, it is
possible that the slurry density could increase to the point
where circulation pressures become unacceptably high, slurry
response properties are adversely effected, and/or formation
of a bridge in the annulus results in a premature job
termination. Additives of this type are typically cellulose
i
CA 02438654 2003-08-28
1$
derivatives, mixtures of cellulose derivatives and other
components, or synthetic polymers. Additives based on
cellulose derivatives are described in U. S. Patent 4, 455, 169,
while additives based on synthetic polymers are described in
U.S. Patent 4,555,269.
HR-5 is a registered trademark of Halliburton Company.
It is a refined sodium lignosulfonate employe3 as a cement
hydration retardant. Products of this type are described in
U.S. Patent 4,047,567.
CA 02438654 2003-08-28
19
Table 3A - Recipe
0.25% Defoamer°
SGS Sea Fresh
SlurryCment Sgeat' KC1 HaCl Water Water Density
.
~~1 L~L~ ~~~~~~ c~li~ l~l~l
'ALL
1 LeNarve'0.05 0.0 0.0 5.36 0.00 15.6
2 LeHatve 0.10 0.0 0.0 5.33 0.00 15.6
3 heHarvs 0.15 0.0 0.0 5.31 0.00 15.6
4 Lellseve0.10 0.0 0.0 6.17 0.00 15.0
LeHatve 0.08 0.0 0.0 7.98 0.00 14.0
6 LeHatve 0.35 0.0 0.0 10.54 0.00 13.0
7 LeHarve 0.30 0.0 0.0 12.37 0.00 12.5
8 LeHarve 0.15 0.0 0.0 12.39 0.00 12.5
9 LeHarve 0.15 0.0 0.0 12.39 0.00 12.5
LeHarve 0.20 0.0 0.0 12.38 0.00 12.5
11 LeHatve 0.15 3.0 0.0 0.00 5.21 15.6
12 LeHarve 0.25 3.0 0.0 0.00 7.76 14.0
13 ISH' 0.50 0.0 6 0.00 12.57 12.5
14 LSH 0.75 0.0 6 0.00 12.56 12.5
LSH 1.00 0.0 6 0.00 12.55 12.5
16 LSH 0.15 0.0 12 0.00 5.45 15.6
1? LSH 0.50 0.0 12 0.00 13.43 12.5
18 LSH 1.00 0.0 12 0.00 13.45 12.5
19 LSH ' 1.15 0.0 12 0.00 13.45 12.5
2C LSH 1.25 0.0 12 0.00 13.45 12.5
'
21 LSH 1.50 0.0 12 0.00 12.95 12.6
22 LSH - 2.00 0.0 12 0.00 11.50 12.5
23 LSH 0.20 0.0 18 0.00 5.57 15.6
24 LSH 0.30 0.0 37.2 0.00 5.82 15.6
ISH 0.40 0.0 37.2 0.00 5.78 15.6
26 LSH 0.50 0.0 37.2 0.00 5.74 15.6
'
27 LSH 0.60 0.0 37.2 0.00 5.70 15.6
28 LSH 1.00 0.0 3?.2 0.00 5.53 15.6
' LeHarve is 1lPI Class H Canent as manufactured by LaFarge Corp., LaFarge,
France
' LSH is 1PI Class H Cement as maaofactured by Lonestar Industries. ~.,
Graeavicb, Coon.
' The S8S ~qeat is aodi~a ahainate in a 354 by weight rster solution having a
specific gravity of
1.45 and a pH of 14Ø The oonceatrati~ of agent is expressed in gallons per
9~1~~lb. ssdc of pat
' The defoaaer is a vo~oerciallp available material hwn as D-lllR 1
Percent by ~rei9ht of eater
i
CA 02438654 2003-08-28
Table 3B Results
Transition Thickening
Slurry Cement Time Time
No. Type (Min) (Hr:Min)
1 LeHarve 30 3:23
2 LeHarve 10 ----
3 LeHarve 22 ----
4 LeHarve 20 ----
5 LeHarve 27 4:35
6 LeHarve 12 ----
7 LeHarve 8 ----
8 LeHarve 32 ----
9 LeHarve 23 6:30
10 LeFiarve 3 0 3 : 2 3
11 LeIiarve 2 6 2 : 5 4
12 LeHarve 18 12:15
13 LSH -- 22:50+
14 LSH -- 22:00+
15 LSH -- 7:00+
16 LSH 29 3:34
17 LSH -- 22:39
18 LSH _- 2 3 : 3 0 _. . . . .._._.
~..___
19 LSH -- 8:06
20 LSH -- 0:42
21 LSH -- 0:34
22 LSH -- 0:31
23 LSH 26 3:30
24 LSH -- 17:18+
LSH -- 16:48+
26 LSH -- 15:25+
27 LSH -- 14:17+
28 LSH -- 32:00+
