Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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SET-DELAYED CEMENT COMPOSITIONS COMPRISING PUMICE AND
ASSOCIATED METHODS
BACKGROUND
[0001] Examples relate to cementing operations and, in certain examples, to
set-
delayed cement compositions and methods of using set-delayed cement
compositions in
surface operations.
[0002] Cement compositions may be used in a variety of surface operations. For
example, a cement composition may be used to make refractory materials such as
bricks and
monolithic shapes. Similarly, cement may be used to make cement boards for use
as tiles, tile
substrates, flooring, underlays, counters, shingles, cladding, and the like.
In construction
applications, molded cement may be used to in construction operations,
including marine
construction.
[0003] A broad variety of cement compositions have been used in surface
cementing
operations. In some instances, set-delayed cement compositions have been used.
Set-delayed
cement compositions are characterized by being capable of remaining in a
pumpable fluid
state for at least about one day (e.g., at least about 7 days, about 2 weeks,
about 2 years or
more) at room temperature (e.g., about 80 F). When desired for use, the set-
delayed cement
compositions should be capable of being activated whereby reasonable
compressive strengths
are developed. For example, a cement set activator may be added to a set-
delayed cement
composition whereby the composition sets into a hardened mass. Among other
things, the
set-delayed cement composition may he suitable for use in surface
applications, for example,
where it is desired to prepare the cement composition in advance. This may
allow, for
example, the cement composition to be stored prior to its use. In addition,
this may allow, for
example, the cement composition to be prepared at a convenient location and
then transported
to the job site. Accordingly, capital expenditures may be reduced due to a
reduction in the
need for on-site bulk storage and mixing equipment. This may be particularly
useful for
applications where space and equipment may be limited.
[0004] While set-delayed cement compositions have been developed heretofore,
challenges exist with their successful use in surface cementing operations.
For example, set-
delayed cement compositions prepared with Portland cement may have undesired
gelation
issues which can limit their use and effectiveness in cementing operations.
Other set-delayed
compositions that have been developed, for example, those comprising hydrated
lime and
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quartz, may be effective in some operations but may have limited use at lower
temperatures
as they may not develop sufficient compressive strength when used in
applications where low
temperature may be an issue.
BRIEF DESCRIPTION OF THE DRAWINGS
[00051 These drawings illustrate certain aspects of some of the embodiments of
the
present method, and should not be used to limit or defme the method.
[0006] FIG. 1 illustrates a system for the preparation of a set-delayed cement
composition and subsequent delivery of the composition to a cementing
application site.
[00071 FIG. 2A illustrates the use of the set-delayed cement composition in a
molding
application.
[0008] FIG. 2B illustrates the further use of the set-delayed cement
compositions in a
molding application.
[0009] FIG. 2C illustrates the further use of the set-delayed cement
composition in a
molding application.
[0010] FIG. 3A illustrates the use of the set-delayed cement composition in
another
molding application.
[00111 FIG. 3B illustrates the further use of the set-delayed cement
composition in
another molding application.
[0012] FIG. 3C illustrates the further use of the set-delayed cement
composition in
another molding application.
DETAILED DESCRIPTION
[0013] Examples relate to cementing operations and, in certain examples, to
set-
delayed cement compositions and methods of using set-delayed cement
compositions in
surface operations. In particular examples, the set-delayed cement
compositions may be used
to make molded cement materials. In further examples, the set-delayed cement
compositions
may be used to make refractory materials such as bricks and monolithic shapes.
Similarly, the
set-delayed cement compositions may be used to make cement boards for use as
tiles, tile
substrates, flooring, underlays, counters, shingles, cladding, and the like.
Additional
examples may comprise using the set-delayed cement compositions for
construction
applications, such as home construction, marine construction, etc.
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[0014] The set-delayed cement compositions may generally comprise water,
pumice,
hydrated lime, and a set retarder. Optionally, the set-delayed cement
compositions may
further comprise a dispersant and/or a cement set activator. The set-delayed
cement
compositions may be foamed. Advantageously, the set-delayed cement
compositions may be
capable of remaining in a pumpable fluid state for an extended period of time.
For example,
the set-delayed cement compositions may remain in a pumpable fluid state for
at least about 1
day, about 2 weeks, about 2 years, or longer. Advantageously, the set-delayed
cement
compositions may develop reasonable compressive strengths after activation at
relatively low
temperatures. While the set-delayed cement compositions may be suitable for a
number of
cementing operations, they may be particularly suitable for use in
applications in which alkali
silicate reactions occur. Alkali silicate reactions may crack or deform
concrete. The set-
delayed cement compositions described herein may prevent alkali silicate
reactions from
occurring, thus mitigating cracks and deformations in any concrete in which
the set-delayed
cement composition is used.
[0015] The water may be from any source provided that it does not contain an
excess
of compounds that may undesirably affect other components in the set-delayed
cement
compositions. For example, a set-delayed cement composition may comprise fresh
water or
salt water. Salt water generally may include one or more dissolved salts
therein and may be
saturated or unsaturated as desired for a particular application. Seawater or
brines may be
suitable for use in embodiments. Further, the water may be present in an
amount sufficient to
form a pumpable slurry. In certain examples, the water may be present in the
set-delayed
cement composition in an amount in the range of from about 33% to about 200%
by weight
of the pumice. In certain examples, the water may be present in the set-
delayed cement
compositions in an amount in the range of from about 35% to about 70% by
weight of the
pumice. One of ordinary skill in the art with the benefit of this disclosure
will recognize the
appropriate amount of water for a chosen application.
[0016] Pumice may be present in the set-delayed cement compositions.
Generally,
pumice is a volcanic rock that can exhibit cementitious properties in that it
may set and
harden in the presence of hydrated lime and water. The pumice may also be
ground.
Generally, the pumice may have any particle size distribution as desired for a
particular
application. In certain examples, the pumice may have a mean particle size in
a range of from
about 1 micron to about 200 microns. The mean particle size corresponds to d50
values as
measured by particle size analyzers such as those manufactured by Malvern
Instruments,
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Worcestershire, United Kingdom. In specific examples, the pumice may have a
mean
particle size in a range of from about 1 micron to about 200 microns, from
about 5 microns to
about 100 microns, or from about 10 microns to about 50 microns. In one
particular example,
the pumice may have a mean particle size of less than about 15 microns. An
example of a
suitable pumice is available from Hess Pumice Products, Inc., Malad, Idaho, as
DS-325
lightweight aggregate, having a particle size of less than about 15 microns.
It should be
appreciated that particle sizes too small may have mixability problems while
particle sizes
too large may not be effectively suspended in the compositions. One of
ordinary skill in the
art, with the benefit of this disclosure, should be able to select a particle
size for the pumice
suitable for a chosen application.
[0017] Hydrated lime may be present in the set-delayed cement compositions. As
used herein, the term "hydrated lime" will be understood to mean calcium
hydroxide. In some
embodiments, the hydrated lime may be provided as quicklime (calcium oxide)
which
hydrates when mixed with water to form the hydrated lime. The hydrated lime
may be
included in the set-delayed cement compositions, for example, to form a
hydraulic
composition with the pumice. The hydrated lime may be included in a pumice-to-
hydrated-
lime weight ratio of about 10:1 to about 1:1 or 3:1 to about 5:1. Where
present, the hydrated
lime may be included in the set-delayed cement compositions in an amount in
the range of
from about 10% to about 100% by weight of the pumice. In some examples, the
hydrated
lime may be present in an amount ranging between any of and/or including any
of about
10%, about 20%, about 40%, about 60%, about 80%, or about 100% by weight of
the
pumice. In some examples, the cementitious components present in the set-
delayed cement
composition may consist essentially of the pumice and the hydrated lime. For
example, the
cementitious components may primarily comprise the pumice and the hydrated
lime without
any additional components (e.g., Portland cement, fly ash, slag cement) that
hydraulically set
in the presence of water. One of ordinary skill in the art, with the benefit
of this disclosure,
will recognize the appropriate amount of the hydrated lime to include for a
chosen
application.
100181 A set retarder maybe present in the set-delayed cement compositions. A
broad
variety of set retarders may be suitable for use in the set-delayed cement
compositions. For
example, the set retarder may comprise phosphonic acids, such as
ethylenediamine
tetra(methylene phosphonic acid), diethylenetriamine penta(methylene
phosphonic acid), etc.;
lignosulfonates, such as sodium lignosulfonate, calcium lignosulfonate, etc.;
salts such as
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stannous sulfate, lead acetate, monobasic calcium phosphate, organic acids,
such as citric
acid, tartaric acid, etc.; cellulose derivatives such as hydroxyl ethyl
cellulose (HEC) and
carboxymethyl hydroxyethyl cellulose (CMHEC); synthetic co- or ter-polymers
comprising
sulfonate and carboxylic acid groups such as sulfonate-functionalized
acrylamide-acrylic acid
co-polymers; borate compounds such as alkali borates, sodium naetaborate,
sodium
tetraborate, potassium pentaborate; derivatives thereof, or mixtures thereof.
Examples of
suitable set retarders include, among others, phosphonic acid derivatives. One
example of a
suitable set retarder is Micro Matrix cement retarder, available from
Halliburton Energy
Services, Inc. Generally, the set retarder may be present in the set-delayed
cement
compositions in an amount sufficient to delay the setting for a desired time.
In some
examples, the set retarder may be present in the set-delayed cement
compositions in an
amount in the range of from about 0.01% to about 10% by weight of the pumice.
In specific
examples, the set retarder may be present in an amount ranging between any of
and/or
including any of about 0.01%, about 0.1%, about 1%, about 2%, about 4%, about
6%, about
8%, or about 10% by weight of the pumice. One of ordinary skill in the art,
with the benefit
of this disclosure, will recognize the appropriate amount of the set retarder
to include for a
chosen application.
[0019] As previously mentioned, examples of the set-delayed cement
compositions
may optionally comprise a dispersant. Examples of suitable dispersants
include, without
limitation, sulfonated-formaldehyde-based dispersants (e.g., sulfonated
acetone formaldehyde
condensate), examples of which may include Daxad 19 dispersant available from
Geo
Specialty Chemicals, Ambler, Pennsylvania. Other suitable dispersants may be
polycarboxylated ether dispersants such as Liquiment 5581F and Liquiment
514L
dispersants available from BASF Corporation Houston, Texas; or Ethacryln" G
dispersant
available from Coatex, Genay, France. An additional example of a suitable
commercially
available dispersant is CFR'-3 dispersant, available from Halliburton Energy
Services, Inc.,
Houston, Texas. The Liquiment 514L dispersant may comprise 36% by weight of
the
polycarboxylated ether in water. While a variety of dispersants may be used,
polycarboxylated ether dispersants may be particularly suitable for use.
Without being limited
by theory, it is believed that polycarboxylated ether dispersants may
synergistically interact
with other components of the set-delayed cement composition. For example, it
is believed
that the polycarboxylated ether dispersants may react with certain set
retarders (e.g.,
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phosphonic acid derivatives) resulting in formation of a gel that suspends the
pumice and
hydrated lime in the composition for an extended period of time.
[0020] The dispersant may be included in the set-delayed cement compositions
in an
amount in the range of from about 0.01% to about 5% by weight of the pumice.
In specific
examples, the dispersant may be present in an amount ranging between any of
and/or
including any of about 0.01%, about 0.1%, about 0.5%, about 1%, about 2%,
about 3%, about
4%, or about 5% by weight of the pumice. One of ordinary skill in the art,
with the benefit of
this disclosure, will recognize the appropriate amount of the dispersant to
include for a
chosen application.
[0021] When desired for use, the set-delayed cement compositions may be
activated
(e.g., by combination with an activator) to set into a hardened mass. The term
"cement set
activator" or "activator", as used herein, refers to an additive that
activates a set-delayed or
heavily retarded cement composition and may also accelerate the setting of the
set-delayed,
heavily retarded, or other cement composition. By way of example, the set-
delayed cement
compositions may be activated to form a hardened mass in a time period in the
range of from
about 10 seconds to about 2 hours. For example, embodiments of the set-delayed
cement
compositions may set to form a hardened mass in a time period ranging between
any of
and/or including any of about 10 seconds, about 30 seconds, about 1 minute,
about 10
minutes, about 30 minutes, about 1 hour, or about 2 hours.
[0022] One or more cement set activators may be added to the set-delayed
cement
compositions. Examples of suitable cement set activators include, but are not
limited to:
zeolite& amines such as triethanolamine, diethanolamine; silicates such as
sodium silicate;
zinc formate; calcium acetate; Groups IA and HA hydroxides such as sodium
hydroxide,
magnesium hydroxide, and calcium hydroxide; monovalent salts such as sodium
chloride;
divalent salts such as calcium chloride; nanosilica (Le., silica having a
particle size of less
than or equal to about 100 nanometers); polyphosphates; and combinations
thereof. In some
embodiments, a combination of the polyphosphate and a monovalent salt may be
used for
activation. The monovalent salt may be any salt that dissociates to form a
monovalent cation,
such as sodium and potassium salts. Specific examples of suitable monovalent
salts include
potassium sulfate, and sodium sulfate. A variety of different polyphosphates
may be used in
combination with the monovalent salt for activation of the set-delayed cement
compositions,
including polymeric metaphosphate salts, phosphate salts, and combinations
thereof. Specific
examples of polymeric metaphosphate salts that may be used include sodium
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hexametaphosphate, sodium trimetaphosphate, sodium tetrametaphosphate, sodium
pentametaphosphate, sodium heptametaphosphate, sodium octametaphosphate, and
combinations thereof. A specific example of a suitable cement set activator
comprises a
combination of sodium sulfate and sodium hexametaphosphate. In a specific
example, the
activator may be provided and added to the set-delayed cement composition as a
liquid
additive, for example, a liquid additive comprising a monovalent salt, a
polyphosphate, and
optionally a dispersant.
[0023] Some embodiments may include a cement set activator comprising
nanosilica.
As used herein, the term "nanosilica" refers to silica having a particle size
of less than or
equal to about 100 nanometers ("nm"). The size of the nanosilica may be
measured using any
suitable technique. It should be understood that the measured size of the
nanosilica may vary
based on measurement technique, sample preparation, and sample conditions such
as
temperature, concentration, etc. One technique for measuring the particle size
of the
nanosilica is Transmission Electron Microscopy (TEM). An example of a
commercially
available product based on laser diffraction is the ZETASIZER Nano ZS particle
size
analyzer supplied by Malvern Instruments, Worcerstershire, UK. In some
examples, the
nanosilica may comprise colloidal nanosilica. The nanosilica may he stabilized
using any
suitable technique. In some examples, the nanosilica may be stabilized with a
metal oxide,
such as lithium oxide, sodium oxide, potassium oxide, and/or a combination
thereof.
Additionally the nanosilica may be stabilized with an amine and/or a metal
oxide as
mentioned above. Without limitation by theory, it is believed that the
nanosilicas have an
additional advantage in that they have been known to fill in pore space in
cements which can
result in superior mechanical properties in the cement after it has set.
(00241 Some examples may include a cement set activator comprising a
combination
of a monovalent salt and a polyphosphate. The monovalent salt and the
polyphosphate may
be combined prior to addition to the set-delayed cement composition or may be
separately
added to the set-delayed cement composition. The monovalent salt may be any
salt that
dissociates to form a monovalent cation, such as sodium and potassium salts.
Specific
examples of suitable monovalent salts include potassium sulfate and sodium
sulfate. A
variety of different polyphosphates may be used in combination with the
monovalent salt for
activation of the set-delayed cement compositions, including polymeric
metaphosphate salts,
phosphate salts, and combinations thereof, for example. Specific examples of
polymeric
metaphosphate salts that may be used include sodium hexametaphosphate, sodium
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trimetaphosphate, sodium tetrarnetaphosphate, sodium pentametaphosphate,
sodium
heptametaphosphate, sodium octametaphosphate, and combinations thereof. A
specific
example of a suitable cement set activator comprises a combination of sodium
sulfate and
sodium hexametaphosphate. Interestingly, sodium hexametaphosphate is also
known in the
art to be a strong retarder of Portland cements. Because of the unique
chemistry of
polyphosphates, polyphosphates may be used as a cement set activator for the
set-delayed
cement compositions disclosed herein. The ratio of the monovalent salt to the
polyphosphate
may range, for example, from about 5:1 to about 1:25 or from about 1:1 to
about 1:10. In
some examples the cement set activator may comprise the monovalent salt and
the
polyphosphate salt in a ratio (monovalent salt to polyphosphate) ranging
between any of
and/or including any of about 5:1, 2:1, about 1:1, about 1:2, about 1:5, about
1:10, about
1:20, or about 1:25.
[0025] In some examples, the combination of the monovalent salt and the
polyphosphate may be mixed with a dispersant and water to form a liquid
additive for
activation of a set-delayed cement composition. Examples of suitable
dispersants include,
without limitation, the previously described dispersants, such as sulfonated-
formaldehyde-
based dispersants and polycarboxylated ether dispersants. One example of a
suitable
sulfonated-formaldehyde-based dispersant is a sulfonated acetone formaldehyde
condensate,
available from Halliburton Energy Services, Inc., as CFR-3' dispersant. One
example of a
suitable polycarboxylated ether dispersant is Liquiment 514L or 5581F
dispersants,
available from BASF Corporation, Houston, Texas.
[0026] The cement set activator may be added to the set-delayed cement
composition
in an amount sufficient to induce the set-delayed cement composition to set
into a hardened
mass. For example, the cement set activator may be added to the set-delayed
cement
composition in an amount in the range of about 0.1% to about 20% by weight of
the pumice.
In specific examples, the cement set activator may be present in an amount
ranging between
any of and/or including any of about 0.1%, about 1%, about 5%, about 10%,
about 15%, or
about 20% by weight of the pumice. One of ordinary skill in the art, with the
benefit of this
disclosure, will recognize the appropriate amount of cement set activator to
include for a
chosen application.
[0027] Other additives suitable for use in subterranean cementing operations
also may
be included in examples of the set-delayed cement compositions. Examples of
such additives
include, but are not limited to: weighting agents, lightweight additives,
mechanical-property-
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enhancing additives, fluid-loss-control additives, defoaming agents, foaming
agents, and
combinations thereof. One or more of these additives may be added to the set-
delayed cement
compositions after storing but prior to the placement of a set-delayed cement
composition
into a subterranean formation. A person having ordinary skill in the art, with
the benefit of
this disclosure, should readily be able to determine the type and amount of
additive useful for
a particular application and desired result.
[0028] Weighting agents may be included in the set-delayed cement
compositions.
Weighting agents are typically materials that weigh more than water and may be
used to
increase the density of the set-delayed cement compositions. By way of
example, weighting
agents may have a specific gravity of about 2 or higher (e.g., about 2, about
4, etc.).
Examples of weighting agents that may be used include, but are not limited to,
hematite,
hausmannite, barite, and combinations thereof. Specific examples of suitable
weighting
agents include HI-DENSE weighting agent, available from Halliburton Energy
Services,
Inc.
[0029] Lightweight additives may be included in the set-delayed cement
compositions, for example, to decrease the density of the set-delayed cement
compositions.
Examples of suitable lightweight additives include, but are not limited to,
bentonite, coal,
diatomaceous earth, expanded perlite, fly ash, gilsonite, hollow microspheres,
low-density
elastic beads, nitrogen, pozzolan-bentonite, sodium silicate, combinations
thereof, or other
lightweight additives known in the art. The resin compositions may generally
have lower
base densities than the set-delayed cement compositions, thus hollow glass
beads and/or foam
may be suitable lightweight additives for the set-delayed cement compositions,
dependent
upon the base densities of the set-delayed cement compositions.
[0030] Optionally, cement foaming additives may be included in the set-delayed
cement compositions, for example, to facilitate foaming and/or stabilize the
resultant foam
formed therewith. The foaming additive may include a surfactant or combination
of
surfactants that reduce the surface tension of the water. As will be
appreciated by those of
ordinary skill in the art, the foaming additives may be used in conjunction
with a gas to
produce a foamed set-delayed cement compositions. By way of example, the
foaming agent
may comprise an anionic, nonionic, amphoteric (including zwitterionic
surfactants), cationic
surfactant, or mixtures thereof. Examples of suitable foaming additives
include, but are not
limited to: betaines; anionic surfactants such as hydrolyzed keratin; amine
oxides such as
alkyl or alkene dimethyl amine oxides; cocoamidopropyl dimethylamine oxide;
methyl ester
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sulfonates; alkyl or alkene arnidobetaines such as cocoamidopropyl betaine;
alpha-olefin
sulfonates; quatemary surfactants such as trimethyltallowammonium chloride and
trimethylcocoammonium chloride; C8 to C22 alkylethoxylate sulfates; and
combinations
thereof. Specific examples of suitable foaming additives include, but are not
limited to:
mixtures of an ammonium salt of an alkyl ether sulfate, a cocoamidopropyl
betaine
surfactant, a cocoamidopropyl dimethylamine oxide surfactant, sodium chloride,
and water;
mixtures of an ammonium salt of an alkyl ether sulfate surfactant, a
cocoamidopropyl
hydroxysultaine surfactant, a cocoamidopropyl dimethylamine oxide surfactant,
sodium
chloride, and water; hydrolyzed keratin; mixtures of an ethoxylated alcohol
ether sulfate
surfactant, an alkyl or alkene amidopropyl betaine surfactant, and an alkyl or
alkene
dimethylamine oxide surfactant; aqueous solutions of an alpha-olefinic
sulfonate surfactant
and a betaine surfactant; and combinations thereof. An example of a suitable
foaming
additive is ZONESEALANTTm 2000 agent, available from Halliburton Energy
Services, Inc.
[0031] Optionally, set accelerators for the set-delayed cement compositions
may be
included in the set-delayed cement compositions, for example, to increase the
rate of setting
reactions. Control of setting time may allow for the ability to adjust to
wellbore conditions or
customize set times for individual jobs. Examples of suitable set accelerators
may include,
but are not limited to, aluminum sulfate, alums, calcium chloride, calcium
sulfate, gypsum-
hemihydrate, sodium aluminate, sodium carbonate, sodium chloride, sodium
silicate, sodium
sulfate, ferric chloride, or a combination thereof. For example, aluminum
sulfate may be used
to accelerate the setting time of the set-delayed cement compositions for
surface uses which
may require fast setting, for example, roadway repair, consumer uses, etc. The
cement set
accelerators may be added alongside any cement set activators when setting of
the set-
delayed cement compositions is desired. Alternatively, the set accelerators
may be added
before the cement set activator if desired, and if the set accelerator does
not induce premature
setting. Without being limited by theory, aluminum sulfate may promote the
formation of
sulfate containing species (e.g., ettringite) which may modify the rheology of
the matrix
during hydration such that textural uniformity and adherence to a surface is
improved. Set
accelerators may produce a set-delayed cement composition with a thickening
time of less
than 10 minutes, alternatively less than 5 minutes, alternatively, less than 1
minute, or further
alternatively less than 30 seconds.
[0032] Optionally, mechanical-property-enhancing additives for set-delayed
cement
compositions may be included in the set-delayed cement compositions, for
example, to
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ensure adequate compressive strength and long-term structural integrity. These
properties can
be affected by the strains, stresses, temperature, pressure, and impact
effects from a
subterranean environment. Examples of mechanical-property-enhancing additives
include,
but are not limited to, carbon fibers, glass fibers, metal fibers, mineral
fibers, silica fibers,
polymeric elastomers, latexes, and combinations thereof.
[0033] Optionally, fluid-loss-control additives for cement may be included in
the set-
delayed cement compositions, for example, to decrease the volume of fluid that
is lost.
Properties of the set-delayed cement compositions may be significantly
influenced by their
water content. The loss of fluid can subject the set-delayed cement
compositions to
degradation or complete failure of design properties. Examples of suitable
fluid-loss-control
additives include, but not limited to, certain polymers, such as hydroxyethyl
cellulose,
carboxymethylhydroxyethyl cellulose, copolymers of 2-acrylamido-2-
methylpropanesulfonic
acid and acrylamide or N,N-dimethylacrylamide, and graft copolymers comprising
a
backbone of lignin or lignite and pendant groups comprising at least one
member selected
from the group consisting of 2-acrylamido-2-methylpropanesulfonic acid,
acrylonitrile, and
N,N-dimethylacrylamide.
[0034] Optionally, cement defoaming additives may be included in the set-
delayed
cement compositions, for example, to reduce the tendency of the set-delayed
cement
compositions to foam during mixing and pumping of the set-delayed cement
compositions.
Examples of suitable defoaming additives include, but are not limited to,
polyol silicone
compounds. Suitable defoaming additives are available from Halliburton Energy
Services,
Inc., under the product name D-AIRTm defoamers.
[0035] Optionally, fibers may be included in the set-delayed cement
compositions, for
example, to enhance the tensile and ductile properties the set-delayed cement
compositions.
Examples of suitable fibers include, but are not limited to, polyvinylalcohol,
polypropylene,
carbon, glass etc. Further, the fluidic nature and storage capabilities of the
set-delayed cement
composition allow for fibers which may, in other compositions, require high
shear and high
pressure pumping conditions for dispersion, to be dispersed using low. This is
particularly
advantageous in systems where the fibers may bridge and plug pumping
equipment.
[0036] Optionally, refractory materials may be included in the set-delayed
cement
compositions, for example, to provide a set-delayed cement composition with
higher heat
resistance. Examples of suitable refractory materials include, but are not
limited to, alumina,
titanium, fire brick grog, etc. These refractory materials may be of
particular importance in
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applications where fire and heat resistance is particularly important, for
example, in consumer
applications in the home.
[0037] The set-delayed cement compositions may possess properties beneficial
for
use in concrete applications. For example, in a typical concrete formulation,
the aggregate
(e.g., chert, quartzite, opal, strained quartz crystals, etc.) may be
dissolved by the basic pore
solution of the cement in what is known as an alkali silicate reaction. The
dissolved portion
of the aggregate may then react with calcium species present in the cement
pore solution to
form a calcium-silicate-hydrate gel. This alkali silicate reaction may be
represented by
Equation 1 below:
Ca(OH)2 + H4SiO4 ¨> Ca' + H2Si042- + 2H20 ¨> CaH2Sia42H20
(Eq. 1)
The calcium-silicate-hydrate gel formed from the aggregate, effectively
increases the size of
the aggregate. This increase in size may exert a force on the surrounding
cement that
consequently causes cracks or deformations in the surrounding cement. Without
limitation by
theory, it is believed that the set-delayed cement compositions may prevent or
mitigate any
alkali silicate reactions by binding the alkali materials present, increasing
the tensile strength
of the concrete, and/or by reducing the dissolution rate of the aggregate
(e.g., the set-delayed
cement compositions may have a pore solution pH of 12.5 as compared to a pH of
13.2 for
standard concrete). Furthermore the set-delayed cement composition may be
formulated such
that the hydrated lime may be completely consumed by the pumice and thus
prevent any
initial dissolution of the aggregate.
[0038] The set-delayed cement compositions may be used in prefabrication
applications. The prefabrication applications may be continuous or
noncontinuous as desired.
The set-delayed cement compositions may be used with molds, dies, extruders,
etc. to be
conformed to various shapes, structures, sizes, etc. The set-delayed cement
compositions may
be used to form tiles, flooring, underlay, counters, backsplashes, roofing,
shingles, shales,
weatherboard, façade cladding, prefabricated houses, exterior and partition
walls, acoustic
and thermal insulation, soffits, ceilings, architraves, bricks, monolithic
shapes, etc. The
materials may have a high heat resistance. Further, refractory materials may
be added to the
materials to increase the heat resistance. The materials may be dyed or may
comprise
decorative aggregate such as glitter or beads if desired. The materials formed
from the set-
delayed cement compositions may also be used in various construction
applications, for
example, in marine construction, home construction, etc.
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[0039] As previously mentioned, the set-delayed cement compositions may have a
delayed set in that they remain in a pumpable fluid state for at least one day
(e.g., at least
about 1 day, about 2 weeks, about 2 years or more) at room temperature (e.g.,
about 80 F) in
quiescent storage. For example, the set-delayed cement compositions may remain
in a
pumpable fluid state for a period of time from about 1 day to about 7 days or
more. In some
examples, the set-delayed cement compositions may remain in a pumpable fluid
state for at
least about 1 day, about 7 days, about 10 days, about 20 days, about 30 days,
about 40 days,
about 50 days, about 60 days, or longer. A fluid is considered to be in a
pumpable fluid state
where the fluid has a consistency of less than 70 Bearden units of consistency
("Bc"), as
measured on a pressurized consistometer in accordance with the procedure for
determining
cement thickening times set forth in API RP Practice 10B-2, Recommended
Practice for
Testing Well Cements, First Edition, July 2005.
[0040] Those of ordinary skill in the art will appreciate that the set-delayed
cement
compositions should have a density suitable for a particular application. By
way of example,
the set-delayed cement compositions may have a density in the range of from
about 4 pounds
per gallon ("lb/gal") to about 20 lb/gal. In certain examples, the set-delayed
cement
compositions may have a density in the range of from about 8 lb/gal to about
17 lb/gal.
Examples of the set-delayed cement compositions may be foamed or unfoamed or
may
comprise other means to reduce their densities, such as hollow microspheres,
low-density
elastic beads, or other density-reducing additives known in the art. In
examples, the density
may be reduced after storing the composition, but prior to placement in a
subterranean
formation. Those of ordinary skill in the art, with the benefit of this
disclosure, will recognize
the appropriate density for a particular application. In some examples, the
set-delayed cement
compositions may set to have a desirable compressive strength after
activation. Compressive
strength is generally the capacity of a material or structure to withstand
axially directed
pushing forces. The compressive strength may be measured at a specified time
after the set-
delayed cement composition has been activated and the resultant composition is
maintained
under specified temperature and pressure conditions. Compressive strength can
be measured
by either destructive or non-destructive methods. The destructive method
physically tests the
strength of treatment fluid samples at various points in time by crushing the
samples in a
compression-testing machine. The compressive strength is calculated from the
failure load
divided by the cross-sectional area resisting the load and is reported in
units of pound-force
per square inch (psi). Non-destructive methods may employ a UCA ultrasonic
cement
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analyzer, available from Fann Instrument Company, Houston, TX. Compressive
strength
values may be determined in accordance with API RP 10B-2, Recommended Practice
for
Testing Well Cements, First Edition, July 2005.
[0041] By way of example, the set-delayed cement compositions may develop a 24-
hour compressive strength in the range of from about 50 psi to about 5000 psi,
alternatively,
from about 100 psi to about 4500 psi, or alternatively from about 500 psi to
about 4000 psi.
In some examples, the set-delayed cement compositions may develop a
compressive strength
in 24 hours of at least about 50 psi, at least about 100 psi, at least about
500 psi, or more. In
some examples, the compressive strength values may be determined using
destructive or non-
destructive methods at a temperature ranging from 100 F to 200 F.
[0042] In some examples, the set-delayed cement compositions may have
desirable
thickening times after activation. Thickening time typically refers to the
time a fluid, such as
a set-delayed cement composition, remains in a fluid state capable of being
pumped. A
number of different laboratory techniques may be used to measure thickening
time. A
pressurized consistometer, operated in accordance with the procedure set forth
in the
aforementioned API RP Practice 10B-2, may be used to measure whether a fluid
is in a
pumpable fluid state. The thickening time may be the time for the treatment
fluid to reach 70
Bc and may be reported as the time to reach 70 Bc. The thickening time may be
modified for
any temperature at atmospheric pressure by modification of the formula,
concentration of
additives (e.g. activator/accelerator), etc. In some examples, the set-delayed
cement
compositions may have a thickening time at atmospheric pressure and surface
temperatures
between about 30 seconds to about 10 hours. For example, the set-delayed
cement
compositions may have a thickening time of greater than about 30 seconds,
greater than about
1 minute, greater than about 10 minutes, greater than about 1 hour, or greater
than about 10
hours_
[0043] In some examples, a set-delayed cement composition may be provided that
comprises water, pumice, hydrated lime, a set retarder, and optionally a
dispersant. The set-
delayed cement composition may be stored, for example, in a vessel or other
suitable
container. The set-delayed cement composition may be permitted to remain in
storage for a
desired time period. For example, the set-delayed cement composition may
remain in storage
for a time period of about 1 day or longer. For example, the set-delayed
cement composition
may remain in storage for a time period of about I day, about 2 days, about 5
days, about 7
days, about 10 days, about 20 days, about 30 days, about 40 days, about 50
days, about 60
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days, or longer. In some examples, the set-delayed cement composition may
remain in
storage for a time period in a range of from about 1 day to about 7 days or
longer. Thereafter,
the set-delayed cement composition may be activated, for example, by addition
of a cement
set activator, used in a cementing or concrete application and allowed to set
in the course of
said application.
[0044] A method of forming a set cement shape may be provided. The method may
be used in conjunction with one or more of the methods, compositions, and/or
systems
illustrated in FIGs. 1-3. The method may comprise providing a set-delayed
cement
composition comprising water, pumice, hydrated lime, and a set retarder;
forming the set-
delayed cement composition into a shape; and allowing the shaped set-delayed
cement
composition to set. The set retarder may comprise at least one retarder
selected from the
group consisting of a phosphate, a phosphonate, a phosphonic acid, a
phosphonic acid
derivative, a lignosulfonate, a salt, an organic acid, a carboxymethylated
hydroxyethylated
cellulose, a synthetic co- or ter-polymer comprising sulfonate and carboxylic
acid groups, a
borate compound, and any mixture thereof. The set-delayed cement composition
may further
comprise a cement set activator selected from the group consisting of a
zeolite, amine,
silicate, Group IA hydroxide, Group HA hydroxide, monovalent salt, divalent
salt, nanosilica,
polyphosphate, and any combination thereof. The set-delayed cement composition
comprising the cement set activator may further comprise a thickening time in
a range
between about 30 seconds to about 10 minutes. The set-delayed cement
composition may
further comprise a fiber. The set-delayed cement composition may further
comprise a
dispersant selected from the group consisting of a sulfonated-formaldehyde-
based dispersant,
a polycarboxylated ether dispersant, and any combination thereof. Prior to the
forming step,
the set-delayed cement composition may be stored for a period of at least
about 1 day.
Forming the set-delayed cement composition into a shape may comprise forming
the set-
delayed cement composition using at least one of a mold, extruder, die, or a
combination
thereof. The method may be a continuous process. The set shaped set-delayed
cement
composition may comprise a shaped set-delayed cement product selected from the
group
consisting of a tile, flooring, underlay, a counter, a backsplash, roofing, a
shingle, a shale,
weatherboard, façade, cladding, a prefabricated house, an exterior wall, a
partition wall,
acoustic insulation, thermal insulation, a soffit, a ceiling, an architrave, a
brick, a monolithic
shape, and any combination thereof. The set-delayed cement composition may
comprise a
refractory material. The set-delayed cement composition may comprise a dye
and/or a bead.
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[0045] A method of forming a molded set cement may be provided. The method may
be used in conjunction with one or more of the methods, compositions, and/or
systems
illustrated in FIGs. 1-3. The method may comprise providing a set-delayed
cement
composition comprising water, pumice, hydrated lime, and a set retarder;
introducing the set-
delayed cement composition into a mold; and allowing the set-delayed cement
composition to
set in the mold. The set retarder may comprise at least one retarder selected
from the group
consisting of a phosphate, a phosphonate, a phosphonic acid, a phosphonic acid
derivative, a
lignosulfonate, a salt, an organic acid, a carboxymethylated hydroxyethylated
cellulose, a
synthetic co- or ter-polymer comprising sulfonate and carboxylic acid groups,
a borate
compound, and any mixture thereof. The set-delayed cement composition may
further
comprise a cement set activator selected from the group consisting of a
zeolite, amine,
silicate, Group IA hydroxide, Group IIA hydroxide, monovalent salt, divalent
salt, nanosilica,
polyphosphate, and any combination thereof. The set-delayed cement composition
comprising the cement set activator may further comprise a thickening time in
a range
between about 30 seconds to about 10 minutes. The set-delayed cement
composition may
further comprise a fiber. The set-delayed cement composition may further
comprise a
dispersant selected from the group consisting of a sulfonated-formaldehyde-
based dispersant,
a polycarboxylated ether dispersant, and any combination thereof. Prior to the
introducing
step, the set-delayed cement composition may be stored for a period of at
least about 1 day.
The introducing the set-delayed cement composition into a mold may comprise
extruding the
set-delayed cement composition through an extruder into the mold. The method
may be a
continuous process. The set molded set-delayed cement composition may comprise
a molded
set-delayed cement product selected from the group consisting of a tile,
flooring, underlay, a
counter, a backsplash, roofing, a shingle, a shale, weatherboard, façade,
cladding, a
prefabricated house, an exterior wall, a partition wall, acoustic insulation,
thermal insulation,
a soffit, a ceiling, an architrave, a brick, a monolithic shape, and any
combination thereof.
The set-delayed cement composition may comprise a refractory material. The set-
delayed
cement composition may comprise a dye and/or a bead.
[0046] A system may be provided. The system may be used in conjunction with
one
or more of the methods, compositions, and/or systems illustrated in FIGs. 1-3.
The system
may comprise a set-delayed cement composition comprising: water, pumice,
hydrated lime,
and a set retarder, wherein the set-delayed cement composition is capable of
remaining in a
pumpable fluid state for at least about one day at about 80 F; a cement
set activator; a
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vessel capable of containing the set-delayed cement composition, and a mold.
The system
may further comprise an extruder. The set-delayed cement composition may
further comprise
a fiber. The set retarder may comprise at least one retarder selected from the
group consisting
of a phosphate, a phosphonate, a phosphonic acid, a phosphonic acid
derivative, a
lignosulfonate, a salt, an organic acid, a carboxymethylated hydroxyethylated
cellulose, a
synthetic co- or ter-polymer comprising sulfonate and carboxylic acid groups,
a borate
compound, and any mixture thereof. The set-delayed cement composition may
further
comprise a cement set activator selected from the group consisting of a
z,eolite, amine,
silicate, Group IA hydroxide, Group IIA hydroxide, monovalent salt, divalent
salt, nanosilica,
polyphosphate, and any combination thereof. The set-delayed cement composition
comprising the cement set activator may further comprise a thickening time in
a range
between about 30 seconds to about 10 minutes. The set-delayed cement
composition may
further comprise a fiber. The set-delayed cement composition may further
comprise a
dispersant selected from the group consisting of a sulfonated-formaldehyde-
based dispersant,
a polycarboxylated ether dispersant, and any combination thereof.
[0047] Referring now to FIG. 1, the preparation of a set-delayed cement
composition
in accordance with the examples described herein will now be described. FIG. 1
illustrates a
fluid handling system 2 for the preparation of a set-delayed cement
composition and
subsequent delivery of the composition to a cementing application site. As
shown, the set-
delayed cement composition may be mixed and/or stored in a vessel 4. Vessel 4
may be any
such vessel suitable for containing and/or mixing the set-delayed cement
composition,
including, but not limited to drums, barrels, tubs, bins, jet mixers, re-
circulating mixers, batch
mixers, and the like. The set-delayed cement composition may then be pumped
via pumping
equipment 6. In some embodiments, the vessel 4 and the pumping equipment 6 may
be
disposed on one or more cementing units as will be apparent to those of
ordinary skill in the
art. In some embodiments, a jet mixer may be used, for example, to
continuously mix the
lime/settable material with the water as it is being pumped to the wellbore.
In set-delayed
embodiments, a re-circulating mixer and/or a batch mixer may be used to mix
the set-delayed
cement composition, and the activator may be added to the mixer as a powder
prior to
pumping the cement composition downhole. Additionally, batch mixer type units
for the
slurry may be plumbed in line with a separate tank containing a cement set
activator. The
cement set activator may then be fed in-line with the slurry as it is pumped
out of the mixing
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unit. Further, in embodiments requiring a concrete, aggregate may be mixed
with the set-
delayed cement composition in vessel 4 before being pumped via pumping
equipment 6.
[0048] FIGs. 2A ¨ 2C illustrate the use of the set-delayed cement composition
in an
injection molding application. Vessel 4 may be used a store a set delayed
cement
composition. Activator injector 8 may be used to store a cement set activator.
The set-delayed
cement composition disposed within vessel 4 may be pumped into injection line
10 where it
may be mixed with cement set activator from activator injector 8. The mixture
of set-delayed
cement composition and cement set activator may be injected into a mold 12
comprising a
top portion 14 and bottom portion 16. As shown by FIG. 2B, heat and pressure
may be
applied to mold 12 and top portion 14 may be pressed together with bottom
portion 16. After
a desired interval of time has passed, the bottom portion 16 of mold 12 may be
separated
from the top portion 14, revealing a set cement product 18. Set cement product
18 may
comprise a shape, size, or general product type as determined by the mold 12.
Examples of
set cement product 18 may include, but should not be limited to, tiles,
flooring, underlay,
counters, backsplashes, roofing, shingles, shales, weatherboard, façade
cladding,
prefabricated houses, exterior and partition walls, acoustic and thermal
insulation, soffits,
ceilings, architraves, bricks, monolithic shapes, etc. The materials may have
a high heat
resistance. Further, refractory materials may be added to the materials to
increase the heat
resistance. The materials may be dyed or may comprise decorative aggregate
such as glitter
or beads if desired. The materials formed from the set-delayed cement
compositions may also
be used in various construction applications, for example, in marine
construction, home
construction, etc.
[0049] FIGs. 3A ¨ 3C illustrate the use of the set-delayed cement composition
in a
casting application. A cast mold 20 comprising a top portion 14 and a bottom
portion 16 is
illustrated on FIG. 3A. The top portion 14 may comprise an opening 22 and
vents 24. A
hollow cavity 26 may be formed on the interior of cast mold 20 by the interior
surfaces of top
portion 14 and bottom portion 16. As shown in FIG. 3B, vessel 4 may be used to
store a set
delayed cement composition that has been mixed with a cement set activator to
form an
activated set-delayed cement composition 28. Activated set-delayed cement
composition 28
may be poured into opening 22 such that the activated set-delayed cement
composition 28
fills the hollow cavity 26 within cast mold 20. The activated set-delayed
cement composition
28 may then be allowed to set. After the activated set-delayed cement
composition 28 has set,
the top portion 14 of cast mold 20 may be removed to reveal set cement product
18. Set
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cement product 18 may comprise and shape, size, or general product type as
determined by
the mold 12. Examples of set cement product 18 may include, but should not be
limited to
tiles, flowing, underlay, counters, backsplashes, roofing, shingles, shales,
weatherboard,
façade cladding, prefabricated houses, exterior and partition walls, acoustic
and thermal
insulation, soffits, ceilings, architraves, bricks, monolithic shapes, etc.
The materials may
have a high heat resistance. Further, refractory materials may be added to the
materials to
increase the heat resistance. The materials may be dyed or may comprise
decorative
aggregate such as glitter or beads if desired. The materials formed from the
set-delayed
cement compositions may also be used in various construction applications, for
example, in
marine construction, home construction, etc.
[0050] A specific example of a molding application is the prefabrication of
cement
boards. Cement boards may be pre-formed from a mixture of the disclosed set-
delayed
cement compositions and reinforcing fibers. Optionally the boards may comprise
an
aggregate such as sand or fly ash. Some of the applications using cement
boards may
comprise tile substrates, flooring, underlay, counters, backsplashes, roofing,
shingles, shales,
weatherboard, façade, cladding, prefabricated houses, exterior and partition
walls, acoustic
and thermal insulation, soffits, ceilings, architraves, and the like. Further,
cement boards
made from the set-delayed cement compositions disclosed herein may replace
Portland
cement made cement boards. The set-delayed cement compositions disclosed
herein produce
less CO2 during manufacture relative to Portland cement, and thus, provide an
environmental
advantage over Portland cement.
[0051] Additional examples may comprise using a set-delayed cement composition
with an extruder. For example, a set-delayed cement composition may be mixed
with a
cement set accelerator (and any optional fibers or dyes as desired) and then
metered and
pumped to an extruder where it may be heated and further mixed. The extruder
may act as a
pump to meter the activated set-delayed cement composition into dies that form
a
predesigned shape (e.g., a tile). Optionally, the shapes may be formed
continuously in a sheet.
The tile (or sheets) may then be passed to a heating and drying over with set
parameters that
allow for measured control over the setting process. If a continuous sheet has
been used, the
dried sheet may then be cut at desired lengths. This process may be continuous
or
noncontinuous as desired. Analogously, the extruder may extrude the activated
set-delayed
cement composition into a mold or molds in a continuous or noncontinuous
process. The
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mold or molds may then be inverted and the set cement products ejected. Such
process may
be used to make a variety of materials including tiles, shingles, bricks, etc.
[0052] Additionally, the set-delayed cement compositions may provide a heat
resistant coating to a surface. The disclosed set-delayed cement composition
may be stable up
to temperatures as high as 400 F. Therefore, coaling a surface with the set-
delayed cement
compositions disclosed herein may impart a heat resistant coating to the
surface. Further, as
discussed above, heat refractory materials may be added to the set-delayed
cement
compositions to increase the heat resistance of the set-delayed cement
compositions. Such
materials may comprise, but are not limited to, alumina, titanium, fire brick
grog, and the
like.
[00531 As discussed above, the set-delayed cement compositions may be used to
make refractory materials such as bricks and monolithic shapes. The set-
delayed cement
compositions may withstand temperatures greater than 400 F. These refractory
materials
may be used in the construction of high temperature reactors, kilns, furnaces,
etc. Further, the
set-delayed cement compositions may constitute an environmentally friendly
alternative as
compared to conventional refractory materials that may be processed through
kilns or firing
processes.
[0054] The set-delayed cement compositions may be used in decorative
applications.
Such as decorative masonry where the control and/or variation of color is
desirable. The set-
delayed cement compositions are easy to dye and may be dyed to a variety of
colors either
during manufacturer of later by an end purchaser. Further, the set-delayed
cement
compositions possess a sufficient rheology for the dispersal of decorative
aggregate such as
beads or glitter. The aggregate may be used to provide aesthetic or textural
effects in the set-
delayed cement composition.
[0055] The exemplary set-delayed cement compositions disclosed herein may
directly
or indirectly affect one or more components or pieces of equipment associated
with the
preparation, delivery, recapture, recycling, reuse, and/or disposal of the
disclosed set-delayed
cement compositions. For example, the disclosed set-delayed cement
compositions may
directly or indirectly affect one or more mixers, related mixing equipment,
mud pits, storage
facilities or units, composition separators, heat exchangers, sensors, gauges,
pumps,
compressors, and the like used generate, store, monitor, regulate, and/or
recondition the
exemplary set-delayed cement compositions. The disclosed set-delayed cement
compositions
may also directly or indirectly affect any transport or delivery equipment
used to convey the
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set-delayed cement compositions to a well site or downhole such as, for
example, any
transport vessels, conduits, pipelines, trucks, tubulars, and/or pipes used to
compositionally
move the set-delayed cement compositions from one location to another, any
pumps,
compressors, or motors (e.g., topside or downhole) used to drive the set-
delayed cement
compositions into motion, any valves or related joints used to regulate the
pressure or flow
rate of the set-delayed cement compositions, and any sensors (i.e., pressure
and temperature),
gauges, and/or combinations thereof, and the like. The disclosed set-delayed
cement
compositions may also directly or indirectly affect the various downhole
equipment and tools
that may come into contact with the set-delayed cement compositions such as,
but not limited
to, wellbore casing, wellbore liner, completion string, insert strings, drill
string, coiled tubing,
slickline, wireline, drill pipe, drill collars, mud motors, downhole motors
and/or pumps,
cement pumps, surface-mounted motors and/or pumps, centralizers, turbolizers,
scratchers,
floats (e.g., shoes, collars, valves, etc.), logging tools and related
telemetry equipment,
actuators (e.g., electromechanical devices, hydromechanical devices, etc.),
sliding sleeves,
production sleeves, plugs, screens, filters, flow control devices (e.g.,
inflow control devices,
autonomous inflow control devices, outflow control devices, etc.), couplings
(e.g., electro-
hydraulic wet connect, dry connect, inductive coupler, etc.), control lines
(e.g., electrical,
fiber optic, hydraulic, etc.), surveillance lines, drill bits and reamers,
sensors or distributed
sensors, downhole heat exchangers, valves and corresponding actuation devices,
tool seals,
packers, cement plugs, bridge plugs, and other wellbore isolation devices, or
components,
and the like.
EXAMPLES
[0056] To facilitate a better understanding of the present embodiments, the
following
examples of certain aspects of some embodiments are given. In no way should
the following
examples be read to limit, or define, the entire scope of the embodiments.
Example 1
[0057] The following series of tests was performed to evaluate the force
resistance
properties of comparative cement compositions comprising pumice and hydrated
lime. Three
different comparative sample settable compositions, designated Samples 1-3,
were prepared
using pumice (DS-325 lightweight aggregate), hydrated lime, Liquiment 514L
dispersant,
and water, as indicated in the table below. After preparation, the samples
were placed in an
UCA and cured at 140 F and 3,000 psi for 24 hours. The cured cement was then
removed
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from the UCA and crushed to yield the compressive strength values provided in
Table 1
below.
Table 1
Compressive Strength Tests
Sample 1 2 3
Density lb/gal 14.3 14.3 14.3
Pumice:Lime WI Ratio 3:1 4:1 5:1
Pumice g 400 400 400
Lime g 134 103 100
Dispersant g 12 4 13
Water g 196 187 220
24-Hr Crush Strength psi 2,240 1,960 2,130
[0058] Example 1 thus indicates that cement compositions that comprise pumice
and
lime in a weight ratio ranging from 3:1 to 5:1 may develop compressive
strengths suitable for
particular applications.
Example 2
[0059] A sample set-delayed cement composition, designated Sample 4, having a
density of 13.3 lb/gal was prepared that comprised 500 grams of pumice (DS-325
lightweight
aggregate), 100 grams of hydrated lime, 13 grams of Liquiment 514L
dispersant, 24 grams
of Micro Matrix cement retarder, and 300 grams of water. The theological
properties of the
sample were measured after storing at room temperature and pressure for
periods of 1 day
and 6 days. After preparation, the theological properties of the sample were
determined at
room temperature (e.g., about 80 F) using a Model 35A Fann Viscometer and a
No. 2 spring,
in accordance with the procedure set forth in API RP Practice 10B-2,
Recommended Practice
for Testing Well Cements. The results of this test are set forth in the table
below.
TABLE 2
Viscosity Tests
Age of Farm Readings Yield Plastic
Sample Point Viscosity
(days) 600 300 200 100 6 3 (1b/100ft2) (centipoise)
1 560 322 244 170 46 38 84 238
6 498 310 228 136 24 20 122 188
[0060] Example 2 thus indicates that set-delayed cement compositions that
comprise
pumice, hydrated lime, a dispersant, a set retarder, and water can remain
fluid after 6 days.
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Example 3
[0061] A sample set-delayed cement composition, designated Sample 5, having a
density of 13.4 lb/gal was prepared that comprised 500 grams of pumice (DS-325
lightweight
aggregate), 100 grams of hydrated lime, 7 grams of Liquiment 514L dispersant,
6.3 grams
of Micro Matrix cement retarder, and 304 grams of water. The rheological
properties of the
sample were measured after storing at room temperature and pressure for
periods of from 1
day to 19 days. The theological properties were measured at room temperature
(e.g., about
80 F) using a Model 35A Fann Viscometer and a No. 2 spring, in accordance with
the
procedure set forth in API RP Practice 10B-2, Recommended Practice for Testing
Well
Cements. The results of this test are set forth in the table below.
Table 3
Viscosity Tests
Age of Sample Fann Readings
(Days) 300 200 100 6 3
1 462 300 130 12 8
2 458 282 122 6 4
420 260 106 3 2
8 446 270 110 4 1
12 420 252 100 3 2
19 426 248 94 2 1
[0062] After 7 days, calcium chloride in the amount indicated in Table 4 below
was
added to a separately prepared sample of the same formulation as above. The
sample was
then placed in an UCA and the initial setting time, which is the time for the
composition to
reach a compressive strength of 50 psi while maintained at 3,000 psi was
determined in
accordance with API RP Practice 10B-2, Recommended Practice for Testing Well
Cements.
The initial setting time of the sample was also determined without addition of
the calcium
chloride. The samples with and without the calcium chloride were heated to a
temperature of
140 F in 30 minutes and then maintained at that temperature throughout the
test.
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Table 4
Compressive Strength Tests
CaCl2
Age of Test
(% by wt of Initial Setting Time
Sample Temperature
Pumice & (hr:min)
(Days) ( F)
Lime)
7 140 0 no set after 4 days
7 140 10 5:11
[0063] Example 3 thus indicates that the set-delayed cement compositions that
comprise pumice, hydrated lime, a dispersant, a set retarder, and water will
not set for a
period of at least 19 days at ambient temperature and over 4 days at 140 F.
Example 3
further indicates that sample set-delayed cement compositions may be activated
at a desired
time by addition of a suitable activator.
Example 4
[0064] A sample set-delayed cement composition, designated Sample 6, having a
density of 13.4 lb/gal was prepared that comprised pumice (DS-325 lightweight
aggregate),
20% hydrated lime, 1.4% Liquiment 514L dispersant, 1.26% Micro Matrix cement
retarder, and 62% of water (all by weight of pumice, referred to in the table
below as "%
bwop"). After 45 days in storage at ambient conditions, the sample was mixed
with 6%
calcium chloride. At 140 F, the sample had a thickening time (time to 70 BC)
of 2 hours and
36 minutes and an initial setting time (time to 50 psi) of 9 hours and 6
minutes as measured
using an UCA while maintained at 3000 psi. After 48 hours, the sample was
crushed with a
mechanical press which gave a compressive strength of 2,240 psi. The
thickening time and
initial setting time were both determined in accordance with API RP Practice
10B-2,
Recommended Practice for Testing Well Cements. The results of this test are
set forth in the
table below.
Table 5
Compressive Strength Tests
Age of Test Calcium Thickening
Initial Setting 48 Hr
C
Sample Temperature Chloride Time Time rush
(Days) ( F) (% bwop) (hr:min) (hr:min) Strength
(psi)
45 140 6 2:36 9:36 2,240
[0065] Example 4 thus indicates that the set-delayed cement compositions that
comprise pumice, hydrated lime, a dispersant, a set retarder, and water will
not set for a
period of at least 45 days at ambient temperature. Example 4 further indicates
that sample
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set-delayed cement compositions may be activated at a desired time by addition
of a suitable
activator.
Example 5
10066] This example was performed to evaluate the ability of sodium hydroxide
and
sodium sulfate to activate a set-delayed cement composition that comprised
pumice (DS-325
lightweight aggregate), hydrated lime, Liquiment 514L dispersant, Micro
Matrix cement
retarder, and water. Four sample set-delayed cement compositions, designated
Samples 7-10,
were prepared having concentrations of components as indicated in the table
below. The
samples were monitored via an UCA. After the samples were placed in the UCA,
the
pressure was increased to 3,000 psi, and the temperature was increased to 100
F over a 15-
minute time period and held for the duration of the test. A portion of the
slurry was retained
and poured into a plastic cylinder to monitor the slurry behavior at room
temperature and
pressure. These procedures were repeated for all samples.
[0067] Sample 7 was monitored for 72 hours over which time no strength was
developed and the slurry was still pourable when removed from the UCA. The
portion kept
at room temperature and pressure was likewise still pourable after 72 hours.
[0068] Sample 8 was prepared using the same slurry design as Sample 7 except
that
sodium hydroxide was added as an activator. The sodium hydroxide was added in
solid form
directly to the mixing jar that contained the prepared sample. As can be seen
from Table 6,
Sample 8, reached 50 psi of compressive strength at 16 hours and 36 minutes.
The strength
continued to build, reaching a maximum of 1,300 psi, when the test was stopped
at 72 hours.
The cured cement was removed from the UCA and crushed with a mechanical press
which
gave a compressive strength of 969 psi. The portion kept at room temperature
and pressure
was crushed after 7 days resulting in a compressive strength of 143 psi.
[0069] Sample 9 was prepared using the same slurry design as Sample 8 except
that
sodium sulfate was added as an activator. The sodium sulfate was added in
solid form
directly to the mixing jar that contained the prepared slurry. Sample 9
reached 50 psi of
compressive strength at 67 hours and 29 minutes. The strength continued to
build, slowly,
reaching a maximum of 78 psi, when the test was stopped at 72 hours. The cured
cement was
removed from the UCA and crushed with a mechanical press which gave a
compressive
strength of 68.9 psi. The portion kept at room temperature and pressure was
still too soft to
be crushed after 7 days.
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100701 Sample 10 was prepared using the same slurry design as Sample 8 except
that
equal amounts of sodium hydroxide and sodium sulfate were added as an
activator. The
sodium hydroxide and sodium sulfate were added in solid form directly to the
mixing jar that
contained the prepared slurry. Sample 10 reached 50 psi of compressive
strength at 22 hours
and 40 minutes. The strength continued to build, reaching a maximum of 900
psi, when the
test was stopped at 72 hours. The cured cement was removed from the UCA and
crushed
with a mechanical press which gave a compressive strength of 786 psi. The
portion kept at
room temperature and pressure was crushed after 7 days resulting in a
compressive strength
of 47.9 psi.
[0071] The results of these tests are set forth in the table below. The
abbreviation "%
bwop" refers to the percent of the component by weight of the pumice. The
abbreviation
"gaVsk" refers to gallons of the component per 46-pound sack of the pumice.
The
abbreviation "RTP" refers to room temperature and pressure.
Table 6
Compressive Strength Tests
Sample 7 8 9 10
Density lb/gal 13.38 13.38 13.38 13.38
Water % bwop 61.97 63.60 64.62 64.11
Pumice % bwop 100 100 100 100
Hydrated Lime % bwop 20 20 20 20
Dispersant gal/sk 0.07 _ 0.07 0.07 0.07
Set Retarder % bwop 0.06 0.06 0.06 0.06
Sodium Hydroxide % bwop 4 2
Sodium Sulfate % bwop 4 2
UCA
Temp/Press F/Psi 100/3000 100/3000 100/3000 100/3000
Initial Set (50 psi) lirmin >78 16:36 67:29 22:40
Final Set (100 psi) hr:min _ 21:08 32:44
24 Hr Comp. Strength psi 138.74 -- 59.60
48 Hr Comp. Strength psi 711.35 -- 331.48
72 Hr Comp. Strength psi , 1300 78 900
72 Hr Crush Strength
(UCA) psi 969 68.90 786
7-Day Crush Strength
(RTP) psi 143.20 0.00 47.90
[0072] Example 5 thus indicates that sodium hydroxide, sodium sulfate, and
combinations of the two can activate the set-delayed cement compositions, but
to varying
degrees. The testing showed that both sodium hydroxide and combinations of
sodium
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hydroxide with sodium sulfate activated the cement compositions to an
acceptable level.
When compared to the non-activated composition, sodium sulfate activated the
cement
compositions, but much less so than the sodium hydroxide or combination of
sodium
hydroxide and sodium sulfate.
[0073] It should be understood that the compositions and methods are described
in
terms of "comprising," "containing," or "including" various components or
steps, the
compositions and methods can also "consist essentially of' or "consist of' the
various
components and steps. Moreover, the indefinite articles "a" or "an," as used
in the claims, are
defined herein to mean one or more than one of the element that it introduces.
[0074] For the sake of brevity, only certain ranges are explicitly disclosed
herein.
However, ranges from any lower limit may be combined with any upper limit to
recite a
range not explicitly recited, as well as, ranges from any lower limit may be
combined with
any other lower limit to recite a range not explicitly recited, in the same
way, ranges from any
upper limit may be combined with any other upper limit to recite a range not
explicitly
recited. Additionally, whenever a numerical range with a lower limit and an
upper limit is
disclosed, any number and any included range falling within the range are
specifically
disclosed. In particular, every range of values (of the form, "from about a to
about b." or,
equivalently, "from approximately a to b," or, equivalently, "from
approximately a-b")
disclosed herein is to be understood to set forth every number and range
encompassed within
the broader range of values even if not explicitly recited. Thus, every point
or individual
value may serve as its own lower or upper limit combined with any other point
or individual
value or any other lower or upper limit, to recite a range not explicitly
recited.
[0075] Therefore, the present embodiments are well adapted to attain the ends
and
advantages mentioned as well as those that are inherent therein. The
particular embodiments
disclosed above are illustrative only, as the present embodiments may be
modified and
practiced in different but equivalent manners apparent to those skilled in the
art having the
benefit of the teachings herein. Although individual embodiments are
discussed, all
combinations of each embodiment are contemplated and covered by the
disclosure.
Furthermore, no limitations are intended to the details of construction or
design herein
shown, other than as described in the claims below. Also, the terms in the
claims have their
plain, ordinary meaning unless otherwise explicitly and clearly defined by the
patentee. It is
therefore evident that the particular illustrative embodiments disclosed above
may be altered
or modified and all such variations are considered within the scope and spirit
of the present
27
disclosure. If there is any conflict in the usages of a word or term in this
specification and one
or more patent(s) or other documents that may referenced herein, the
definitions that are
consistent with this specification should be adopted.
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