Note: Descriptions are shown in the official language in which they were submitted.
CA 02974105 2017-07-17
1
WO 2016/137623
PCMS2016/014690
SET-DELAYED CEMENT COMPOSITIONS COMPRISING PUMICE AND
ASSOCIATED METHODS
BACKGROUND
Ron] 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, in spraying application, a cement handling system may spray cement
into a pond,
creek, or ditch, in order to line the structures with an impermeable barrier.
Similarly, cement
may be used to coat other structures such as walls, floors, or ceilings in
order to provide
support and in some applications, heat resistance. In construction
applications, cement may
be used to stabilize supports in a mine or attached to a pier.
[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 be 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
CA 02974105 2017-07-17
WO 2016/137623
PCT/US2016/014690
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.
2
CA 02974105 2017-07-17
WO 2016/137623
PCT/US2016/014690
BRIEF DESCRIPTION OF THE DRAWINGS
[0005] These drawings illustrate certain aspects of some of the embodiments of
the
present method, and should not be used to limit or define 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.
[0007] FIG. 2 illustrates the use of the set-delayed cement composition in a
spray
application for a pond.
[0008] FIG. 2A illustrates an enlarged perspective of a portion of the example
illustrated in FIG. 2.
[0009] FIG. 3 illustrates a marine construction application, wherein a set-
delayed
cement composition may be pumped through a conduit to secure in place a beam
to be used
in the extension of pier.
[0010] FIG. 4 illustrates the use of a set-delayed cement composition in a
mine
operation.
3
CA 02974105 2017-07-17
=
WO 2016/137623
PCT/US2016/014690
DETAILED DESCRIPTION
[0011] 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 line ponds, creeks, ditches, etc. In further examples, the set-delayed
cement compositions
may be used for marine construction, mine construction, or cement operations
necessitating
cement spraying. Additional examples may comprise using the set-delayed cement
compositions to coat structures to amongst other reasons, impart heat
resistance to the
stmctures.
[0012] 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 andior 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.
[0013] 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
4
CA 02974105 2017-07-17
WO 2016/137623
PCT/US2016/014690
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.
[0014] 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,
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.
[0015] 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
CA 02974105 2017-07-17
=
=
WO 2016/137623
PCT/US2016/014690
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.
[0016] 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
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 metaborate,
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.
[0017] As previously mentioned, examples of the set-delayed cement
compositions
may optionally comprise a dispersant. Examples of suitable dispersants
include, without
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
6
CA 02974105 2017-07-17
=
WO 2016/137623
PCT/US2016/014690
dispersants available from BASF Corporation Houston, Texas; or Ethacryr G
dispersant
available from Coatex, Genay, France. An additional example of a suitable
commercially
available dispersant is CFRThi-3 dispersant, available from Halliburton Energy
Services, Inc.,
Houston, Texas. The Liquimene' 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.,
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.
[0018] 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.
[0019] 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.
[0020] 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:
zeolites, amines such as triethanolamine, diethanolamine; silicates such as
sodium silicate;
zinc formate; calcium acetate; Groups IA and IIA hydroxides such as sodium
hydroxide,
magnesium hydroxide, and calcium hydroxide; monovalent salts such as sodium
chloride;
7
CA 02974105 2017-07-17
=
WO 2016/137623
PCT/US2016/014690
divalent salts such as calcium chloride; nanosilica (i.e., 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
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.
[0021] 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 be 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.
8
CA 02974105 2017-07-17
WO 2016/137623
PCT/US2016/014690
[0022] 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
trimetaphosphate, sodium tetrametaphosp hate, 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
andior 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.
[0023] 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 Liquimere 5141, or 5581F
dispersants,
available from BASF Corporation, Houston, Texas.
[0024] 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
9
CA 02974105 2017-07-17
WO 2016/137623
PCT/US2016/014690
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.
[0025] 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-
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.
[0026] 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.
[0027] 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.
CA 02974105 2017-07-17
WO 2016/137623
PCT/US2016/014690
[0028] 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
sulfonates; alkyl or alkene amidobetaines such as cocoamidopropyl betaine;
alpha-olefin
sulfonates; quaternary 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 ZONESEALANTrm 2000 agent, available from Halliburton Energy
Services, Inc.
[00291 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-
t].
CA 02974105 2017-07-17
WO 2016/137623
PCUUS2016/014690
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.
[0030] Optionally, mechanical-property-enhancing additives for set-delayed
cement
compositions may be included in the set-delayed cement compositions, for
example, to
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.
[0031] 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,
carboxymethylhvdroxyethyl 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.
[0032] 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.
12
CA 02974105 2017-07-17
WO 2016/137623
PCT/US2016/014690
[0033] 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.
[0034] 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
applications where fire and heat resistance is particularly important, for
example, in consumer
applications in the home.
[0035] 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 ¨4 Ca2+ + H2Si042- + 2H20 ¨4 CaH2SiO4-2H20
(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.
13
CA 02974105 2017-07-17
WO 2016/137623
PCT/US2016/014690
[0036] The set-delayed cement compositions may be used in applications of
spray-
applied cement and concrete. Spray-applied cement and concrete may be used
through either
a wet process or a dry process. The dry-mix process comprises pumping a dry
cementitious
material through a conduit and adding water at the exit of the conduit. In the
wet-mix process,
the cementitious material is mixed with water before being loaded into the
conduit. When
loaded into the conduit, the cement or concrete slurry is pumped to the exit
of the conduit
(e.g., a nozzle), where it may be sprayed onto a target area using compressed
gas added at the
conduit exit. The set-delayed cement compositions disclosed herein may be used
in wet-mix
spray-applications. In particular, the set-delayed cement composition may be
spray-applied in
cementing applications for tunnels, mines, reservoirs, swimming pools, repair
works, fire
damaged structures, retaining walls, refractory linings, zoological
structures, bridges, dams,
and the like. In a specific example, a set-delayed cement composition may be
prepared in
advance and then stored as a stable slurry until needed, whereby the set-
delayed cement
composition may be loaded into a cement spraying apparatus and sprayed onto a
target area.
In the aforementioned example, on-site mixing of the cement is no longer
needed and thus the
cement may be prepared off-site under stricter control standards and
conditions.
[0037] 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.
{0038] 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.
14
CA 02974105 2017-07-17
WO 2016/137623
PCMS2016/014690
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
analyzer, available from Farm_ 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, fitly 2005.
[0039] 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.
[0040] 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
CA 02974105 2017-07-17
WO 2016/137623
PCT/US2016/014690
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.
[0041] 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
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 I 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.
[0042] A method of spraying a surface with a set-delayed cement composition
may be
provided. The method may be used in conjunction with one or more of the
methods,
compositions, and/or systems illustrated in FIGs. 1-4. The method may comprise
providing a
set-delayed cement composition comprising water, pumice, hydrated lime, and a
set retarder;
spraying a surface with the set-delayed cement composition: and allowing the
set-delayed
cement composition to set on the surface. 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
carboxytnethylated
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 11A hydroxide,
monovalent salt,
CA 02974105 2017-07-17
WO 2016/137623
PCT/US2016/014690
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
spraying step, the set-delayed cement composition may be stored for a period
of at least about
1 day. The surface may be disposed about, on, or within a mine, a pond, a
creek, a river, the
ocean floor, a beach shore, a wall, a ceiling, a floor, an attic, or a
basement. The set-delayed
cement composition may be disposed within a mine and wherein the set-delayed
cement
composition may be pumped from a vessel outside of the mine into the mine. The
set-delayed
cement composition may be foamed. The set-delayed cement composition may
comprise
refractory materials. The set-delayed cement composition may comprise a dye
and/or beads.
[0043] A method of coating a surface with a set-delayed cement composition may
be
provided. The method may be used in conjunction with one or more of the
methods,
compositions, and/or systems illustrated in FIGs. 1-4. The method may comprise
providing a
set-delayed cement composition comprising water, pumice, hydrated lime, and a
set retarder;
coating a surface with the set-delayed cement composition; and allowing the
set-delayed
cement composition Co set on the surface. 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
coating step, the set-delayed cement composition may be stored for a period of
at least about
I day. The surface may be disposed about, on, or within a mine, a pond, a
creek, a river, the
17
CA 02974105 2017-07-17
WO 2016/137623
PCT/US2016/014690
ocean floor, a beach shore, a wall, a ceiling, a floor, an attic, or a
basement. The set-delayed
cement composition may be disposed within a mine and wherein the set-delayed
cement
composition may be pumped from a vessel outside of the mine into the mine. The
set-delayed
cement composition may be foamed. The set-delayed cement composition may
comprise
refractory materials. The set-delayed cement composition may comprise a dye
and/or beads.
Coating a surface with the set-delayed cement composition may comprise
painting the
surface with the set-delayed cement composition or dipping the surface into a
vessel
containing the set-delayed cement composition
[0044] A cementing 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. 1-4. 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 80 F; a cementing
unit comprising: a
vessel, a conduit; and a nozzle coupled to the conduit. The cementing unit may
further
comprise a pneumatic system comprising a gas compressor, a compressed gas, and
a
compressed gas conduit, wherein the compressed gas conduit is coupled to the
nozzle, and
wherein the compressed gas is capable of spraying the set-delayed cement
composition. The
nozzle may comprise an applicator capable of applying a cement set activator
to the set-
delayed cement composition. The cementing unit may further comprise a
hydraulic system
coupled to the nozzle, wherein the hydraulic system may be capable of spraying
the set-
delayed cement composition. 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 Ii2nosulfonate, 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.
The set-delayed
18
CA 02974105 2017-07-17
WO 2016/137623
PCT/US2016/014690
cement composition may be foamed. The set-delayed cement composition may
comprise
refractory materials. The set-delayed cement composition may comprise a dye
and/or beads.
[0045] 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 (e.g., cementing unit 8 as shown on
FIG. 2) 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 limeisettable 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 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
[0046] FIG. 2 illustrates the use of the set-delayed cement composition in a
spraying
application. Cementing unit 8, which may comprise vessel 4 and pumping
equipment 6 as
described in FIG. 1, may be used to spray a set-delayed cement composition on
a rock lined
pond bed 10. Cementing unit 8 may comprise a vessel capable of storing a set-
delayed
cement composition (e.g., vessel 4) and/or equipment used to deliver a set-
delayed cement
composition to a job site, illustrated by pumping equipment 6 and conduit 12.
As illustrated
by FIG. 2, rock lined pond bed 10 may comprise pores, voids, gaps, etc. that
may make
permeable and prone to erosion. Due to the inherent nature of the set-delayed
cement
composition, the set-delayed cement composition may be delivered through
conduit 12 and
sprayed onto rock lined pond bed 10 using a pneumatic system comprising gas
compressor 14
and compressed gas conduit 16, which may be utilized to spray the set delayed
cement
19
CA 02974105 2017-07-17
WO 2016/137623
PCT/US2016/014690
composition from nozzle 18. Alternatively, the spraying may be accomplished by
a hydraulic
system (not shown), for example, comprising an incompressible liquid to exert
a direct or
indirect force on the set-delayed cement composition such that the set-delayed
cement
composition may be sprayed from an exit in the conduit 12. Once sprayed, the
set-delayed
cement composition may be activated for use by a cement set activator,
alternatively an
applicator within the nozzle 18 of conduit 12 may apply the cement set
activator as it exits
nozzle 18 as shown in the inset of FIG. 2. Applicator 20 may comprise an
opening and a
valve through which activator conduit 22 may convey cement set activator to
nozzle 18
where it may mix with a set-delayed cement composition in conduit 12.
Additionally,
activator pump 24 my pump cement set activator through activator conduit 22.
The activated
set-delayed cement composition may then be sprayed from the nozzle 18 using
the
compressed gas carried to nozzle 18 via compressed gas conduit 16. The
strength of the
cement set activator may be adjusted to adjust the thickening time of the set-
delayed cement
composition. The strength may be adjusted by using a relatively stronger
cement set activator
and/or also by increasing the cement set activator concentration. For example,
a higher
concentration of more reactive cement set activator may be used to induce
setting of the set-
delayed cement as soon as it is applied to a surface. Similarly, the set-
delayed cement
composition may be used in applications where the lining of porous or erosion
prone
structures would be desired. For example, the set-delayed cement composition
may be used
on ponds, reservoirs, drainage ditches, creek beds, rivers banks, and the
like. Once set, the
set-delayed cement composition may prevent leakage and/or erosion through and
within the
covered surfaces.
[0047] FIG. 3 illustrates a marine construction application, wherein a set-
delayed
cement composition may be pumped through conduit 12 to secure in place a beam
28 to be
used in the extension of pier 26. The set-delayed cement composition may be
sprayed from
nozzle 18 using a pneumatic system, for example, one comprising compressed gas
from
compressed gas conduit 16. Alternatively, the spraying may be accomplished by
a hydraulic
system (not shown), for example, comprising an incompressible liquid to exert
a direct or
indirect force on the set-delayed cement composition such that the set-delayed
cement
composition may be sprayed from an exit in the conduit 12. As discussed above,
the set-
delayed cement composition is capable of extended storage wherein it remains
in a stable
fluid, slurry state until activated by the addition of a suitable cement set
activator and allowed
to set to form set cement 30. Set cement 30 is a set-delayed cement
composition that has been
CA 02974105 2017-07-17
WO 2016/137623
PCT/US2016/014690
activated and allowed to set in place. As such, the set-delayed cement
composition may be
placed near a location or removed to a logistically convenient position and
pumped to a
desired area. The cement set activator may be added while mixing the set-
delayed cement
composition prior to pumping, or may added while pumping the set-delayed
cement
composition, for example, through an applicator within the nozzle of conduit
10. Set-delayed
cement composition may be well suited for marine environments and may be
particularly
advantageous in deep-water scenarios due to its simplified delivery mechanism,
reduced
transport risk, and easier logistics since powder transport and mixing are not
required.
[0048] FIG. 4 illustrates the use of a set-delayed cement composition for mine
construction/repair. Cementing unit 8, which may comprise vessel 4, pumping
equipment 6,
and conduit 12, may be used to store, mix, and transport a set-delayed cement
composition
into a mine or other underground structure where it may be difficult to
transport equipment.
As illustrated by FIG. 4, the bulk of the cementing equipment and the set-
delayed cement
composition may be stored above ground. When desired, the set-delayed cement
composition
may be pumped by cementing unit 8 via conduit 12 to the underground job site
where the set-
delayed cementing composition may be used to consolidate, seal, or reinforce
the tunnel/mine
structure. Thus, transport time and or size constraint issues of the cementing
equipment may
be reduced or eliminated. The set-delayed cement composition may be poured
from conduit
12 or it may be sprayed using a pneumatic system, for example, one comprising
compressed
gas from gas compressor 14 and compressed gas conduit 16. Alternatively, the
spraying may
be accomplished by a hydraulic system (not shown), for example, comprising an
incompressible liquid to exert a direct or indirect force on the set-delayed
cement
composition such that the set-delayed cement composition may be sprayed from
an exit in the
conduit 12. With the benefit of this disclosure, one of ordinary skill in the
art will be able to
determine the best method of applying a set-delayed cement and/or concrete.
[0049] Additional examples may comprise using the set-delayed cement
composition
for coating applications. In these examples, a coating may be applied by
spraying, painting,
rolling-on dipping, etc. The coating may be applied to decorative or
structural purposes. The
set-delayed cement composition may be easily dyed and can be formulated to
provide a fast-
setting adhesive coating of a desirable color. The coating may be used to
aesthetically
enhance walls, floors, ceilings, sculptures, or any such desirable structure.
Further,
ornamental aggregate may be added to the set-delayed cement composition for
additional
aesthetic effects. Ornamental aggregate may comprise glitter, beads, and the
like.
21
CA 02974105 2017-07-17
WO 2016/137623
PCT/US2016/014690
[0050] Additionally, the set-delayed cement compositions may provide a heat
resistant coating to a surface. The disclosed set-delayed cement composition
is stable up to
temperatures as high as 400 F. Therefore, coating 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.
[0051] Further. the set-delayed cement compositions may be foamed. The set-
delayed
cement composition may be formed using a foaming additive as described above
or a
pressurized gas. Equipment, such as fluid handling system 2 (as shown in FIG.
1) or
cementing unit 8 (as shown in FIGs. 2 and 4), may be used to continuously
produce foamed
set-delayed cement composition that may be sprayed or coated onto a targeted
surface where
it may remain in place due to the rheology of the foamed set-delayed cement
composition.
Optionally, the foamed set-delayed cement composition may be passed through a
heat
exchanger and/or supplied a cement set accelerator to accelerate the setting
process. The
foamed set-delayed cement composition may be used in many applications. An
example of an
application comprises a fire retardant insulation which may be applied to many
types of
surfaces.
[0052] 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
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
22
CA 02974105 2017-07-17
WO 2016/137623
PCT/US2016/014690
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
[0053] 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
[0054] 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, Liquimeie 514L
dispersant,
and water, as indicated in the table below. After preparation, the samples
were placed in an
UCA and cured at 1400F and 3,000 psi for 24 hours. The cured cement was then
removed
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 lbig_al 14.3 14.3 14.3
23
CA 02974105 2017-07-17
WO 2016/137623 PCT/US2016/014690
Pumice:Lime Wt. 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
[0055] 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
[0056] 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 Liquirnent" 514L
dispersant, 24 grams
of Micro Matrix cement retarder, and 300 grams of water. The rheoloeical
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 Fann 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
[0057] 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.
Example 3
[0058] 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 Liquimentt 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
24
CA 02974105 2017-07-17
WO 2016/137623
PCT/US2016/014690
80 F) using a Model 35A Farm 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
462 300 130 12 8
2 458 282 122 6 4
5 420 , 260 106 3 2
8 446 270 110 4 1
12 420 252 100 3 2
19 426 248 94 2 1
[0059] 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.
Table 4
Compressive Strength Tests
CaCl2
Age of Test
(% by wt of Initial Setting Time
Sample Temperature
Pumice & (hr:min)
(Days) ( F)
Lime)
140 0 no set after 4 days
7 140 10 5:11
[0060] 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.
CA 02974105 2017-07-17
WO 2016/137623
PCT/US2016/014690
Example 4
[0061] 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% Liqiiiment ' 514L dispersant, 1.26% Micro Matrix
cement
retarder, and 62% of water (all by weight of pumice, referred to in the table
below as cc%
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 fir Testing Well Cements. The results of this test are
set forth in the
table below.
Table 5
Compressive Strength Tests
48 Hr
Age of Test Calcium Thickening Initial Setting
Crush
Sample Temperature Chloride Time Time
(Days) ( F) (% bwop) (hr: min) (hr:min) Strength
(psi)
45 140 6 2:36 9:36 2,240
[0062] 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
set-delayed cement compositions may be activated at a desired time by addition
of a suitable
activator.
Example 5
[0063] 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, Liquimene' 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
26
CA 02974105 2017-07-17
WO 2016/137623
PCT/US2016/014690
and poured into a plastic cylinder to monitor the slurry behavior at room
temperature and
pressure. These procedures were repeated for all samples.
[0064] 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.
[0065] 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.
100661 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.
[0067] 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.
[0068] 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
27
CA 02974105 2017-07-17
WO 2016/137623
PCT/US2016/014690
"gallsk" refers to gallons of the component per 46-pound sack of the pumice_
The
abbreviation "RIP" 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 'A bwop 61.97 63.60 64.62 64.11
_
Pumice % bwop 100 100 100 100
Hydrated Lime % bwop 20 20 20 20
Dispersant gallsk 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) hr:min >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
[0069] 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
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.
[0070] 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.
28
[0071] 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.
[0072] 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
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 be referenced herein, the
definitions that are
consistent with this specification should be adopted.
CA 2974105 2019-02-06
29
