# Patent

## Title
Method of using lignite grafted fluid loss control additives in cementing operations

## Abstract

Methods of cementing in a subterranean formation are provided. An exemplary embodiment comprises introducing a cement composition into a subterranean formation. The cement composition comprises water, a cement and a fluid loss control additive comprising a graft polymer. The graft polymer comprises a backbone comprising a lignite. The graft polymer further comprises grafted monomers selected from the group consisting of 2-acrylamido-2-methylpropanesulfonic acid, acrylamide, acrylic acid, vinylphosphonic acid, diallyldimethylammonium chloride and salts thereof.

## Background
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is related to U.S. patent application Ser. No. 11/702,324, entitled “Cement Compositions Comprising Lignite Grafted Fluid Loss Control Additives”, filed on the same date herewith, the entire disclosure of which is incorporated herein by reference.
BACKGROUND
The present invention relates to cementing operations. More particularly, the present invention relates to the use of a graft polymer as a fluid loss control additive in cementing operations, the graft polymer comprising a lignite backbone and grafted monomers selected from the group consisting of 2-acrylamido-2-methylpropanesulfonic acid, acrylamide, acrylic acid, vinylphosphonic acid, diallyldimethylammonium chloride and salts thereof.
Well cement compositions are commonly utilized in subterranean operations, particularly subterranean well construction and remedial operations. For example, in subterranean well construction, a pipe string (e.g., casing and liners) may be run into a well bore and cemented in place. The process of cementing the pipe string in place is commonly referred to as “primary cementing.” In a typical primary cementing operation, a cement composition may be pumped into an annulus between the walls of the well bore and the exterior surface of the pipe string disposed therein. The cement composition sets in the annular space, thereby forming an annular sheath of hardened, substantially impermeable cement that supports and positions the pipe string in the well bore and bonds the exterior surface of the pipe string to the subterranean formation. Among other things, the annular sheath of set cement surrounding the pipe string functions to prevent the migration of fluids in the annulus, as well as protecting the pipe string from corrosion. Cement compositions also may be used in plugging and abandonment operations and remedial cementing operations, such as squeeze cementing and the placement of cement plugs.
For such subterranean cementing operations to be successful, the cement compositions typically include a fluid loss control additive to reduce the loss of fluid, from the cement compositions, e.g., when they contact permeable subterranean formations and zones. Excessive fluid loss may cause, for example, a cement composition to become prematurely dehydrated, which limits the amount of the cement composition that can be pumped. Due to this premature dehydration, excessive pump pressure may be required to place the cement composition, potentially resulting in breakdown of the formation and/or destabilization of the well bore.
Certain polymers have been used heretofore as fluid loss control additives in cementing operations. For example, cellulosic materials such as hydroxyethyl cellulose and carboxymethylhydroxyethyl cellulose have been used as fluid loss control additives. Copolymers of 2-acrylamido-2-methylpropanesulfonic acid and acrylamide or N,N-dimethylacrylamide have also been used as fluid loss control additives. In addition, graft polymers 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 have been used as fluid loss control additives. These fluid loss control additives, however, may not provide a desired level of fluid loss control at high temperatures (e.g., at least about 500° F. (260° C.)) and/or may be exhibit undesirable properties (e.g., dispersive).
SUMMARY
The present invention relates to cementing operations. More particularly, the present invention relates to the use of a graft polymer as a fluid loss control additive in cementing operations, the graft polymer comprising backbone of a lignite and grafted monomers selected from the group consisting of 2-acrylamido-2-methylpropanesulfonic acid, acrylamide, acrylic acid, vinylphosphonic acid, diallyldimethylammonium chloride and salts thereof.
An exemplary embodiment of the present invention provides a method of cementing in a subterranean formation. The method comprises introducing a cement composition into a subterranean formation. The cement composition comprises water, a cement and a fluid loss control additive comprising a graft polymer. The graft polymer comprises a backbone comprising a lignite. The graft polymer further comprises a first grafted monomer selected from the group consisting of 2-acrylamido-2-methylpropanesulfonic acid, salts thereof and combinations thereof. The graft polymer further comprises a second grafted monomer comprising diallyldimethylammonium chloride.
Another exemplary embodiment of the present invention provides a method of cementing in a subterranean formation. The method comprises introducing a cement composition into a subterranean formation. The cement composition comprises water, a cement and a fluid loss control additive comprising a graft polymer. The graft polymer comprises a backbone comprising a lignite. The graft polymer further comprises a first grafted monomer selected from the group consisting of 2-acrylamido-2-methylpropanesulfonic acid, salts thereof and combinations thereof. The graft polymer further comprises a second grafted monomer selected from the group consisting of vinylphosphonic acid, salts thereof and combinations thereof.
Another exemplary embodiment of the present invention provides a method of cementing in a subterranean formation. The method comprises introducing a cement composition into a space between a pipe string and a subterranean formation. The cement composition comprises water, a cement and a fluid loss control additive comprising a graft polymer. The graft polymer comprises a backbone comprising a lignite. The graft polymer further comprises a first grafted monomer comprising 2-acrylamido-2-methylpropanesulfonic acid, salts thereof and combinations thereof. The graft polymer further comprises a second grafted monomer comprising diallyldimethylammonium chloride. The graft polymer further comprises a third grafted monomer comprising acrylamide. The graft polymer further comprises a fourth grafted monomer selected from the group consisting of acrylic acid, vinylphosphonic acid, salts thereof and combinations thereof. The method further comprises allowing the cement composition to set in the space between the pipe string and the subterranean formation.


DESCRIPTION OF SPECIFIC EMBODIMENTS
The present invention relates to cementing operations. More particularly, the present invention relates to the use of a graft polymer as a fluid loss control additive in cementing operations, the graft polymer comprising a lignite backbone and grafted monomers selected from the group consisting of 2-acrylamido-2-methylpropanesulfonic acid (AMPS® acid), acrylamide, acrylic acid, vinylphosphonic acid (VPA), diallyldimethylammonium chloride (DADMAC) and salts thereof. While these graft polymers are effective at reducing fluid loss from cement compositions in a variety of cementing applications, they may be particularly useful for reducing fluid loss in high temperature applications, for example, in wells having a bottom hole circulating temperature (BHCT) of at least about 500° F. (260° C.).
An exemplary embodiment of the cement compositions of the present invention comprises water, cement and a fluid loss control additive comprising a graft polymer, the graft polymer comprising a backbone that comprises a lignite. The graft polymer further comprises grafted monomers selected from the group consisting of 2-acrylamido-2-methylpropanesulfonic acid (AMPS® acid), acrylamide, acrylic acid, vinylphosphonic acid (VPA), diallyldimethylammonium chloride (DADMAC) and salts thereof. For example, in one exemplary embodiment, the graft polymer may comprise a first grafted monomer selected from the group consisting of 2-acrylamido-2-methylpropanesulfonic acid, salts thereof and combinations thereof, and a second grafted monomer comprising diallyldimethylammonium chloride. In another exemplary embodiment, the graft polymer may comprise a first grafted monomer selected from the group consisting of 2-acrylamido-2-methylpropanesulfonic acid, salts thereof and combinations thereof, and a second grafted monomer selected from the group consisting of vinylphosphonic acid, salts thereof and combinations thereof. The graft polymer further may comprise additional grafted monomers, such as those listed above. In general, the grafted monomers may be present in one or more pendant groups attached to the lignite backbone in a random nature. By way of example, each pendant group attached to the lignite backbone may contain one or more of the monomers in a random nature.
Those of ordinary skill in the art will appreciate that the exemplary cement compositions generally should have a density suitable for a particular application. By way of example, exemplary embodiments of the cement compositions may have a density in the range of from about 8 pounds per gallon (“ppg”) to about 21 ppg.
The water used in exemplary embodiments of the cement compositions of the present invention may be freshwater or saltwater (e.g., water containing one or more salts dissolved therein, seawater, brines, saturated saltwater, etc.). In general, the water may be present in an amount sufficient to form a pumpable slurry. In exemplary embodiments, the water may be present in the cement compositions in an amount in the range of from about 33% to about 200% by weight of the cement (“bwoc”). In exemplary embodiments, the water may be present in an amount in the range of from about 35% to about 70% bwoc.
Exemplary embodiments of the cement compositions of the present invention comprise a cement. Any of a variety of cements suitable for use in subterranean cementing operations may be used in accordance with exemplary embodiments of the present invention. Suitable examples include hydraulic cements that comprise calcium, aluminum, silicon, oxygen and/or sulfur, which set and harden by reaction with water. Such hydraulic cements, include, but are not limited to, Portland cements, pozzolana cements, gypsum cements, high alumina content cements, slag cements, silica cements and combinations thereof. In certain embodiments, the hydraulic cement may comprise a Portland cement. In some embodiments, the Portland cements that are suited for use in exemplary embodiments of the present invention are classified as Class A, C, H and G cements according to American Petroleum Institute, API Specification for Materials and Testing for Well Cements, API Specification 10, Fifth Ed., Jul. 1, 1990.
In addition, exemplary embodiments of the cement compositions of the present invention comprise a fluid loss control additive. As previously mentioned, such fluid loss control additives comprise a graft polymer that comprises a lignite backbone grafted with monomers selected from the group consisting of 2-acrylamido-2-methylpropanesulfonic acid (AMPS® acid), acrylamide, acrylic acid, vinylphosphonic acid (VPA), diallyldimethylammonium chloride (DADMAC), and salts thereof. In general, these graft polymers are effective at reducing fluid loss from cement compositions in a variety of cementing operations. By way of example, these graft polymers may be particularly suitable for use as fluid loss control additives in high temperature applications, for example, in wells with a BHCT of at least about 500° F. (260° C.).
Generally, the backbone of the graft polymer comprises a lignite. As used in this disclosure, the term “lignite” refers to a variety of low rank coals, including oxidized lignite (e.g., leonardite), mined lignin, brown coal or slack. In addition, in exemplary embodiments, the backbone may further comprise polyvinyl alcohol, polyethylene oxide, polypropylene oxide, polyethyleneimine and combinations thereof. Those of ordinary skill in the art will appreciate that the lignite may be treated with a caustic (for example, potassium hydroxide, sodium hydroxide or ammonium hydroxide) to solubilize the lignite in water. By way of example, treatment of the lignite with a caustic solution generally may dissolve or disperse a portion of the lignite into the solution. Such solution may then be concentrated to increase the lignite content or may be used directly in the polymerization.
The graft polymer may comprise a sufficient amount of the lignite backbone to provide a desirable level of fluid loss control. In exemplary embodiments, the backbone may be present in the graft polymer in an amount in the range of from about 5% to about 95% by weight of the graft polymer on a dry basis. In exemplary embodiments, the backbone may be present in the graft polymer in an amount in the range of from about 10% to about 50% by weight of the graft polymer on a dry basis. In exemplary embodiments, the backbone may be present in the graft polymer in an amount in the range of from about 10% to about 20% by weight of the graft polymer on a dry basis.
As previously mentioned, the lignite backbone of the graft polymer may be grafted with any combination of monomers selected from the group consisting of AMPS® acid, DADMAC, acrylamide, acrylic acid, VPA and salts thereof. In general, the grafted monomers may be present in pendant groups attached to the lignite backbone in a random nature. By way of example, each pendant group attached to the lignite backbone may contain one or more of the monomers in a random nature. It is believed that the various monomers (e.g., the AMPS® acid, acrylamide, acrylic acid, VPA and DADMAC) attach at free radicals created in the lignite backbone. In exemplary embodiments, the monomers selected from the group consisting of the AMPS® acid, acrylamide, acrylic acid, VPA, DADMAC and salts thereof may be admixed with the lignite prior to initiation of the polymerization reaction.
Generally, the graft polymer may comprise a sufficient amount of these grafted monomers to provide a desirable level of fluid loss control. In exemplary embodiments, the grafted monomers may be present in the graft polymer in an amount in the range of from about 5% to about 95% by weight of the graft polymer on a dry basis. In exemplary embodiments, the grafted monomers may be present in the graft polymer in an amount in the range of from about 50% to about 90% by weight of the graft polymer on a dry basis. In exemplary embodiments, the grafted monomers may be present in the graft polymer in an amount in the range of from about 80% to about 90% by weight of the graft polymer on a dry basis.
An exemplary fluid loss control additive comprises a lignite backbone grafted with a first monomer comprising AMPS® acid, salts thereof or combinations thereof, a second monomer comprising DADMAC, a third monomer comprising acrylamide and a fourth monomer comprising acrylic acid, salts thereof or combinations thereof. Each of these grafted monomers may be present in the exemplary graft polymer in a variety of different mole ratios. In an exemplary embodiment, the exemplary graft polymer may have a first grafted monomer-to-third grafted monomer mole ratio in the range of from about 1:1 to about 4:1. In an exemplary embodiment, the exemplary graft polymer may have a first grafted monomer-to-fourth grafted monomer mole ratio in the range of from about 1:1 to about 10:1. In an exemplary embodiment, the exemplary graft polymer may have a first grafted monomer-to-second grafted monomer mole ratio in the range of from about 1:1 to about 10:1. In an exemplary embodiment, the exemplary graft polymer may have a first grafted monomer-to-third grafted monomer-to-fourth grafted monomer-to-second grafted monomer mole ratio in the range of from about 4:3:2:1 to about 4:1:0.5:0.1. In another exemplary embodiment, the exemplary graft polymer may a first grafted monomer-to-third grafted monomer-to-fourth grafted monomer-to-second grafted monomer mole ratio in the range of from about 4:3:1:1 to about 4:2:1:0.25.
Another exemplary fluid loss control additive comprises a lignite backbone grafted with a first monomer comprising AMPS® acid, salts thereof or combinations thereof, a second monomer comprising DADMAC, a third monomer comprising acrylamide and a fourth monomer comprising VPA, salts thereof or combinations thereof. Each of these grafted monomers may be present in the exemplary graft polymer in a variety of different mole ratios. In an exemplary embodiment, the exemplary graft polymer may have a first grafted monomer-to-third grafted monomer mole ratio in the range of from about 1:1 to about 4:1. In an exemplary embodiment, the exemplary graft polymer may have a first grafted monomer-to-fourth grafted monomer salt mole ratio in the range of from about 2:1 to about 10:1. In an exemplary embodiment, the exemplary graft polymer may have a first grafted monomer-to-second grafted monomer mole ratio in the range of from about 1:1 to about 10:1. In an exemplary embodiment, the exemplary graft polymer may have a first grafted monomer-to-third grafted monomer-to-fourth grafted monomer-to-second grafted monomer mole ratio in the range of from about 4:4:1:2 to about 4:1:0.1:0.1. In another exemplary embodiment, the exemplary graft polymer may have a first grafted monomer-to-third grafted monomer-to-fourth grafted monomer-to-second grafted monomer mole ratio in the range of from about 4:4:1:2 to about 4:2:1:0.25.
Those of ordinary skill in the art will appreciate that the amount of each of the grafted monomers present in the graft polymer is dependent upon a number of factors, including cost, the temperature of use, the desired molecular weight of the graft polymer, dispersive properties and desired amount of fluid loss control, to name a few examples.
Those of ordinary skill in the art will appreciate that suitable graft polymers may be in an acid form or in a salt form. As will be appreciated, a variety of salts of the graft polymers may be prepared, for example, by neutralizing the acid form of the AMPS® acid, acrylic acid monomer and/or VPA monomer with an alkaline agent. By way of example, suitable alkaline agents may include sodium hydroxide, ammonium hydroxide or the like. This neutralization may occur, for example, either prior to or after the polymerization of the graft polymer. By way of example, a salt of AMPS® acid (such as the sodium salt of AMPS® acid) may be used in the polymerization of the graft polymer. In addition, neutralization of the monomers may occur, for example, due to calcium ions present in the exemplary cement compositions.
The fluid loss control additive should be included in exemplary embodiments of the cement compositions of the present invention in an amount sufficient to provide a desired level of fluid loss control. The fluid loss control additive may be present in exemplary embodiments of the cement compositions in an amount in the range of from about 0.1% to about 5% bwoc. The fluid loss control additive may be present in exemplary embodiments of the cement compositions in an amount in the range of from about 0.2% to about 3% bwoc.
Graft polymers used as fluid loss control additives in accordance with exemplary embodiments of the present invention may be prepared using any suitable polymerization technique. By way of example, suitable graft polymers may be prepared using any of a variety of free radical polymerization techniques. The initiators employed in these free radical techniques to produce exemplary embodiments of the graft polymer may generally comprise a redox initiator capable of generating a free radical in the lignite that will initiate polymerization by reacting with the monomers. While various ceric salts and other compounds may be suitable to effect the free radical initiation, an ammonium persulfate-sodium bisulfite redox system may be employed for the preparation of exemplary embodiments of the lignite graft polymers. In certain exemplary embodiments, water may be employed as the solvent in the polymerization reactions. Those of ordinary skill in the art, however, will appreciate that other solvents capable of solubilizing the reactants as desired also may be utilized.
Other additives suitable for use in subterranean cementing operations also may be added to exemplary embodiments of the cement compositions. Examples of such additives include dispersing agents, set retarding agents, accelerants, defoaming agents, lost circulation materials, salts, fly ash, fiber, strength retrogression additives, weighting agents, vitrified shale, lightweight additives (e.g., bentonite, gilsonite, glass spheres, etc.) and combinations thereof. A person having ordinary skill in the art, with the benefit of this disclosure, will readily be able to determine the type and amount of additive useful for a particular application and desired result.
As will be appreciated by those of ordinary skill in the art, exemplary embodiments of the cement compositions of the present invention may be used in a variety of subterranean applications, including primary and remedial cementing. Exemplary embodiments of the cement compositions may be introduced into a subterranean formation and allowed to set therein. Exemplary embodiments of the cement compositions may comprise water, cement and a fluid loss control additive comprising a graft polymer. The graft polymer comprising a lignite backbone. The graft polymer further comprises grafted monomers selected from the group consisting of 2-acrylamido-2-methylpropanesulfonic acid (AMPS® acid), acrylamide, acrylic acid, vinylphosphonic acid (VPA), diallyldimethylammonium chloride (DADMAC) and salts thereof. By way of example, in one exemplary embodiment, the graft polymer may comprise a first grafted monomer selected from the group consisting of 2-acrylamido-2-methylpropanesulfonic acid, salts thereof and combinations thereof, and a second grafted monomer comprising diallyldimethylammonium chloride. In another exemplary embodiment, the graft polymer may comprise a first grafted monomer selected from the group consisting of 2-acrylamido-2-methylpropanesulfonic acid, salts thereof and combinations thereof, and a second grafted monomer selected from the group consisting of vinylphosphonic acid, salts thereof and combinations thereof. By way of example, in exemplary primary cementing embodiments, a cement composition may be introduced into a space between a subterranean formation and a pipe string located in the subterranean formation. The cement composition may be allowed to set to form a hardened mass in the space between the subterranean formation and the pipe string. In addition, in exemplary remedial cementing embodiments, a cement composition may used, for example, in squeeze cementing operations or in the placement of cement plugs.
To facilitate a better understanding of the present technique, the following examples of some specific exemplary embodiments are given. In no way should the following examples be read to limit, or to define, the scope of the invention.
EXAMPLE 1
Graft polymers comprising a lignite backbone grafted with a salt of AMPS® acid, acrylamide, acrylic acid (or VPA) and DADMAC were prepared in accordance with the following procedure. First, a sodium salt of lignite, water, a defoamer and ethylenediaminetetraacetic acid (EDTA) were added to a reactor vessel. To this vessel, a 58% by weight solution of the sodium salt of AMPS® acid, a 48% by weight solution of acrylamide, acrylic acid (or VPA as set forth in the table below) and DADMAC were then added. This mixture was heated and held at a temperature of about 158° F. (70° C.) for one hour while purging with nitrogen. After one hour, ammonium persulfate was added to initiate polymerization. This mixture was held at a temperature of about 158° F. (70° C.) for two hours. After two hours, sodium metabisulfite was added, and the mixture was allowed to cool. When the mixture reached room temperature, a 50% solution of sodium hydroxide was added to adjust the pH in the range of from about 7 to about 8. The weight percent of each component utilized in the graft polymer's preparation is listed in the table below.











TABLE 1








Formulation #1
Formulation #2



Component
(% by wt)
(% by wt)




















Sodium Salt of
5.6
5.6



Lignite



Water
40.67
38.36



NaOH
2.96
3.03



(50% solution)



Defoamer
0.01
0.01



NaAMPS
31.48
31.48



(58% solution)



Acrylamide
5.92
5.92



(48% solution)



Acrylic Acid
1.44
—



VPA
—
1.08



DADMAC
5.22
7.82



(62% solution)



NaEDTA
0.1
0.1



Ammonium
3.3
3.3



Persulfate



(27% solution)



Sodium
3.3
3.3



Metabisulfite



(27% solution)










EXAMPLE 2
The following series of tests were performed to compare the performance of exemplary embodiments of the fluid loss control additives of the present invention with HALAD®-413 fluid loss additive, which is described in U.S. Pat. No. 4,676,317, the disclosure of which is incorporated herein by reference. Accordingly, sample cement compositions were prepared that comprised Portland Class H cement, HR®-12 retarder (0.6% bwoc), a free water control additive (0.1% bwoc), a fluid loss control additive (1% bwoc) and sufficient water to provide a density of 16.4 ppg. HR®-12 retarder is a cement set retarder available from Halliburton Energy Services, Inc. In addition, the free water control additive used was hydroxyethyl cellulose, available from Halliburton Energy Services, Inc.
With respect to the fluid loss control additives, Sample No. 1 included HALAD®-413 fluid loss additive as the fluid loss control additive. Sample Nos. 2-9 comprised the exemplary embodiments of the fluid loss control additive of the present invention having a lignite concentration of between 12% to 16% by weight and mole ratios of the grafted monomers as set forth in the table below.









TABLE 2









Mole Ratio















Acrylic




Polymer
NaAMPS
Acrylamide
Acid
VPA
DADMAC















Lignite Graft
0.4
0.2
0.1
—
0.1


Polymer 1


Lignite Graft
0.4
0.25
0.1
—
0.05


Polymer 1A


Lignite Graft
0.4
0.275
0.1
—
0.025


Polymer 1B


Lignite Graft
0.3
0.375
0.1
—
0.025


Polymer 1C


Lignite Graft
0.4
0.2
—
0.05
0.15


Polymer 2


Lignite Graft
0.4
0.275
—
0.05
0.075


Polymer 2A


Lignite Graft
0.4
0.3125
—
0.05
0.0375


Polymer 2B


Lignite Graft
0.3
0.4125
—
0.05
0.0375


Polymer 2C









After preparation, each sample cement composition was poured into a pre-heated cell with a 325-mesh screen, and a fluid loss test was performed for 30 minutes at 1,000 psi and the temperature listed in the table below. The fluid loss tests were performed in accordance with API RP 10B, Recommended Practices for Testing Well Cements. Additionally, the rheological properties of the sample cement compositions were also determined using a FANN MODEL 35 viscometer at the temperature listed in the table below, in accordance with the above-mentioned API RP 10B. The results of these tests are given in the table below.












TABLE 3









Fluid Loss

Fluid





Control

Loss
Rheology Tests: Viscometer Readings



















Sample
Density
Additive
Temp.
(cc/30
300
200
100
60
30
6
3
600


No.
(ppg)
(1% bwoc)
(° F.)
min.)
RPM
RPM
RPM
RPM
RPM
RPM
RPM
RPM






















1
16.4
HALAD ®-413
80
n/d
300+
300+
250
172
101
29
16
300+





180
30
300+
232  
127
 80
 43
10
5
300+


2
16.4
Lignite Graft
80
n/d
300+
300+
265
182
108
31
18
300+




Polymer 1
180
24
300+
255  
138
 88
 48
11
5
300+


3
16.4
Lignite Graft
80
n/d
300+
300+
254
170
 98
25
14
300+




Polymer 2
180
26
300+
232  
122
 75
 39
8
4
300+


4
16.4
Lignite Graft
80
n/d
300+
300+
190
—
—
51
10
300+




Polymer 1A
180
30
212  
148  
80
—
—
16
3
300+


5
16.4
Lignite Graft
80
n/d
300+
300+
173
—
—
31
8
300+




Polymer 2A
180
18
197  
137  
76
—
—
25
3
300+


6
16.4
Lignite Graft
80
n/d
300+
300+
234
—
—
38
12
300+




Polymer 1B
180
30
241  
169  
93
—
—
23
3
300+


7
16.4
Lignite Graft
80
n/d
300+
300+
211
—
—
44
10
300+




Polymer 2B
180
20
230  
160  
85
—
—
21
3
300+


8
16.4
Lignite Graft
80
n/d
300+
300+
259
175
103
29
16
300+




Polymer 1C
180
28
300+
245  
127
 78
 40
8
4
300+


9
16.4
Lignite Graft
80
n/d
300+
300+
221
—
—
52
10
300+




Polymer 2C
180
17
240  
167  
89
—
—
24
3
300+









Thus, Example 2 indicates, inter alia, that the use of exemplary embodiments of the fluid loss control additives of the present invention provides improved fluid loss control and more desirable rheology as compared to HALAD®-413 fluid loss additive.
EXAMPLE 3
Additional tests were performed to compare the performance of exemplary embodiments of the fluid loss control additives of the present invention with HALAD®-413 fluid loss additive at high temperatures. Accordingly, sample cement compositions were prepared that comprised Portland Class H cement, HR®-12 retarder, a free water control additive, SSA-1 strength stabilizing agent, a fluid loss control additive, and sufficient water to provide a density of 16.4 ppg. The free water control additive used was hydroxyethyl cellulose, available from Halliburton Energy Services, Inc. Sample No. 10 did not include the free water control additive. SSA-1 is a strength stabilizing agent (crystalline silica) available from Halliburton Energy Services, Inc. The specific fluid loss control additive included in each sample is set forth in the table below.
After preparation, fluid loss tests were performed at 1,000 psi and the temperature listed in the table below. For this series of tests, the fluid loss was determined using a stirring fluid loss apparatus rated for testing at temperatures up to 400° F. and pressures up to 2,000 psi. The stirring fluid loss apparatus is described in API RP10B-2/ISO 10426-2 in section 10. For these fluid loss tests, the sample was stirred in the test cell while the temperature was increased to the test temperature. After the sample reached the test temperature, rotation of the paddle inside the cell was stopped, the cell was rotated to place the sample against the filter medium (a 325-mesh sieve), and the fluid loss was determined. The filtrate from the sample flowed into a filtrate collection chamber that had back pressure applied to it in order to keep it from boiling for any tests containing salt. The results of these tests are given in the table below.














TABLE 4












Fluid




HR ®-12


Fluid Loss

Loss


Sample
Density
Retarder
FWCA
SSA-1
Control Additive
Temp.
(cc/30


No.
(ppg)
(% bwoc)
(% bwoc)
(% bwoc)
(1% bwoc)
(° F.)
min.)






















10
16.4
0.6
—
35
Lignite Graft
250
42







Polymer 2


11
16.4
1.5
0.1
35
Lignite Graft
300
52







Polymer 2


12
16.4
1.75
0.1
35
Lignite Graft
350
60







Polymer 1B


13
16.4
1.75
0.1
35
Lignite Graft
350
58







Polymer 2B


14
16.4
2
0.1
35
HALAD ®-413
400
82


15
16.4
2
0.1
35
Lignite Graft
400
122







Polymer 1B


16
16.4
2
0.1
35
Lignite Graft
400
175







Polymer 2B


17
16.4
2
0.1
35
Lignite Graft
400
98







Polymer 1C


18
16.4
2
0.1
35
Lignite Graft
400
183







Polymer 2C









Thus, Example 3 indicates, inter alia, that the use of exemplary embodiments of the fluid loss control additives of the present invention provides comparable fluid loss control as HALAD®-413 fluid loss additive.
EXAMPLE 4
Additional tests were performed to evaluate the performance of exemplary embodiments of the fluid loss control additives of the present invention. Accordingly, sample cement compositions were prepared that comprised Portland Class G cement, SSA-1 strength stabilizing agent (35% bwoc), HR®-5 retarder (0.3% bwoc), MICROBOND expanding additive (0.2% bwoc), a fluid loss control additive (1% bwoc), SILICALITE cement additive (10% bwoc), bentonite (2% bwoc) and sufficient water to provide a density of 15.2 ppg. HR®-5 retarder is a cement set retarder available from Halliburton Energy Services, Inc. MICROBOND expanding additive is a cement additive available from Halliburton Energy Services, Inc. SILICALITE cement additive is a finely divided, high surface area amorphous silica available from Halliburton Energy Services, Inc. The specific fluid loss control additive included in each sample is set forth in the table below.
After preparation, each sample cement composition was poured into a pre-heated cell with a 325-mesh screen, and a fluid loss test was performed for 30 minutes at 1,000 psi and the temperature listed in the table below. The fluid loss tests were performed in accordance with API RP 10B, Recommended Practices for Testing Well Cements. Additionally, the rheological properties of the sample cement compositions were also determined using a FANN MODEL 35 viscometer at the temperature listed in the table below, in accordance with the above-mentioned API RP 10B. The results of these tests are given in the table below.












TABLE 5











Fluid





Fluid Loss Control

Loss
Rheology Tests: Viscometer Readings



















Sample
Density
Additive
Temp.
(cc/30
300
200
100
60
30
6
3
600


No.
(ppg)
(1% bwoc)
(° F.)
min.)
RPM
RPM
RPM
RPM
RPM
RPM
RPM
RPM






















19
15.2
Lignite Graft Polymer
80
n/d
128
95
56
38
24
9
6
224




1B
180
68
125
89
51
34
20
7
4
215


20
15.2
Lignite Graft Polymer
80
n/d
101
73
41
28
17
5
3
182




2B
180
72
145
105
61
42
26
10
8
203









Thus, Example 4 indicates, inter alia, that the use of exemplary embodiments of the fluid loss control additives of the present invention may provide desirable fluid loss control and rheology.
EXAMPLE 5
Additional tests were performed to evaluate the performance of exemplary embodiments of the fluid loss control additives of the present invention. Accordingly, sample cement compositions were prepared that comprised Portland Class H cement, SSA-1 strength stabilizing agent (35% bwoc), SCR®-100 retarder (0.25% bwoc), HR®-25 retarder (0.1% bwoc), a fluid loss control additive (1% bwoc) and sufficient water to provide a density of 17.5 ppg. HR®-25 retarder is a cement set retarder available from Halliburton Energy Services, Inc. SCR®-100 retarder is a cement set retarder available from Halliburton Energy Services, Inc. The specific fluid loss control additive included in each sample is set forth in the table below.
After preparation, each sample cement composition was poured into a pre-heated cell with a 325-mesh screen, and a fluid loss test was performed for 30 minutes at 1,000 psi and the temperature listed in the table below. The fluid loss tests were performed in accordance with API RP 10B, Recommended Practices for Testing Well Cements. The results of these tests are given in the table below.












TABLE 6









Fluid Loss

Howco
Fluid




Control

Consistometer
Loss


Sample
Density
Additive
Temp.
Reading
(cc/30













No.
(ppg)
(1% bwoc)
(° F.)
0 min
20 min
min.)
















21
17.5
HALAD ®-413
180
18
14
100


22
17.5
Lignite Graft
180
27
18
50




Polymer 2B









Thus, Example 5 indicates, inter alia, that the use of exemplary embodiments of the fluid loss control additives of the present invention provides improved fluid loss control as compared to HALAD®-413 fluid loss additive.
EXAMPLE 6
Compressive strength and thickening time tests were performed to compare the performance of sample cement compositions that comprised exemplary embodiments of the fluid loss control additives of the present invention with HALAD®-413 fluid loss additive. Accordingly, sample cement compositions were prepared that comprised Portland Class H cement, SSA-1 strength stabilizing agent (35% bwoc), a free water control additive (0.1% bwoc), HR®-12 retarder, a fluid loss control additive (1% bwoc) and sufficient water to provide a density of 16.4 ppg. HR®-12 retarder was included in Sample Nos. 23-25 in an amount of 0.6% bwoc and in Samples Nos. 26-28 in an amount of 2% bwoc. The free water control additive used was hydroxyethyl cellulose, available from Halliburton Energy Services, Inc. The specific fluid loss control additive included in each sample is set forth in the table below.
After preparation, the sample cement compositions were subjected to 48-hour compressive strength tests and thickening time tests at the temperature listed in the table below, in accordance with API RP10B, Recommended Practices for Testing Well Cements. The results of these tests are set forth in the table below.













TABLE 7








Fluid Loss

Thickening





HR ®-12
Control

Time to 70
Comp.


Sample
Density
Retarder
Additive
Temp.
BC
Strength


No.
(ppg)
(% bwoc)
(1% bwoc)
(° F.)
(Hr:Min)
(psi)







23
16.4
0.6
HALAD ®-413
250
6:46
3,963


24
16.4
0.6
Lignite Graft
250
6:57
3,750





Polymer 1B


25
16.4
0.6
Lignite Graft
250
6:58
3,243





Polymer 2B


26
16.4
2.0
HALAD ®-413
325
4:46
n/d


27
16.4
2.0
Lignite Graft
325
3:35
n/d





Polymer 1B


28
16.4
2.0
Lignite Graft
325
2:17
n/d





Polymer 2B









Thus, Example 6 indicates, inter alia, that the use of exemplary embodiments of the fluid loss control additives of the present invention may provide desirable thickening times and compressive strengths.
The particular embodiments disclosed above are illustrative only, as the present invention may be susceptible to various modifications and alternative forms. However, it should be understood that the invention is not intended to be limited to the particular embodiments disclosed. Rather, the present invention is to cover all modifications, equivalents and alternatives falling within the scope and spirit of the present invention as defined by the following appended claims.

## Claims

1. A method of cementing comprising:
introducing a cement composition into a well bore having a bottom hole circulating temperature of at least about 500° F., the cement composition comprising:
water;
a cement; and
a fluid loss control additive comprising a graft polymer, the graft polymer comprising:
a backbone comprising a lignite;
a first grafted monomer comprising at least one monomer selected from the group consisting of 2-acrylamido-2-methylpropanesulfonic acid, any salt thereof and any combination thereof; and
a second grafted monomer comprising diallyldimethylammonium chloride.

2. The method of claim 1, wherein the cement comprises a hydraulic cement.

3. The method of claim 1, wherein the graft polymer comprises the backbone in an amount in the range of from about 10% to about 50% by weight of the graft polymer on a dry basis.

4. The method of claim 1, wherein the backbone comprises at least one polymer selected from the group consisting of polyvinyl alcohol, polyethylene oxide, polypropylene oxide, polyethyleneimine and any combination thereof.

5. The method of claim 1, wherein the lignite comprises a salt of the lignite.

6. The method of claim 1, wherein the graft polymer comprises a third grafted monomer comprising acrylamide.

7. The method of claim 6, wherein the graft polymer comprises a fourth grafted monomer comprising at least one monomer selected from the group consisting of acrylic acid, vinylphosphonic acid, any salt thereof and any combination thereof.

8. The method of claim 7, wherein the first grafted monomer, the second grafted monomer, the third grafted monomer and the fourth grafted monomer are individually present in one or more pendant groups of the graft polymer, wherein each of the one or more pendant groups comprise at least one member selected from the group consisting of the first grafted monomer, the second grafted monomer, the third grafted monomer, the fourth grafted monomer and any combination thereof.

9. The method of claim 6, wherein the graft polymer comprises a fourth grafted monomer comprising at least one monomer selected from the group consisting of acrylic acid, any salt thereof and any combination thereof, and wherein the graft polymer has a first grafted monomer-to-third grafted monomer-to-fourth grafted monomer-to-second grafted monomer mole ratio in the range of from about 4:3:2:1 to about 4:1:0.5:0.1.

10. The method of claim 6, wherein the graft polymer comprises a fourth grafted monomer comprising at least one monomer selected from the group consisting of a vinylphosphonic acid, any salt thereof and any combination thereof, and wherein the graft polymer has a first grafted monomer-to-third grafted monomer-to-fourth grafted monomer-to-second grafted monomer mole ratio in the range of from about 4:4:1:2 to about 4:1:0.1:0.1.

11. The method of claim 1, comprising allowing the cement composition to set in the subterranean formation.

12. A method of cementing comprising:
introducing a cement composition into a subterranean formation, the cement composition comprising:
water;
a cement; and
a fluid loss control additive comprising a graft polymer, the graft polymer comprising:
a backbone comprising a lignite;
a first grafted monomer comprising at least one monomer selected from the group consisting of 2-acrylamido-2-methylpropanesulfonic acid, any salt thereof and any combination thereof; and
a second grafted monomer comprising at least one monomer selected from the group consisting of vinylphosphonic acid, any salt thereof and any combination thereof.

13. The method of claim 12, wherein the fluid loss control additive comprises at least one monomer selected from the group consisting of acrylamide, acrylic acid, diallyldimethylammonium chloride, any salt thereof and any combination thereof.

14. A method of cementing comprising:
introducing a cement composition into a space between a pipe string and a subterranean formation, the cement composition comprising:
water;
a cement; and
a fluid loss control additive comprising a graft polymer, the graft polymer comprising:
a backbone comprising a lignite;
a first grafted monomer comprising at least one monomer selected from the group consisting of 2-acrylamido-2-methylpropanesulfonic acid, any salt thereof and any combination thereof;
a second grafted monomer comprising diallyldimethylammonium chloride;
a third grafted monomer comprising acrylamide; and
a fourth grafted monomer comprising at least one monomer selected from the group consisting of vinylphosphonic acid, any salt thereof and any combination thereof; and


allowing the cement composition to set in the space between the pipe string and the subterranean formation.

15. The method of claim 14, wherein the graft polymer comprises the backbone in an amount in the range of from about 10% to about 50% by weight of the graft polymer on a dry basis.

16. The method of claim 14, wherein the graft polymer comprises a first grafted monomer-third grafted monomer-fourth grafted monomer-second grafted monomer mole ratio in the range of from about 4:4:1:2 to about 4:1:0.1:0.1.

17. The method of claim 14, wherein introducing a cement composition into a space between a pipe string and a subterranean formation comprises introducing the cement composition into a well bore having a bottom hole circulating temperature of at least about 500° F.

18. The method of claim 14, comprising running the pipe string into a well bore penetrating the subterranean formation.