CA2431857A1 - Cementing subterranean zones using cement compositions containing biodegradable dispersants - Google Patents
Cementing subterranean zones using cement compositions containing biodegradable dispersants Download PDFInfo
- Publication number
- CA2431857A1 CA2431857A1 CA002431857A CA2431857A CA2431857A1 CA 2431857 A1 CA2431857 A1 CA 2431857A1 CA 002431857 A CA002431857 A CA 002431857A CA 2431857 A CA2431857 A CA 2431857A CA 2431857 A1 CA2431857 A1 CA 2431857A1
- Authority
- CA
- Canada
- Prior art keywords
- cement
- side chain
- composition
- chain forming
- dispersant
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/42—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells
- C09K8/46—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells containing inorganic binders, e.g. Portland cement
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/28—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/287—Polyamides
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/28—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/32—Polyethers, e.g. alkylphenol polyglycolether
Abstract
Methods of cementing subterranean zones using cement compositions containing biodegradable dispersants are provided. The methods are basically comprised of the steps of preparing a hydraulic cement, a biodegradable dispersant comprised of polyaspartic acid containing side chains formed by reacting one or more side chain chemicals with said polyaspartic acid and sufficient water to form a pumpable slurry, placing the cement composition into a zone to be cemented and allowing the cement composition to set into an impermeable solid mass therein.
Description
CEMENTING SUBTERRANEAN
ZONES USING CEMENT COMPOSITIONS
CONTAINING BIODEGRADABLE DISPERSANTS
Background of the Invention 1. Field of the Invention.
The present invention relates to methods of cementing subterranean zones using cement compositions containing biodegradable dispersants.
ZONES USING CEMENT COMPOSITIONS
CONTAINING BIODEGRADABLE DISPERSANTS
Background of the Invention 1. Field of the Invention.
The present invention relates to methods of cementing subterranean zones using cement compositions containing biodegradable dispersants.
2. Descriution of the Prior Art.
In the cementing of oil and gas wells and the like, dispersants are extensively used to reduce the rheologies of cement compositions, i.e., the apparent viscosities and other properties of the cement compositions, as well as to reduce the water content of the cement compositions. The reduction of the rhealogy of a cement composition allows the cement composition to be pumped with less friction pressure which utilizes less pump horsepower.
In addition, the lower rheology often allows the cement composition to be pumped in turbulent flow. Turbulent flow characteristics are desirable when pumping cement compositions in oil and gas wells to more efficiently remove drilling fluid from surfaces in the well bore as the drilling fluid is displaced by the cement composition being pumped. The inclusion of dispersants in cement compositions is also desirable in that the presence of the dispersants reduces the Water required for preparation of the cement compositions. Cement compositions having reduced water content are characterized by improved compressive strength development.
A number of dispersing agents have been utilized heretofore in cement compositions, particularly in cement compositions used for primary and remedial cementing in oil and gas wells. For example, certain organic acids such as gluconic acid and citric acid have been recognized by those skilled in the art as cement dispersants. However, such organic acids are also strong cement composition set retarding agents which is often undesirable. That is, the presence of an organic acid dispersant in a cement composition prevents the cement composition from setting for a relatively long period of time which is often costly or otherwise detrimental. Other dispersants which are commonly used in hydraulic cement compositions include polynapthylene sulfonate which is commercially available under the trade designation "CFR-2TM" from Halliburton Energy Services of Duncan, Oklahoma, the condensation product of formaldehyde, acetone and a sulfite which is commercially available under the trade designation "CFR-3TM" from Halliburton Energy Services, poly-B-naphthol sulfonate, polymelamine sulfonate and many others. Another highly efficient dispersant for use in cement compositions is disclosed in U.S. Patent No. 6,136,950 issued to Vickers, Jr. et al. on October 24, 2000 which is incorporated herein by reference. The dispersant is a polycarboxylate polymer comprised of a functionalized polyamide main chain polymer onto which are grafted at least some oligomeric or polymeric hydrophilic side chains.
Commercially available dispersants are generally not environmentally acceptable, especially in offshore operations, in that they do not undergo complete biodegradation in the environment and can cause damage to aquatic and other life therein.
Thus, there are needs for improved methods of cementing subterranean zones penetrated by well bores using cement compositions containing biodegradable dispersants.
Summary of the Invention The present invention provides methods of using improved cement compositions containing biodegradable dispersants for cementing subterranean zones penetrated by well bores which meet the needs described above and overcome the deficiencies of the prior art.
The cement compositions which are useful in accordance with the methods of this invention are basically comprised of a hydraulic cement, a biodegradable dispersant comprised of polyaspartic acid containing side chains formed by reacting one or mare side chain forming chemicals with said polyaspartic acid and sufficient water to form a pumpable slurry. The side chain containing biodegradable dispersant is present in an amount sufficient to reduce the rheology and water content of the cement composition. Preferably, the side chain containing polyaspartic acid dispersant has a molecular weight in the range of from about 5,000 to about 500,000 daltons.
The methods of cementing a subterranean zone penetrated by a well bore of this invention are basically comprised of the following steps. A cement composition is prepared comprised of a hydraulic cement, a biodegradable dispersant comprised of the above described side chain containing polyaspartic acid present in an amount sufficient to reduce the rheology and water content of the cement composition and sufficient water to form a pumpable slurry. Thereafter, the cement composition is placed in the subterranean zone to be cemented and is allowed to set into an impermeable solid mass therein.
In addition to functioning as a cement composition rheology and water content reducing dispersant, the side chain containing polyaspartic acid also functions to enhance the effectiveness of a fluid loss control agent when such an agent is included in the cement composition. For example, a hydroxyethylcellulose or a polyethylene imine fluid loss control agent can be included in the cement composition and the side chain containing polyaspartic acid therein functions with the fluid loss control agent to reduce fluid loss to a substantially greater degree than when the side chain containing polyaspartic acid is not present.
Thus, it is a general object of the present invention to provide improved methods of cementing subterranean zones using cement compositions containing biodegradable dispersants.
Other and further objects, features and advantages of the present invention will be readily apparent to those skilled in the art upon a reading of the description of preferred embodiments which follows.
Description of Preferred Embodiments As mentioned, the improved methods of this invention utilize cement compositions basically comprised of a hydraulic cement, a biodegradable dispersant comprised of polyaspartic acid containing side chains present in an amount sufficient to reduce the rheology and water content of the cement composition and sufficient water to form a pumpable slurry.
The biodegradable side chain containing polyaspartic acid dispersant can be prepared by the condensation reaction of malefic acid and ammonia under heat. The polyaspartic acid formed is then reacted with a side chain forming chemical. The side chain forming chemical can be one or more of ethylene oxide, propylene oxide, a vinyl functional polyethylene glycol, a vinyl functional polypropylene glycol, an amino functional polyethylene glycol (the most preferred being those terminated by an NHz group), a polyester, a polyamide, polyethyleneoxide, polypropyleneoxide and the like. The molecular weight of the resulting side chain containing polyaspartic acid is increased to in the range of from about 5,000 to about 500,000 daltons. The formation of the side chains on the polyaspartic acid reduces the cement set retarding properties of the acid in addition to reducing the rheology and water content of cement compositions to which it is added. The side chain containing polyaspartic acid dispersant is included in a cement composition in a relatively small amount, i.e., an amount in the range of from about 0.10% to about 2.0% by weight of cement therein, preferably in an amount of about 0.20%.
A variety of hydraulic cements can be utilized in accordance with the present invention including those comprised of calcium, aluminum, silicon, oxygen andlor 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, silica cements and high alkalinity cements. Portland cements are generally preferred for use in accordance with the present invention, and Portland cements of the types defined and described in API Specification For Materials And Testing For Well Cements, API Specification 10, 5~' Edition, dated July 1, 1990 of the American Petroleum Institute and their equivalents are particularly preferred. API Portland cements including classes A, B, C, G and H can be utilized with API classes G and H being preferred and class H
being the most preferred.
The water utilized in the cement compositions of this invention can be fresh water, unsaturated salt water and saturated salt water including brines or seawater.
Generally, the water can be from any source provided it does not contain an excess of compounds that adversely affect other components in the cement compositions. The water is present in a cement composition of this invention in an amount sufficient to form a pumpable slurry.
More particularly, the water is present in the cement compositions in an amount in the range of from about 18% to about 110% by weight of hydraulic cement therein, more preferably in an amount of from about 25% to about 56%.
As mentioned, the cement compositions of this invention can also include a fluid loss control additive which when utilized in combination with the biodegradable dispersant of this invention provides synergistically low fluid loss from the cement composition.
Examples of fluid loss control agents which can be utilized in combination with the biodegradable dispersants of this invention, include, but are not limited to, hydroxyethylcellulose, hydroxymethylcellulose, carboxymethylhydroxyethylcellulose, hydroxypropylcellulose, a copolymer of 2-acrylamido-2-methyl propane sulfonic acid and N,N-dimethylacrylamide, a graft lignin or lignite polymer, starch, guar gum, hydroxypropylguar, polyethyleneimine, polyvinylalcohol, polyvinylacetate, carragenan and xanthane. Of these, hydroxyethylcellulose is preferred. When used, the fluid loss control additive is included in a cement composition of this invention in an amount in the range of from about 0.2% to about 2.0% by weight of cement therein.
The biodegradable side chain containing polyaspartic acid dispersants of this invention can be effectively utilized in cement compositions which are subjected to temperatures in the range of from about 32°F to about 500°F. The cement composition densities utilized can range from about 0.66 to about 2.50 kilograms per liter. As mentioned, the biodegradable side chain containing polyaspartic acid dispersants of this invention are biodegradable and nontoxic.
As will be understood by those skilled in the art, when the cement compositions of this invention are utilized for cementing subterranean zones penetrated by well bores, they can also include a variety of other conventional well cement additives. For example, the cement compositions can include weighting materials, set retarding additives, set accelerators, strength stabilizers, strength enhancers, lightweight additives, anti-gas migration additives, defoamers, foamers, expansion additives and the like.
The methods of the present invention for cementing a subterranean zone penetrated by a well bore basically comprise the following steps: (a) preparing a cement composition of this invention comprised of a hydraulic cement, a biodegradable dispersant comprised of side chain containing polyaspartic acid present in an amount sufficient to reduce the rheology and water content of the cement composition and sufficient water to form a pumpable slurry, (b) placing the cement composition in the zone to be cemented and (c) allowing the cement composition to set into an impermeable solid mass therein.
As mentioned above, the cement compositions of this invention containing the above described biodegradable dispersant have reduced rheology and reduced water content as compared to cement compositions which do not include the biodegradable dispersant. The lower rheology of the cement composition allows the cement composition to be pumped with less friction pressure utilizing less pump horsepower. The lower rheology also allows the cement composition to be pumped in turbulent flow which is highly advantageous in primary cementing operations. The reduced water content of the cement compositions of this invention substantially improves the compressive strengths of the cement compositions when set. As also mentioned above, the biodegradable dispersant utilized in the cement compositions of this invention synergistically function in combination with certain fluid loss control agents to reduce the fluid loss from the cement compositions to a substantially greater degree than cement compositions which include the fluid loss control agent but not the biodegradable dispersant.
In order to further illustrate the cement compositions and methods of the present invention, the following examples are given.
Example 1 Test cement compositions were prepared containing fresh water, Dyckerhoff API
Class G Portland cement and a biodegradable dispersant of this invention, i.e., an ethylene oxide side chain containing polyaspartic acid having a molecular weight of about 10,000 daltons. The thickening times of the test cement compositions at 125°F, the rheology of the cement compositions after preparation at room temperature, the rheology of the cement compositions after conditioning at 125°F, the free water of the cement compositions, the settling of the cement compositions and the compressive strengths of the cement compositions at 3,000 psi and 125°F were determined. The quantities of the components in the test cement compositions and the test results are given in Table I below.
TABLE I
Effect Of Concentration On Rheology Test Cement Composition No. 1 2 3 4 Fresh Water, % by wt. of cement44 44 44 44 Ethylene Oxide Side Chain 0.1 0.2 0,3 0.4 Containing Polyaspartic Acid, % by wt.
of cement Class G Cement, kilograms 100 100 100 100 Cement Composition Density, 1.92 1.92 1.92 1.92 kilograms/liter Thickenin~Time at 125F
30 Bc 2:57 5:43 - -70 Bc 3:30 6:09 - -100 Bc 3:37 6:17 - -Rheolo~y After Preparation At Room Tem erature 25-17-9 29-18-9 25-16-18 23-15-8 300-200-100- 6-4-3-2 6-3.5-2-1.55-3-2-1 4-3-2-1 60-30-6-3 rpm Rheology A$er Conditioning At 125F
60-30-6-3 rpm 10-8-6-54-3-2-1.5 3-2-2-1 3-2-2-1 Free Water, % by vol. 9 16 44 38 Settlin_ ,~%by vol. 0 4.8 56 62 Universal Cement Analyzer Data 50 psi, Hrs:Min 7:44 - - -500 psi, Hrs:Min 9:15 10:02 -24 Hrs, psi 4161 2500 set set 72 Hrs, psi 5843 4141 - -g As shown in Table I, the improved cement compositions of this invention containing a biodegradable dispersant comprised of ethylene oxide side chain containing polyaspartic acid have excellent properties. While the thickening times, the free water, settling and the set times increase with increased dispersant concentrations, at concentrations of the biodegradable dispersant below about 0.3% by weight of cement, the dispersant provides excellent cement composition properties.
Example 2 Additional test cement compositions were prepared utilizing fresh water and Dyckerhoff API Class G Portland cement. Test Cement Composition No. 1 contained only fresh water, cement and hydroxyethylcellulose fluid loss control agent. Test Cement Composition No. 2 contained fresh water, cement, the dispersant of this invention and hydroxyethylcellulose fluid loss control agent. The Theologies after preparation at room temperature and after conditioning at 125°F were determined as well as the fluid loss from the test cement compositions at 125°F. The quantities of the components and the results of the tests are given in Table II below.
TABLE II
Synergistic Effect With Fluid Loss Control Additives Test Cement Composition No. #1 #2 Fresh Water, % by wt. of cement 45 45 Ethylene Oxide Side Chain Containing Polyaspartic0 0.2 Acid, % by wt.
of cement Hydroxyethylcellulose Fluid Loss Agent, % 0.75 0.75 by wt. of cement Class G Cement, kilograms 100 100 Cement Composition Density, kilograms/liter 1.9 1.9 Rheology After PreQaration At Room Temperature Rheology After Conditioning, At 125F
API Fluid Loss At 125F. m1130 min 245 60 As shown in Table II, the cement composition containing the dispersant of the present invention (Test Cement Composition No. 2) produced lower rheology and substantially less fluid loss than the cement composition without the dispersant (Test Cement Composition No.
1).
Example 3 Additional test cement compositions were prepared comprised of water, Dyckerhoff Class G cement and the biodegradable dispersant of this invention. The test compositions included varying amounts of water, but the same amounts of cement and dispersant. The rheologies of the test cement compositions after preparation at room temperature and after conditioning at 125°F were determined as well as the set times and compressive strengths of the cement compositions. The results of these tests are set forth in Table III
below.
TABLE III
Water Reducing Properties Test Cement Composition No. 1 2 3 4 Fresh Water, % by wt. of cement 44 35 30 25 Ethylene Oxide Side Chain Containing 0.2 0.2 0.2 0.2 Polyaspartic Acid, % by wt. of cement Class G Cement, kilograms 100 100 100 100 Cement Composition Density, 1.92 2.03 2.11 2.21 kilogramsJliter Rheolosv After Preparation At Room Temperature 29-18-9 67-41-18 163-95-36 300+-243-300-200-100- 6-3.5-2- 10-5-3-2 17-6-1-0 94 60-30-6-3 1.5 45-15-1.5-Rheolo~y After Conditioning At 125°F
300-200-100- 21-13-7 38-21-8 119-70-30 300+-211-60-30-6-3 4-3-2-1.5 4-2-1-0 16-7-1-0 94 Universal Cement Analvzer Data 50 psi, Hrs:Min - 5:36 4;39 4:32 500 psi, Hrs:Min 10:02 6:38 5:26 5:08 24 Hrs, psi 2500 6000 6547 9000 72 Hrs, psi 4141 7531 - 10529 From Table III it can be seen that the biodegradable dispersant of this invention reduces the water content required while maintaining pumpability. In addition, the set cement compositions have excellent compressive strengths.
Example 4 Three additional cement compositions of this invention were prepared comprised of salt water containing various concentrations of salt, the biodegradable dispersant of this invention and Dyckerhoff Class G cement. The rheologies of the test compositions after preparation at room temperature and after conditioning at 125°F were determined as well as the set times and compressive strengths of the cement compositions. The results of these tests are set forth in Table IV below.
O 'O O ~ ~ N ~!1 ~ h V
O O ~ N ~ O ~ ~ v ~ O
N
O
N 0o O V~ 'd. p' V~ O, h ~.' O l~
O ~r O OW.r ..!~ f ~ v~ ,-... M o0O O
'-r N M r.~.., '; .--i .-M-~ M N
N
M ~ O ~ ~ O
r.r O d p O1 ,..~~., ~ rM., O, O d; ~O
'-r M ~ pp N 00 ~ N M
N M .-~ M
U
~"'q eQ o O ;b ~
d H _ U
i _ td O" cps 4r z ~ ~ ' O
~.
o w o v ~ ~ i :~ ~ .., '~
U 3 ,>; ~ Ga O
O ~ N
~d U .~ O
~
O .~ c ~
~
~b U ' . o ~
- a~
d ~ .y ~ o 'n ~~ ~ ~ U
~' ~ ' a, ~ o ~" ;
~" ~ o ~
dog .~ .., U~~ ~u.
~
a~ U U N O N O ~ -'" -'."
" O p O p M ~
M ~ ~, ~, x~ x ~n ~ O O ~ U O O d' ~ O p O O N
M ~ M ~O ~ N O N
I~
W fl% ~ ~
W U U
,- C
~CA 02431857 2003-06-09 From Table IV it can be seen that the biodegradable dispersant of this invention is salt tolerant and that the Theologies of the test cement compositions were low even when the salt water was saturated at 37°l° salt by weight of water. While the set times are somewhat longer, the compressive strengths are excellent.
Thus, the improved methods of this invention are well adapted to carry out the objects and attain the ends and advantages mentioned as well as those which are inherent therein.
While numerous changes may be made by those skilled in the art, such changes are encompassed within the spirit of this invention as defined by the appended claims.
In the cementing of oil and gas wells and the like, dispersants are extensively used to reduce the rheologies of cement compositions, i.e., the apparent viscosities and other properties of the cement compositions, as well as to reduce the water content of the cement compositions. The reduction of the rhealogy of a cement composition allows the cement composition to be pumped with less friction pressure which utilizes less pump horsepower.
In addition, the lower rheology often allows the cement composition to be pumped in turbulent flow. Turbulent flow characteristics are desirable when pumping cement compositions in oil and gas wells to more efficiently remove drilling fluid from surfaces in the well bore as the drilling fluid is displaced by the cement composition being pumped. The inclusion of dispersants in cement compositions is also desirable in that the presence of the dispersants reduces the Water required for preparation of the cement compositions. Cement compositions having reduced water content are characterized by improved compressive strength development.
A number of dispersing agents have been utilized heretofore in cement compositions, particularly in cement compositions used for primary and remedial cementing in oil and gas wells. For example, certain organic acids such as gluconic acid and citric acid have been recognized by those skilled in the art as cement dispersants. However, such organic acids are also strong cement composition set retarding agents which is often undesirable. That is, the presence of an organic acid dispersant in a cement composition prevents the cement composition from setting for a relatively long period of time which is often costly or otherwise detrimental. Other dispersants which are commonly used in hydraulic cement compositions include polynapthylene sulfonate which is commercially available under the trade designation "CFR-2TM" from Halliburton Energy Services of Duncan, Oklahoma, the condensation product of formaldehyde, acetone and a sulfite which is commercially available under the trade designation "CFR-3TM" from Halliburton Energy Services, poly-B-naphthol sulfonate, polymelamine sulfonate and many others. Another highly efficient dispersant for use in cement compositions is disclosed in U.S. Patent No. 6,136,950 issued to Vickers, Jr. et al. on October 24, 2000 which is incorporated herein by reference. The dispersant is a polycarboxylate polymer comprised of a functionalized polyamide main chain polymer onto which are grafted at least some oligomeric or polymeric hydrophilic side chains.
Commercially available dispersants are generally not environmentally acceptable, especially in offshore operations, in that they do not undergo complete biodegradation in the environment and can cause damage to aquatic and other life therein.
Thus, there are needs for improved methods of cementing subterranean zones penetrated by well bores using cement compositions containing biodegradable dispersants.
Summary of the Invention The present invention provides methods of using improved cement compositions containing biodegradable dispersants for cementing subterranean zones penetrated by well bores which meet the needs described above and overcome the deficiencies of the prior art.
The cement compositions which are useful in accordance with the methods of this invention are basically comprised of a hydraulic cement, a biodegradable dispersant comprised of polyaspartic acid containing side chains formed by reacting one or mare side chain forming chemicals with said polyaspartic acid and sufficient water to form a pumpable slurry. The side chain containing biodegradable dispersant is present in an amount sufficient to reduce the rheology and water content of the cement composition. Preferably, the side chain containing polyaspartic acid dispersant has a molecular weight in the range of from about 5,000 to about 500,000 daltons.
The methods of cementing a subterranean zone penetrated by a well bore of this invention are basically comprised of the following steps. A cement composition is prepared comprised of a hydraulic cement, a biodegradable dispersant comprised of the above described side chain containing polyaspartic acid present in an amount sufficient to reduce the rheology and water content of the cement composition and sufficient water to form a pumpable slurry. Thereafter, the cement composition is placed in the subterranean zone to be cemented and is allowed to set into an impermeable solid mass therein.
In addition to functioning as a cement composition rheology and water content reducing dispersant, the side chain containing polyaspartic acid also functions to enhance the effectiveness of a fluid loss control agent when such an agent is included in the cement composition. For example, a hydroxyethylcellulose or a polyethylene imine fluid loss control agent can be included in the cement composition and the side chain containing polyaspartic acid therein functions with the fluid loss control agent to reduce fluid loss to a substantially greater degree than when the side chain containing polyaspartic acid is not present.
Thus, it is a general object of the present invention to provide improved methods of cementing subterranean zones using cement compositions containing biodegradable dispersants.
Other and further objects, features and advantages of the present invention will be readily apparent to those skilled in the art upon a reading of the description of preferred embodiments which follows.
Description of Preferred Embodiments As mentioned, the improved methods of this invention utilize cement compositions basically comprised of a hydraulic cement, a biodegradable dispersant comprised of polyaspartic acid containing side chains present in an amount sufficient to reduce the rheology and water content of the cement composition and sufficient water to form a pumpable slurry.
The biodegradable side chain containing polyaspartic acid dispersant can be prepared by the condensation reaction of malefic acid and ammonia under heat. The polyaspartic acid formed is then reacted with a side chain forming chemical. The side chain forming chemical can be one or more of ethylene oxide, propylene oxide, a vinyl functional polyethylene glycol, a vinyl functional polypropylene glycol, an amino functional polyethylene glycol (the most preferred being those terminated by an NHz group), a polyester, a polyamide, polyethyleneoxide, polypropyleneoxide and the like. The molecular weight of the resulting side chain containing polyaspartic acid is increased to in the range of from about 5,000 to about 500,000 daltons. The formation of the side chains on the polyaspartic acid reduces the cement set retarding properties of the acid in addition to reducing the rheology and water content of cement compositions to which it is added. The side chain containing polyaspartic acid dispersant is included in a cement composition in a relatively small amount, i.e., an amount in the range of from about 0.10% to about 2.0% by weight of cement therein, preferably in an amount of about 0.20%.
A variety of hydraulic cements can be utilized in accordance with the present invention including those comprised of calcium, aluminum, silicon, oxygen andlor 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, silica cements and high alkalinity cements. Portland cements are generally preferred for use in accordance with the present invention, and Portland cements of the types defined and described in API Specification For Materials And Testing For Well Cements, API Specification 10, 5~' Edition, dated July 1, 1990 of the American Petroleum Institute and their equivalents are particularly preferred. API Portland cements including classes A, B, C, G and H can be utilized with API classes G and H being preferred and class H
being the most preferred.
The water utilized in the cement compositions of this invention can be fresh water, unsaturated salt water and saturated salt water including brines or seawater.
Generally, the water can be from any source provided it does not contain an excess of compounds that adversely affect other components in the cement compositions. The water is present in a cement composition of this invention in an amount sufficient to form a pumpable slurry.
More particularly, the water is present in the cement compositions in an amount in the range of from about 18% to about 110% by weight of hydraulic cement therein, more preferably in an amount of from about 25% to about 56%.
As mentioned, the cement compositions of this invention can also include a fluid loss control additive which when utilized in combination with the biodegradable dispersant of this invention provides synergistically low fluid loss from the cement composition.
Examples of fluid loss control agents which can be utilized in combination with the biodegradable dispersants of this invention, include, but are not limited to, hydroxyethylcellulose, hydroxymethylcellulose, carboxymethylhydroxyethylcellulose, hydroxypropylcellulose, a copolymer of 2-acrylamido-2-methyl propane sulfonic acid and N,N-dimethylacrylamide, a graft lignin or lignite polymer, starch, guar gum, hydroxypropylguar, polyethyleneimine, polyvinylalcohol, polyvinylacetate, carragenan and xanthane. Of these, hydroxyethylcellulose is preferred. When used, the fluid loss control additive is included in a cement composition of this invention in an amount in the range of from about 0.2% to about 2.0% by weight of cement therein.
The biodegradable side chain containing polyaspartic acid dispersants of this invention can be effectively utilized in cement compositions which are subjected to temperatures in the range of from about 32°F to about 500°F. The cement composition densities utilized can range from about 0.66 to about 2.50 kilograms per liter. As mentioned, the biodegradable side chain containing polyaspartic acid dispersants of this invention are biodegradable and nontoxic.
As will be understood by those skilled in the art, when the cement compositions of this invention are utilized for cementing subterranean zones penetrated by well bores, they can also include a variety of other conventional well cement additives. For example, the cement compositions can include weighting materials, set retarding additives, set accelerators, strength stabilizers, strength enhancers, lightweight additives, anti-gas migration additives, defoamers, foamers, expansion additives and the like.
The methods of the present invention for cementing a subterranean zone penetrated by a well bore basically comprise the following steps: (a) preparing a cement composition of this invention comprised of a hydraulic cement, a biodegradable dispersant comprised of side chain containing polyaspartic acid present in an amount sufficient to reduce the rheology and water content of the cement composition and sufficient water to form a pumpable slurry, (b) placing the cement composition in the zone to be cemented and (c) allowing the cement composition to set into an impermeable solid mass therein.
As mentioned above, the cement compositions of this invention containing the above described biodegradable dispersant have reduced rheology and reduced water content as compared to cement compositions which do not include the biodegradable dispersant. The lower rheology of the cement composition allows the cement composition to be pumped with less friction pressure utilizing less pump horsepower. The lower rheology also allows the cement composition to be pumped in turbulent flow which is highly advantageous in primary cementing operations. The reduced water content of the cement compositions of this invention substantially improves the compressive strengths of the cement compositions when set. As also mentioned above, the biodegradable dispersant utilized in the cement compositions of this invention synergistically function in combination with certain fluid loss control agents to reduce the fluid loss from the cement compositions to a substantially greater degree than cement compositions which include the fluid loss control agent but not the biodegradable dispersant.
In order to further illustrate the cement compositions and methods of the present invention, the following examples are given.
Example 1 Test cement compositions were prepared containing fresh water, Dyckerhoff API
Class G Portland cement and a biodegradable dispersant of this invention, i.e., an ethylene oxide side chain containing polyaspartic acid having a molecular weight of about 10,000 daltons. The thickening times of the test cement compositions at 125°F, the rheology of the cement compositions after preparation at room temperature, the rheology of the cement compositions after conditioning at 125°F, the free water of the cement compositions, the settling of the cement compositions and the compressive strengths of the cement compositions at 3,000 psi and 125°F were determined. The quantities of the components in the test cement compositions and the test results are given in Table I below.
TABLE I
Effect Of Concentration On Rheology Test Cement Composition No. 1 2 3 4 Fresh Water, % by wt. of cement44 44 44 44 Ethylene Oxide Side Chain 0.1 0.2 0,3 0.4 Containing Polyaspartic Acid, % by wt.
of cement Class G Cement, kilograms 100 100 100 100 Cement Composition Density, 1.92 1.92 1.92 1.92 kilograms/liter Thickenin~Time at 125F
30 Bc 2:57 5:43 - -70 Bc 3:30 6:09 - -100 Bc 3:37 6:17 - -Rheolo~y After Preparation At Room Tem erature 25-17-9 29-18-9 25-16-18 23-15-8 300-200-100- 6-4-3-2 6-3.5-2-1.55-3-2-1 4-3-2-1 60-30-6-3 rpm Rheology A$er Conditioning At 125F
60-30-6-3 rpm 10-8-6-54-3-2-1.5 3-2-2-1 3-2-2-1 Free Water, % by vol. 9 16 44 38 Settlin_ ,~%by vol. 0 4.8 56 62 Universal Cement Analyzer Data 50 psi, Hrs:Min 7:44 - - -500 psi, Hrs:Min 9:15 10:02 -24 Hrs, psi 4161 2500 set set 72 Hrs, psi 5843 4141 - -g As shown in Table I, the improved cement compositions of this invention containing a biodegradable dispersant comprised of ethylene oxide side chain containing polyaspartic acid have excellent properties. While the thickening times, the free water, settling and the set times increase with increased dispersant concentrations, at concentrations of the biodegradable dispersant below about 0.3% by weight of cement, the dispersant provides excellent cement composition properties.
Example 2 Additional test cement compositions were prepared utilizing fresh water and Dyckerhoff API Class G Portland cement. Test Cement Composition No. 1 contained only fresh water, cement and hydroxyethylcellulose fluid loss control agent. Test Cement Composition No. 2 contained fresh water, cement, the dispersant of this invention and hydroxyethylcellulose fluid loss control agent. The Theologies after preparation at room temperature and after conditioning at 125°F were determined as well as the fluid loss from the test cement compositions at 125°F. The quantities of the components and the results of the tests are given in Table II below.
TABLE II
Synergistic Effect With Fluid Loss Control Additives Test Cement Composition No. #1 #2 Fresh Water, % by wt. of cement 45 45 Ethylene Oxide Side Chain Containing Polyaspartic0 0.2 Acid, % by wt.
of cement Hydroxyethylcellulose Fluid Loss Agent, % 0.75 0.75 by wt. of cement Class G Cement, kilograms 100 100 Cement Composition Density, kilograms/liter 1.9 1.9 Rheology After PreQaration At Room Temperature Rheology After Conditioning, At 125F
API Fluid Loss At 125F. m1130 min 245 60 As shown in Table II, the cement composition containing the dispersant of the present invention (Test Cement Composition No. 2) produced lower rheology and substantially less fluid loss than the cement composition without the dispersant (Test Cement Composition No.
1).
Example 3 Additional test cement compositions were prepared comprised of water, Dyckerhoff Class G cement and the biodegradable dispersant of this invention. The test compositions included varying amounts of water, but the same amounts of cement and dispersant. The rheologies of the test cement compositions after preparation at room temperature and after conditioning at 125°F were determined as well as the set times and compressive strengths of the cement compositions. The results of these tests are set forth in Table III
below.
TABLE III
Water Reducing Properties Test Cement Composition No. 1 2 3 4 Fresh Water, % by wt. of cement 44 35 30 25 Ethylene Oxide Side Chain Containing 0.2 0.2 0.2 0.2 Polyaspartic Acid, % by wt. of cement Class G Cement, kilograms 100 100 100 100 Cement Composition Density, 1.92 2.03 2.11 2.21 kilogramsJliter Rheolosv After Preparation At Room Temperature 29-18-9 67-41-18 163-95-36 300+-243-300-200-100- 6-3.5-2- 10-5-3-2 17-6-1-0 94 60-30-6-3 1.5 45-15-1.5-Rheolo~y After Conditioning At 125°F
300-200-100- 21-13-7 38-21-8 119-70-30 300+-211-60-30-6-3 4-3-2-1.5 4-2-1-0 16-7-1-0 94 Universal Cement Analvzer Data 50 psi, Hrs:Min - 5:36 4;39 4:32 500 psi, Hrs:Min 10:02 6:38 5:26 5:08 24 Hrs, psi 2500 6000 6547 9000 72 Hrs, psi 4141 7531 - 10529 From Table III it can be seen that the biodegradable dispersant of this invention reduces the water content required while maintaining pumpability. In addition, the set cement compositions have excellent compressive strengths.
Example 4 Three additional cement compositions of this invention were prepared comprised of salt water containing various concentrations of salt, the biodegradable dispersant of this invention and Dyckerhoff Class G cement. The rheologies of the test compositions after preparation at room temperature and after conditioning at 125°F were determined as well as the set times and compressive strengths of the cement compositions. The results of these tests are set forth in Table IV below.
O 'O O ~ ~ N ~!1 ~ h V
O O ~ N ~ O ~ ~ v ~ O
N
O
N 0o O V~ 'd. p' V~ O, h ~.' O l~
O ~r O OW.r ..!~ f ~ v~ ,-... M o0O O
'-r N M r.~.., '; .--i .-M-~ M N
N
M ~ O ~ ~ O
r.r O d p O1 ,..~~., ~ rM., O, O d; ~O
'-r M ~ pp N 00 ~ N M
N M .-~ M
U
~"'q eQ o O ;b ~
d H _ U
i _ td O" cps 4r z ~ ~ ' O
~.
o w o v ~ ~ i :~ ~ .., '~
U 3 ,>; ~ Ga O
O ~ N
~d U .~ O
~
O .~ c ~
~
~b U ' . o ~
- a~
d ~ .y ~ o 'n ~~ ~ ~ U
~' ~ ' a, ~ o ~" ;
~" ~ o ~
dog .~ .., U~~ ~u.
~
a~ U U N O N O ~ -'" -'."
" O p O p M ~
M ~ ~, ~, x~ x ~n ~ O O ~ U O O d' ~ O p O O N
M ~ M ~O ~ N O N
I~
W fl% ~ ~
W U U
,- C
~CA 02431857 2003-06-09 From Table IV it can be seen that the biodegradable dispersant of this invention is salt tolerant and that the Theologies of the test cement compositions were low even when the salt water was saturated at 37°l° salt by weight of water. While the set times are somewhat longer, the compressive strengths are excellent.
Thus, the improved methods of this invention are well adapted to carry out the objects and attain the ends and advantages mentioned as well as those which are inherent therein.
While numerous changes may be made by those skilled in the art, such changes are encompassed within the spirit of this invention as defined by the appended claims.
Claims (19)
1. A method of cementing a subterranean zone penetrated by a well bore comprising the steps of:
(a) preparing a cement composition comprising a hydraulic cement, a biodegradable dispersant comprised of polyaspartic acid containing side chains formed by reacting one or more side chain forming chemicals therewith and sufficient water to form a pumpable slurry;
(b) placing said cement composition in said zone to be cemented; and (c) allowing said cement composition to set into an impermeable solid mass therein.
(a) preparing a cement composition comprising a hydraulic cement, a biodegradable dispersant comprised of polyaspartic acid containing side chains formed by reacting one or more side chain forming chemicals therewith and sufficient water to form a pumpable slurry;
(b) placing said cement composition in said zone to be cemented; and (c) allowing said cement composition to set into an impermeable solid mass therein.
2. The method of claim 1 wherein said one or more side chain forming chemicals are selected from the group consisting of ethylene oxide, propylene oxide, a vinyl functional polyethylene glycol, a vinyl functional polypropylene glycol, an amino functional polyethylene glycol, a polyester, a polyamide, polyethylene oxide and polypropylene oxide.
3. The method of claim 1 wherein said side chain forming chemical is ethylene oxide.
4. The method of claim 1 wherein said side chain forming chemical is a vinyl functional polyethylene glycol.
5. The method of claim 1 wherein said side chain forming chemical is a vinyl functional polypropylene glycol.
6. The method of claim 1 wherein said side chain forming chemical is an amino functional polyethylene glycol.
7. The method of claim 1 wherein said side chain forming chemical is a polyester.
8. The method of claim 1 wherein said side chain forming chemical is a polyamide.
9. The method of claim 1 wherein said side chain forming chemical is polyethylene oxide.
10. The method of claim 1 wherein said dispersant has a molecular weight in the range of from about 5,000 to about 500,000 daltons.
11. The method of claim 1 wherein said dispersant has a molecular weight of about 10,000 daltons.
12. The method of claim 1 wherein said dispersant is present in said composition in an amount in the range of from about 0.1% to about 2.0% by weight of cement therein.
13. The method of claim 1 wherein said hydraulic cement is selected from the group consisting of Portland cements, pozzolana cements, gypsum cements, alumina cements and silica cements.
14. The method of claim 1 wherein said hydraulic cement in said composition is Portland cement.
15. The method of claim 1 wherein said water in said composition is selected from the group consisting of fresh water, unsaturated salt water and saturated salt water.
16. The method of claim 1 wherein said water is present in said composition in an amount in the range of from about 18% to about 110% by weight of cement therein.
17. The method of claim 1 wherein said composition further comprises a fluid loss control agent selected from the group consisting of hydroxyethylcellulose, hydroxymethylcellulose, carboxymethylhydroxyethylcellulose, hydroxypropylcellulose, a copolymer of 2-acrylamido-2-methyl propane sulfonic acid and N,N-dimethylacrylamide, a graft lignin a lignite polymer, starch, guar, hydroxypropylguar, polyethyleneimine, polyvinylalcohol, polyvinylacetate, carragenan and xanthane.
18. The method of claim 1 wherein said fluid loss control agent in said composition is hydroxyethylcellulose.
19. The method of claim 1 wherein said fluid loss control agent is present in said composition in an amount in the range of from about 0.2% to about 2.0% by weight of cement therein.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US10/170,399 | 2002-06-13 | ||
| US10/170,399 US20030230407A1 (en) | 2002-06-13 | 2002-06-13 | Cementing subterranean zones using cement compositions containing biodegradable dispersants |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2431857A1 true CA2431857A1 (en) | 2003-12-13 |
Family
ID=22619712
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002431857A Abandoned CA2431857A1 (en) | 2002-06-13 | 2003-06-09 | Cementing subterranean zones using cement compositions containing biodegradable dispersants |
Country Status (5)
| Country | Link |
|---|---|
| US (2) | US20030230407A1 (en) |
| EP (1) | EP1375819B1 (en) |
| CA (1) | CA2431857A1 (en) |
| DE (1) | DE60328340D1 (en) |
| NO (1) | NO20032375L (en) |
Families Citing this family (45)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7273100B2 (en) | 2003-04-15 | 2007-09-25 | Halliburton Energy Services, Inc. | Biodegradable dispersants for cement compositions and methods of cementing in subterranean formations |
| US7166160B2 (en) * | 2003-04-22 | 2007-01-23 | Halliburton Energy Services, Inc. | Biodegradable cement retarder compositions and methods of cementing in a subterranean formation |
| US8541051B2 (en) | 2003-08-14 | 2013-09-24 | Halliburton Energy Services, Inc. | On-the fly coating of acid-releasing degradable material onto a particulate |
| US7833944B2 (en) | 2003-09-17 | 2010-11-16 | Halliburton Energy Services, Inc. | Methods and compositions using crosslinked aliphatic polyesters in well bore applications |
| US7829507B2 (en) | 2003-09-17 | 2010-11-09 | Halliburton Energy Services Inc. | Subterranean treatment fluids comprising a degradable bridging agent and methods of treating subterranean formations |
| US7674753B2 (en) | 2003-09-17 | 2010-03-09 | Halliburton Energy Services, Inc. | Treatment fluids and methods of forming degradable filter cakes comprising aliphatic polyester and their use in subterranean formations |
| US7648946B2 (en) | 2004-11-17 | 2010-01-19 | Halliburton Energy Services, Inc. | Methods of degrading filter cakes in subterranean formations |
| US8703659B2 (en) * | 2005-01-24 | 2014-04-22 | Halliburton Energy Services, Inc. | Sealant composition comprising a gel system and a reduced amount of cement for a permeable zone downhole |
| US20080009423A1 (en) * | 2005-01-31 | 2008-01-10 | Halliburton Energy Services, Inc. | Self-degrading fibers and associated methods of use and manufacture |
| US8598092B2 (en) | 2005-02-02 | 2013-12-03 | Halliburton Energy Services, Inc. | Methods of preparing degradable materials and methods of use in subterranean formations |
| US20060172894A1 (en) * | 2005-02-02 | 2006-08-03 | Halliburton Energy Services, Inc. | Degradable particulate generation and associated methods |
| US7608567B2 (en) * | 2005-05-12 | 2009-10-27 | Halliburton Energy Services, Inc. | Degradable surfactants and methods for use |
| US7662753B2 (en) | 2005-05-12 | 2010-02-16 | Halliburton Energy Services, Inc. | Degradable surfactants and methods for use |
| US7713916B2 (en) | 2005-09-22 | 2010-05-11 | Halliburton Energy Services, Inc. | Orthoester-based surfactants and associated methods |
| US8329621B2 (en) | 2006-07-25 | 2012-12-11 | Halliburton Energy Services, Inc. | Degradable particulates and associated methods |
| US20080026955A1 (en) * | 2006-07-25 | 2008-01-31 | Halliburton Energy Services, Inc. | Degradable particulates and associated methods |
| DE102006038809A1 (en) * | 2006-08-18 | 2008-02-21 | Basf Construction Polymers Gmbh | Water-soluble and biodegradable polyamide-based copolymers and their use |
| US7686080B2 (en) | 2006-11-09 | 2010-03-30 | Halliburton Energy Services, Inc. | Acid-generating fluid loss control additives and associated methods |
| US7576040B2 (en) * | 2007-01-11 | 2009-08-18 | Halliburton Energy Services, Inc. | Cement compositions comprising humic acid grafted fluid loss control additives |
| US7523784B2 (en) | 2007-01-11 | 2009-04-28 | Halliburton Energy Services, Inc. | Method of using humic acid grafted fluid loss control additives in cementing operations |
| US8220548B2 (en) | 2007-01-12 | 2012-07-17 | Halliburton Energy Services Inc. | Surfactant wash treatment fluids and associated methods |
| US7360598B1 (en) | 2007-02-05 | 2008-04-22 | Halliburton Energy Services, Inc, | Method of using lignite grafted fluid loss control additives in cementing operations |
| US7388045B1 (en) | 2007-02-05 | 2008-06-17 | Halliburton Energy Services, Inc. | Cement compositions comprising lignite grafted fluid loss control additives |
| US8586508B2 (en) | 2007-05-30 | 2013-11-19 | Halliburton Energy Services, Inc. | Polysaccharide based cement additives |
| US8569214B2 (en) | 2007-05-30 | 2013-10-29 | Halliburton Energy Services, Inc. | Methods of using polysaccharide based cement additives |
| US7861955B2 (en) | 2007-11-15 | 2011-01-04 | United States Gypsum Company | Wet-grinding gypsum with polycarboxylates |
| US8006760B2 (en) | 2008-04-10 | 2011-08-30 | Halliburton Energy Services, Inc. | Clean fluid systems for partial monolayer fracturing |
| US7906464B2 (en) | 2008-05-13 | 2011-03-15 | Halliburton Energy Services, Inc. | Compositions and methods for the removal of oil-based filtercakes |
| US7833943B2 (en) | 2008-09-26 | 2010-11-16 | Halliburton Energy Services Inc. | Microemulsifiers and methods of making and using same |
| US8082992B2 (en) | 2009-07-13 | 2011-12-27 | Halliburton Energy Services, Inc. | Methods of fluid-controlled geometry stimulation |
| US9409820B2 (en) | 2010-04-21 | 2016-08-09 | Basf Se | Use of CSH suspensions in well cementing |
| MX2012009398A (en) * | 2010-04-21 | 2012-09-12 | Basf Se | Use of csh suspensions in cementing wells. |
| RU2452758C1 (en) * | 2010-12-06 | 2012-06-10 | Общество с ограниченной ответственностью "ЛУКОЙЛ-Инжиниринг" (ООО "ЛУКОЙЛ-Инжиниринг") | Expanding backfill solution with controlled properties |
| US9181781B2 (en) | 2011-06-30 | 2015-11-10 | Baker Hughes Incorporated | Method of making and using a reconfigurable downhole article |
| US9038719B2 (en) * | 2011-06-30 | 2015-05-26 | Baker Hughes Incorporated | Reconfigurable cement composition, articles made therefrom and method of use |
| RU2504568C1 (en) * | 2012-07-19 | 2014-01-20 | Общество с ограниченной ответственностью "ТюменНИИгипрогаз" | Expanding plugging composition |
| MX358877B (en) | 2012-09-28 | 2018-08-31 | Halliburton Energy Services Inc | Methods and compositions for treating a subterranean formation with salt-tolerant cement slurries. |
| US9914870B2 (en) | 2013-01-22 | 2018-03-13 | Carnegie Mellon University | Lignin-containing polymers and compositions including lignin-containing polymers |
| RU2535766C1 (en) * | 2013-05-27 | 2014-12-20 | федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Пермский национальный исследовательский политехнический университет" | Expanding cement slurry for water influx limitation |
| RU2536725C1 (en) * | 2013-05-27 | 2014-12-27 | федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Пермский национальный исследовательский политехнический университет" | Expanding cement slurry with adjustable process properties |
| BR112017001339A2 (en) | 2014-08-28 | 2018-02-06 | Halliburton Energy Services Inc | method, cement paste and system |
| US10995253B2 (en) | 2014-09-16 | 2021-05-04 | Halliburton Energy Services, Inc. | Lithium-containing calcium aluminate phosphate cement admixtures |
| WO2017176952A1 (en) | 2016-04-08 | 2017-10-12 | Schlumberger Technology Corporation | Polymer gel for water control applications |
| US11162012B2 (en) * | 2020-04-06 | 2021-11-02 | Halliburton Energy Services, Inc. | Well treatment fluid having biodegradable fluid loss control agent |
| CN112778990B (en) * | 2021-02-05 | 2022-06-03 | 西南石油大学 | Sewage mixing temporary plugging agent for oilfield water injection well and preparation method thereof |
Family Cites Families (30)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3359225A (en) * | 1963-08-26 | 1967-12-19 | Charles F Weisend | Cement additives containing polyvinylpyrrolidone and a condensate of sodium naphthalene sulfonate with formaldehyde |
| US3937282A (en) * | 1973-06-28 | 1976-02-10 | Halliburton Company | Method for cementing wells in low temperature formations |
| US4028125A (en) * | 1976-03-25 | 1977-06-07 | The Dow Chemical Company | Cement composition |
| US4557763A (en) * | 1984-05-30 | 1985-12-10 | Halliburton Company | Dispersant and fluid loss additives for oil field cements |
| US4676832A (en) * | 1984-10-26 | 1987-06-30 | Halliburton Company | Set delayed cement compositions and methods of using the same |
| DE3800091A1 (en) * | 1987-08-28 | 1989-07-13 | Sandoz Ag | COPOLYMERS, THEIR PRODUCTION AND USE |
| US5284512A (en) * | 1991-03-06 | 1994-02-08 | Donlar Corporation | Polyaspartic acid and its salts for dispersing suspended solids |
| US5340860A (en) * | 1992-10-30 | 1994-08-23 | Halliburton Company | Low fluid loss cement compositions, fluid loss reducing additives and methods |
| AT399340B (en) * | 1993-02-01 | 1995-04-25 | Chemie Linz Gmbh | COPOLYMERS BASED ON MALEINIC ACID DERIVATIVES AND VINYL MONOMERS, THEIR PRODUCTION AND USE |
| JPH07172888A (en) * | 1993-12-21 | 1995-07-11 | Mitsui Toatsu Chem Inc | Mixing agent for cement |
| DE4427233A1 (en) | 1994-06-29 | 1996-01-04 | Basf Ag | Process for the preparation of polyaspartic acid and / or polyaspartic acid imides |
| US5660626A (en) * | 1995-01-31 | 1997-08-26 | Ohta; Akira | Cement dispersing agent |
| DE19513126A1 (en) * | 1995-04-07 | 1996-10-10 | Sueddeutsche Kalkstickstoff | Copolymers based on oxyalkylene glycol alkenyl ethers and unsaturated dicarboxylic acid derivatives |
| US5688904A (en) * | 1995-11-16 | 1997-11-18 | Calwood Chemical Industries Inc. | Polyaspartic acid catalysis |
| US5610264A (en) * | 1995-11-16 | 1997-03-11 | Calwood Chemical Industries, Inc. | Continuous process for polyaspartic acid synthesis |
| DE19603052A1 (en) | 1996-01-29 | 1997-07-31 | Bayer Ag | Process for the preparation of polymers with repeating succinyl units |
| US5614017A (en) * | 1996-03-26 | 1997-03-25 | Arco Chemical Technology, L.P. | Cement additives |
| US5670578A (en) * | 1996-12-10 | 1997-09-23 | Arco Chemical Technology, L.P. | Cement additives |
| US5876623A (en) * | 1996-09-20 | 1999-03-02 | Nalco Chemical Company | Biodegradable aspartic acid polymers for preventing scale formation in boilers |
| JPH1036156A (en) * | 1996-07-26 | 1998-02-10 | Mitsui Petrochem Ind Ltd | Cement admixture |
| US6174980B1 (en) * | 1996-12-26 | 2001-01-16 | Nippon Shokubai Co., Ltd. | Cement dispersant, method for producing polycarboxylic acid for cement dispersant and cement composition |
| US5908885A (en) * | 1997-07-01 | 1999-06-01 | University Of South Alabama | Polysuccinimide and polyaspartate as additives to cementitious materials |
| DE19834173A1 (en) * | 1997-08-01 | 1999-02-04 | Sueddeutsche Kalkstickstoff | Copolymer based on unsaturated di:carboxylic acid derivatives and oxyalkylene glycol-alkenyl ether(s) |
| US6136950A (en) * | 1997-09-23 | 2000-10-24 | Mbt Holding Ag | Highly efficient cement dispersants |
| DE19914367A1 (en) * | 1998-04-17 | 1999-10-21 | Henkel Kgaa | Hydraulic binder compositions based on inorganic hydraulic binder and assistant |
| US6429266B2 (en) * | 1998-06-30 | 2002-08-06 | University Of South Alabama | Thermal grafts of polyamides with pendant carboxylic acid groups, methods for producing the same, compositions containing the same, and methods of using the same |
| US6133347A (en) * | 1999-07-09 | 2000-10-17 | Mbt Holding Ag | Oligomeric dispersant |
| US6454004B2 (en) * | 1999-07-15 | 2002-09-24 | Halliburton Energy Services, Inc. | Cementing casing strings in deep water offshore wells |
| US6182758B1 (en) * | 1999-08-30 | 2001-02-06 | Halliburton Energy Services, Inc. | Dispersant and fluid loss control additives for well cements, well cement compositions and methods |
| US6405801B1 (en) * | 2000-12-08 | 2002-06-18 | Halliburton Energy Services, Inc. | Environmentally acceptable well cement fluid loss control additives, compositions and methods |
-
2002
- 2002-06-13 US US10/170,399 patent/US20030230407A1/en not_active Abandoned
-
2003
- 2003-05-27 NO NO20032375A patent/NO20032375L/en not_active Application Discontinuation
- 2003-05-27 EP EP03253307A patent/EP1375819B1/en not_active Expired - Fee Related
- 2003-05-27 DE DE60328340T patent/DE60328340D1/en not_active Expired - Lifetime
- 2003-06-09 CA CA002431857A patent/CA2431857A1/en not_active Abandoned
- 2003-11-17 US US10/715,009 patent/US6953090B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| NO20032375D0 (en) | 2003-05-27 |
| DE60328340D1 (en) | 2009-08-27 |
| US6953090B2 (en) | 2005-10-11 |
| US20040099416A1 (en) | 2004-05-27 |
| EP1375819B1 (en) | 2009-07-15 |
| NO20032375L (en) | 2003-12-15 |
| EP1375819A1 (en) | 2004-01-02 |
| US20030230407A1 (en) | 2003-12-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US6953090B2 (en) | Cementing subterranean zones using cement compositions containing biodegradable dispersants | |
| CA2525931C (en) | Methods of cementing in subterranean zones penetrated by well bores using biodegradable dispersants | |
| US6591910B1 (en) | Methods and compositions for cementing subterranean zones | |
| US7073585B2 (en) | Cement compositions with improved fluid loss characteristics and methods of cementing in surface and subterranean applications | |
| US4557763A (en) | Dispersant and fluid loss additives for oil field cements | |
| EP1081112B1 (en) | Dispersant and fluid loss control additive for well cement | |
| US8153563B2 (en) | Cement compositions comprising stevia retarders | |
| US7285165B2 (en) | Cement compositions comprising set retarder compositions and associated methods | |
| US6616753B2 (en) | Methods and compositions for sealing subterranean zones | |
| US7297207B2 (en) | Biodegradable dispersants for cement compositions and methods of cementing in subterranean formations | |
| US20050034864A1 (en) | Cement compositions with improved fluid loss characteristics and methods of cementing in surface and subterranean applications | |
| US5116421A (en) | High temperature fluid loss additive for cement slurry and method of cementing | |
| US7303625B2 (en) | Treatment fluids comprising chlorinated carbohydrates | |
| US7422062B2 (en) | Methods of treating subterranean formations using treatment fluids comprising chlorinated carbohydrates | |
| US7547664B2 (en) | Additives comprising chlorinated carbohydrates |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| FZDE | Discontinued |