|Número de publicación||USRE31190 E|
|Tipo de publicación||Concesión|
|Número de solicitud||US 06/297,581|
|Fecha de publicación||29 Mar 1983|
|Fecha de presentación||31 Ago 1981|
|Fecha de prioridad||2 Feb 1976|
|Número de publicación||06297581, 297581, US RE31190 E, US RE31190E, US-E-RE31190, USRE31190 E, USRE31190E|
|Inventores||William J. Detroit, Michael E. Sanford, Jiten Chatterji, Charles R. George, Jerry D. Childs, Roosevelt Love|
|Cesionario original||Halliburton Company|
|Exportar cita||BiBTeX, EndNote, RefMan|
|Citas de patentes (11), Citada por (119), Clasificaciones (10), Eventos legales (1)|
|Enlaces externos: USPTO, Cesión de USPTO, Espacenet|
This invention relates to cement compositions and more particularly to the use of hydraulic cement compositions for sealing or cementing subterranean zones or subterranean zones penetrated by a well such as cementing the annular space in an oil well between the surrounding formation and casing. In particular the invention relates to an improved hydraulic cement composition for cementing zones at elevated temperatures in which the setting time of the cement composition is controlled or extended by the addition of a highly efficient non-gelling retarding agent which produces a hydraulic cement composition having a degree of predictability for the setting time.
Typically, the subterranean zones are cemented or sealed by pumping an aqueous hydraulic cement slurry into the zone. In cementing the annular space of an oil well, the cement slurry is pumped down the inside of the casing and back up the outside of the casing through the annular space. Any cement slurry remaining in the casing is displaced and segregated using plugs and an aqueous displacement fluid. Frequently the high temperatures encountered in subterranean zones will cause premature setting of the hydraulic cement. This requires additives which extend or retard the setting time of the cement slurry so that there is adequate pumping time in which to place and displace the aqueous cement slurry in the desired zones. Previously known retarding agents are frequently unpredictable, typically produce erratic results with different brands of cement and frequently cause premature gelation of the cement slurry. Gelation refers to an abnormal increase of viscosity of the aqueous cement slurry to a value without a significant increase in the compressive strength of the cement composition. This increase in aqueous cement slurry viscosity makes the slurry difficult or impossible to pump at a viscosity of 70 poise or above which is defined as the set point herein. The cement composition has not attained an adequate compressive strength.
Prior art cement compositions and additives are described in the following list of 14 patents:
U.S. Pat. No. 2,549,507 to Morgan et al
U.S. Pat. No. 2,579,453 to Post et al
U.S. Pat. No. 2,674,321 to Cutforth
U.S. Pat. No. 2,676,170 to Patterson et al
U.S. Pat. No. 2,680,113 to Adler et al
U.S. Pat. No. 2,775,580 to Scarth
U.S. Pat. No. 2,872,278 to Putnam et al
U.S. Pat. No. 3,034,982 to Monroe
U.S. Pat. No. 3,053,673 to Walker
U.S. Pat. No. 3,135,727 to Monroe
U.S. Pat. No. 3,344,063 to Stratton
U.S. Pat. No. 3,748,159 to George
U.S. Pat. No. 3,766,229 to Turner
U.S. Pat. No. 3,821,985 to George.
Fundamentals of oil well cementing are described in the book PETROLEUM ENGINEERING DRILLING AND WELL COMPLETIONS, by Carl Gatlin, Prentice Hall, 1960. Background of and information on hydraulic cement compositions and additives can be found in the following books:
LIGNIN STRUCTURE AND REACTIONS, ADVANCES IN CHEMISTRY SERIES, 1959, American Chemical Society, 1966;
MECHANICAL BEHAVIOR OF HIGH POLYMERS, by Turner Alfrey, Interscience Publishers, 1948; and
HACKH'S CHEMICAL DICTIONARY, 4th Ed., McGraw-Hill, 1969.
The above references and information cited therein are incorporated herein by reference to the extent necessary.
The hydraulic cement compositions of this invention solve or eliminate many of the problems pointed out above. The hydraulic cement compositions of this invention do not have the gelation problem; the retarder composition is more efficient than prior art retarder compositions, the retarder has less variation with different brands of cement; cement compositions have much better predictability or reproducibility of setting times with a given brand of cement; and hydraulic cement compositions have better rheology characteristics. Thus the improved cement compositions of this invention have practically eliminated the problems of unpredictability and irreproducibility of results which are particularly severe in high pressure deep wells where the temperatures may exceed 300° F. and 15,000 PSI.
The concentration of retarder composition of this invention required to produce the desired pumping time for or delay in setting of a cement slurry at a given circulating temperature is not as critical as with conventional lignosulfonate retarders. The thickening time at a given retarder concentration is less temperature dependent than with conventional retarders. This reduces the possibility of over retarded slurries at cooler temperatures encountered at the top of long liners or tie back strings. The retarder compositions of this invention provide the desired pumping times and allow earlier strength development. When cementing long strings this can reduce the WOC (waiting on cement to set) time by 8-12 hours. Thus, the retarder compositions of this invention are more predictable in performance than conventional lignosulfonate retarders especially with various brands of cement. The compositions of this invention act not only as retarders but also as a dispersing agent which can reduce fluid loss from gel type or high clay cement slurries. When the retarder composition of this invention is blended in a cement slurry, viscosity of the slurry decreases slightly and remains constant or does not increase significantly until the cement begins to set. This improvement in rheology or viscosity characteristics with improved predictability makes use of the compositions much easier than with conventional retarders. In addition, the retarder compositions of this invention are generally non-toxic, non-flammable, non-hazardous; compatible with cements, other additives and with most other well fluids and mix readily in aqueous systems with minimum agitation.
The high efficiency, non-gelling cement retarder composition of this invention has a high degree of predictability for controlling rheology and setting time of hydraulic cement comprising a low molecular weight sulfoalkylated lignin which is substantially sulfoalkylated in the lignin molecule at positions on the benzene ring which are ortho to the phenolic hydroxyl group. In the sulfoalkyl group the sulfonic acid group (--SO3 H) is connected to the ortho position on the benzene ring by a methylene or substituted methylene groups. This methylene or substituted methylene group is referred to herein as an alkylidene radical having one to five carbon atoms. This alkylidene radical with sulfonic acid radical can be represented by the formula (--R--SO3 H) wherein R is the methylene group or alkyl portion having one to five carbon atoms and preferably one to three carbon atoms.
The unexpected properties of this retarder are thought to be due to the differences in average molecular weight or average molecular size and molecular structure. The evidence showing these differences is illustrated in the examples which show the unexpected properties. The sulfoalkylated lignin of this invention is a low molecular weight material having an average molecular weight or molecular size in the range of about 2,000-10,000 and preferably about 3,000-5,000. It is also thought to have a narrow molecular weight distribution. Prior art lignosulfonate compounds have a molecular weight or molecular size of about 10,000 and higher and the sulfonate substituent or radical attached directly on the carbon atom of the lignin molecule which is in the alpha position of the phenyl propyl side chain. This phenyl propyl or aliphatic chain is attached at a position on the benzene ring which is para to the phenolic hydroxyl group discussed herein. For lignosulfonate the phenolic hydroxyl group can be replaced by an alkoxy group as indicated by R1 --Ph--OR2 wherein R1 is the phenyl propyl side chain, Ph is phenyl or the benzene ring and R2 is hydrogen or alkyl. The sulfoalkylated retarder composition of this invention has substantially all of the sulfoalkyl group (i.e., --R--SO3 H) in the position ortho to the phenolic hydroxyl group of the benzene ring of the lignin molecule.
The sulfoalkylated lignin retarder of this invention does not have a significant degree of sulfonation at the alpha carbon atom as do the prior art lignosulfonates. Thus, the sulfoalkylated lignin retarder of this invention is an entirely different chemical composition as shown by the unexpected and significantly different properties shown herein. The sulfoalkylated lignin retarder of this invention can be considered to be a sulfoalkylated lignin of high purity, low molecular weight with a narrow molecular weight distribution. This is thought to be due to the significantly different procedure used for its preparation.
The sulfoalkylated lignin retarder for compositions of this invention can be prepared by catalytic oxidation of the sulfite liquor from a wood pulping process. This oxidation removes polysaccharides and wood sugars and substantially desulfonates the lignin molecule which is recovered as a residue. This purified lignin is separated from the liquor. The high purity, low molecular weight lignin molecule is then substantially sulfoalkylated by the addition of sulfonating agent such as sodium sulfite in the presence of an aldehyde or ketone having one to five carbon atoms at about 150°-190° C. and 180-220 atmospheres. In this process, the aldehyde or ketone furnishes the alkylidene group which attaches at a vacant ortho position on the benzene ring in the lignin molecule and connects the sulfonate group through a methylene radical to the benzene ring at a position ortho to the free phenolic hydroxyl group. Some benzene rings may have more than one sulfoalkyl group attached and some benzene rings may have no sulfoalkyl substituents. The sulfur content of the sulfoalkylated lignin is between about 3-10% and preferably 3-8%.
This sulfonate group can be in the form of the acid, a salt or combinations thereof. The salt can be in the form of ammonium or metal salt involving an alkali metal; an alkaline earth metal; or metals such as iron, copper, zinc, vanadium, titanium, aluminum, manganese, chromium, cobalt or nickel; or combinations thereof. The salts which are readily soluble in aqueous systems, such as those of the alkali metals, sodium and potassium, are preferred although the salts of alkaline earth metals and other metals can be used under certain circumstances.
The alkyl portion of the sulfonate substituent is derived from the aldehyde or ketone used in the sulfoalkylation step. Formaldehyde is a preferred alkyl source because it simply connects the sulfonate group to the ortho position by a one-carbon atom methylene group. Acetone would produce an alkylidene group having a methyl group on each side of the methylene group; methyl ethyl ketone would result in a methyl and an ethyl alkyl group attached to the methylene group; and propionaldehyde would result in an ethyl group attached to the methylene bridge. Theoretically, any aldehyde or ketone could be used for forming the alkylidene radical but the stereo chemistry and solubility must be considered in selecting the size and configuration of the aldehyde or ketone use for this component. A preferred sulfoalkylated lignin of this invention has a molecular weight in the range of about 3,000-4,000, a one carbon atom alkylidene radical and a sulfur content of about 3-8% by weight.
Another preferred hydraulic cement composition of this invention can be considered to be a modified low molecular weight sulfoalkylated lignin. This modified retarder composition is a combination of the high purity substantially sulfoalkylated lignin described above and at least one water soluble hydroxy carboxylic acid. These hydroxy carboxylic acids have a synergistic effect of increasing the effectiveness and operable temperature range of the basic retarder composition. The preferred carboxylic acids are substantially alphatic carboxylic acids and preferably polyhydroxy carboxylic acids having at least one terminal carboxy group which can be in the form of the acid, a salt or mixtures thereof as described above for the sulfonate groups.
Particularly preferred polyhydroxy carboxylic acids have a molecular weight in the range of about 125-250 and have a hydroxyl group attached to the carbon atom adjacent to the carboxy group as show by the formula ##STR1## These carboxylic acids include gluconic acid, tartaric acid and equivalents thereof. These equivalents include the various stereoisomers of the above acids particularly the asymmetric or optically active isomers. Thus, the preferred group of hydroxy carboxylic acids are substantially linear aliphatic acids having about 4-10 carbon atoms, and preferably 4-8 carbon atoms. The molecular size and number of hydroxy and carboxylic groups will affect the water solubility. The hydroxy carboxylic acid is preferably present with the sulfoalkylated lignin in a weight ratio of acid to lignin preferably in the range of about 1:0.1-5.0 and preferably in the range of about 1:0.2-3.0.
The hydraulic cement compositions of this invention are typically used in the form of an aqueous slurry of hydraulic cement with a concentration of retarder mixed in the aqueous slurry to control or delay the cement setting time so that it exceeds the pumping time with an adequate safety margin. Sufficient water is added to the slurry to make the composition pumpable. As used herein the hydraulic cement is typically a Portland cement which is set by the water of the slurry in the absence of air which is excluded by placement of the cement in the zone to be sealed. The low molecular weight sulfoalkylated lignin retarder of this invention is preferably present in the aqueous hydraulic cement slurry in a concentration up to about 2%, and preferably up to 1%, by weight based on the dry cement. Higher retarder concentrations and other cement can be used when necessary in unusual circumstances. A deforming agent is typically added as are fluid loss additives, friction reducing additives, salts such as sodium chloride and potassium chloride, weighting additives and other conventional additives as described in the references cited above. Pozzolana cement, high alumina cement or high gel (high clay content) cement can be used for special applications. The low molecular weight sulfoalkylated retarder composition of this invention has high reproducibility and predictability when used with most high quality cements which are typically used in the petroleum industry. However, certain brands which are not manufactured to standard specifications, such as those which are not sufficiently calcined or having varying degrees of free lime remaining in the cement, will produce substantial variations from the standard high quality brands. It is not clear whether the free lime causes the problems or is merely an indication when the problems exist. These variations can be readily determined by preliminary tests which make even these substandard cements readily predictable and may merely require slightly higher retarder concentrations to offset the chemical composition variations of the cement of excess lime content.
In a preferred process for using the non-gelling hydraulic cement composition of this invention having a degree of predictability of setting time and containing the high efficiency retarder, the retarder composition is mixed with the hydraulic cement as an aqueous slurry with the retarder concentration up to about 2% on a dry cement weight basis. The hydraulic cement mixture is pumped without gelation into the zone to be sealed or cemented and the hydraulic cement mixture is maintained in the zone until an adequate compressive strength is attained. In this process the retarder concentration preferably up to about 2% on a dry cement weight basis is calculated to control the setting time of the hydraulic cement slurry to exceed the pumping time within an adequate safety margin. Due to the higher efficiency of the retarder and greater predictability of the hydraulic cementing compositions of this invention, the portion of the safety margin previously required for these variations can be substantially reduced. The safety margin now need primarily allow time only for unexpected equipment difficulties. This reduction in the safety margin time or time which the typical oil drilling rig is waiting for the cement to set can result in a substantial economic advantage due to the higher efficiency and predictablity of the hydraulic cement compositions of this invention. The modified low molcular weight sulfoalkylated lignin of this invention or the combination of the sulfoalkylated lignin with the hydroxy carboxylic acids improve the efficiency and predictability of the compositions of this invention even more and therefore are preferably used. The basic sulfoalkylated lignin retarder composition of this invention can be used up to a temperature (i.e., BHCT) slightly in excess of about 210° F. and the modified retarder composition containing the hydroxy carboxylic acids can be used up to a temperature of about 400° F.
The molecular weight of the sulfoallkylated portion of the composition of this invention is determined by diffusion techniques. These differences between the sulfoalkylated lignin compositions of this invention and the prior art lignosulfonates are shown by the examples.
The following examples serve to illustrate various embodiments of the invention and enable one skilled in the art to practice the invention. Parts, percentages, proportions and concentrations are by weight unless indicated otherwise.
Samples of calcium (CaLS) and sodium lignosulfonates (NaLS) and a preferred sulfomethylated lignin (SML) composition of this invention were analyzed chemically by spectroscopy using X-ray, infrared, and ultraviolet radiation techniques. The samples were prepared and analyzed by standard procedures such as those described in ABSORPTION SPECTROSCOPY, by Robert P. Bauman, John Wiley & Sons, Inc., 1962, which is incorporated herein by reference to the extent necessary. X-ray diffraction merely showed that both the lignosulfonate and sulfoalkylated lignin were non-crystalline.
Chemical analysis indicated the following constituents by weight:
______________________________________ % C % H2 % Ca % S______________________________________CaLS 39.1 4.3 7.6 3.9NaLS 42.2 4.6 0.3 7.4SML 45.0 3.8 0.2 6.2______________________________________
The sulfur content of NaLS and SML was thought to include some inorganic sulfur (e.g. CaSO4) entrained from cation exchange or sulfonation liquor.
For ultraviolet (UV) technique which scanned 190-360 millimicrons (mμ) for both NaLS and SML showed a major peak at about 202-205 millimicrons with shoulder or decreasing peaks at about 230 and 310-320 millimicrons. The samples were in water at a 0.02 gram per liter concentration and were run in a one cm path length cell.
The infrared (IR) transmittance scan from 2.5-30 microns or 300-400 cm-1 showed peaks at the following wave lengths (λ) in cm-1 :
NaLS*3440; 2940; 2840*; 1590; 1495; 1450; 1415; 1250*; 1200; 1140*; 1035; 930*; 640 and 590.
SML: 3440; 2940; 2840; 1675; 1590; 1495; 1450; 1415; 1355; 1250*; 1200; 1140*; 1070; 1035; 930*; 850; 775; 735; 590 and 525.
The starred values (*) are shoulder peaks or peaks which are not very distinct. Samples for the IR scan were mulled in NUJOL mineral oil and run between salt plates.
For the following examples each sample was prepared by measuring an 800-gram portion of the designated dry cement into a cylindrical container of approximately 800 milliliters volume. Dry or powdered additives are designated as a percentage of the weight of the dry powdered cement unless indicated otherwise. Dry powdered additives are measured and blended with cement. A portion of tap water equal to the weight percentage of the dry cement is slurried with the dry cement and additives with vigorous mixing. The slurry is stirred for an additional 30 seconds at a high rate. Liquid additives are blended into the water. Samples were tested according to standard procedures as set forth in API Method RP-10B which is incorporated herein by reference.
For thickening time tests a sample portion is stirred in a container of about 500 milliliters at a temperature and pressure schedule determined by API method RP 10B. The container is heated from ambient temperature under pressure. It contains a direct reading consistometer which is calibrated with a potentiometer calibrating device to read directly in units of consistency (API-RP-10B). The set time or setting point is the time or point at 70 units of consistency or viscosity.
API Method RP-10B provides the following casing schedule for bottom hole circulating temperature (BHCT) and bottom hole static temperature (BHST) at the indicated depths:
______________________________________Depth (ft.) BHCT (°F.) BHST (°F.)______________________________________ 8,000 (2440 m)* 125 (51.67° C.)* 200 (93.33° C.)*10,000 (3050 m) 144 (62.22° C.) 230 (110.00° C.)12,000 (3660 m) 172 (77.78° C.) 260 (126.67° C.)14,000 (4270 m) 206 (96.67° C.) 290 (143.33° C.)15,000 (4575 m) 226 (107.78° C.) 305 (151.66° C.)16,000 (4880 m) 248 (120.00° C.) 320 (160.00° C.)18,000 (5490 m) 300 (148.89° C.) 350 (176.67° C.)20,000 (6100 m) 340 (171.11° C.) 380 (193.33° C.)22,000 (6710 m) 380 (193.33° C.) 410 (210.00° C.)______________________________________ *Metric Equivalents
Fluid loss is the number of milliliters or cubic centimeters of liquid forced through No. 50 Whatman filter paper or through 325 mesh screen according to API publication RP-10B (Section 8).
TABLE I______________________________________Predictable Behavior Thickening Times Hours:MinutesSML* API Casing Simulation Tests% Retarder 8,000' 10,000' 12,000' 14,000'______________________________________Lone Star Class H Cement38% H2 O0.20 2:35 2:04 1:33 --0.25 4:20 2:37 -- --0.30 5:50 3:11 2:31 1:580.35 -- 5:20 -- --0.40 -- -- 4:12 3:010.50 -- -- 7:18 3:470.60 -- -- -- 4:090.70 -- -- -- 5:12Lone Star Class H Cement46% H2 O0.16 2:43 -- -- --0.20 -- 2:25 2:15 1:550.24 3:51 -- -- --0.30 6:40 3:28 3:01 2:320.34 -- -- 3:58 --0.35 -- 6:13 -- --0.38 -- -- 4:17 --0.40 -- 11.22 -- 3:320.44 -- -- 5:37 --0.60 -- -- -- 6:10______________________________________ *Sulfomethylated lignin retarder.
Increasing the retarder concentration results in corresponding increase in thickening time until a saturation point is reached. Beyond this point, slight increases in the retarder concentration result in greatly increased thickening times.
TABLE II______________________________________Set Times Obtained with Commercially AvailableCalcium Lignosulfonate and the Sodium Salt ofSulfomethylated Lignina Percent Set Times - Percent Sodium Hours:Minutes Retarder Chloride API Casing (by wt. (by wt. Simulation TestsRetarder Cement water) 14,000'-206° F.______________________________________Sulfomethylated Lignin 0.3 0 1:58 0.4 0 3:01 0.5 0 3:47 0.6 0 4:09 0.7 0 5:12Calcium Lignosulfonate 0.3 0 3:25 0.4 0 4:05 0.5 0 .sup. 1:34b 0.6 0 .sup. 1:35bSulfomethylated Lignin 0.3 18.0 1:44 0.4 18.0 2:27 0.5 18.0 2:45 0.6 18.0 3:42 0.7 18.0 4:33 0.8 18.0 5:12Calcium Lignosulfonate 0.2 18.0 .sup. 1:32b 0.3 18.0 .sup. 1:40b 0.4 18.0 .sup. 1:48b 0.5 18.0 .sup. 2:05b 0.6 18.0 .sup. 2:40b______________________________________ a All slurries consisted of 800 grams Lone Star Class H Cement with 304 grams (38%) water, and indicated amounts of additive and sodium chloride. b Slurry gelation was observed, i.e., viscosity reached 70 units of consistency but slurry had not developed significant compressive strength at that time. Others reached a viscosity of 70 units and set with compressive strength at approximately the same time.
At higher temperatures slurries containing the conventional retarder tend to form unpumpable heavy gels prior to development of significant compressive strength, however, use of the sulfomethylated compound yielded slurries which were well dispersed until final hard set of the cement was obtained. This is illustrated in Table II which lists the set time and percent added retarder for both fresh and salt water slurries containing either the commercially available calcium salt of lignosulfonate or the sodium salt of the new sulfomethylated compound. As noted in the table, many of the slurries containing the calcium salt tended to form heavy gels (i.e., slurry is unpumpable and thus, considered set when the viscosity reaches 70 units of consistency even though it may have gelled with no compressive strength at that time); this results in an erratic dependence of set time on retarder concentration. For example, in the fresh water slurries, increases in retarder concentration in excess of approximately 0.4% (Table II) result in decreased rather than the expected increased set times; this effect is not found for the new compound which shows a reasonable set time increase as the retarder concentration is increased in both fresh and salt water slurries.
Predictable Behavior One Cement to Another
TABLE III______________________________________Predictable Behavior One Cement to AnotherEffect of Cement Brand on Set Timea Percent Additive Set Time - (by wt. Hours:Minutes of API CasingType of Cement Additive cement) 14,000'-206° F.______________________________________Lone Star Class H Sulfomethylated(Maryneal)b Lignin 0.5 3:37Lone Star Class H Calcium(Maryneal)b Lignosulfate 0.5 .sup. 1:34hLone Star Class H Sulfomethylated(New Orleans)c Lignin 0.5 2:45Lone Star Class H Calcium(New Orleans)c Lignosulfate 0.5 .sup. 0:40hTrinity Class Hd Sulfomethylated Lignin 0.5 2:46Trinity Class Hd Calcium Lignosulfate 0.5 .sup. 3:02hSouthwestern SulfomethylatedClass He Lignin 0.5 3:19Southwestern CalciumClass He Lignosulfate 0.5 4:05Oklahoma Class Hf Sulfomethylated Lignin 0.5 3:00Oklahoma Class Hf Calcium Lignosulfate 0.5 .sup. 3:45hDyckerhoff Class Bg Sulfomethylated Lignin 0.5 2:44Dyckerhoff Class Bg Calcium Lignosulfate 0.5 2:45______________________________________ a Slurries consisted of 800 grams indicated cement, 304 grams (38%) water (by wt. of cement), and additive with the exception of the slurries containing Dyckerhoff Class B which contained 368 grams (46%) water. b Cement manufactured by Lone Star Industries, Inc., Maryneal, Texas c Cement manufactured by Lone Star Industries, Inc., New Orleans, Louisiana. d Cement manufactured by Trinity, Portland Cement Division, Dallas, Ft. Worth, Houston, Texas. e Cement manufactured by Southwestern Portland Cement Company, El Paso, Texas. f Cement manufactured by OKC Corporation, Pryor, Oklahoma. g Cement manufactured by Dyckerhoff Zementwerke AG, WiesbadenBiebrich, Germany. h These slurries gelled prior to hard set.
At constant concentration of the new retarder, reasonably consistent set times are obtained for slurries containing cements produced by different manufacturers (Table III). This contrasts with the similar results for calcium lignosulfonate which vary drastically from one cement to another.
TABLE IV______________________________________Slurry Gelation EffectViscosity versus Pumping Time for the SlurriesContaining Calcium Lignosulfonate or the SodiumSalt of Sulfomethylated Lignin Pumping Times Hours:Minutes ViscosityType Percent 14,000' API In Units ofof Cement Additived Additive Casing - 206° F. Consistencye______________________________________Lone Star SML 0.5 0:00 9Class H 0:30 6(Maryneal) 0:45 6 1:00 6 1:15 6 1:30 6 2:00 12 2:15 21 3:00 26 3:15 29 3:30 31 .sup. 3:47b 70 NaLS 0.5 0:00 1 0:30 4 0:45 13 1:00 37 1:15 41 1:30 45 .sup. 1:34c 70______________________________________ a Slurries consisted of cement, 38% water and additive. b Slurry reached a viscosity of 70 units and set with compressive strength at approximately the same time. c Slurry reached a viscosity of 70 units but had no compressive strength until approximately two hours later. d SML is sulfomethylated lignin and NaLS is sodium lignosulfonate. e Consistency measured directly in units of consistency according to API publication RP10B.
TABLE V______________________________________Lower TemperaturesSet Times Obtained with Calcium Lignosulfonateand the Sodium Salt of Sulfomethylated Lignin Percent Retarder Set Times - Hours:Minutes (by wt. API Casing Simulation TestsRetarder Cement) 10,000' 12,000'______________________________________SulfomethylatedLignina 0.3 -- 2:30 0.4 -- 3:57 0.5 -- 8:00CalciumLignosulfonatea 0.3 -- 3:10 0.4 -- 2:21 0.6 -- 1:40SulfomethylatedLigninb 0.08 2:58 -- 0.12 3:29 -- 0.16 4:00 -- 0.20 4:50 -- 0.24 6:33 --CalciumLignosulfonateb 0.40 .sup. 1:44c -- 0.80 .sup. 3:20c --______________________________________ a Slurries consisted of Dyckerhoff Class G, 44% water and indicated additive. b Slurry consisted of Longhorn Class H Cement with 44% water, 35% coarse silica flour (60-140 mesh), 0.75% CFR2 friction reducer and 18% sodium chloride salt. CFR2 is beta naphthalene sulfonic acid condensed with formaldehyde and mixed with 10% polyvinyl pyrrolidone. CFR2 is described in U.S. Pat. No. 3,359,225 which is incorporated herein by reference. c Slurries showed severe gelation effects.
TABLE VI______________________________________Compressive StrengthClass H Cement with 38% WaterRetarder Concentration Giving 4.0 Hr. PumpingTime on 12,000 ft. ScheduleSlurries Pumped 2 hrs. on 12,000 ft. Scheduleand placed in Autoclaves at IndicatedTemperatureCompressive Strength Compressive StrengthUsing Conventional Using SMLLignosulfonate Retarder Cement Retarder(PSI) Temperature (PSI)8 hrs. 12 hrs. 24 hrs. °F. 8 hrs. 12 hrs 24 hrs______________________________________NS* 290 2260 170 650 1690 2790NS 2080 2660 200 1010 2020 3980NS 2270 2840 230 1670 2800 42601360 3480 3310 260 2040 3660 5420______________________________________ *Not Set
Compressive strength tests were run on slurries containing calcium lignosulfonate or sulfomethylated lignin. The cement employed in these tests was Lone Star Class H. In these tests, slurries containing retarder to give four hour pumping times on a 12,000' casing schedule were used. The slurries were pumped two hours at a 12,000' casing schedule and placed in autoclaves at four different temperatures to simulate the actual conditions encountered from the top to the bottom of a cement column in a well. The compressive strengths were then determined after 8, 12 and 24 hours according to API publication RP-10B (Section 6). After 8 hours, the slurries containing lignosulfonate had not set at the lower temperatures. However, the slurries containing sulfomethylated lignin were all set with significant strengths. The sulfomethylated lignin slurries consistently showed more rapid strength development throughout these tests.
TABLE VII__________________________________________________________________________Compatability With Fluid Loss AdditivesCompatibility of New Sulfomethylated Lignin and Common Fluid LossAdditivesaConsistometer Percent Fluid Loss Additive SodiumReadings Retarder 1b 2c Chloride Fluidat 100° F. (Poise) By Wt. % By Wt. % By Wt. % By Wt. LossInitialFinal Retarder Cement Cement Cement Water (cc)__________________________________________________________________________ Sulfomethylated 9 8 Lignin 0.5 0.6 0 -- 44 Calcium 9 10 Lignosulfonate 0.5 0.6 0 0 141 Sulfomethylated10 10 Lignin 0.5 0.6 0 18.0 98 Calcium10 10 Lignosulfonate 0.5 0.6 0 18.0 188 Sulfomethylated12 12 Lignin 0.5 0 0.6 0 38 Calcium10 10 Lignosulfonate 0.5 0 0.6 0 137 Sulfomethylated12 12 Lignin 0.5 0 0.6 18.0 82 Calcium11 11 Lignosulfonate 0.5 0 0.6 18.0 154__________________________________________________________________________ .sup. a All slurries contained Lone Star Class H Cement, 28% water, and indicated amounts of retarder, Halliburton fluid loss additive, and sodiu chloride. After mixing, the slurries were stirred on the Halliburton Consistometer for 20 minutes at 100° F. and fluid loss determination conducted at 100 PSI pressure on a 325 mesh screen at the same temperature. b 56% HEC (hydroxyethyl cellulose) with 44% CFR2. c 60% HEC, 20% defoamer with 20% CFR2.
TABLE VIII__________________________________________________________________________Dispersant and Fluid Loss Properties in Gel Cement SlurriesClass H Cement12% Gel11.46 gal. water/sack Fluid Loss cc/30 Min. 100 PSI % Addition Fann Data No. 50 1000 PSI (By wt. Shear Stress lb/ft2 at 80° F. Whatman 325 MeshRetarder Cement) 600 RPM 300 RPM 200 RPM 100 RPM Paper Screen__________________________________________________________________________SulfomethylatedLignin 0 1.22 1.16 1.12 1.05 190 372 0.34 0.47 0.34 0.31 0.26 132 265 0.52 0.42 0.27 0.21 0.17 104 188Calcium SodiumaLignosulfonate 0.34 0.58 0.47 0.43 0.37 149 258 0.52 0.69 0.56 0.51 0.46 113 217__________________________________________________________________________ a A mixed calciumsodium lignosulfonate is used in gel cement slurrie instead of simple calcium lignosulfonate due to the tendency of the latte to gel slurries of this type.
Sulfomethylated lignin functions in gel cement slurries as a dispersant and fluid loss additive. Previously, two separate retarders were required; one for non-gel slurries which was calcium lignosulfonate and another for gel slurries which was calcium sodium lignosulfonate.
TABLE IX______________________________________Extension with Tartaric AcidSet Times Obtained with a Mixture of the SodiumSalt of Sulfomethylated Lignin and Tartaric Acidin a 2:1 Weight Ratio* Set Times% Retarder Hours:Minutes(By Wt. API Casing Simulation TestsCement) 16,000' 18,000' 20,000' 22,000'______________________________________0.4 1:55 -- -- --0.5 4:20 -- -- --0.6 5:57 1:40 -- --0.8 -- 2:31 -- --0.9 -- 3:43 -- --1.0 -- 4:34 -- --1.1 -- 5:13 -- 2:001.2 -- -- 3:43 --1.3 -- -- -- 2:281.6 -- -- 5:10 --1.8 -- -- 6:32 3:122.0 -- -- -- 3:252.6 -- -- -- 4:10______________________________________ *All slurries consisted of Lone Star Class H Cement, 35% SSA1, 54% water, and indicated amounts of retarder. SSA1 is fine silica flour which is added to cement slurries at high temperature to prevent strength retrogression. Over 97% of the silica particles pass through a 200mesh (U.S. Std. Sieve Series) screen.
TABLE X______________________________________Extension of Set Times of Slurries ContainingSulfomethylated Lignin by the Addition of BoraxPercent PercentSulfomethylated Borax Set Time - Hours:MinutesLignin (By Wt. (By Wt. API Casing ScheduleCement) Cement) 15,000' 16,000'______________________________________0.7 0.6 3:00 --0.8 0.6 4:22 --0.9 0.6 5:12 --0.4 0.7 -- 1:540.6 0.7 -- 3:540.8 0.7 -- 5:200.95 0.7 -- 7:10______________________________________
Set times obtained with sulfomethylated lignin can be extended by the addition of boric acid or water soluble salt of boric acid (e.g., salts of ammonia, alkali or alkaline earth metals). This extension makes possible the use of the sulfomethylated lignin retarder at higher temperatures. Examples of extenders of this type are:
1. Boric acid,
2. Na2 B4 O7.10 H2 O (Borax),
3. Na2 B5 O8.5 H2 O,
4. KB5 O8.4 H2 O,
5. Li1 B5 O8.5 H2 O,
6. NaBO2.4 H2 O,
similar compounds and mixtures thereof.
|Patente citada||Fecha de presentación||Fecha de publicación||Solicitante||Título|
|US2674321 *||19 Dic 1949||6 Abr 1954||Phillips Petroleum Co||Low water-loss cement slurry|
|US2676170 *||15 Jul 1950||20 Abr 1954||Du Pont||Water-soluble derivatives of unsulfonated lignin|
|US2680113 *||19 Dic 1950||1 Jun 1954||Svenska Cellulosaforeningens C||Method of producing water-soluble products from black liquor lignin|
|US2775580 *||25 May 1953||25 Dic 1956||Phillips Petroleum Co||Sulfobenzyl lignins|
|US3053673 *||18 Mar 1960||11 Sep 1962||Halliburton Co||Oil well cement compositions|
|US3296159 *||19 Oct 1962||3 Ene 1967||Diamond Alkali Co||Waste sulfite liquor aliphatic aldehyde reaction products|
|US3634387 *||2 Jun 1969||11 Ene 1972||Westvaco Corp||Sulfomethylated lignin-ferrochrome complex and process for producing same|
|US3662830 *||1 Jun 1970||16 May 1972||Dow Chemical Co||Aqueous hydraulic cement composition having improved retardation to set and use thereof in high temperature environments|
|US3723145 *||5 Abr 1971||27 Mar 1973||Lone Star Cement Corp||Well cementing compositions and method|
|US3772045 *||5 Abr 1971||13 Nov 1973||Lone Star Cement Corp||Additive cement compositions and method|
|US3821985 *||30 Abr 1973||2 Jul 1974||Halliburton Co||Well cementing method using high temperature cementing compositions|
|Patente citante||Fecha de presentación||Fecha de publicación||Solicitante||Título|
|US4990191 *||21 Feb 1989||5 Feb 1991||Westvaco Corporation||Aminated sulfonated or sulfomethylated lignins as cement fluid loss control additives|
|US6315042||26 Jul 2000||13 Nov 2001||Halliburton Energy Services, Inc.||Oil-based settable spotting fluid|
|US6524384||18 Sep 2001||25 Feb 2003||Halliburton Energy Services, Inc.||Oil-based settable spotting fluid|
|US6558461 *||21 Nov 2001||6 May 2003||Lignotech Usa, Inc.||Set retarders for foamed cements|
|US6666268||16 Dic 2002||23 Dic 2003||Halliburton Energy Services, Inc.||Methods and oil-based settable drilling fluid compositions for drilling and cementing wells|
|US6668929||16 Dic 2002||30 Dic 2003||Halliburton Energy Services, Inc.||Methods and oil-based settable spotting fluid compositions for cementing wells|
|US6715552||20 Jun 2002||6 Abr 2004||Halliburton Energy Services, Inc.||Well cementing methods and compositions|
|US6716282||16 Dic 2002||6 Abr 2004||Halliburton Energy Services, Inc.||Methods and oil-based settable spotting fluid compositions for cementing wells|
|US6855201||14 Nov 2003||15 Feb 2005||Halliburton Energy Services, Inc.||Cementing compositions|
|US7063153||6 Feb 2004||20 Jun 2006||Eoff Larry S||Methods and compositions for cementing wells|
|US7077203||9 Sep 2005||18 Jul 2006||Halliburton Energy Services, Inc.||Methods of using settable compositions comprising cement kiln dust|
|US7174962||3 May 2006||13 Feb 2007||Halliburton Energy Services, Inc.||Methods of using lightweight settable compositions comprising cement kiln dust|
|US7199086||10 Nov 2005||3 Abr 2007||Halliburton Energy Services, Inc.||Settable spotting compositions comprising cement kiln dust|
|US7204307||25 May 2006||17 Abr 2007||Halliburton Energy Services, Inc.||Methods of using settable compositions comprising cement kiln dust|
|US7204310||11 Abr 2006||17 Abr 2007||Halliburton Energy Services, Inc.||Methods of use settable drilling fluids comprising cement kiln dust|
|US7213646||12 Jul 2006||8 May 2007||Halliburton Energy Services, Inc.||Cementing compositions comprising cement kiln dust, vitrified shale, zeolite, and/or amorphous silica utilizing a packing volume fraction, and associated methods|
|US7252147||22 Jul 2004||7 Ago 2007||Halliburton Energy Services, Inc.||Cementing methods and systems for initiating fluid flow with reduced pumping pressure|
|US7270183||16 Nov 2004||18 Sep 2007||Halliburton Energy Services, Inc.||Cementing methods using compressible cement compositions|
|US7284608||26 Oct 2004||23 Oct 2007||Halliburton Energy Services, Inc.||Casing strings and methods of using such strings in subterranean cementing operations|
|US7284609 *||10 Nov 2005||23 Oct 2007||Halliburton Energy Services, Inc.||Methods of using settable spotting compositions comprising cement kiln dust|
|US7290611||22 Jul 2004||6 Nov 2007||Halliburton Energy Services, Inc.||Methods and systems for cementing wells that lack surface casing|
|US7290612||16 Dic 2004||6 Nov 2007||Halliburton Energy Services, Inc.||Apparatus and method for reverse circulation cementing a casing in an open-hole wellbore|
|US7303008||26 Oct 2004||4 Dic 2007||Halliburton Energy Services, Inc.||Methods and systems for reverse-circulation cementing in subterranean formations|
|US7303014||26 Oct 2004||4 Dic 2007||Halliburton Energy Services, Inc.||Casing strings and methods of using such strings in subterranean cementing operations|
|US7322412||30 Ago 2004||29 Ene 2008||Halliburton Energy Services, Inc.||Casing shoes and methods of reverse-circulation cementing of casing|
|US7335252||3 May 2006||26 Feb 2008||Halliburton Energy Services, Inc.||Lightweight settable compositions comprising cement kiln dust|
|US7337842||24 Oct 2005||4 Mar 2008||Halliburton Energy Services, Inc.||Methods of using cement compositions comprising high alumina cement and cement kiln dust|
|US7338923||11 Abr 2006||4 Mar 2008||Halliburton Energy Services, Inc.||Settable drilling fluids comprising cement kiln dust|
|US7353870||9 Sep 2005||8 Abr 2008||Halliburton Energy Services, Inc.||Methods of using settable compositions comprising cement kiln dust and additive(s)|
|US7357181||20 Sep 2005||15 Abr 2008||Halliburton Energy Services, Inc.||Apparatus for autofill deactivation of float equipment and method of reverse cementing|
|US7381263||24 Oct 2005||3 Jun 2008||Halliburton Energy Services, Inc.||Cement compositions comprising high alumina cement and cement kiln dust|
|US7387675||9 Sep 2005||17 Jun 2008||Halliburton Energy Services, Inc.||Foamed settable compositions comprising cement kiln dust|
|US7389815||27 Sep 2007||24 Jun 2008||Halliburton Energy Services, Inc.||Methods for reverse-circulation cementing in subterranean formations|
|US7392840||20 Dic 2005||1 Jul 2008||Halliburton Energy Services, Inc.||Method and means to seal the casing-by-casing annulus at the surface for reverse circulation cement jobs|
|US7395860||9 Sep 2005||8 Jul 2008||Halliburton Energy Services, Inc.||Methods of using foamed settable compositions comprising cement kiln dust|
|US7401646||27 Sep 2007||22 Jul 2008||Halliburton Energy Services Inc.||Methods for reverse-circulation cementing in subterranean formations|
|US7404440||27 Sep 2007||29 Jul 2008||Halliburton Energy Services, Inc.||Methods of using casing strings in subterranean cementing operations|
|US7409991||27 Sep 2007||12 Ago 2008||Halliburton Energy Services, Inc.||Methods of using casing strings in subterranean cementing operations|
|US7445669||9 Sep 2005||4 Nov 2008||Halliburton Energy Services, Inc.||Settable compositions comprising cement kiln dust and additive(s)|
|US7451817||27 Sep 2007||18 Nov 2008||Halliburton Energy Services, Inc.||Methods of using casing strings in subterranean cementing operations|
|US7478675||21 Feb 2008||20 Ene 2009||Halliburton Energy Services, Inc.||Extended settable compositions comprising cement kiln dust and associated methods|
|US7503399||14 Nov 2007||17 Mar 2009||Halliburton Energy Services, Inc.||Casing shoes and methods of reverse-circulation cementing of casing|
|US7533728||4 Ene 2007||19 May 2009||Halliburton Energy Services, Inc.||Ball operated back pressure valve|
|US7533729||1 Nov 2005||19 May 2009||Halliburton Energy Services, Inc.||Reverse cementing float equipment|
|US7559369||10 May 2007||14 Jul 2009||Halliubrton Energy Services, Inc.||Well treatment composition and methods utilizing nano-particles|
|US7597146||6 Oct 2006||6 Oct 2009||Halliburton Energy Services, Inc.||Methods and apparatus for completion of well bores|
|US7607482||11 Sep 2008||27 Oct 2009||Halliburton Energy Services, Inc.||Settable compositions comprising cement kiln dust and swellable particles|
|US7607484||3 Nov 2008||27 Oct 2009||Halliburton Energy Services, Inc.||Foamed cement compositions comprising oil-swellable particles and methods of use|
|US7614451||16 Feb 2007||10 Nov 2009||Halliburton Energy Services, Inc.||Method for constructing and treating subterranean formations|
|US7621336||14 Nov 2007||24 Nov 2009||Halliburton Energy Services, Inc.||Casing shoes and methods of reverse-circulation cementing of casing|
|US7621337||14 Nov 2007||24 Nov 2009||Halliburton Energy Services, Inc.||Casing shoes and methods of reverse-circulation cementing of casing|
|US7631692||8 Abr 2009||15 Dic 2009||Halliburton Energy Services, Inc.||Settable compositions comprising a natural pozzolan and associated methods|
|US7654324||16 Jul 2007||2 Feb 2010||Halliburton Energy Services, Inc.||Reverse-circulation cementing of surface casing|
|US7674332||7 Ene 2009||9 Mar 2010||Halliburton Energy Services, Inc.||Extended settable compositions comprising cement kiln dust and associated methods|
|US7743828||27 Oct 2009||29 Jun 2010||Halliburton Energy Services, Inc.||Methods of cementing in subterranean formations using cement kiln cement kiln dust in compositions having reduced Portland cement content|
|US7784542||27 May 2009||31 Ago 2010||Halliburton Energy Services, Inc.||Cement compositions comprising latex and a nano-particle and associated methods|
|US7789150||30 Oct 2009||7 Sep 2010||Halliburton Energy Services Inc.||Latex compositions comprising pozzolan and/or cement kiln dust and methods of use|
|US7806183||20 Abr 2009||5 Oct 2010||Halliburton Energy Services Inc.||Well treatment compositions and methods utilizing nano-particles|
|US7892352||20 Abr 2009||22 Feb 2011||Halliburton Energy Services. Inc.||Well treatment compositions and methods utilizing nano-particles|
|US7927419||11 Sep 2009||19 Abr 2011||Halliburton Energy Services Inc.||Settable compositions comprising cement kiln dust and swellable particles|
|US7938186||14 Nov 2007||10 May 2011||Halliburton Energy Services Inc.||Casing shoes and methods of reverse-circulation cementing of casing|
|US8030253||20 Ago 2009||4 Oct 2011||Halliburton Energy Services, Inc.||Foamed cement compositions comprising oil-swellable particles|
|US8157009||3 Sep 2009||17 Abr 2012||Halliburton Energy Services Inc.||Cement compositions and associated methods comprising sub-micron calcium carbonate and latex|
|US8162047||12 Nov 2009||24 Abr 2012||Halliburton Energy Services Inc.||Reverse-circulation cementing of surface casing|
|US8261827||16 Abr 2012||11 Sep 2012||Halliburton Energy Services Inc.||Methods and compositions comprising kiln dust and metakaolin|
|US8281859||17 Feb 2012||9 Oct 2012||Halliburton Energy Services Inc.||Methods and compositions comprising cement kiln dust having an altered particle size|
|US8297357||28 Jun 2010||30 Oct 2012||Halliburton Energy Services Inc.||Acid-soluble cement compositions comprising cement kiln dust and/or a natural pozzolan and methods of use|
|US8307899||23 Jun 2010||13 Nov 2012||Halliburton Energy Services, Inc.||Methods of plugging and abandoning a well using compositions comprising cement kiln dust and pumicite|
|US8318642||27 Jun 2012||27 Nov 2012||Halliburton Energy Services, Inc.||Methods and compositions comprising kiln dust and metakaolin|
|US8324137||27 Jul 2010||4 Dic 2012||Roddy Craig W||Latex compositions comprising pozzolan and/or cement kiln dust and methods of use|
|US8327939||24 May 2012||11 Dic 2012||Halliburton Energy Services, Inc.||Settable compositions comprising cement kiln dust and rice husk ash and methods of use|
|US8333240||3 Nov 2008||18 Dic 2012||Halliburton Energy Services, Inc.||Reduced carbon footprint settable compositions for use in subterranean formations|
|US8399387||14 Sep 2012||19 Mar 2013||Halliburton Energy Services, Inc.||Settable compositions comprising cement kiln dust and rice husk ash and methods of use|
|US8403045||21 Dic 2010||26 Mar 2013||Halliburton Energy Services, Inc.||Settable compositions comprising unexpanded perlite and methods of cementing in subterranean formations|
|US8434553||7 Sep 2012||7 May 2013||Halliburton Energy Services, Inc.||Settable compositions comprising unexpanded perlite and methods of cementing in subterranean formations|
|US8440596||7 Sep 2012||14 May 2013||Halliburton, Energy Services, Inc.||Settable compositions comprising unexpanded perlite and methods of cementing in subterranean formations|
|US8476203||4 Ene 2010||2 Jul 2013||Halliburton Energy Services, Inc.||Cement compositions comprising sub-micron alumina and associated methods|
|US8486868||5 Nov 2012||16 Jul 2013||Halliburton Energy Services, Inc.|
|US8486869||27 Jul 2012||16 Jul 2013||Halliburton Energy Services, Inc.||Methods of plugging and abandoning a well using compositions comprising cement kiln dust and pumicite|
|US8505629||27 Jun 2012||13 Ago 2013||Halliburton Energy Services, Inc.||Foamed spacer fluids containing cement kiln dust and methods of use|
|US8505630||21 Dic 2012||13 Ago 2013||Halliburton Energy Services, Inc.||Consolidating spacer fluids and methods of use|
|US8522873||30 Sep 2010||3 Sep 2013||Halliburton Energy Services, Inc.||Spacer fluids containing cement kiln dust and methods of use|
|US8544543||27 Mar 2013||1 Oct 2013||Halliburton Energy Services, Inc.||Consolidating spacer fluids and methods of use|
|US8551923||8 May 2013||8 Oct 2013||Halliburton Energy Services, Inc.||Foamed spacer fluids containing cement kiln dust and methods of use|
|US8555967||26 Abr 2013||15 Oct 2013||Halliburton Energy Services, Inc.||Methods and systems for evaluating a boundary between a consolidating spacer fluid and a cement composition|
|US8586512||27 Sep 2009||19 Nov 2013||Halliburton Energy Services, Inc.||Cement compositions and methods utilizing nano-clay|
|US8598093||9 Jul 2010||3 Dic 2013||Halliburton Energy Services, Inc.||Cement compositions comprising latex and a nano-particle|
|US8603952||27 Mar 2012||10 Dic 2013||Halliburton Energy Services, Inc.||Cement compositions and methods utilizing nano-clay|
|US8609595||26 Oct 2012||17 Dic 2013||Halliburton Energy Services, Inc.||Methods for determining reactive index for cement kiln dust, associated compositions, and methods of use|
|US8672028||11 Jul 2011||18 Mar 2014||Halliburton Energy Services, Inc.||Settable compositions comprising interground perlite and hydraulic cement|
|US8685903||21 Mar 2011||1 Abr 2014||Halliburton Energy Services, Inc.||Lost circulation compositions and associated methods|
|US8691737||27 Mar 2013||8 Abr 2014||Halliburton Energy Services, Inc.||Consolidating spacer fluids and methods of use|
|US8741818||11 Abr 2012||3 Jun 2014||Halliburton Energy Services, Inc.||Lost circulation compositions and associated methods|
|US8895485||22 May 2012||25 Nov 2014||Halliburton Energy Services, Inc.||Methods and compositions comprising cement kiln dust having an altered particle size|
|US8895486||14 Sep 2012||25 Nov 2014||Halliburton Energy Services, Inc.||Methods and compositions comprising cement kiln dust having an altered particle size|
|US8921284||14 Feb 2013||30 Dic 2014||Halliburton Energy Services, Inc.||Spacer fluids containing cement kiln dust and methods of use|
|US8940670||30 Mar 2012||27 Ene 2015||Halliburton Energy Services, Inc.||Cement compositions comprising sub-micron alumina and associated methods|
|US8950486||27 Ago 2012||10 Feb 2015||Halliburton Energy Services, Inc.||Acid-soluble cement compositions comprising cement kiln dust and methods of use|
|US9006152||28 Feb 2012||14 Abr 2015||Halliburton Energy Services, Inc.||Cement compositions and associated methods comprising sub-micron calcium carbonate and latex|
|US9006154||23 Oct 2013||14 Abr 2015||Halliburton Energy Services, Inc.||Methods for determining reactive index for cement kiln dust, associated compositions and methods of use|
|US9006155||23 Jun 2014||14 Abr 2015||Halliburton Energy Services, Inc.||Placing a fluid comprising kiln dust in a wellbore through a bottom hole assembly|
|US9023150||19 Sep 2012||5 May 2015||Halliburton Energy Services, Inc.||Acid-soluble cement compositions comprising cement kiln dust and/or a natural pozzolan and methods of use|
|US9051505||26 Nov 2013||9 Jun 2015||Halliburton Energy Services, Inc.||Placing a fluid comprising kiln dust in a wellbore through a bottom hole assembly|
|US20040094070 *||14 Nov 2003||20 May 2004||Eoff Larry S.||Cementing compositions|
|US20040159431 *||6 Feb 2004||19 Ago 2004||Eoff Larry S.||Methods and compositions for cementing wells|
|EP2551249A2||4 Oct 2006||30 Ene 2013||Halliburton Energy Services, Inc.||Lightweight settable compositions comprising cement kiln dust|
|EP2848666A1||12 Sep 2014||18 Mar 2015||Halliburton Energy Services, Inc.||Well treatment fluids and methods utilizing nano-particles|
|WO2007054663A1||6 Oct 2006||18 May 2007||Halliburton Energy Serv Inc||Settable spotting compositions comprising cement kiln dust and methods of using them|
|WO2007116196A1||4 Oct 2006||18 Oct 2007||Halliburton Energy Serv Inc||Settable drilling fluids comprising cement kiln dust and methods of using them|
|WO2007128945A1||4 Oct 2006||15 Nov 2007||Hallburton Energy Services Inc||Lightweight settable compositions comprising cement kbln dust and methods of using them|
|WO2010029281A1||17 Ago 2009||18 Mar 2010||Halliburton Energy Services, Inc.||Settable compositions comprising cement kiln dust and swellable particles|
|WO2010116143A1||8 Abr 2010||14 Oct 2010||Halliburton Energy Services, Inc.||Settable compositions comprising a natural pozzolan and associated methods|
|WO2010122277A1||18 Mar 2010||28 Oct 2010||Halliburton Energy Services, Inc.||Well treatment compositions and methods utilizing nano-particles|
|WO2010136760A1||26 May 2010||2 Dic 2010||Halliburton Energy Services, Inc.||Cement compositions comprising latex and a nano-particle and associated methods|
|WO2011051664A1||26 Oct 2010||5 May 2011||Halliburton Energy Services Inc||Methods of cementing in subterranean formations using cement kiln dust in compositions having reduced portland cement content|
|WO2011051684A1||29 Oct 2010||5 May 2011||Halliburton Energy Services, Inc.||Cement compositions comprising latex, pozzolan and/or cement kiln dust and methods of use|
|WO2011161405A1||21 Jun 2011||29 Dic 2011||Halliburton Energy Services Inc||Methods of plugging and abandoning a well using compositions comprising cement kiln dust and pumicite|
|WO2012001343A1||21 Jun 2011||5 Ene 2012||Curtis, Philip, Anthony||Acid-soluble cement compositions comprising cement kiln dust and/or a natural pozzolan and methods of use|
|WO2012085509A1||21 Dic 2011||28 Jun 2012||Haliburton Energy Services, Inc.|
|Clasificación de EE.UU.||166/293, 530/500, 106/815, 106/803|
|Clasificación internacional||C09K8/46, C04B24/18|
|Clasificación cooperativa||C04B24/18, C09K8/46|
|Clasificación europea||C04B24/18, C09K8/46|
|1 Feb 1982||AS||Assignment|
Owner name: HALLIBURTON COMPANY, DUNCAN, OK. A CORP.OF DE.
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNORS:DETROIT, WILLIAM J.;SANFORD, MICHAEL E.;CHATTERJI, JITEN;AND OTHERS;REEL/FRAME:003947/0555;SIGNING DATES FROM 19810126 TO 19820126