THIXOTROPIC CEMENTS FOR USE IN WELLS

Abstract: A thixotropic cement composition for cementing subter­ ranean wells comprises water, hydraulic cement, a titanium chelate crosslinking agent, and one or more crosslinkable resins selected from water-soluble cellulose ethers; poly­ vinyl alcohol; homopolymers, copolymers and terpolymers of AMPS (2-arylamido - 2-methylpropane sulfonic acid), sodium vinylsulfonate, acrylamide, N,N dimethylacrylamide and acrylic acid. The cement slurry quickly forms a high static gel strength and is thus useful for cementing under pressure. It is also useful for combatting lost circulation in a zone.

Description: THIXOTROPIC CEMENTS FOR USE IN WELLS This invention relates to thixotropic cement compositions and to their use in sealing or cementing subterranean zones penetrated by a borehole, such as cementing the annular space between an oil or gas well casing and the surrounding formation. Subterranean oil, gas and water reservoirs are under great pressures. Drilling into these formations requires a borehole pressure at least sufficient to counter the formation pressure to prevent the uncontrolled flow of these formation fluids into the well bore. Borehole pressures are hydrostatic and are obtained by circulating -drilling fluids. Commonly, the first step in operations conducted to produce hydrocarbons from subterranean formations, is to cement or seal the area between the casing and the formation wall. This is accomplished either by directly introducing the cement into thK+space between the formation wall and the outer side of the casing, or by pumping the cement into the casing with sufficient pressure to force the cement back up the annular space between the outside of the casing and the formation wall. Such initial cementing operations are referred to as primary cement. Other types of jobs utilizing cement during the life of a well are referred to as secondary or remedial cementing. Such secondary cementing deals with completion and remedial repairs on a well after the producing zone is reached. Such activities include squeeze cementing (a procedure whereby a slurry is forced into the formation by pumping into the hole while maintaining a back pressure), plugging back with cement to shut off bottomhole water, plugging of crevices, cavities, leaks, and "thirsty" formations that cause lost circulation, and cementing casing leaks. Whilst cementing conditions in wells vary widely, there are two fundamental conditions which are not normally found in above-ground cementing, namely extremes of temperature and high pressure. For example, temperatures may range from below freezing in the permafrost in Alaska and Canada to 7000F. (371 0C.) in geothermal steam wells of the Salton area of Southern California. Pressures in the deep, hot wells may exceed 20,000 psi (138 MPa) and, along the Gulf Coast, cementing pressures in excess of 10,000 psi (69 MPa) are not uncommon. Both have their influence in the effective placement of cement beneath of earth's surface. Cavernous or interconnected vugular zones require only that the fluid pressure in the zone be exceeded to create complete lost circulation. The most common type of lost circulattion is attributed to the formation pressure parting or fracturing Breakdown gradients of 0.60 to 0.65 psi/ft (13.8 to 15.0 kPa/m) are common in many areas and weak, low-resistant formations with parting pressure less than 0.50 psi/ft (11.5 kPa/m) are occasionally encountered. Not all formations which have low fracturing gradients result in lost circulation problems. Many formations are drilled with mud densities in excess of the fracturing pressure. Apparently the mini-fractures which are encountered promptly plug with mud solids and drill cuttings. This build-up conditions the wellbore which allows the mud pressure to exceed the normal fracturing extension pressure. Unfortunately, many zones will accept large amounts of drilling mud (or cement slurry) without plugging. Such formations act as pressure relief valves and can often result in cement loss where the critical pressure is exceeded. Squeeze cementing is a well-known procedure in the art relating to the oil field industry. In general, squeeze cementing is utilized to attempt to obtain a positive and permanent seal between the well bore at the subterranean earth formation surrounding the well bore at a desired location. A problem frequently encountered in squeeze cementing is the loss of the slurry to the formation. In highly permeable or porous formation, a substantial portion of the cement utilized may be absorbed by the formation due to its low resistance to fluid flow thereby preventing a positive seal from being obtained. The petroleum industry has employed thixotropic cements primarily to assist in controlling lost circulation problems, in certain squeeze cementing applications and in situations where maintaining annular fill is a problem. Cements possessing thixotropic properties are desirable since they provide rapid development of static gel strength after placement. That is to say, thixotropic cements are designed so that slurry viscosities remain low while the slurry is moving, but when allowed to remain static will rapidly gel. An example of a thixotropic cement composition and a method of using same to seal subterranean formations is described in U.S. Patent Nos. 3,835,926 and 3,928,052. The composition is comprised of water, hydraulic cement, a silicate compound, a hydroxide and a salt. U.S. Patent Nos. 3,959,003 and 3,80h,174 describe a cement composition that includes as an additive a complex reaction product of a water-solublecarboxyalkyl, hydroxyalkyl or mixed carboxyalkylhydroxyalkyl ether of cellulose and a polyvalent metal salt. The composition exhibits thixotropic properties and the preferred reaction product uses hydroxyethylcellulose and zirconyl chloride Unfortunately, new testing procedures have indicated that the compositions of these patents exhibit rather limit thixotropic properties. There are several disadvantages associated with the above compositions. In many slurry designs, it is difficult to control the magnitude of static gel strength development through adjustments in additive level. Increasing the additive levels tend to prohibitively shorten the thickening time. Further, acceptable thixotropic response beyond about 2000F. (930C.) is difficult to achieve. Still further, acceptable thixotropic response in light weight slurries is also difficult to attain. Accordingly, a need exists for a method of cementing oil and gas wells that provides a highly thixotropic cement slurry that develops high gel strengths in a sufficiently short time span to be useful in combating lost circulation problems. Another problem encountered in cementing subterranean wells relates to annular gas flow (also called gas leakage or gas migration), i.e. the flow or migration of gas from a formation into a cemented casing-borehole annulus. Such gas can flow right back to the surface, create communication between producing or other subterranean zones and can, when in high enough volume, create blow-outs between the period of placement and before actual set. Minor interzone gas flow problems can sometimes be tolerated, although often at the expense of lower production. When the magnitude of leakage requires remedial action, expensive squeeze cementing jobs are necessary to control such interzone gas flow. The theory of how formation fluid flow occurs revolves around two key cement slurry parameters, static gel strength and volume reduction. These parameters affect the cement column's ability to transmit hydrostatic pressure. The first parameter, static gel strength, is the development of some internal rigidity in the matrix of the cement that will resist a force placed upon it. The development of static gel strength will start to occur immediately after pumping has stopped and will continue to increase until the cement has set. At some time before actual set, the cement will develop a static gel strength high enough to prevent any fluid from moving through it. Tests have indicated that a gel strength of 500 lbs/100 ftê (240 Pa) is sufficient to prevent any movement, although at certain conditions such gel strength can be considerably lower. When the cement has developed a static gel strength high enough to prevent formation fluids from moving through it, the cement is said to have completed its transition phase. The cement column can now begin to support some of its own weight. Volume reduction can occur in two ways. Fluids can be lost from the matrix of the cement slurry to the formation. Even when fluid loss values are very low, small amounts of fluid are still lost from the slurry and can result in a large pressure drop. Additionally, as the cement hydrates there is a hydration volume reduction. Such reduction can ultimately be as high as 3 percent. Where the static gel strength development and the volume reduction are sufficient for a pressure drop to be realized, the hydrostatic pressure can fall below the formation pressure and formation fluids can enter the cement filled annulus. If the gel strength of the cement slurry is not high enough to prevent further movement of formation fluids, a fingering or migration phenomenon will occur. However, where the gel strength is high enough and the formation fluids are not already moving through the cement column, flow will not be initiated. Traditionally, the petroleum industry has attempted to prevent formation fluid flow by increasing the slurry density, improving mud displacement, controlling mud-cement slurry compatibility, using fluid loss control additives, and multiple stage cementing. Although these techniques are helpful and have shown some measure of success, none have completely solved formation fluid flow problems. U.S. Patent Nos. 3,959,003 and 3,804,174 (previously referred to) describe a cement composition which exhibits thixotropic properties but not to the extent required to prevent formation fluid migration. Newer techniques using cement slurries containing a stabilized, dispersed gas or cement slurries capable of internally generating gas have achieved a much greater degree of success. Such techniques are described in U.S. Patent Nos. 4,304,298 and 4,340,427. However, there are cases where it is undesirable to use such compressible cements, be it from logistical, economic, time or other standpoints. Accordingly, a need exists for a method of cementing oil and gas wells that provides a highly thixotropic cement slurry that develops high gel strengths in a sufficiently short time span so as to prevent fluid invasion of the annulus even though the hydrostatic pressure may fall below the gas reservoir pressure during the transition of the slurry to a solid mass. We have now devised a thixotropic cement composition which is useful for both the purposes discussed above, namely for combatting lost circulation problems and for preventing migration of formation fluids. According to the invention, there is provided a thixotropic cement composition for well cementing operations, which comprises water, hydraulic cement, a titanium chelate crosslinking agent, and one or more crosslinkable resins selected from water-soluble cellulose ethers; polyvinyl alcohol; homopolymers, copolymers and terpolymers of AMPS (2-acrylamido - 2-methylpropane sulfonic acid), sodium vinylsulfonate, acrylamide, N,N dimethylacrylamide and acrylic acid. These cements have pronounced thixotropic properties and rapidly develop very high static gel strengths. The magnitude of the static gel strength can be controlled by the level of added titanium chelate and cellulose derivatives. To effectively combat formation fluid flow a thixotropic cement slurry must develop static gel strength at a rate sufficient to maintain the hydrostatic pressure above the reservoir pressure during the period when pumping ends and static gel strength of sufficient magnitude to prevent fluid migration is reached. The thixotropic cement slurries of the invention achieve this. In well completion operations, cement slurries are almost universally used to fill the annular space between casing an open hole. After setting, the principal functions of such cement slurries are to restrict fluid movement between formations to protect the casing from corrosion and to support the casing. Cements are made from high calcium carbonate materials, such as limestone, and clay shale, iron and aluminum oxides are sometimes added to supplement the amount of each found in the clay or shale. The API publication, "API Specifications for Materials and Testing for Well Cements", API Spec 10, First Edition, January, 1982, describes specifications for cement used in the formulation of cementing slurries for oil well applications. The cement slurry thickening time is strongly dependent upon temperature and pressure. To obtain optimum results a variety of additives are often included in the formulation of a cement slurry to vary cement density, increase or decrease strength, accelerate or retard setting time, control filtration rate, reduce slurry viscosity, increase resistance to corrosive fluids, bridge formations for lost circulation control, and improve economics. Essentially, a cement meeting API specifications is mixed with water and other additives to provide a cementing slurry appropriate for the conditions existing in each individual oil well. In accordance with the present inventon, we have found that certain titanium chelates can be used as crosslinking agents and provide excellent thixotropic properties and gel strength development. Further, these titanium chelates along with an appropriate crosslinkable additive can promote the development of sufficient static gel strength in a sufficiently short time frame so as to be effective in combating lost circulation. When the static gel strength achieved is of the order of 500 lbs/100 ft2 (240 Pa), this will prevent gas penetration through a cement column. However, the titanium chelate crosslinking agents are somewhat sensitive to temperature, and hence, in developing a specific slurry one must be concerned with the downhole circulating temperature. Another related benefit of the present invention relates to the discovery that use of titanium chelate cement additives in thixotropic or even conventional cement slurries containing conventional additives (including dispersants) result in the achievement of uniform or enhanced compressive strength develop ent. Often the development of adequate compressive strength in 12 or 24 hours can be extremely difficult to obtain at liner tops, especially when the liner is long enough that the static temperature at the top of the liner is near or below the Bottom Hole circulating Temperature (BHCT). In some liner jobs the top of the liner static temperature is 15 (80) to 40 F (22 0C) cooler than the BHCT. In these cases the cement slurries may take an excessive amount of time to reach enough compressive strength for the company to continue operations. The cement compositions of the present invention combat this delay in compressive strength. The present compositions are shear sensitive, meaning that while undergoing shear such compositions remain fluid and pumpable for an ample period of time, but when static, such compositions develop high gel strength in a short period of time followed by rapid compressive strength development. The material to be crosslinked is selected from the group consisting of water-soluble crosslinkable resins such as cellulose ethers exemplified by hydroxyalkyl cellulose, a carboxyalkyl group consisting of cellulose or carboxyalkylhydroxyalkyl cellulose; polyvinyl alcohol; homopolymers, copolymers and terpolymers of AMPS (2-acrylamido - 2-methylpropane sulfonic acid), sodium vinylstulfonate, acrylamide, N, N-dimethylacrylamide, and acrylic acid; and mixtures thereof. The titanium crosslinking agents are titanium chelates. Titanium chelates are formed by the reaction of titanium tetrach chloride or titanium alkoxides (usually C2-C4) with a wide variety of bi- or multi-functional organic compounds. One of the functional groups of the organic compound is usually hydroxyl (or enolic carbonyl) for -interchange with a chloride or alkoxyl group attached to the titanium atom in the titanium chloride or alkoxide, thus liberating one mole of HC1 or alcohol. The other group of the organic compound can also be hydroxyl or carboxyl, carbonyi or amino, and as a result glycols, hydroxy acids, dicarboxylic acids, diketones, keto esters and alkanolamines are available for chelation. For the most part glycols, hydroxy acids and dicarboxylic acids are stable in aqueous solution, while diketones, keto esters and alkanolamines are solvent-soluble and hydrolize at varying rates in aqueous systems. a series of tests were conducted to determine how effective a variety of titanium chelates were in producing thixotropic behavior. The cement slurries tested were prepared by dry blending all the additives with the cement prior to addition of water. If any liquid additives were used, the liquid was added to the mixing water prior to adding cement. The cement slurry was placed in static gel strength measuring device and a standard thixotropic test was conducted. The static gel strength measuring apparatus consists of three major components, the chamber and lid, the magnetic drive assembly, and the cord pulling assembly. The chamber is a heavy wall, high strength metal vessel equipped with strip heaters attached directly to the outside of the chamber. A thermocouple is inserted into the vessel to allow the temperature of the vessel to be controlled. The lid of the chamber is equipped so that the principle drive shaft of the magnetic drive assembly can be inserted. On the shaft a stirring paddle is fitted over one end of the shaft and secured with a shear pin. On the other end of the principal drive shaft the magnetic drive head is connected. The magnetic drive head is then in turn connected by a belt system to a variable speed magnetic drive power source and torque measuring device. A thermocouple is inserted through the top of the magnetic drive head and down the middle of the hollow principal drive shaft. The lid of the chamber is equipped with two ports. One port is connected to a pressure volume pump used to generate pressure and the other port is equipped with a quick opening saftey valve. The bottom of the chamber is equipped with a quick opening valve and used to relieve the pressure and discharge the test slurry at the end of the test period. The cord pulling mechanism consists of a cord pulling capstan or drum arrangement driven by a variable speed gear motor with the cord running through the pulley arrangement to a load -cell and then to the top of the magnetic drive head. To determine the gel strength development of cement under down hole conditions, this equipment was specifically designed for measuring static gel strength after a stirring period that simulated slurry placement. The equipment is designed to operate at a maximum temperature of 9000F (2040C) at 10,000 psi (69 MPa). The low friction magnetic drive allows the slurry' to be stirred while monitoring consistency during the stirring time. After simulating placement time, the motor is shut off and the cord pulling system is attached to the magnetic drive head. Static gel strength is determined by continuously measuring the torque required.to rotate the paddle at a very slow speed (0.5 to 2.00 per minute). At such speeds, a magnetic drive has very low friction and very accurate torque measurements can be made. Since the torque measuring system consists of a cordpulling capstan or drum arrangement driven by a variable speed gear motor accurate continuous rotation and means for continuously recording the torque is provided. The gel strength is then calculated from the torque measurement and the vessel geometry. The slow movement of the paddle allows static gel strength to be measured but does not inhibit gel strength development. Gel strength properties can be measured up to a maximum of10001bs1100ft2 (480 Pa). The standard thixotropic test procedure is as follows: 1. Stir the slurry with the magnetic drive consistometer for one hour while increasing temperature and pressure for ambient conditions to bottom hole circulating tem perature (BBCT) and bottom hole pressure (BHP) according to schedule. 2. After one hour's stirring, set static for 15 minutes while continually measuring static gel strength. 3. After a static period of 15 minutes, stir for 15 minutes while continually measuring consistency. 4. Repeat static and stirring times a total of three times. In the data that was developed, one basic slurry composition was tested. This slurry consisted of API Class H cement, 0.4% carboxymethylhydroxyethyl.cellulose by weight of cement, 44% water by weight of cement and retarder as given in Table I. Table I provides the range of temperatures, pressures and retarder amounts used in each simulated well condition. The tem perature range varied from 1400F (600C) to 2750F (T350C). The amount of retarder utilized was sufficient to provide at least 3 hours thickening time at test conditions where thickening time is taken as the definition given in API Specification 10. TABLE I Test Conditions and Retarder Amounts Temp Pressure Percent by Weight 0F ( C) psi (MPa) Retarder * 140 (60) 6000 (41.3) 0.4 170 (71) 8000 (55.1) 1.2 180 (82) 8000 (55.1) 1.2 200 (94) 8000 (55.1) 1.6 215 (102) 8000 (55.1) 2.0 245 (118) 8000 (55.1) 2.2 275 (135) 8000 (55.1) 2.4 * The retarder used was a 1 :1 mixture of calcium ligno sulfonate and potassium pentaborate. Table II provides the physical and chemical properties of the titanium compounds tested. Excepting the zirconium containing additives, all compounds were DuPont products. TABLE II Physical and Chemical Properties of Titanium Compounds Considered as Thixotropic Cement Additives Physical Compound Form Chemical Description zirconium Solid Zirconium oxychloride (zlrconyl oxychioride chloride) -zrccl2 zirconium Liquid Zirconium chelate of acetylacetone acetylacetonate Titanium Liquid Titanium oxychloride (TiOCl2) oxychloride Titanium Liquid triethanolamine (Non-aqueous) Prepared by reaction of titanium isopropoxide with two moles of triethanolamine. Ti (OCH(CH3)2)4 + 2N(CH2CH2OH)3 EMI15.1 (C3H7O)2Ti[OCH2CH2N(CH2CH2OH)2]2 + 2C3H7OH The two moles of isopropyl alcohol are left in the reaction mixture. Thus, this compound consists of triethanolamine titanate plus isopropyl alcohol. Titanium Solid Titanium Monotriethanolamine, monotriethanolamine (NCH2CH2O-)3Ti(OCH(CH3)2), contains about 19.0% Titanium by weight. Titanium Solid A mixture of 57% titanium monotriethanolamine monotriethanolamine and 43% fructose plus fructose (Blend I) by wt. Titanium Solid A mixture of 73% titanium monotriethanolamine monotriethanolamine and 27% fructose plus fructose (Blend II) by wt. Titanium Solid Titanium triethanolamine deposited triethanolamine on diatomaceus earth. Contains deposited on about 4.1% Ti by wt. diatomaceous earth Titanium Liquid Solution of titanium monotriethanolamine monotriethanolamine containing solution about 7.6% Ti by wt. Hydrolyzel, Solid Organic titanate (chelate) fran partially hydrolyzed titanium polymerized titanium acetylacetonate. Prepared by acetylacetonate controlled addition of water as illustrated below. EMI16.1 partially polymerized, - solid product. Titanium Liquid Preparated by the reaction of lactate (Aqueous) titanium isopropoxide with two moles of lactic acid in presence of water. Ti(OCH(CH3)2)4 + 2CH3CH(OH)COOH [Ti(OH)2(OCH(CH3)COO-)2][H+]2 + EMI16.2 4C3H7CH The acidic protons are neutralized with ammonium hydroxide. This product ray be described as the ammonium salt of titanium lactate. Bowever, the structure of this product is complicated by polymerization of the titanium dielate to some degree. Polymerized Solid Polymerized titanium lactate. titanium Prepared from the titanium lactate. lactate Extent of polymerization has been increased to insolublize the chelate and yield a solid containing about 21.48 Ti. Lactic acid Solid One mole of lactic acid reacted reacted with with two moles of hydrated TiO2. hydrated TiO2 Ti content is about 20.8% by wt. Titanium Liquid Tartaric acid analog of titanium tartrate lactate. Contains about 8.2% Ti by wt. Titanium malate Solid Titanium malate which has been spray dried. Contains about 7.9% Ti by wt. Titanium Liquid Prepared by the reaction of acetylacetonate (Non-aqueous) titanium iscoropoxide with two moles of acetylacetone. Ti(OCH(CH3)2)4 + 2(CH3COCH2COCH3) EMI16.3 Ti(OC3H7)2[OC(CH3)=CHOCH3]2 + 2C3H7OH The two moles of isopropyl alcohol are left in the reaction mixture. Table III provides the actual data obtained. The additive description along with the amount of additive used (by weight of cement), temperatures and actual gel strength measurements are shown. The retarder level at each temperature is given in Table I. The gel strengths given are the maximum strength reached during each 15 minute period. TABLE III Gel Strength Measurementsa Percent Gel Strength Addition Temperature lbs/100 ft2 (pascals) Additive (bwe) F ( C) 1 2 3 None -0- 140 (60) 12(6) 30(14) 70(34) Zirconium 1.0 140 (60) 60(29) 70(34) 60(29) oxychloride 1.0 200 (93) 75(36) 100(48) 95(47) Zirconium 0.5 140 (60) 75(36) 100(48) 160(77) acetylacetonate Titanium 0.5 140 (60) 365(175) oxychloride Titanium tri- 0.25 140 (60) 30(14) 40(19) 32(15) ethanolamine 0.50 140 (60) 0 0 20(10) 0.50 200 (93) 350(168) 205(98) 212(102) 0.50 275 (135) 305(146) 310(149) 225(108) Titanium 0.25 140 (60) 50(24) 5(2) 15(7) Monotriethanol 0.25 140 (60) 40(19) 20(10) 15(7) amine 0.50 140 (60) 50(24) 50(24) 50(24) 0.50 140 (60) 25(12) 25(12) 25(12) 0.25 180 (82) 200(96) 320(154) 270(130) 0.25 215 (102) 500(240) 500(240) 500 (240) 0.25 275 (135) 265(127) 250(120) 220(106) 0.50 275 (135) 225(108) 500 (240) 500 (240) Titanium 0.50 140(60) 500(240)500 (240) 500(240) monotriethanol- 0.50 275(135) 80(38) 90(43) 85(41) amine plus 0.50 275(135) 70(34) 100(48) 100(48) fructose (Blend I) Titanium 0.25 140(60) 400(192) 500(240) monotriethanol- 0.50 140(60) 500(240) 500(240) 500(240) amine plus 0.50 180(82) 200(96) 210(100 fructose 0.50 215(102) 500(240) 500(240) 500(240) (Blend II) 0.50 275(135) 500(240) 500(240) 500(240) Titanium tri- 0.50 140(60) 135(65) 120(58) 100(48) ethanolamine deposited on diatomaceous earth Titanium 0.25 180(82) 500(240) 200(96) 250(120) monotriethanol- 0.50 180(82) 450(216) 500(240) 500(240) amine solution Hydrolyzed, 0.5 140 (60) 205(98) 200 (96) 205(98) partially polymerized titanium acetylacetonate Titanium lactate 0.25 170(77) 160(77) 200 (96) 215(103) Polymerized 0.5 275(135) 270(130) 330(158) 235(113) titanium lactate Lactic acid 0.5 140(60) 350(168)400 (192) 300(144) reacted with 0.5 200(93) 160(77) 160(77) 195(94) hydrated TiO2 0.5 275(135) 40(19) 35(17) 40(19) Titanium tartrate 0.5 140(60) 115(55) 150 (72) 155 (74) 0.5 275(135) 180(86) 390 (187) 280(134) Titanium palate 0.5 140(60) 500(240)500 (240) 500 (240) 0.5 275(135) 20(10) 40 (19). 45(22) Titanium 0.5 245(118) 450(216) 500(240) 500(240) acetylacetonateb aSlurry composition: Class H Cement, 0.4% CMHEC, 44% H2O bReplacement of CMHEC with HEC in slurry formulation This data indicates that certain titanium containing agents can impart thixotropic properties to cements under the above conditions. Such agents are represented by the formula: EMI19.1 where X1 and X2 represent functional groups containing oxygen or nitrogen, yl and y2 represent two or three carbon atom chains, and R1 and R2 may be hydrogen, substituted or unsubstituted alkyl and aryl groups such as methyl, ethyl, allyl, n-propyl, isopropyl, benzyl, etc., or combinations thereof. Additionally, -OR1, or -OR2 may be halogen atoms. Additionally, variations of the structure believed effective include complete or partial replacement of the' alkoxide, -OR, or halogen atoms with one or more of the allowable -OY1X1- or -OY2X2- functional groups or replacement of one or more of the -OY1X1-or -0Y2X2- functional groups with alkoxide -OR or halogen. The resultant agent may be used in solid or liquid form, dissolved in aqueous or nonaqueous media, or placed on carriers such as silica, diatomaceous earth or other inert, solid media. Examples of products observed to be useful in the present invention are more particularly described in the three following formulas (a) Acetylacetonate Titanium Chelate [(CH3)2CHO]2Ti[OC(CH3)=CHCCH3O]2 schematically written: EMI20.1 and modifications of this product which include replacement of the -C3H7 group with various other alkyl or aryl groups or replacement of the -OC3H7 groups with hydroxide or halogens. Partially polymerized versions of this product which involve polymerization at the titanium atom are also useful in this invention. In addition, one or both of the acetylacetonate ligands may be replaced by other beta-diketones. Also, the pro ducts may involve only one beta-diketone ligand. (b) Lactic Acid Titanium Chelate [(HO)2Ti(OCH(CH3)COO-)2][M+]2, schematically written: EMI21.1 and modifications of this product where M+ is hydrogen, alkali metal cation, ammonium, or protonated amine. Partially polymerized versions of this product which involve polymerization at the titanium atom are also useful in this invention. One or both of the lactate ligands may be replaced by a wide variety of other alpha-hydroxy acids such as salicyclic, glycolic, malic, tartaric, citric, alpha-hydroxybutyric, and numerous sugar-derived acids from glyceric to saccharic and gluconic acids. It is also possible to prepare chelates using dicarboxylic acids. Two common chelates of this type are prepared with oxalic and phthalic acids or their salts. (c) Triethanolamine Titanium Chelate [(CH3)2CHO]2Ti[OCH2CH2N(CH2CH2OH]2 schematically written: EMI22.1 and modifications of this product which include replacement of the -C3H7 group with various other alkyl or aryl groups or replacement of the -OC3H7 groups with hydroxide or halogen atoms, and partially polymerized versions of these products. Other liqands useful in this class which may replace one or both of the triethanolamine ligands include tripropanolamine, (R1)2N-R2-OH where R1 is hydrogen, methyl, or ethyl and R2 is ethyl or propyl, 2-(2-aminoethylamino)ethanol, (HOR)(R1)N-Rê-NR1R where R is an ethylenic group and R1, R2, R3 are alkyl, hydroxyalkyl, or aminoalkyl groups, quadrol [(HOCH(CH3)CH2)2NCH2CH2N(CH3)HCOH)2], theed l(HoCH2CH2)2NCH2CH2N{CH2CH2OH)2lS and various other alkanolamines. These complexes may contain one to four alkanolamine ligands per titanium. A perferred titanium chelate from this class is prepared by the reaction of titanium isopropoxide with two moles of triethanolamine to yield titanium triethanolamine plus two moles of isopropyl alcohol. The product is a liquid containing about 8.38 titanium. --A preferred class of solid titanium chelate is described in U.S. Patent No. 2,935,522. These agents have the following general formula: EMI23.1 where R is isopropyl (-C3H7) and R1 is ethylene or isopropylene. A preferred titanium crosslinking agent of this invention is titanium monotriethanolamine represented by the general structure where R is isopropyl and R1 is ethylene. This material is a white, free flowing solid which can be dry blended with the cement. Modifications of this structure include products contanning two triethanolamine groups with proposed structure represented by: EMI24.1 and dimers with a structure assumed to be similar to the following: EMI24.2 where R1 is ethylene or isopropylene. In addition, it has been observed that the blending of certain compounds with the titanium chelates tanks to enhance the thixotropic response observed with a given chelate. At low temperatures, especially below about 140 F (60dC), the cement compositions containing the described titanium chelates show limited thixotropic properties. The reason for this is believed to be a tendency at these low temperatures for the titanium to be in a form which renders it ineffective as a crosslinking agent. The addition of an effective amount of certain sugars activates the titanium at the low temperatures and allows it to act as an effective crosslinking agent. A perferred compound of this type is fructose although it is presumed that compounds such as mannose, glu cose, arabinose, galactose, catechol and other compounds containing hydroxyl groups in the cis configuration would function as well. EXAMPLE 1 A preferred embodiment of the present invention was tested under actual downhole conditions. The well conditions were as follows: Total depth: 22,000' (6706 m) Liner: 5" (23 lb/ft) (12.7 cm (34 kg/m)) Bottom hole static temperature: 3250 F (1630C) Cement placement: 17,264' (5262 m) to 22,000' (6706m) The well was in an area which had a highly fractured zone from 19,-1-00' (5822 m) to 19,200' (5852). The zone had been detected by a 10' (3 m) drill bit drop while drilling. At this point the well began taking 8.7 lb/gal (1.04 kg/L) drilling fluid at a rate which exceeded 10 barrels/hr (1.6 kL/hr). A slurry having the following composition was first prepared and tested in the laboratory: 50/50 (by volume) API Class H Cement/fly ash 17% fine silica flour 0.14% calcium lignosulfonate 0.4% Potassium pentaborate 1.0% Carboxymethylhydroxyethyl cellulose 0.4% Titanium triethanolamine Sufficient water to achieve a 13.4 lb/gal (1.61 kg/L) slurry weight The cementing operation was performed in a one stage operation with partial returns maintained throughout the job. Cement was located at 453 feet (138 m) above the liner top. Bond logs indicated satisfactory to excellent bond throughout the interval. Slurry density - 16.4lbs/gal (1.96 kg/L) Slurry volume - 1.35 ft3/sk (38.2 L/sk) Slurry water - 5.2 gal/sk (19.7 L/sk) The laboratory gel strength tests indicated this slurry gelled to 500 lbs/100 ft2 (240 Pa) in 20 minutes at a bottom hole circulat-ing temperature of 2400F (1160C) and a pressure of 8000 psi (55.1 MPa). The job was run and considered successful by the customer. No gas flow was observed on the well and the casing shoe withstood the pressure test. It should be noted that a variety of retarders may be used in the cement compositions of the present invention, but these retarders must not significantly disperse the slurry in question. The reason for avoiding retarders that will thin the slurry is that such dispersants will also adversely affect the slurries thixotropic properties. An example of a preferred retarder system is calcium lignosulfonate and potassium pentaborate in a 1:1 ratio by weight. The crosslinkable material may also work as a retarder. This is one reason that CMHEC and HEC are preferred materials at higher temperatures. Both CMHEC and HEC are known to act as cement set retarders. The polymers containing acrylic acid also display retardation properties. The other named crosslinkable materials do not significantly retard the set of a cement slurry and as such are useful primarily at lower temperatures. It should be noted that the extent of retardation does not significantly affect the thixotropic properties of the cement composition, so long as the retarder used doesn't significantly disperse the slurry in question. For example, the time to develop static gel strength remains the same whether or not the composition is pumped for 2 or 8 hours. The amount of titanium necessary to impart significant thixotropic properties to the cement composition will vary with respect to desired static gel strength, the amount of crosslinkable material present and temperature. Hence, the general amount required may vary from approximately 0.01 ; to about 10% by weight of cement. The preferred range will generally be about 0.25% to about 0.75% by weight of cement. A preferred subclass of titanium chelate is the alkanolamines. Within this preferred subclass, a preferred alkanolamine is titanium triethanolamine. The most preferred titanium chelate is the solid form of titanium monotriethanolamine. Hence, the most preferred composition would be comprised of one or more of the preferred titanium chelates, one or more of the preferred crosslinkable agents and fructose. While particular embodiments of the invention have been described, it will be understood that the invention is not limited thereto, since modifications may be made and will become apparent to those skilled in the art. For example, the titanium chelate can be deposited on an inert carrier to facilitate blending into the dry cement. Such carriers could include diatomaceous earth or silica flour. EXAMPLE 2 A preferred embodiment of the present invention was tested under actual downhole conditions. The cement job was a production string. Production strings typically have histories of gas flow problems. The well conditions were as follows: Total depth : 12,000' (3658 m) Hole Size : 6·" (15.9 cm) Casing Size : 27/8" (7.3 cm) long string Bottom Hole Circulating Temperature : 239 0F (1150C) Bottom Hole Static Temperature : 3000F (149 C) Well Fluid : 15.4 lbs/gal mud (1.85 kg/l) Displacement Fluid : 2% KCl water A slurry having the following composition was first prepared and tested in the laboratory: Lone Star Class H Cement + 30% Coarse Silica + 4% CMHEC + .5% Potassium Pentaborate + .5% Calcium Lignosulfonate + .25% Titanium Triethanolamine.

Claims: CLAIMS: 1. A thixotropic cement composition for well cementing operations, which comprises water, hydraulic clement, a titanium chelate crosslinking agent, and one or more cross linkable resins selected from water-soluble cellulose ethers; polyvinyl alcohol; homopolymers, copolymers and terpolymers of AMPS (2-acrylamido - 2-methylpropane sulfonic acid), sodium vinylsulfonate, acrylamide, N,N dimethylacrylamide and acrylic acid. 2. A composition according to claim 1, wherein the crossslinking agent has the formula: EMI29.1 where R is isopropyl and R is an ethylene group. 3. A composition according to claim 1 wherein said crosslinking agent is titanium triethanolamine or titanium monotriethanolamine. A A composition according to claim 1, 2 or 3, wherein said resin is carboxymethylhydroxyethyl cellulose or hydroxyethyl cellulose. 5. A composition according to claim 1,2,3 or 4, which also includes between 5% and 50% by weight of one or more sugars, said sugar(s) preferably being selected from fructose, mannose, glucose, arabinese, galactose and catechol. 6. A composition according to any of claims 1 to 5, wherein said titanium chelate is present in an amount of from 0.01% to 10%, preferably from 0.25% to 0.75%, by weight of cement. 7. A composition according to any of claims 1 to 6, wherein said titanium chelate is deposited on a neutral carrier, preferably diatomaceous earth or silica flour. 8. A method of combatting lost circulation in a zone during cementing of oil, gas, and water wells, comprising pumping into said zone a slurry of a thixotropic cement as claimed in any of claims 1 to 7, terminating pumping, and allowing said static slurry to set. 9. A method of cementing a zone under pressure comprising pumping into said zone a slurry of a thixotropic cement as claimed in any of claims 1 to 7, terminating pumping, and allowing said slurry to set. 10. A method according to claim 8 or 9, wherein the titanium chelate is monotriethanolamine which is in solid form and wherein between 5% and 50%, preferably from 10% -to 30%, by weight of one or more of the sugars fructose, mannose, glucose, arabinose, galactose and catechol, is dry blended therewith.

Inventors: CHILDS, JERRY DALE, SABINS, FREDDIE LYNNE, TAYLOR, MARY JO
Applicants: HALLIBURTON COMPANY
Application year: 1984
Main classification: E21B33
IPC codes: C04B24, E21B21, C09K8, C04B28