Squeeze cementing

Abstract: An undesirable flow of water from a highly permeable portion of, or a fracture in, a subterranean formation is terminated by the use of a hydraulic cement consisting of discrete particles having a particle size not greater than about 30 microns, the cement being in a slurry with a hydrocarbon liquid and a surfactant. The surfactant comprises an alkyl aromatic sulfonic acid of formula where R₁ is a linear alkyl group of 12 or 16 to 24 carbon atoms, and R₂ amd R₃ are each a linear alkyl group of 12 carbon atoms.

Description: This invention relates to wells used in the introduction of fluids into and the recovery of fluids from subterranean formations. It further relates to the use of hydraulic cement compositions to construct and repair such wells. This invention particularly relates to methods of using a very finely divided hydraulic cement composition to construct and repair such wells. In the operation of wells used in the recovery of fluids from, or the introduction of fluids into, subterranean formations problems relating to the unwanted passage of fluids and/or fine solids into or from undesirable locations in the formation or well bore sometimes occur. This unwanted passage of fluids and/or fine solids can severely disrupt or in fact terminate the desired operation of a well. To be more specific, the problems involving unwanted passage of fluids, referred to above, ordinarily involve the movement of fluids, such as oil, gas or water through very small undesirable openings. These problems are not unique and the solutions have traditionally involved apparatus, methods and compositions adapted to cover, seal or to otherwise plug the openings to thereby terminate the unwanted passage of fluid through the opening. The openings referred to above include: holes or cracks in a well casing; spaces such as holes, cracks, voids or channels in a cement sheath inserted into the annular space between a formation face and the well casing; very small spaces - called microannuli - between the cement sheath, and an exterior surface of the well casing or formation; and permeable spaces in gravel packs and formations. Holes or cracks in the well casing and/or cement sheath can permit the unwanted and therefore uncontrolled passage of fluid therethrough. Sometimes, of course, holes are deliberately made in the well casing and the cement sheath, known as perforating, in order to permit the controlled recovery of fluid from a formation or to allow the controlled introduction or injection of fluid into a formation. Sealing or plugging such holes or cracks, whether or not made deliberately, is carried out by placing or otherwise forcing a substance into the hole or crack and allowing the substance to remain therein to thereby plug the opening. Of course, the substance will not plug the opening if it will not enter the opening. If the substance does not fit then, at best, a bridge, patch, or skin may be formed over the opening and a temporary termination of the unwanted fluid flow results. Substances used in methods to terminate the unwanted passage of fluids through holes or cracks in a well casing and/or a cement sheath have been compositions comprised of hydraulic cement, wherein the methods employ hydraulic pressure to force a water slurry of the cement into the cracks and holes wherein the cement is permitted to harden. These methods are variously referred to in the art as squeeze cementing, squeezing or as squeeze jobs. Subterranean formations sometimes produce unwanted water from natural fractures as well as from fractures produced by forces applied deliberately or accidentally during production operations. It is known that such fractures provide a path of least resistance to the flow of fluid from a formation to a wellbore. When the fluid flowing in a fracture is primarily oil, the fracture is considered to be beneficial and thus desirable; however, when the fluid flowing in the fracture from the formation to the wellbore is primarily water the fracture is considered to be a problem and thus undesirable. Fine particle size cement used in squeeze cementing techniques can be placed into a subterranean fracture as well as into a high permeability zone of the formation by the application of conventional procedures. The cement itself, although it is highly reactive due to its small particle size, can be rendered temporarily non-reactive by preventing contact between it and water prior to actual placement of the cement into the fracture. Accordingly it is known for fine cement to be dispersed in a relatively low viscosity, relatively non-volatile liquid hydrocarbon, such as diesel oil, to form a pumpable slurry of cement in oil (see US Patent 4,126,003 to Tomic). The dispersion of the cement in the non-volatile liquid hydrocarbon must be assisted by use of an appropriate surfactant. In this regard it has been discovered that a mixture of the fine cement with the liquid hydrocarbon, in the absence of a surfactant, produces a blend having a viscosity so high that the blend cannot be pumped by conventional means into the desired location in the formation. Use of a surfactant, results in a blend of cement in hydrocarbon having a sufficiently low viscosity to permit convenient conventional introduction of the blend into the desired location in the formation. Furthermore, it is known that the high beneficial hydraulic activity of the fine particle size cement can be unduly reduced upon contact with a hydrocarbon, but that the problem can be avoided by use of a surfactant. Thus, the use of a surfactant is necessary to enable the production of a cement in hydrocarbon slurry having a sufficiently low viscosity to permit convenient placement in the desired zone, and to prevent the liquid hydrocarbon carrier from oil wetting the surface of the small particle size cement because such oil wetting would cause the fine cement to suffer a loss of hydraulic activity. The slurry is then introduced into the fracture. After the slurry of cement and oil is located in the fracture, water flowing in the fracture slowly contacts the cement to thereby render the cement reactive so as to initiate hydration, hardening and ultimate formation of a permanent plug in the fracture. By this technique the cement in the hydrocarbon/surfactant/cement slurry will only set when contacted by water in the fracture and thus will not set if the slurry enters a fracture containing oil. Accordingly, oil producing portions of a reservoir will remain relatively damage free. One prior art suggestion for formulating a cement in a hydrocarbon oil slurry is disclosed in our US-A-5086850 where dodecylbenzenesulphonic acid and alkali and alkaline earth metal salts thereof, are used as the surfactant. We have now found that successful formulation of a cement in hydrocarbon oil slurry to obtain the goals set out above depends upon sufficient dispersion of the cement in the oil. We have found certain surfactants which can be used to achieve these goals. According to the present invention there is provided a method of terminating the flow of water from a portion of a subterranean formation into a wellbore, said method comprising the steps of: placing within the wellbore adjacent said portion a volume of a slurry of hydraulic cement, said volume being in an amount at least sufficient to saturate said portion; permitting said slurry volume to penetrate into said portion; and maintaining said slurry in said portion for a time sufficient to enable said slurry to form a rigid mass of cement in said portion; wherein said slurry consists essentially of a mixture of said hydraulic cement, a hydrocarbon liquid, and a liquid surfactant soluble in said hydrocarbon liquid, the particle size of said hydraulic cement is not greater than about 30 microns, the Blaine Fineness of said hydraulic cement is no less than about 6000 cm 2 /gram, and said hydraulic cement is Portland cement or slag or a mixture thereof characterised in that said liquid surfactant includes as an essential component an alkyl aromatic sulphonic acid of formula or or an alkaline earth metal salt thereof, wherein R 1 is a linear alkyl group having 16 to 24 carbon atoms and R 2 and R 3 are each a linear alkyl group containing 12 carbon atoms. The preferred order of blending of the ingredients is by adding the correct quantity of surfactant to the hydrocarbon liquid with thorough mixing and then slowly adding the cement to the oil/surfactant blend with continued mixing to obtain the desired slurry of uniform consistency. The surfactant useful herein which is a solution consisting of an aromatic sulfonic acid or a salt thereof dissolved in a low molecular weight alcohol, is mixed with the hydrocarbon liquid such as diesel oil, in an amount in the range of from about 37.8 litres (10 US gallons) to about 94.6 litres (25 US gallons) and preferably about 75.7 litres (20 US gallons) of surfactant solution per 3785.4 litres (1000 US gallons) of hydrocarbon liquid. The quantity of hydrocarbon liquid to be utilized is dependant upon the quantity of fine particle size cement employed and is in the range of from about 22.7 to about 37.8 litres (6 to about 10 US gallons) of hydrocarbon liquid per 45.4kg (100 pounds) of fine cement. The amount of hydrocarbon liquid and surfactant utilized within the scope of the above proportions, will determine the density of the resulting cement/hydrocarbon slurry wherein the slurry density is inversely proportional to the quantity of liquid. Accordingly, 1995.8kg (4400 pounds) of fine cement, 20.8 litres (5.5 US gallons) of a preferred surfactant and 1041.0 (275 US gallons) of diesel will produce a slurry having a density of about 1.7kg per litre (14.1 pounds per gallon) while 1995.8kg (4400 pounds) of fine cement, 30.3 litres (8.0 US gallons) of surfactant and 1514.2 litres (400 US gallons) of diesel will produce a slurry having a density of about 1.5kg per litre (12.5 pounds per gallon.) The low viscosity, non-volatile hydrocarbon liquid useful herein can be an aliphatic compound, such as hexane, heptane or octane, an aromatic compound such as benzene, toluene or xylene and mixtures thereof such as kerosene, diesel oil, mineral oil and lubricating oil. The preferred organic acid components of the surfactant of the present invention are calcium didodecylbenzenesulphonate and calcium salts of benzenesulphonic acid having linear alkyl groups containing 16 to 24 carbon atoms. The low molecular weight alcohol solvent component of the surfactant solution is selected from aliphatic alcohols having in the range of from 1 to 5 carbon atoms wherein isopropanol is preferred. The alcohol is present in the surfactant in the range of from about 20 to about 40 and preferably about 25 parts alcohol per 100 parts by volume of the surfactant solution. The organic acid or salt component of the surfactant solution is present in the surfactant in the range of from about 60 to about 80 and preferably about 75 parts acid or salt per 100 parts by volume of the surfactant solution. The surfactants known to be useful herein were identified by means of the following screening tests. The test results are provided in Table A, below. Evaluation procedure for screening surfactants: Slurries were prepared by mixing 50 grams of small particle size cement that had been vacuum oven dried with a solution of 25 ml of water-free kerosene and 0.5 ml of a compound as shown in Table A. Solubility of the compound in the kerosene was noted and the dispersability of the cement in the solution was observed and recorded. To this slurry was added 2.5 ml of fresh water. The slurry was then shaken vigorously for 2 minutes, following which, the slurry was checked for pourability and pumpability. If applicable, the samples were checked again at 1 hour to determine gel strength attainment. Those compounds which were not soluble in the kerosene and were neither a free acid nor a calcium or magnesium salt were washed with both a 10% CaCl 2 and a 50% CaCl 2 solution through a separatory funnel in order to produce calcium salts. Compound (Calcium salts) Soluble in Kerosene Dispersability Remains Pourable After 2 Minutes Set After 1 Hour Dinonylnapthalene sulphonic acid passed passed failed N/A Dodecyl ether ethoxylate sulphonate failed N/A N/A N/A Aliphatic Phosphate Ester passed failed N/A N/A Amine salt of naphthalene sulphonate failed N/A N/A N/A diethyl naphthalene sulphonate failed N/A N/A N/A Ammonium xylene sulphonate failed N/A N/A N/A oleic acid and linoleic acid passed passed passed never set Octyl and dioctyl phosphonate failed N/A N/A N/A Sodium lauryl sulphonate failed N/A N/A N/A Sodium alkylsulphate failed N/A N/A N/A Magnesium sulphonate passed passed failed N/A Calcium sulphonate passed failed N/A N/A benzene sulphonic acid passed passed failed N/A salt of sulphonic acid passed passed failed N/A Overbased magnesium sulphonate passed passed failed N/A Benzene sulphonic acid, C 16 - C 24 alkyl derivatives passed passed passed passed Amine salt of dinonyl naphthalene sulphonate passed passed failed N/A Didodecyl benzene sulphonate passed passed passed passed phosphoric acid failed N/A N/A N/A Sulphate lauryl sulphate failed N/A N/A N/A No compound N/A passed passed did not set in 72 hours Hydraulic cement useful in the present invention has a particle size no greater than about 30 microns, preferably no larger than about 17 microns, and still more preferably no larger than about 11 microns. The distribution of various sized particles within the cementitious material, ie., the particle size distribution, features 90 percent of them having a diameter not greater than about 25 microns, preferably about 10 microns and still more preferably about 7 microns, 50 percent having a diameter not greater than about 10 microns, preferably about 6 microns and still more preferably about 4 microns and 20 percent of the particles having a diameter not greater than about 5 microns, preferably about 3 microns and still more preferably about 2 microns. The particle size of hydraulic cement can also be indirectly expressed in terms of the surface area per unit weight of a given sample of material. This value, sometimes referred to as Blaine Fineness or as a specific surface area, can be expressed in the units square centimetres per gram (cm 2 /gram) and is an indication of the ability of a cementitious material to chemically interact with other materials. Reactivity is believed to increase with increase in Blaine Fineness. The Blaine Fineness of the hydraulic cement used in the cementing methods of this invention is no less than about 6000 cm 2 /gram. The value is preferably greater than about 7000, more preferably about 10,000, and still more preferably greater than about 13,000 cm 2 /gram. Cementitious materials of particle size and fineness as defined above are disclosed in various prior US Patents including US 4,761,183 to Clark, which is drawn to slag, as defined herein, and mixtures thereof with Portland cement, and US 4,160,674 to Sawyer, which is drawn to Portland cement. The cementitious materials preferred for use in the present invention are Portland cement and combinations thereof with slag wherein the quantity of Portland cement included in any mixture of Portland cement and slag used in the methods of this invention can be as low as 10 percent but is preferably no less than about 40 percent, more preferably about 60 percent, still more preferably about 80 percent and most preferably no less than about 100% Portland cement by weight of mixture. The use of a cementitious material of very small particle size is advantageous to enable passage thereof through very narrow openings and penetration thereof into low permeability gravel packs and formations. Another particular advantage of using the fine particle size Portland cement of this invention is the observed unexpected expansion of the cement during setting. This expansion property can help the formation of very tightly fitting plugs - when the cement is used in squeeze cementing. It is believed that this desirable expansive feature of the fine particle size Portland cement is due to the chemical content thereof and particularly to the high concentration of crystalline tricalcium aluminate (C 3 A) and sulphates present therein. It is thought that a Portland cement having a maximum particle size of about 11 microns, a Blaine Fineness of preferably greater than about 10,000 cm 2 /gram, a C 3 A crystalline content of preferably about 3.0 percent or more and a sulphate content of preferably about 1.0 percent or more will exhibit expansive characteristics desirable in an oil field cement. Slurries of water and the fine particle size cement used in the present invention are very useful to penetrate, fill and harden in fine holes, cracks and spaces such as might be expected to be found in well casing, cement sheaths, gravel packs and subterranean formations in the vicinity of a well bore. By way of example, it is believed that such slurries are useful to penetrate subterranean formations having effective permeabilities as low as about 3000 to about 5000 millidarcies. Accordingly, a condition known as water coning, in which water from a subterranean formation enters the wellbore in a rising or coning fashion, can be terminated by squeezing a slurry of fine particle size cement of this invention into fonnations producing such water, wherein the formations to be penetrated can have effective permabilities as low as 3000 to 5000 millidarcies. It is considered for commercial design purposes that a particle of given size in a suitable slurry as described herein can penetrate, fill and set in a crack, hole or void having the size of approximately 5 times greater than the size of the particle. Thus the 0.05 millimeter (50 micron) crack referred to above can be penetrated by a slurry of particles having a size of about 10 microns which is within the scope of the cement of this invention. The rate of hardening of the fine cement of this invention is related to the Blaine Fineness wherein the hardening rate increases as Blaine Fineness increases. In addition, the hardening rate is also related to the specific cementitious material being used and the temperature of the environment wherein the hardening reaction is proceeding. Thus fine particle size Portland cement, hardens more rapidly in low temperature environments in the range of from about - 1°C (30°F) to about 38°C (100°F) than does fine particle size slag cement. Also Portland cement hardens more rapidly at elevated temperatures than does slag cement. Accordingly, to adjust to specific environments, specific slurries of fine cement can include mixtures of Portland cement and slag consistent with the concentrations previously disclosed. In general, longer set times can be achieved by increasing slag content with accompanying decrease in compressive strength and/or increasing slurry density or both. Additives may be utilized to still further decrease the slurry density of the cement composition of this invention. Such lightweight additives include nitrogen, perlite, fly ash, silica fume, microspheres and the like. The following procedure may be employed in order to carry out the present invention. 1. Locate the zone within the subterranean formation from which water is being produced. This task may be performed by using known methods of identifying casing perforations through which water is flowing. The water may be flowing from a fracture or from a high permeability portion in the zone. 2. Isolate the identified perforations by placing a bridge plug in the casing, a bridge plug below the perforations and a packer in the casing above the perforations to thereby define a space within the casing between the bridge plug and packer which is in communication with the zone via the perforations; establish communication with the wellhead via tubing from the wellhead to the packer. 3. Introduce a spacer fluid such as diesel oil into the zone via the tubing and perforations. 4. Introduce a slurry of the cement composition of the invention in a hydrocarbon liquid into the zone. The cement must be of sufficient volume to form a plug in the zone to prevent passage of fluid therethrough. Introduction of the cement is preferably effected at a pressure less than the pressure required to fracture the zone. 5. Introduce an overflush fluid such as diesel oil into the zone via the tubing and perforations to help in the introduction of the hydrocarbon-cement slurry into the zone. 6. Shut well in for 24 hours, preferably under pressure, to permit the cement to hydrate with formation water in zone and harden. Remove the tubing, the packer and the bridge plug from the well.

Claims: A method of terminating the flow of water from a portion of a subterranean formation into a wellbore, said method comprising the steps of: placing within the wellbore adjacent said portion a volume of a slurry of hydraulic cement, said volume being in an amount at least sufficient to saturate said portion; permitting said slurry volume to penetrate into said portion; and maintaining said slurry in said portion for a time sufficient to enable said slurry to form a rigid mass of cement in said portion; wherein said slurry consists essentially of a mixture of said hydraulic cement, a hydrocarbon liquid, and a liquid surfactant soluble in said hydrocarbon liquid, the particle size of said hydraulic cement is not greater than about 30 microns, the Blaine Fineness of said hydraulic cement is no less than about 6000 cm2/gram, and said hydraulic cement is Portland cement or slag or a mixture thereof characterised in that said liquid surfactant includes as an essential component an alkyl aromatic sulphonic acid of formula or or an alkaline earth metal salt thereof, wherein R 1 is a linear alkyl group having 16 to 24 carbon atoms and R 2 and R 3 are each a linear alkyl group containing 12 carbon atoms. A method according to claim 1, wherein said portion has an effective permeability as low as about 3000 to 5000 millidarcies. A method according to claim 1 or 2, wherein said hydrocarbon liquid is present in said slurry in an amount of from 22.7 to 37.8 dm 3 (6 to about 10 US gallons) per 45.4 kg (100 pounds) of said cement. A method according to claim 1, 2 or 3, wherein the liquid surfactant soluble in said hydrocarbon liquid is present in said slurry in an amount of from 10 to 25 volumes surfactant per 1000 volumes of hydrocarbon liquid. A method according to claim 1, 2, 3 or 4, wherein said liquid surfactant consists of a solution of said essential component dissolved in a low molecular weight alcohol wherein said essential component is present in said solution in the range of from 60 to 80 parts per 100 parts by volume of said surfactant. A method according to any of claims 1 to 5, wherein said cement is Portland cement. A method according to any of claims 1 to 6, wherein said volume of said slurry is permitted to penetrate into said portion by applying pressure against said slurry in said wellbore. A method according to any of claims 1 to 7, wherein 90 percent of said particles have a diameter not greater than about 25 microns, 50 percent of said particles have a diameter not greater than about 10 microns and 20 percent of said particles have a particle size not greater than about 5 microns. A method according to claim 8, wherein said particle size of said cement is not greater than about 17 microns and said Blaine Fineness is no less than about 7000 cm 2 /gram.

Inventors: DAHL JEFFREY A, DALRYMPLE E DWYANN, STANFORD JAMES R, DAHL, JEFFREY A., DALRYMPLE, E. DWYANN, STANFORD, JAMES R.
Applicants: HALLIBURTON ENERGY SERV INC, HALLIBURTON ENERGY SERVICES, INC.
Application year: 1993
Main classification: E21B33
IPC codes: C09K8, C04B7, C04B28, C04B24