WELL CEMENTING METHODS AND COMPOSITIONS

Abstract: 1. A set retarded cement composition for cementing high temperature zones in wells, comprising: hydraulic cement; sufficient water to form a pumpable slurry; and an effective amount of one or more methylene phospho­ nic acid derivative retarders selected from: (a) compounds having the general formula: wherein: R₁, R₂ and R₃ are independently hydrogen, -CH₂PO₃(X)₂ or -CH₂CH₂-O-PO₃(X)₂ with the limitation that one of R₁, R₂ and R₃ is always -CH₂PO₃(X)₂ or -CH₂CH₂-O-PO₃(X)₂; X is hydrogen, an alkali metal cation, ammonium, a protonated amine or an alkaline earth metal cation in which case there is only one X per methylene phosphonate group; and at least one X is hydrogen which is associated with the nitrogen atom by way of an intramolecular hydrogen bond between the nitrogen atom and an oxygen atom attached to a phosphorus atom; (b) compounds having the structural formula: wherein: n is an integer from 1 to 4; R₁ is hydrogen or -CH₂PO₃(X)₂; R₂ is hydrogen, -CH₂PO₃(X)₂ or -CH₂CH₂N(R₃)₂ wherein R₃ is hydrogen or -CH₂PO₃(X)₂; X is hydrogen, an alkali metal cation, ammonium, a protonated amine or an alkaline earth metal cation in which case there is only one X per methylene phosphonate group; and at least one of R₁, R₂ or R₃ is -CH₂PO₃(X)₂ and one of X is hydrogen which is associated with a nitrogen atom by way of an intramolecular hydrogen bond between the nitrogen atom and an oxygen bond between the nitrogen atom and an oxygen atom attached to a phosphorus atom; (c) compounds having the structural formula: wherein: n is an integer from 0 to 4; R₁ is hydrogen or -CH₂PO₃(X)₂; R₂ is hydrogen, -CH₂PO₃(X)₂ or -CH₂CH₂N(R₄)₂ wherein R₄ is hydrogen or-CH₂PO₃(X)₂; R₃ is -N(R₅)₂ or wherein R₅ is hydrogen or -CH₂PO₃(X)₂; X is hydrogen, an alkali metal cation, ammonium, a protonated amine or an alkali earth metal cation in which case there is only one X per methylene phosphonate group; and at least one of R₁, R₂ or R₃ is -CH₂PO₃(X)₂ and one of X is hydrogen which is associated with a nitrogen atom by way of an intramolecular hydrogen bond between the nitrogen atom and an oxygen atom to a phosphorus atom; (d) compounds having the structural formula: or wherein: n is an integer from 2 to 6; R is hydrogen, -CH₂PO₃(X)₂ or -CH₂CH₂N(R₁)₂ wherein R₁ is hydrogen or -CH₂PO₃(X)₂; X is hydrogen, an alkali metal cation, ammonium, a protonated amine or an alkaline earth metal cation in which case there is only one X per methylene phosphonate group; and at least one R is -CH₂PO₃(X)₂ and one X is hydrogen which is associated with a nitrogen atom by way of an intramolecular hydrogen bond between the nitrogen atom and an oxygen atom attached to a phosphorus atom; (e) compounds having the structural formula: or wherein: R₁ is hydrogen or -CH₃; R₂ is -CH₂PO₃(X)₂ -CH₂NHCH₂PO₃(X)₂; X is hydrogen, an alkali metal action, ammonium, a protonated amine or an alkaline earth metal cation in which case there is only one X per methylene phosphonate group; and when nitrogen is present, at least one X is hydrogen which is associated with the nitrogen atom by way of an intramolecular hydrogen bond between the nitrogen atom and an oxygen atom attached to a phosphorus atom. The compositions may also further comprise a hydratable gel-­ forming material.

Description: This invention relates to cementing compositions having a retarded set time, which compositions are particularly but not exclusively useful for cementing in wells. In cementing operations carried out in oil, gas and water wells, Portland cement is normally mixed with about 40% to 50% of water, based on the weight of dry cement, to form a pumpable slurry which is pumped into a subterranean zone to be cemented by way of the wellbore penetrating such zone. After placement in the zone, the cement slurry sets into a hard mass. While cement compositions are utilized in carrying out a variety of operations in wells to accomplish a variety of purposes, cement compositions are most commonly used in well operations for bonding casing within the wellbore and sealing zones whereby undesirable communication between zones is prevented. With the drilling of wells for the production of hydrocarbons to increased depths during recent years, extended cementing times are required to mix cement compositions and pump them to the desired zones in the wells. In addition, at the greater depths, elevated temperatures are encountered which accelerate the normal sets of cement compositions to the point where the cementing times, i.e., the mixing and placement times, exceed the pumpable times of the cement compositions, making it difficult or impossible to place the cement compositions at the desired locations in the wells. The term "pumpable time" is used herein to mean the total time between when a cement composition is mixed and when the composition becomes too thick to pump. Various methods of retarding the sets of cement compositions and thereby increasing the pumpable times thereof have heretofore been employed in order to make possible the cementing of deep wells where high temperatures are encountered. These include the use of special slow setting hydraulic cements and/or the addition of set retarding agents to the cement slurries. While various set retarding agents have been effective in extending the pumpable times of cement compositions subjected to temperatures up to about 400°F (204°C), problems have been encountered where the cement compositions are subjected to higher temperatures. That is, heretofore, even when the cement compositions include set retarders, in deep wells where the cement compositions are subjected to temperatures above about 400°F (204°C), the cementing times often have exceeded the pumpable times of the cement compositions whereby cementing operations have been unsuccessful or incomplete. In one aspect, the present invention provides set retarded cement compositions which are particularly suitable for use in cementing subterranean zones wherein the cement compositions are subjected to elevated temperatures. Methods of cementing high temperature subterranean zones penetrated by wellbores using the cement compositions are also provided. The set retarded cement compositions of the present invention are comprised of a hydraulic cement, sufficient water to form a pumpable cement slurry which will set into a hard mass, and an effective amount of a set retarder comprised of a methylene phosphonic acid derivative or a mixture of such derivatives. While the use of certain methylene phosphonic acid derivatives of aminoethyl piperazine as set retarder additives for cement slurries is described in US-A-4466836, these compounds have not been noted to be effective at elevated temperatures. The pumpable times of the compositions of the present invention are of durations such that the compositions can be effectively utilized for cementing wells wherein the compositions are subjected to temperatures up to 550°F (288°C) and higher. The methylene phosphonic acid derivatives which are suitable for use in accordance with this invention as set retarders are as follows: (1) Compounds having the structural formula: wherein R₁, R₂ and R₃ are independently hydrogen or -CH₂PO₃(X)₂ with the limitation that one of R₁, R₂ and R₃ is always -CH₂PO₃(X)₂; X is hydrogen, an alkali metal cation, ammonium, a protonated amine or an alkaline earth metal cation in which case there is only one X per methylene phosphonate group; and at least one X is hydrogen which is associated with the nitrogen atom by way of an intramolecular hydrogen bond between the nitrogen atom and an oxygen atom attached to a phosphorus atom. (2) Compounds having the structural formula: wherein: n is an integer from 1 to 4; R₁ is hydrogen or -CH₂PO₃(X)₂; R₂ is hydrogen, -CH₂PO₃(X)₂ or -CH₂CH₂N(R₃)₂ wherein R₃ is hydrogen or -CH₂PO₃(X)₂; X is hydrogen, an alkali metal cation, ammonium, a protonated amine or an alkaline earth metal cation in which case there is only one X per methylene phosphonate group; and at least one of R₁, R₂ or R₃ is -CH₂PO₃(X)₂ and one X is hydrogen which is associated with a nitrogen atom by way of an intramolecular hydrogen bond between the nitrogen atom and an oxygen atom attached to a phosphorus atom. (3) Compounds having the structural formula: wherein: n is an integer from 0 to 4; R₁ is hydrogen or -CH₂PO₃(X)₂; R₂ is hydrogen, -CH₂PO₃(X)₂ or -CH₂CH₂N(R₄)₂ wherein R₄ is hydrogen or -CH₂PO₃(X)₂; R₃ is -N(R₅)₂ or R₅ wherein R₅ is hydrogen or -CH₂PO₃(X)₂; X is hydrogen, an alkali metal cation, ammonium, a protonated amine or an alkaline earth metal cation in which case there is only one X per methylene phosphonate group; and at least one of R₁, R₂ or R₃ is -CH₂PO₃(X)₂ and one X is hydrogen which is associated with a nitrogen atom by way of an intramolecular hydrogen bond between the nitrogen atom and an oxygen atom attached to a phosphorus atom. (4) Compounds having the structural formula: wherein: n is an integer from 2 to 6; R is hydrogen, -CH₂PO₃(x)₂ or -CH₂CH₂N(R₁)₂ wherein R₁ is hydrogen or -CH₂PO₃(X)₂; X is hydrogen, an alkali metal cation, ammonium, a protonated amine or an alkaline earth metal cation in which case there is only one X per methylene phosphonate group; and at least one R is -CH₂PO₃(X)₂ and one X is hydrogen which is associated with a nitrogen atom by way of an intramolecular hydrogen bond between the nitrogen atom and an oxygen atom attached to a phosphorus atom. (5) Compounds having the structural formula: wherein: R is hydrogen, -CH₂PO₃(X)₂ or -CH₂CH₂N(R₁)₂ wherein R₁ is hydrogen or -CH₂PO₃(X)₂; X is hydrogen, an alkali metal cation, ammonium, a protonated amine or an alkaline earth metal cation in which case there is only one X per methylene phosphonate group; and at least one R is -CH₂PO₃(X)₂ and one X is hydrogen which is associated with a nitrogen atom by way of an intramolecular hydrogen bond between the nitrogen atom and an oxygen atom attached to a phosphorus atom. (6) A compound having the structural formula: wherein: R is hydrogen, -CH₂PO₃(X)₂ or -CH₂CH₂N(R₁)₂ wherein R₁ is hydrogen or -CH₂PO₃(X)₂; X is hydrogen, an alkali metal cation, ammonium, a protonated amine or an alkaline earth metal cation in which case there is only one X per methylene phosphonate group; and at least one R is -CH₂PO₃(X)₂ and one X is hydrogen which is associated with a nitrogen atom by way of an intramolecular hydrogen bond between the nitrogen atom and an oxygen atom attached to a phosphorus atom. (7) Compounds having the structural formula: wherein: R₁ is hydrogen or -CH₃; R₂ is -CH₂PO₃(X)₂ or -CH₂NHCH₂PO₃(X)₂; X is hydrogen, an alkali metal cation, ammonium, a protonated amine or an alkaline earth metal cation in which case there is only one X per methylene phosphonate group; and when nitrogen is present, at least one X is hydrogen which is associated with the nitrogen atom by way of an intramolecular hydrogen bond between the nitrogen atom and an oxygen atom attached to a phosphorus atom. As mentioned above, most of the derivatives include at least one intramolecular hydrogen bond between a nitrogen atom and an oxygen atom which is attached to a phosphorus atom. The hydrogen involved in this bond is different from the other acidic hydrogens in that it is difficult to neutralize and should be left intact in the compound. That is, the removal of the intra-molecular hydrogen bond formed when the methylene phosphonic acid derivative contains nitrogen greatly decreases or eliminates the effectiveness of the derivative as a cement composition setting rate retarder. The other acidic protons may however be neutralized as indicated above. In this specification, references are made to compounds having substituents therein. The amount of substituent relative to the compound is generally expressed in terms of the number of moles or groups of substituent, and this means the number of moles (or other unit) of substituent per mole (or other unit) of the compound in question. Examples of suitable compounds falling in the various categories listed above are as follows: (1) aminotri(methylene phosphonic acid), the sodium salt of aminotri(methylene phosphonic acid), and triethanolamine substituted with 3 moles of methylene phosphonic acid; (2) ethylenediamine substituted with 1 to 4, preferably 2 or 3, moles methylene phosphonic acid, the sodium salt of the foregoing compound diethylenetriamine substituted with 1 to 5, preferably 2 or 3, moles of methylene phosphonic acid and triethylenetetramine substituted with 1 to 6 moles of methylene phosphonic acid; (3) piperazinoethylethylethyenediamine substituted with 1 to 4, preferably 3, moles of methylene phosphonic acid and the sodium salt of this compound; (4) propylenediamine substituted with 1 to 4 moles, preferably 3 moles, of methylene phosphonic acid, the sodium salt of the foregoing compound, and butylenediamine substituted with 1 to 4, preferably 3, moles of methylene phosphonic acid; (5) urea substituted with 1 to 4, preferably 1 to 3, moles of methylene phosphonic acid; (6) diethyleneamine ether substituted with 1 to 4, preferably 2 to 3, moles of methylene phosphonic acid; and (7) ethanol substituted with 1 or 2 moles of methylene phosphonic acid. Of the foregoing compounds ethylenediamine substituted with 2 or 3 moles of methylene phosphonic acid, diethylenetriamine substituted with 2 or 3 moles of methylene phosphonic acid, triethylenetetramine substituted with 1 to 6 moles of methylene phosphonic acid, and mixtures of such compounds are preferred. The most preferred compounds for use in the set retarded cement compositions of the first aspect of this invention are methylene phosphonic acid substituted triethylenetetramine compounds having in the range of from 1 to 6 methylene phosphonic acid groups per molecule, preferably from 1 to 3 methylene phosphonic acid groups per molecule and most preferably 3 methylene phosphonic acid groups per molecule. The substituted triethylenetetramine compounds are formed by the addition of formaldehyde and orthophosphorous acid to triethylenetetramine in the presence of an acid catalyst, preferably hydrochloric acid. Methylene phosphonic acid is generated in situ and substitutes at one or more of the six active sites of the triethylenetetramine to form a methylene phosphonic acid substituted triethylenetetramine compound having in the range of from 1 to 6 methyl phosphonic acid groups per molecule. A liquid product can be formed by neutralization of the acid reaction product to a pH of 7.0 ± 0.1 with additional triethylenetetramine. A solid product can be formed by adding calcium hydroxide to the acid reaction product until a pH of 2.0 ± 0.1 has been reached. The thick viscous product produced is then precipitated as the calcium salt in an excess of methyl alcohol, filtered and dried. An alternate and more preferred technique for producing a solid product is to adsorb the liquid product onto a quantity of silica flour at about 50% loading rate. Generally, the methylene phosphonic acid derivatives or mixture of derivatives are present in the cement compositions in an amount of from about 1% to about 10% by weight of dry cement utilized. A preferred setting rate retarded cement composition is comprised of a hydraulic cement and water slurry containing a set retarder selected from the group consisting of ethylenediamine substituted with 2 or 3 moles of methylene phosphonic acid, diethylenetriamine substituted with 2 or 3 moles of methylene phosphonic acid, triethylenetetramine substituted with 1 to 6 moles of methylene phosphonic acid and mixtures of such compounds, the retarder being present in said composition in an amount of from about 1% to about 10% by weight of dry cement utilized in the slurry. A more preferred set retarded cement composition of this invention is comprised of a hydraulic cement, sufficient water to form a pumpable slurry which will set into a hard mass, and methylene phosphonic acid substituted triethylenetetramine having in the range of from 1 to 6 methyl phosphonic acid groups per molecule present in the composition in an amount in the range of from about 1% to about 10% by weight of dry cement. In a most preferred such composition, the retarder is comprised of methylene phosphonic acid substituted triethylenetetramine having 3 methyl phosphonic acid groups per molecule present in the composition in an amount in the range of from about 2% to about 8% by weight of dry cement. A particularly suitable composition is comprised of Portland cement, water present in the composition in an amount in the range of from about 35% to about 62% by weight of dry cement, and methylene phosphonic acid substituted triethylemetetramine having 3 methylene phosphonic acid groups per molecule present in the composition in an amount in the range of from about 2% to about 8% by weight of dry cement. In order to improve the stability and permanent strength of the cement composition after setting in a high temperature environment, a particulate crystalline silica component can be included in the composition. The silica material is a particulate crystalline silica having a particle size of less than about 10 mesh (2mm sieve aperture), preferably 20-80 mesh (0.8 - 0.18mm sieve aperture) and most preferably 30 mesh (0.60mm sieve aperture). When particulate crystalline silica is included in the cement compositions of this invention it is preferably present in the compositions in an amount in the range of from about 17% to about 35% by weight of dry cement therein with the methylene phosphonic acid derivative retarder or retarders being present therein in an amount in the range of from about 2% to about 8% by weight of dry cement. A particularly preferred composition which includes particulate crystalline silica is comprised of Portland cement, silica present in the composition in an amount in the range of from about 25% to about 35% by weight of dry cement, water present in the composition in an amount in the range of from about 45% to about 55% by weight of dry cement and methylene phosphonic acid substituted triethylenetetramine having 3 methylene phosphonic acid groups per mole present in the composition in an amount in the range of from about 3% to about 6% by weight of dry cement. The most preferred composition including silica is comprised of Portland API Class H cement, particulate crystalline silica present in an amount of about 35% by weight of dry cement, water present in an amount of about 54% by weight of dry cement and methylene phosphonic acid substituted triethylenetetramine having 3 methylene phosphonic acid groups per mole present in an amount in the range of from about 3% to about 6% by weight of dry cement. The water utilized to form the compositions of this invention can be fresh water, salt water, brine, seawater or other water which does not contain materials adversely reactive with components of the compositions. As will be understood by those skilled in the art, known components and/or additives can also be included in the compositions for bringing about desired results such as dispersing agents, density reducing components, fluid loss reducing additives, friction reducing additives, etc. In carrying out the methods of the present invention for cementing a zone penetrated by a wellbore using a settable hydraulic cement slurry wherein the slurry is subjected to elevated temperatures, a pumpable set retarded cement composition described above is first prepared using conventional equipment. The methylene phosphonic acid derivative retarder or retarders can be added to the cement in either solid or liquid form prior to combining water therewith to form a slurry thereof or the retarder can be mixed with the slurry after it is formed. Once the cement composition has been prepared, it is pumped or otherwise introduced into the zone to be cemented and then allowed to set into a hard mass therein. The particular quantity of retarder utilized in a cement composition of this invention determines the pumpable time of the composition and the pumpable time is increased by increasing the quantity of retarder. Generally, compositions containing relatively small quantities of retarder (1% to 3% by weight of cement) have long pumpable times (up to 8 hours) at temperatures above 400°F (204°C). The compositions have sufficient pumpable times, i.e., pumpable times exceeding cementing times for deep wells wherein the compositions are subjected to temperatures up to 600°F (316°C). We have described above a first aspect of the present invention in which the setting time of certain cement compositions is retarded by the use of certain methylene phosphonic acid derivatives. These compositions are particularly (but not exclusively) suited to high temperature environments. In accordance with a second aspect of the present invention, we have found that the above compositions can advantageously also contain a hydratable gel-forming material to minimise the setting of solids and separation of free water. These compositions are not so suited to high temperature applications (because of the presence of the gel-forming material) and are usually selectively activated to set into a hard mass by mixing therewith a suitable activating agent. The compositions of the first aspect of the invention can also, of course, be so activated if desired. The preferred compositions of the second aspect of the invention are as defined for the first aspect except that they also comprise a hydratable gel forming material selected from hydratable cellulose derivatives, polyvinyl alcohol, and polymers of 2-acrylamido-2-methylpropane sulfonic acid, sodium vinylsulfonate, acrylamide, N,N-dimethylacrylamide, acrylic acid, and mixtures of the foregoing compounds present in said slurry in an amount in the range of from about 0.01% to about 1.5% by weight of the dry cement, to minimize the settling of solids and separation of free water therefrom; and wherein the retarder 1. selected from (a), (b), (c), (d) and (e) as defined in claim 1 Of the preferred retarders listed above for the first aspect of the invention, aminotri(methylenephosphonic acid), ethylenediamine substituted with from 1 to 4 moles of methylenephosphonic acid, diethylenetriamine substituted with from 1 to 5 moles of methylenephosphonic acid, triethylenetetramine substituted with from 1 to 6 moles of methylenephosphonic acid, and mixtures of such compounds, are preferred for the second aspect of the invention. The most preferred compounds for use in the second aspect of the invention are aminotri(methylenephosphonic acid) and methylenephosphonic acid substituted diethylenetriamine compounds having in the range of from 1 to 5 methylenephosphonic acid groups per molecule, preferably from 3 to 5 methylenephosphonic acid groups per molecule, and most preferably 5 methylenephosphonic acid groups per molecule. The aminotri(methylenephosphonic acid) and substituted diethylenetriamine compounds are formed by the addition of formaldeyde and orthophosphorous acid to aqueous solutions of ammonia or diethylenetriamine in the presence of an acid catalyst, preferably hydrochloric acid. Methylenephosphonic acid is generated in situ and substitutes at the nitrogen atom(s) of the ammonia or diethylenetriamine. In the case of ammonia, three methylenephosphonic acid groups are attached to the nitrogen atom. In diethylenetriamine, there are five sites which can be substituted with methylenephosphonic acid groups corresponding to each (-N-H) functionality in the molecule. The degree of substitution depends on the molar ratio of the starting reactants and the reaction conditions. It is possible for a diethylenetriamine molecule to contain from 1 to 5 methylenephosphonic acid groups. When aldehydes or ketones having boiling points below the temperatures at which this invention is practiced are utilized in the practice of the invention, usually significantly better yields of the desirable aminoalkylene phosphonic acids (based on the amount of aldehyde or ketone charged into the reaction vessel) can be attained if the aldehyde or ketone is added slowly to the mixture of orthophosphorous acid and reactive nitrogenous material, while the temperature of said mixture is within the desired range. For example, when an aqueous mixture consisting of one mole of ammonia, three moles of orthophosphorus acid, and three moles of formaldehyde (calculated theoretically to result in the production of one mole of ammonium trimethylenephosphonic acid) is held at 100°C. for an extended period of time (in order to assure "complete" reaction), only about 0.45 mole of the desired product is made. However, if the same amount of formaldehyde is added slowly (i.e., over a period of about 15 minutes) to a blend of the same amount of water, one mole of ammonia, and three moles of phosphorous acid held at a temperature of about 100°C., more than 0.70 mole of the desired product is produced. Thus, the addition of the aldehyde or ketone slowly to a hot mixture of phosphorous acid plus one of the desirable reactive nitrogenous materials described above is preferred. The particular quantity of the retarder (or set delaying agent) added to an aqueous hydraulic cement slurry controls the duration of the time the cement composition will remain in a pumpable fluid state. However, in accordance with the present invention, a quantity is utilized which will allow the resulting cement composition to be retained in a pumpable fluid state for a period of time exceeding the required time. After this time, the cement composition of the second aspect is preferably activated by mixing a set activating agent therewith just prior to placement as will be described in detail hereinbelow. Generally, in the second aspect of the invention, the phosphonic acid retarder derivative or derivatives utilized are combined with an aqueous hydraulic cement slurry in an amount in the range of from about 0.1% to about 5.0% by weight of dry cement utilized to form the slurry. Such a quantity will cause the slurry to remain in a pumpable fluid state for a time period ranging from about 1 day up to about 45 days. The hydratable gel forming materials used in the second aspect of the invention prevent or at least reduce the settling of solids and/or the separation of free water from the set delayed cement composition during long-term storage. They hydrate to provide gel strength and limited viscosity to the compositions. While various hydratable materials can be utilized, particularly suitable such materials are those selected from the group consisting of hydratable cellulose derivatives, polyvinyl alcohol, and homopolymers, copolymers and/or terpolymers of 2-acrylamido-2-methylpropane sulfonic acid, sodium vinylsulfonate, acrylamide, N,N-dimethylacrylamide, acrylic acid, and mixtures of the foregoing compounds. Of these, hydratable cellulose derivatives such as hydroxyalkylcellulose, carboxyalkylcellulose and carboxyalkylhydroxyalkylcellulose are preferred. The most preferred such hydratable material is hydroxyethylcellulose. As mentioned above, the hydratable gel forming material or materials used are combined with the cement compositions in relatively small amounts so that the settling of solids and separation of free water are minimized but the viscosity of the cement composition is not increased to the point whereby pumpability is reduced. Generally, the hydratable material is combined with a cement composition of this invention in an amount in the range of from about 0.01% to about 1.5% by weight of dry cement therein. When the hydratable material is selected from the group consisting of hydroxyalkylcellulose, carboxyalkylcellulose, carboxyalkylhydroxyalkylcellulose and mixtures thereof, the material or materials are combined with the cement slurry in an amount in the range of from about 0.1% to about 1.0% by weight of dry cement therein. The preferred hydratable gel forming material i.e., hydroxyethylcellulose, is preferably combined with the aqueous cement slurry in an amount in the range of from about 0.1% to about 0.5% by weight of dry cement therein, most preferably about 0.2%. A preferred set delayed cement composition capable of being retained in a pumpable fluid state for a long time period and then caused to set by mixing a set activating agent therewith just prior to placement is comprised of a hydraulic cement, sufficient water to form a pumpable slurry, a hydratable gel forming materials selected from the group consisting of hydroxyalkylcellulose, carboxyalkylcellulose, carboxyalkylhydroxyalkylcellulose, and mixtures thereof present in the composition in an amount in the range of from about 0.1% to about 1.0% by weight of dry cement therein, and a set delaying agent selected from the group consisting of aminotri(methylenephosphonic acid), diethylenetriamine substituted with 5 moles of methylenephosphonic acid, and mixtures of such compounds present in the composition in an amount in the range of from about 0.1% to about 2.5% by weight of dry cement therein. Portland cement is generally preferred for use in the compositions of this invention because of its low cost, availability and general utility, but other cements can also be utilized such as high alumina content, pozzolan, high gypsum cements, high silica cements and cements which contain a high calcium aluminate content. Portland cements of API Classes H and G are preferred cements for use in this invention in most instances, although the other API classes of cement can also be utilized. The characteristics of these cements are described in API Specification 10, Second Edition dated June 15, 1984, of the American Petroleum Institute to which reference should be made for further details. A highly useful and effective cement slurry base for use in practicing this invention utilizes API Class H Portland cement mixed with water to provide a density of from about 11.3 to about 18.0 pounds per gallon (1.36 to 2.16 g/cm³). A particularly preferred set retarded cement composition of the second aspect of this invention capable of being retained in a pumpable fluid state for a long time period and then caused to set by mixing a set activating agent therewith is comprised of API Class H Portland cement, water in an amount in the range of from about 38% to about 46% by weight of dry cement, hydroxyethylcellulose in an amount in the range of from about 0.1% to about 0.5% by weight of dry cement therein, most preferably 0.2% and aminotri(methylenephosphonic acid) or diethylenetriamine substituted with 5 moles of methylenephosphonic acid present in an amount in the range of from about 0.2% to about 0.7% by weight of dry cement. Most preferably, the set retarder agent is aminotri(methylenephosphonic acid) and is present in the composition in an amount of about 0.5% by weight of dry cement therein. The set delaying or retarding effect imparted to the set delayed cement compositions of the second aspect of this invention is preferably terminated by heating the cement compositions to a high temperature, e.g., above roughly 300°F (149°C ) depending on the concentration of the set delaying agent. Thus, when using the cement compositions for carrying out cementing operations in such temperature environments, the compositions can be placed therein whereby they are activated upon being heated and eventually set into hard masses. A more preferred technique for activating the set delayed compositions is to mix one or more set activating agents with the compositions just prior to placement. Particularly suitable such set activating agents are aqueous sodium silicate solutions, paraformaldeyde, calcium chloride and mixtures of two or more such agents. Sodium silicate is readily commercially available in aqueous solutions of various grades. An aqueous sodium silicate solution having a density of 11.67 pounds per gallon (1.4g/cm³) and an Na₂O:SiO₂ weight ratio of about 1:3.22 is particularly suitable for use in accordance with this invention, but other solutions can be used. When a low density cement composition is desired, an aqueous sodium silicate solution extender can be combined with a set delayed cement composition of this invention in a relatively large quantity (up to 100% by volume of the cement composition) to produce a light-weight activated cement composition (the sodium silicate solution functions as an extender to lower the density and also as an activating agent). Preferably, a small quantity of calcium chloride or paraformaldehyde set activating agent is combined with the set delayed cement composition in addition to the aqueous sodium silicate solution. The preferred set activating agent for normal density cement compositions (those not including an extender) is a mixture of paraformaldehyde and calcium chloride in equal proportions. Generally, the set activating agent used is combined with a set delayed cement composition in an amount in the range of from about 0.5% to about 2.5% by weight of the cement composition. In carrying out the methods of this invention for cementing a zone at a remote location, a set delayed cement composition of the type described above is first prepared at a convenient location. Once prepared, the set delayed composition is then transported to the remote location and, if required, stored at such location. When all or part of the stored cement composition which is in a pumpable fluid state is to be used, it is mixed with a set activating agent or agents of the type described above followed by the placement of the activated mixture in the zone to be cemented. A particularly convenient technique for mixing the activating agent and other components such as an aqueous sodium silicate solution extender and/or other additives is to combine the activating agent and other components and/or additives with the set delayed cement composition on the fly, i.e., the activating agent and other components and/or additives are continuously mixed with the set delayed cement composition as they both are pumped into the zone to be cemented. As will be understood by those skilled in the art, a variety of additives can be incorporated in the cement compositions to modify the properties thereof such as dispersants, viscosifiers, and weight adjusting materials. Also, additives for reducing fluid loss to surrounding formations, for reducing friction during pumping, and for imparting other properties to the cement compositions can be utilized. In order to facilitate a clear understanding of the invention, the following Examples are given. With regard to amounts given in the Examples, the term "sack" refers to a standard sack weighing 94 pounds (42.5 kg) as defined in API Bulletin 10-C, Third Edition, April 15th, 1984, of the American Petroleum Institute. This publication sets forth the nomenclature used in oil well cementing technology and is also incorporated herein by reference. Examples 1 to 5 illustrate the first aspect of the invention, and Examples 6 to 10 illustrate the second aspect of the invention. Example 1 A number of cement compositions comprised of Portland Cement, i.e., Lone Star Class H cement, particulate crystalline silica having a particle size of from 20-80 mesh (0.81 - 0.18mm sieve aperture) in an amount of 35% by weight of dry cement, fresh water in an amount of 54% by weight of dry cement (6.1 gallons water/sack - 0.55 dm³/kg) and various quantities of methylene phosphonic acid substituted triethylenetetramine (TETA) having various degrees of methyl phosphonic acid group (-CH₂PO₃H₂) substitution are prepared. The compositions are tested for thickening time at 450°F (232°C) in accordance with the standard API thickening time testing procedures set forth in the publication API Specification 10, Second Edition, June 15, 1984, which is also incorporated herein by reference. The results of these tests are given in Table I below. From Table I it can be seen that the cement compositions of the present invention have excellent thickening times at 450°F (232°C) The compositions containing TETA substituted with one, two and three -CH₂PO₃H₂ substituents per molecule all yielded good response properties with the compositions containing TETA substituted with three -CH₂PO₃H₂ substituents giving the best results, i.e., the longest thickening times with the least retarder quantities. The compositions containing TETA substituted with four and six -CH₂PO₃H₂ substituents responded similarly except that gelation prior to strength development occurs at some retarder concentrations. Example 2 A number of cement compositions comprised of Lone Star Class H cement, Trinity Class H cement or Centex Class H cement, particulate crystalline silica having a particle size of 20-80 mesh (0.81 - 0.18mm sieve aperture) in an amount of 35% by weight of dry cement, fresh water in an amount of 54% by weight of dry cement (6.1. gallons/sacks - 0.55 dm³/kg) and various quantities of TETA substituted with three -CH₂PO₃H₂ groups per molecule are prepared. The substituted TETA is prepared by reacting formaldehyde and phosphorus acid with TETA in the presence of a hydrochloric acid catalyst. The resulting liquid is adsorbed onto silica flour at a 50% loading rate. The resulting solid retarder is utilized in preparing the compositions. The compositions are tested for thickening times in accordance with the testing procedures set forth in the publication API Specification 10, Second Edition, June 15, 1984, at 400°F (204°C), 450°F (232°C), 500°F (260°C) and 550°F (288°C). The results of these tests are given in Table II below. From Table II it can be seen that the compositions of this invention have excellent thickening times at elevated temperatures. Example 3 Cement compositions of the type described in Example 1 above are prepared using salt (NaCl) water instead of fresh water. These compositions are tested for thickening times at 450°F (232°C). The results of these tests are given in Table III below. Example 4 Cement compositions of the present invention containing additional components and additives to form high density (19.0 lb/gal. - 2.28 g/cm³) slurries are prepared. The compositions are comprised of Lone Star Class H cement, fresh water in an amount of 6.8 gal/sack (0.61 dm³/kg) of dry cement, particulate crystalline silica having a particle size of 20-80 mesh (0.81 - 0.18mm sieve aperture) in an amount of 35% by weight of dry cement, Hematite in an amount of 73 lb/ sack, (0.77 kg/kg), sodium chloride in the amount of 21.1 lb/sack (0.22 kg/kg), carboxymethylhydroxyethylcellulose in an amount of 1.0% by weight of dry cement, an additive containing an admixture of deltagluconolactone in an amount of 1.0% by weight of dry cement, an additive containing polypropylene glycol in an amount of about 0.25% by weight of dry cement and various amounts of TETA substituted with three -CH₂PO₃H₂ groups The compositions are tested for thickening times at 450°F (232°C). The results of these tests are given in Table IV below. Example 5 Methylene phosphonic acid derivative compounds from the seven categories of derivatives set forth above are utilized to form set retarded cement compositions. Each of the compositions includes Lone Star Class H cement, particulate crystalline silica having a particle size of 20-80 mesh (0.81 - 0.18mm sieve aperture) in an amount of 35% by weight of dry cement, fresh water in an amount of 54% by weight of dry cement and a quantity of one of the set retarding compounds. The compositions are tested for thickening time at 450°F (232°C) or 500°F (260°C) in accordance with the standard API thickening time procedures set forth in API Specification 10, Second Edition, June 15, 1984. The results of these tests are set forth in Table V below. Example 6 The set delayed cement compositions of the second aspect of the invention are capable of being retained in pumpable fluid states for long periods of time and have a minimum settling of solids and separation of free water during storage. Once the cement compositions are to be pumped, they must be capable of being activated whereby hydration of the cement occurs and reasonable compressive strengths are developed. The activating agents must not flash-set the compositions in that the compositions must be placed with adequate margins of safety after the activating agents are mixed therewith. Three basic types of tests are performed to show the above requirements, i.e., free water and settling tests, pumpability tests and compressive strength tests. The free water and settling tests consist of preparing aqueous hydraulic cement slurries containing various amounts of hydratable gel forming material (hydroxyethylcellulose) and set delaying agent (aminotri(methylenephosphonic acid)) and placing the slurries in covered 500 cm³ plastic beakers. The slurries are observed on a daily basis for solids settlement and free water separation over time periods up to 33 days. The results of these tests are set forth in Table VI. The pumpability (maintenance of the compositions in a fluid state) tests are carried out in the same manner as the free water and settling tests described above. That is, various set delayed cement slurries are prepared and placed in additional 500 cm³ plastic beakers which are observed for pumpability, i.e., the samples ale stirred by hand and visually examined for pumpability. The results of these tests are shown in Table VII below. Cement compositions containing various amounts of hydratable gel forming material (hydroxyethylcellulose) and set delaying agent (aminotri(methylenephosphonic acid)) are combined with various set activating agents and then allowed to set. The set compositions are tested for compressive strength at 24, 48 and 72 hours in accordance with the standard API compressive strength testing procedures set forth in the publication API Specification 10, Second Edition, June 15, 1984, which is incorporated herein by reference. The results of these tests are given in Table VIII below. From Table VI above, it can be seen that a concentration of about 0.5% hydratable gel forming material in the cement compositions provides good settling and free water control without resulting in high viscosity. Table VII shows that the time period the compositions remain in a pumpable fluid state depends upon the quantity of set delaying agent utilized. Example 7 Set delayed cement compositions are prepared and combined with various amounts of various set activating agents as well as with various diluted aqueous sodium silicate solutions to produce low densities. The slurries are poured into 250 cm³ plastic beakers with lids and placed in water baths at 80°F (27°C). A penetrometer is used to determine 24, 48 and 72 hour and 7 day compressive strengths. The results of these tests are shown in Tables IX and X below. Table IX shows that the compositions containing 1% paraformaldehyde activating agent produce equivalent compressive strength to the compositions containing 1% amounts of both paraformaldehyde and calcium chloride activating agents. Table X shows the compressive strengths of cement compositions activated with paraformaldehyde and/or an aqueous sodium silicate solution after the compositions have remained fluid for 28 days. The compositions are diluted with various amounts of sea water containing 18% by volume aqueous sodium silicate to obtain three different densities at the time the activating agents are added to the compositions. Example 8 Set delayed cement compositions containing various amounts of set delaying agent are prepared. The compositions are refrigerated at 20°F (-6.7°C) for 7 days add then heated to 80°F (26.7°C) for 4 hours. After heating, the compositions are combined with various quantities and combinations of set activating agents, allowed to set and tested for compressive strengths using a penetrometer at 1 and 2 days. The results of these tests are given in Table XI below. As shown in Table XI, paraformaldehyde in combination with calcium chloride produces the most rapid compressive strength development and the compressive strength is not affected by storing the set delayed slurry at 20°F (-6. 7°C) for seven days. Example 9 Set delayed cement compositions are prepared using fresh water, sea water and various set delaying agents. The descriptions of the set delaying agents used are set forth in Table XII below. Free water, settling and fluid time tests are carried out on the compositions in the manner described in Example 6. The results of these tests are set forth in Tables XII, XIII and XIV below. The above data shows that a variety of methylenephosphonic acid set delaying agents can be utilized and that API Class A cement slurries are delayed differently than when API Class H cement is utilized. Also, the utilization of sea water changes the effect of the set delaying agents. Example 10 A set delayed cement composition of this invention is prepared containing API Class H cement, water, hydroxyethylcellulose and aminotri(methylenephosphonic acid). The set delayed composition is combined with various set activating agent or agents and various quantities of sodium silicate solution and allowed to set. The set compositions are tested for compressive strength at 6 months in accordance with the standard API compressive strength testing procedures set forth in the publication API Specification 10, Second Edition, June 15, 1984. The results of these tests are given in Table XX below. The data of Table XX shows that good compressive strengths are obtained using the cement compositions of the present invention.

Claims: A set-retarded cement composition for cementing high temperature zones in wells, comprising: hydraulic cement; sufficient water to form a pumpable slurry; and an effective amount of one or more set retarders derived from methylene phosphonic acid and selected from: (a) compounds having the general formula: wherein: R₁, R₂ and R₃ are independently hydrogen or -CH₂PO₃(X)₂ with the limitation that one of R₁, R₂ and R₃ is always -CH₂PO₃(X)₂ ; X is hydrogen, an alkali metal cation, ammonium, a protonated amine or an alkaline earth metal cation in which case there is only one X per methylene phosphonate group; and at least one X is hydrogen which is associated with the nitrogen atom by way of an intramolecular hydrogen bond between the nitrogen atom and an oxygen atom attached to a phosphorus atom; (b) compounds having the structural formula: wherein: n is an integer from 1 to 4; R₁ is hydrogen or -CH₂PO₃(X)₂; R₂ is hydrogen, -CH₂PO₃(X)₂ or -CH₂CH₂N(R₃)₂ wherein R₃ is hydrogen or -CH₂PO₃(X)₂; X is hydrogen, an alkali metal cation, ammonium, a protonated amine or an alkaline earth metal cation in which case there is only one X per methylene phosphonate group: and at least one of R₁, R₂ or R₃ is -CH₂PO₃(X)₂ and one X is hydrogen which is associated with a nitrogen atom by way of an intramolecular hydrogen bond between the nitrogen atom and an oxygen atom attached to a phosphorus atom; (c) compounds having the structural formula: wherein: n is an integer from 0 to 4; R₁ is hydrogen or -CH₂PO₃(X)₂; R₂ is hydrogen, -CH₂PO₃(X)₂ or -CH₂CH₂N(R₄)₂ wherein R₄ is hydrogen or -CH₂PO₃(X)₂; R₃ is -N(R₅)₂ or wherein R₅ is hydrogen or -CH₂PO₃(X)₂; X is hydrogen, an alkali metal cation, ammonium, a protonated amine or an alkaline earth metal cation in which case there is only one X per methylene phosphonate group; and at least one of R₁, R₂ or R₃ is -CH₂PO₃(X)₂ and one X is hydrogen which is associated with a nitrogen atom by way of an intramolecular hydrogen bond between the nitrogen atom and an oxygen atom attached to a phosphorus atom; (d) compounds having the structural formula: wherein: n is an integer from 2 to 6; R is hydrogen, -CH₂PO₃(X)₂ or -CH₂CH₂N(R₁)₂ wherein R₁ is hydrogen or -CH₂PO₃(X)₂; X is hydrogen, an alkali metal cation, ammonium, a protonated amine or an alkaline earth metal cation in which case there is only one X per methylene phosphonate group; and at least one R is -CH₂PO₃(X)₂ and one X is hydrogen which is associated with a nitrogen atom by way of an intramolecular hydrogen bond between the nitrogen atom and an oxygen atom attached to a phosphorus atom; (e) compounds having the structural formula: wherein: R₁ is hydrogen or -CH₃; R₂ is -CH₂PO₃(X)₂ or -CH₂NHCH₂PO₃(X)₂; X is hydrogen, an alkali metal cation, ammonium, a protonated amine or an alkaline earth metal cation in which case there is only one X per methylene phosphonate group; and when nitrogen is present, at least one X is hydrogen which is associated with the nitrogen atom by way of an intramolecular hydrogen bond between the nitrogen atom and an oxygen atom attached to a phosphorus atom. A composition according to claim 1, wherein said retarder is present in said composition in an amount of 1% to 10% by weight of the dry cement. A composition according to claim 1 or 2, which further includes particulate crystalline silica having a particle size of less than 10 mesh (sieve aperture 2mm) in an amount of 17% to 35% by weight of the dry cement. A composition according to claim 1,2 or 3, wherein the set retarder is one or more of ethylenediamine substituted with 2 or 3 moles of methylene phosphonic acid, diethylenetriamine substituted with 2 or 3 moles of methylene phosphonic acid, and triethylenetetramine substituted with 1 to 6 moles of methylene phosphonic acid. A composition according to any of claims 1 to 4, wherein said hydraulic cement is Portland cement, said water is present in an amount of 35% to 62% by weight of the dry cement, and the retarder is present in an amount of 2% to 8% by weight of the dry cement. A composition according to claim 3, wherein the hydraulic cement is Portland cement, the silica is present in an amount of 25% to 35% by weight of dry cement, the water is present in an amount of 45% to 55% by weight of dry cement, and the retarder is methylene phosphonic acid substituted triethylenetetramine having 3 methylene phosphonic acid groups per molecule and is present in an amount of 3% to 6% by weight of the dry cement. A method of cementing a high temperature subterranean zone penetrated by a wellbore wherein a settable aqueous hydraulic cement slurry is placed in said zone, characterised in that the cement composition is as defined in any of claims 1 to 6. A composition according to claim 1, which also comprises a hydratable gel forming material selected from hydratable cellulose derivatives, polyvinyl alcohol, and polymers of 2-acrylamido-2-methylpropane sulfonic acid, sodium vinylsulfonate, acrylamide, N,N-dimethylacrylamide, acrylic acid, and any mixture of two or more of the foregoing compounds present in said slurry in an amount in the range of 0.01% to 1.5% by weight of the dry cement, to minimize the settling of solids and separation of free water therefrom; and wherein the retarder is selected from (a), (b), (c), (d) and (e) as defined in claim 1. A composition according to claim 8, wherein said retarder is one or more of aminotri(methylenephosphonic acid), ethylenediamine substituted with from 1 to 4 moles of methylenephosphonic acid, diethylenetriamine substituted with from 1 to 5 moles of methylenephosphonic acid, and triethylenetetramine substituted with from 1 to 6 moles of methylenephosphonic acid. A composition according to claim 8 or 9, wherein the hydratable gel forming material is one or more of hydroxyalkylcellulose, carboxyalkylcellulose, and carboxyalkylhydroxyalkylcellulose, and is present in an amount of 0.1% to 1.0% by weight of the dry cement; and the retarder is present in an amount of 0.1% to 2.5% by weight of the dry cement. A composition according to claim 10, wherein said gel forming material is hydroxyethylcellulose present in an amount of 0.1% to 0.5% by weight of the dry cement, and optionally said retarder is aminotri(methylenephosphonic acid) present in an amount of 0.2% to 0.7% by weight of the dry cement. A composition according to claim 8, wherein the hydraulic cement comprises API Class H Portland cement; the water is present in an amount of 38% to 46% by weight of the dry cement; the hydratable gel forming material is hydroxyethylcellulose present in an amount of 0.1% to 0.5% by weight of the dry cement and the retarder is aminotri-(methylenephosphonic acid) present in an amount of 0.2% to 0.7% preferably 0.5% by weight of the dry cement. A composition according to any of claims 1 to 6 and 8 to 12, which further includes one or more set activating agents selected from aqueous sodium silicate solution, paraformaldehyde, and calcium chloride. A method of cementing a zone at a remote location comprising the steps of: preparing a set retarded cement composition as claimed in any of claims 8 to 12; transporting said set retarded cement composition to said remote location; mixing one or more set activating agents with said cement composition just prior to the placement thereof, said agent(s) being selected from aqueous sodium silicate solution, paraformaldehyde and calcium chloride; and placing the resulting mixture in said zone.

Inventors: CHILDS, JERRY DALE, LOVE, ROOSEVELT, SABINS, FREDDIE LYNNE, SUTTON, DAVID LEROY, WEIGAND, WILLIS ALAN
Applicants: HALLIBURTON COMPANY
Application year: 1985
Main classification: C04B24
IPC codes: C04B28, C04B24, C09K8