Set delayed cement compositions and methods of using the same

Claim 1

A set delayed cement composition capable of being retained in a pumpable fluid state for a long period of time and then activated to set into a hard mass comprising: a hydraulic cement; sufficient water to form a pumpable slurry; a hydratable gel forming material selected from the group consisting of 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 dry cement to minimize the settling of solids and separation of free water therefrom; and a set delaying agent comprised of a methylenephosphonic acid derivative present in said slurry in an amount in the range of from about 0.1% to about 5.0% by weight of dry cement therein, said methylenephosphonic acid derivative being selected from the group consisting of compounds having the general formula: ##STR16## wherein: R 1 , R 2 and R 3 are independently hydrogen, --CH 2 PO 3 (X) 2 or --CH 2 CH 2 --O--PO 3 (X) 2 with the limitation that one of R 1 , R 2 and R 3 is always --CH 2 PO 3 (X) 2 or --CH 2 CH 2 --O--PO 3 (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 methylenephosphonate group; and at leat 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; compounds having the structural formula: ##STR17## wherein: n is an integer from 1 to 4; R 1 is hydrogen or --CH 2 PO 3 (X) 2 ; R 2 is hydrogen, --CH 2 PO 3 (X) 2 or --CH 2 CH 2 N(R 3 ) 2 wherein R 3 is hydrogen or --CH 2 PO 3 (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 methylenephosphonate group; and at least one of R 1 , R 2 or R 3 is --CH 2 PO 3 (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; compounds having the structural formula: ##STR18## wherein: n is an integer from 0 to 4; R 1 is hydrogen or --Ch 2 PO 3 (X) 2 ; R 2 is hydrogen, --CH 2 PO 3 (X) 2 or --CH 2 CH 2 N(R 4 ) 2 wherein R 4 is hydrogen or --CH 2 PO 3 (X) 2 ; R 3 is --N(R 5 ) 2 or ##STR19## wherein R 5 is hydrogen or --CH 2 PO 3 (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 methylenephosphonate group; and at least one of R 1 , R 2 or R 3 is --CH 2 PO 3 (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; compounds having the structural formula: ##STR20## wherein: n is an integer from 2 to 6; R is hydrogen, --CH 2 PO 3 (X) 2 or --CH 2 CH 2 N(R 1 ) 2 wherein R 1 is hydrogen or --CH 2 PO 3 (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 methylenephosphonate group; and at least one R is --CH 2 PO 3 (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; compounds having the structural formula: ##STR21## wherein: R 1 is hydrogen or --CH 3 ; R 2 is --CH 2 PO 3 (X) 2 --CH 2 NHCH 2 PO 3 (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 methylenephosphonate 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; and mixtures of such compounds.

Claim 13

A method of cementing a zone at a remote location comprising the steps of: preparing a set delayed cement composition comprised of hydraulic cement, sufficient water to form a pumpable slurry, a hydratable gel forming material selected from the group consisting of 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 dry cement to minimize the settling of solids and separation of free water therefrom, and a set delaying agent comprised of a methylene-phosphonic acid derivative present in said slurry in an amount in the range of from about 0.1% to about 5.0% by weight of dry cement therein, said methylenephosphonic acid derivative being selected from the group consisting of compounds having the general formula: ##STR22## wherein: R 1 , R 2 and R 3 are independently hydrogen, --CH 2 PO 3 (X) 2 or --CH 2 CH 2 --O--PO 3 (X) 2 with the limitation that one of R 1 , R 2 and R 3 is always --CH 2 PO 3 (X) 2 or --CH 2 CH 2 --O--PO 3 (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 methylenephosphonate 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; compounds having the structural formula: ##STR23## wherein: n is an integer from 1 to 4; R 1 is hydrogen or --CH 2 PO 3 (X) 2 ; R 2 is hydrogen, --CH 2 PO 3 (X) 2 or --CH 2 CH 2 N(R 3 ) 2 wherein R 3 is hydrogen or --CH 2 PO 3 (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 methylenephosphonate group; and at least one of R 1 , R 2 or R 3 is --CH 2 PO 3 (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; compounds having the structural formula: ##STR24## wherein: n is an integer from 0 to 4; R 1 is hydrogen or --CH 2 PO 3 (X) 2 ; R 2 is hydrogen, --CH 2 PO 3 (X) 2 or --CH 2 CH 2 N(R 4 ) 2 wherein R 4 is hydrogen or --CH 2 PO 3 (X) 2 ; R 3 is --N(R 5 ) 2 or ##STR25## wherein R 5 is hydrogen or --CH 2 PO 3 (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 methylenephosphonate group; and at least one of R 1 , R 2 or R 3 is --CH 2 PO 3 (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; compounds having the structural formula: ##STR26## wherein: n is an integer from 2 to 6; R is hydrogen, --CH 2 PO 3 (X) 2 or --CH 2 CH 2 N(R 1 ) 2 wherein R 1 is hydrogen or --CH 2 PO 3 (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 methylenephosphonate group; and at least one R is --CH 2 PO 3 (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; compounds having the structural formula: ##STR27## wherein: R 1 is hydrogen or --CH 3 ; R 2 is --CH 2 PO 3 (X) 2 --CH 2 NHCH 2 PO 3 (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 methylenephosphonate group; and when nitrogen is present, at leat 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, and mixtures of each compounds; transporting said set delayed cement composition to said remote location; mixing a set activating agent with said cement composition just prior to the placement thereof selected from the group consisting of an aqueous sodium silicate solution, paraformaldehyde, calcium chloride and mixtures thereof; and placing the resulting mixture in said zone.

Claim 14

A method of cementing a zone at a remote location comprising the steps of: preparing a set delayed cement composition comprised of hydraulic cement, sufficient water to form a pumpable slurry, a hydratable gel forming material selected from the group consisting of 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 dry cement to minimize the settling of solids and separation of free water therefrom, and a set delaying agent comprised of a methylene-phosphonic acid derivative present in said slurry in an amount in the range of from about 0.1% to about 5.0% by weight of dry cement therein, said methylenephosphonic acid derivative being selected from the group consisting of compounds having the general formula: ##STR22## wherein: R 1 , R 2 and R 3 are independently hydrogen, --CH 2 PO 3 (X) 2 or --CH 2 CH 2 --O--PO 3 (X) 2 with the limitation that one of R 1 , R 2 and R 3 is always --CH 2 PO 3 (X) 2 or --CH 2 CH 2 --O--PO 3 (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 methylenephosphonate 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; compounds having the structural formula: ##STR23## wherein: n is an integer from 1 to 4; R 1 is hydrogen or --CH 2 PO 3 (X) 2 ; R 2 is hydrogen, --CH 2 PO 3 (X) 2 or --CH 2 CH 2 N(R 3 ) 2 wherein R 3 is hydrogen or --CH 2 PO 3 (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 methylenephosphonate group; and at least one of R 1 , R 2 or R 3 is --CH 2 PO 3 (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; compounds having the structural formula: ##STR24## wherein: n is an integer from 0 to 4; R 1 is hydrogen or --CH 2 PO 3 (X) 2 ; R 2 is hydrogen, --CH 2 PO 3 (X) 2 or --CH 2 CH 2 N(R 4 ) 2 wherein R 4 is hydrogen or --CH 2 PO 3 (X) 2 ; R 3 is --N(R 5 ) 2 or ##STR25## wherein R 5 is hydrogen or --CH 2 PO 3 (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 methylenephosphonate group; and at least one of R 1 , R 2 or R 3 is --CH 2 PO 3 (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; compounds having the structural formula: ##STR26## wherein: n is an integer from 2 to 6; R is hydrogen, --CH 2 PO 3 (X) 2 or --CH 2 CH 2 N(R 1 ) 2 wherein R 1 is hydrogen or --CH 2 PO 3 (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 methylenephosphonate group; and at least one R is --CH 2 PO 3 (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; compounds having the structural formula: ##STR27## wherein: R 1 is hydrogen or --CH 3 ; R 2 is --CH 2 PO 3 (X) 2 --CH 2 NHCH 2 PO 3 (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 methylenephosphonate group; and when nitrogen is present, at leat 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, and mixtures of each compounds; transporting said set delayed cement composition to said remote location; mixing a set activating agent with said cement composition just prior to the placement thereof selected from the group consisting of an aqueous sodium silicate solution, paraformaldehyde, calcium chloride and mixtures thereof; and placing the resulting mixture in said zone.

Claim 17

A method of cementing a zone at a remote location comprising the steps of: preparing a set delayed cement composition comprising a hydraulic cement, sufficient water to form a pumpable slurry, a hydratable gel forming material selected from the group consisting of hydroxyalkylcellulose, carboxyalkylcellulose and carboxyalkylhydroxyalkyl cellulose, present in said 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), ethylenediamine substituted with in the range of from 1 to 4 moles of methylenephosphonic acid, diethylenetriamine substituted with in the range of from 1 to 5 moles of methylenephosphonic acid, triethylenetetramine substituted with in the range of from 1 to 6 moles of methylenephosphonic acid, and mixtures thereof present in said composition in an amount in the range of from about 0.1% to about 2.5% by weight of dry cement therein; transporting said set delayed cement composition to said remote location; mixing a set activating agent selected from an aqueous sodium silicate solution, paraformaldehyde, calcium chloride, and mixtures thereof with said cement composition just prior to the placement thereof; and placing said composition in said zone.

Claim 18

A method of cementing a zone at a remote location comprising the steps of: preparing a set delayed cement composition comprising a hydraulic cement, sufficient water to form a pumpable slurry, a hydratable gel forming material selected from the group consisting of hydroxyalkylcellulose, carboxyalkylcellulose and carboxyalkylhydroxyalkyl cellulose, present in said 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), ethylenediamine substituted with in the range of from 1 to 4 moles of methylenephosphonic acid, diethylenetriamine substituted with in the range of from 1 to 5 moles of methylenephosphonic acid, triethylenetetramine substituted with in the range of from 1 to 6 moles of methylenephosphonic acid, and mixtures thereof present in said composition in an amount in the range of from about 0.1% to about 2.5% by weight of dry cement therein; transporting said set delayed cement composition to said remote location; mixing a set activating agent selected from an aqueous sodium silicate solution, paraformaldehyde, calcium chloride, and mixtures thereof with said cement composition just prior to the placement thereof; and placing said composition in said zone.

Claim 22

A method of cementing a zone at a remote location comprising the steps of: preparing a set delayed cement composition comprising 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, and aminotri(methylenephosphonic acid) present in said composition an amount in the range of from about 0.2% to about 0.7% by weight of dry cement; transporting said set delayed cement composition to said remote location; storing said set delayed cement composition at said remote location; mixing a set activating agent selected from the group consisting of an aqueous sodium silicate solution, paraformaldehyde, calcium chloride and mixtures thereof with said cement composition just prior to the placement thereof in said zone; and placing the resulting mixture in said zone.

Claim 23

A method of cementing a zone at a remote location comprising the steps of: preparing a set delayed cement composition comprising 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, and aminotri(methylenephosphonic acid) present in said composition an amount in the range of from about 0.2% to about 0.7% by weight of dry cement; transporting said set delayed cement composition to said remote location; storing said set delayed cement composition at said remote location; mixing a set activating agent selected from the group consisting of an aqueous sodium silicate solution, paraformaldehyde, calcium chloride and mixtures thereof with said cement composition just prior to the placement thereof in said zone; and placing the resulting mixture in said zone.