US 4,676,832 AGranted

Set delayed cement compositions and methods of using the same

AssigneeHalliburton Company

InventorsJerry D. Childs, David L. Sutton, Freddie L. Sabins

Life of this patent

Estimating the term…

Abstract

Set delayed cement compositions capable of being retained in pumpable fluid states for long time periods and then activated to set into hard masses and methods of using such compositions for cementing zones at remote locations are provided. The compositions are comprised of hydraulic cement, water, one or more hydratable gel forming materials and one or more methylenephosphonic acid derivative set delaying agents.

Claims18

Dependent claims

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.sub.1, R.sub.2 and R.sub.3 are independently hydrogen, --CH.sub.2 PO.sub.3 (X).sub.2 or --CH.sub.2 CH.sub.2 --O--PO.sub.3 (X).sub.2 with the limitation that one of R.sub.1, R.sub.2 and R.sub.3 is always --CH.sub.2 PO.sub.3 (X).sub.2 or --CH.sub.2 CH.sub.2 --O--PO.sub.3 (X).sub.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.sub.1 is hydrogen or --CH.sub.2 PO.sub.3 (X).sub.2 ;
R.sub.2 is hydrogen, --CH.sub.2 PO.sub.3 (X).sub.2 or --CH.sub.2 CH.sub.2 N(R.sub.3).sub.2 wherein R.sub.3 is hydrogen or --CH.sub.2 PO.sub.3 (X).sub.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.sub.1, R.sub.2 or R.sub.3 is --CH.sub.2 PO.sub.3 (X).sub.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.sub.1 is hydrogen or --Ch.sub.2 PO.sub.3 (X).sub.2 ;
R.sub.2 is hydrogen, --CH.sub.2 PO.sub.3 (X).sub.2 or --CH.sub.2 CH.sub.2 N(R.sub.4).sub.2 wherein R.sub.4 is hydrogen or --CH.sub.2 PO.sub.3 (X).sub.2 ;
R.sub.3 is --N(R.sub.5).sub.2 or ##STR19## wherein R.sub.5 is hydrogen or --CH.sub.2 PO.sub.3 (X).sub.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.sub.1, R.sub.2 or R.sub.3 is --CH.sub.2 PO.sub.3 (X).sub.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.sub.2 PO.sub.3 (X).sub.2 or --CH.sub.2 CH.sub.2 N(R.sub.1).sub.2 wherein R.sub.1 is hydrogen or --CH.sub.2 PO.sub.3 (X).sub.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.sub.2 PO.sub.3 (X).sub.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.sub.1 is hydrogen or --CH.sub.3 ;
R.sub.2 is --CH.sub.2 PO.sub.3 (X).sub.2 --CH.sub.2 NHCH.sub.2 PO.sub.3 (X).sub.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.

40 more elements

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.sub.1, R.sub.2 and R.sub.3 are independently hydrogen, --CH.sub.2 PO.sub.3 (X).sub.2 or --CH.sub.2 CH.sub.2 --O--PO.sub.3 (X).sub.2 with the limitation that one of R.sub.1, R.sub.2 and R.sub.3 is always --CH.sub.2 PO.sub.3 (X).sub.2 or --CH.sub.2 CH.sub.2 --O--PO.sub.3 (X).sub.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.sub.1 is hydrogen or --CH.sub.2 PO.sub.3 (X).sub.2 ;
R.sub.2 is hydrogen, --CH.sub.2 PO.sub.3 (X).sub.2 or --CH.sub.2 CH.sub.2 N(R.sub.3).sub.2 wherein R.sub.3 is hydrogen or --CH.sub.2 PO.sub.3 (X).sub.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.sub.1, R.sub.2 or R.sub.3 is --CH.sub.2 PO.sub.3 (X).sub.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.sub.1 is hydrogen or --CH.sub.2 PO.sub.3 (X).sub.2 ;
R.sub.2 is hydrogen, --CH.sub.2 PO.sub.3 (X).sub.2 or --CH.sub.2 CH.sub.2 N(R.sub.4).sub.2 wherein R.sub.4 is hydrogen or --CH.sub.2 PO.sub.3 (X).sub.2 ;
R.sub.3 is --N(R.sub.5).sub.2 or ##STR25## wherein R.sub.5 is hydrogen or --CH.sub.2 PO.sub.3 (X).sub.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.sub.1, R.sub.2 or R.sub.3 is --CH.sub.2 PO.sub.3 (X).sub.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.sub.2 PO.sub.3 (X).sub.2 or --CH.sub.2 CH.sub.2 N(R.sub.1).sub.2 wherein R.sub.1 is hydrogen or --CH.sub.2 PO.sub.3 (X).sub.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.sub.2 PO.sub.3 (X).sub.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.sub.1 is hydrogen or --CH.sub.3 ;
R.sub.2 is --CH.sub.2 PO.sub.3 (X).sub.2 --CH.sub.2 NHCH.sub.2 PO.sub.3 (X).sub.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.

39 more elements

Dependencies are inferred from the claim text.

Facts

Application: 06/665,248Filed 26 Oct 1984
Granted: 30 Jun 1987
Term ends: Not estimatedThe source records don’t support an estimate.

Classification6 codes

C09K 8/206
Natural organic compounds or derivatives thereof, e.g. polysaccharides or lignin derivatives: derivatives of other natural products, e.g.…
C04B 24/003
Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers: phosphorus-containing compounds
C04B 28/02
Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic…
C09K 8/467
Containing inorganic binders, e.g. Portland cement: containing additives for specific purposes

Family

No related US applications are recorded in the indexed filing history.

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Abstract

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.sub.1, R.sub.2 and R.sub.3 are independently hydrogen, --CH.sub.2 PO.sub.3 (X).sub.2 or --CH.sub.2 CH.sub.2 --O--PO.sub.3 (X).sub.2 with the limitation that one of R.sub.1, R.sub.2 and R.sub.3 is always --CH.sub.2 PO.sub.3 (X).sub.2 or --CH.sub.2 CH.sub.2 --O--PO.sub.3 (X).sub.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.sub.1 is hydrogen or --CH.sub.2 PO.sub.3 (X).sub.2 ;
R.sub.2 is hydrogen, --CH.sub.2 PO.sub.3 (X).sub.2 or --CH.sub.2 CH.sub.2 N(R.sub.3).sub.2 wherein R.sub.3 is hydrogen or --CH.sub.2 PO.sub.3 (X).sub.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.sub.1, R.sub.2 or R.sub.3 is --CH.sub.2 PO.sub.3 (X).sub.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.sub.1 is hydrogen or --Ch.sub.2 PO.sub.3 (X).sub.2 ;
R.sub.2 is hydrogen, --CH.sub.2 PO.sub.3 (X).sub.2 or --CH.sub.2 CH.sub.2 N(R.sub.4).sub.2 wherein R.sub.4 is hydrogen or --CH.sub.2 PO.sub.3 (X).sub.2 ;
R.sub.3 is --N(R.sub.5).sub.2 or ##STR19## wherein R.sub.5 is hydrogen or --CH.sub.2 PO.sub.3 (X).sub.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.sub.1, R.sub.2 or R.sub.3 is --CH.sub.2 PO.sub.3 (X).sub.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.sub.2 PO.sub.3 (X).sub.2 or --CH.sub.2 CH.sub.2 N(R.sub.1).sub.2 wherein R.sub.1 is hydrogen or --CH.sub.2 PO.sub.3 (X).sub.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.sub.2 PO.sub.3 (X).sub.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.sub.1 is hydrogen or --CH.sub.3 ;
R.sub.2 is --CH.sub.2 PO.sub.3 (X).sub.2 --CH.sub.2 NHCH.sub.2 PO.sub.3 (X).sub.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.

40 more elements

Facts

Application

06/665,248Filed 26 Oct 1984

Granted

30 Jun 1987

Term ends

Not estimatedThe source records don’t support an estimate.

Classification6 codes

C09K 8/206
Natural organic compounds or derivatives thereof, e.g. polysaccharides or lignin derivatives: derivatives of other natural products, e.g.…
C04B 24/003
Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers: phosphorus-containing compounds
C04B 28/02
Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic…
C09K 8/467
Containing inorganic binders, e.g. Portland cement: containing additives for specific purposes