Claims
- 1. A well cement composition having improved mechanical properties including elasticity and ductility comprising:
- a hydraulic cement;
- fumed silica present in an amount in the range of from about 5% to about 30% by weight of hydraulic cement in said composition;
- an aqueous rubber latex present in an amount in the range of from about 2.5% to about 45% by weight of hydraulic cement in said composition; and
- an effective amount of a latex stabilizer.
- 2. The composition of claim 1 wherein said latex stabilizer is selected from the group consisting of surfactants having the formula
- R--Ph--O(OCH.sub.2 CH.sub.2).sub.m OH
- wherein R is an alkyl group having from about 5 to about 30 carbon atoms, Ph is phenyl and m is an integer in the range of from about 5 to about 50, and surfactants of the general formula
- R.sub.1 (OR.sub.2).sub.n SO.sub.3 X
- wherein R.sub.1 is selected from the group consisting of alkyl groups having from 1 to about 30 carbon atoms, cycloalkyl groups having 5 or 6 carbon atoms, C.sub.1 -C.sub.4 alkyl substituted cycloalkyl groups, phenyl, alkyl substituted phenyl of the general formula (R.sub.3).sub.a Ph-- wherein Ph is phenyl, R.sub.3 is an alkyl group having from 1 to about 18 carbon atoms and a is an integer of from 1 to 3, and phenyl-alkyl groups wherein the alkyl groups have from 1 to about 18 carbon atoms and the phenyl-alkyl groups have a total of from about 8 to about 28 carbon atoms, R.sub.2 is a substituted ethylene group of the formula --CH.sub.2 CH.sub.2 R.sub.4 wherein R.sub.4 is selected from hydrogen, methyl, ethyl or mixtures thereof, and n is a number from 0 to about 40 provided that when R.sub.1 is phenyl or alkyl substituted phenyl n is at least one, and X is any compatible cation.
- 3. The composition of claim 1 wherein water is present in said composition in an amount in the range of from about 22% to about 95% by weight of cement therein.
- 4. The composition of claim 1 wherein said hydraulic cement is Portland cement.
- 5. The composition of claim 1 wherein said aqueous rubber latex is an aqueous styrene/butadiene latex.
- 6. The composition of claim 5 wherein said aqueous styrene/butadiene latex contains water in an amount of about 50% by weight of said latex, and the weight ratio of styrene to butadiene in said latex is about 25%:75%.
- 7. The composition of claim 5 wherein said latex stabilizer is present in said cement composition in an amount in the range of from about 90 to about 35% by weight of said aqueous styrene/butadiene latex therein.
- 8. The composition of claim 1 wherein said latex stabilizer is selected from the group consisting of surfactants of the general formula
- R.sub.5 --Ph(OR.sub.6).sub.o SO.sub.3 X
- wherein R.sub.5 is an alkyl group having in the range of from 1 to about 9 carbon atoms, R.sub.6 is the group --CH.sub.2 CH.sub.2 --, o is an integer from about 10 to about 20 and X is a compatible cation.
- 9. The composition of claim 1 wherein said latex stabilizer is selected from the group consisting of surfactants of the general formula
- R.sub.7 (OR.sub.8).sub.p SO.sub.3 X
- wherein R.sub.7 is an alkyl group having in the range of from about 5 to about 20 carbon atoms, R.sub.8 is the group --CH.sub.2 CH.sub.2 --, p is an integer in the range of from about 10 to about 40 and X is a compatible cation.
- 10. The composition of claim 1 wherein said latex stabilizer is selected from the group consisting of nonylphenol ethoxylated with in the range of from about 15 to about 40 moles of ethylene oxide and the sodium salt of a sulfonated and ethoxylated compound having the formula H (CH.sub.2).sub.12-15 (CH.sub.2 CH.sub.2 O).sub.15 SO.sub.3 Na.
- 11. The composition of claim 1 which further comprises a defoaming agent comprised of polydimethylsiloxane present in said composition in an amount in the range of from about 0.1% to about 0.9% by weight of hydraulic cement in said composition.
- 12. The composition of claim 11 which further comprises:
- a gas present in an amount sufficient to foam said cement composition and produce a cement composition density in the range of from about 8 to about 16 pounds per gallon;
- an effective amount of a foaming agent; and
- an effective amount of a foam stabilizer.
- 13. The composition of claim 12 wherein said foaming agent is the sodium salt of alpha-olefinic sulfonic acid and is present in an amount in the range of from about 4% to about 9.5% by weight of water in said composition.
- 14. The composition of claim 12 wherein said foam stabilizer is an amidopropylbetaine of the formula:
- R--CONHCH.sub.2 CH.sub.2 CH.sub.2 N.sup.+ (CH.sub.3).sub.2 CH.sub.2 CO.sub.2.sup.-
- wherein R is a cocoyl group, present in an amount in the range of from about 2% to about 5% by weight of water in said composition.
- 15. A well cement composition having improved mechanical properties including elasticity and ductility comprising:
- a hydraulic cement;
- fumed silica present in an amount in the range of from about 5% to about 30% by weight of hydraulic cement in said composition;
- an aqueous rubber latex present in an amount in the range of from about 2.5% to about 45% by weight of hydraulic cement in said composition;
- an effective amount of a latex stabilizer;
- a defoaming agent comprised of polydimethylsiloxane present in an amount in the range of from about 0.1% to about 0.9% by weight of cement in said composition;
- a gas present in an amount sufficient to foam said cement composition and produce a cement composition density in the range of from about 8 to about 16 pounds per gallon;
- an effective amount of a foaming agent; and
- an effective amount of a foam stabilizer.
- 16. The composition of claim 15 wherein the latex stabilizer is selected from the group consisting of surfactants having the formula
- R--Ph--O(OCH.sub.2 CH.sub.2).sub.m OH
- wherein R is an alkyl group having from about 5 to about 30 carbon atoms, Ph is phenyl and m is an integer in the range of from about 5 to about 50, and surfactants of the general formula
- R.sub.1 (OR.sub.2).sub.n SO.sub.3 X
- wherein R.sub.1 is selected from the group consisting of alkyl groups having from 1 to about 30 carbon atoms, cycloalkyl groups having 5 or 6 carbon atoms, C.sub.1 -C.sub.4 alkyl substituted cycloalkyl groups, phenyl, alkyl substituted phenyl of the general formula (R.sub.3).sub.a Ph-- wherein Ph is phenyl, R.sub.3 is an alkyl group having from 1 to about 18 carbon atoms and a is an integer of from 1 to 3, and phenyl-alkyl groups wherein the alkyl groups have from 1 to about 18 carbon atoms and the phenyl-alkyl groups have a total of from about 8 to about 28 carbon atoms, R.sub.2 is a substituted ethylene group of the formula --CH.sub.2 CH.sub.2 R.sub.4 wherein R.sub.4 is selected from hydrogen, methyl, ethyl or mixtures thereof, and n is a number from 0 to about 40 provided that when R.sub.1 is phenyl or alkyl substituted phenyl n is at least one, and X is any compatible cation.
- 17. The composition of claim 15 wherein said foaming agent is comprised of the sodium salt of alpha-olefinic sulfonic acid and is present in an amount in the range of from about 4% to about 9.5% by weight of water in said composition.
- 18. The composition of claim 15 wherein said foam stabilizer is comprised of an amidopropylbetaine of the formula:
- R--CONHCH.sub.2 CH.sub.2 CH.sub.2 N.sup.+ (CH.sub.3).sub.2 CH.sub.2 CO2.sup.-
- wherein R is a cocoyl group, and present in an amount in the range of from about 2% to about 5% by weight of water in said composition.
- 19. The composition of claim 15 wherein water is present in said composition in an amount in the range of from about 22% to about 95% by weight of cement therein.
- 20. The composition of claim 15 wherein said hydraulic cement is Portland cement.
- 21. The composition of claim 15 wherein said aqueous rubber latex is an aqueous styrene/butadiene latex.
- 22. The composition of claim 21 wherein said aqueous styrene/butadiene latex contains water in an amount of about 50% by weight of said latex, and the weight ratio of styrene to butadiene in said latex is about 25%:75%.
- 23. The composition of claim 21 wherein said latex stabilizer is present in said cement composition in an amount in the range of from about 9% to about 35% by weight of said aqueous styrene/butadiene latex therein.
- 24. The composition of claim 23 wherein said latex stabilizer is selected from the group consisting of nonylphenol ethoxylated with in the range of from about 15 to about 40 moles of ethylene oxide and the sodium salt of a 5 sulfonated and ethoxylated compound having the formula H (CH.sub.2).sub.12-15 (CH.sub.2 CH.sub.2 O).sub.15 SO.sub.3 Na.
- 25. A method of cementing in a subterranean well whereby the set cement can withstand impacts, shocks and cemented pipe movements subsequently generated by drilling and other well operations without cracking, shattering or otherwise failing comprising the steps of:
- introducing a cement composition which sets into a high strength solid mass having elasticity and ductility into said well, said cement composition comprising:
- a hydraulic cement,
- fumed silica present in an amount in the range of from about 5% to about 30% by weight of hydraulic cement in said composition,
- an aqueous rubber latex present in an amount in the range of from about 2.5% to about 45% by weight of hydraulic cement in said composition, and
- an effective amount of a latex stabilizer; and
- allowing said cement composition to set in said well.
- 26. The method of claim 25 wherein said latex stabilizer in said cement composition is selected from the group consisting of surfactants having the formula
- R--Ph--O(OCH.sub.2 CH.sub.2).sub.m OH
- wherein R is an alkyl group having from about 5 to about 30 carbon atoms, Ph is phenyl and m is an integer in the range of from about 5 to about 50, and surfactants of the general formula
- R.sub.1 (OR.sub.2).sub.n SO.sub.3 X
- wherein R.sub.1 is selected from the group consisting of alkyl groups having from 1 to about 30 carbon atoms, cycloalkyl groups having 5 or 6 carbon atoms, C.sub.1 -C.sub.4 alkyl substituted cycloalkyl groups, phenyl, alkyl substituted phenyl of the general formula (R.sub.3).sub.a Ph-- wherein Ph is phenyl, R.sub.3 is an alkyl group having from 1 to about 18 carbon atoms and a is an integer of from 1 to 3, and phenyl-alkyl groups wherein the alkyl groups have from 1 to about 18 carbon atoms and the phenyl-alkyl groups have a total of from about 8 to about 28 carbon atoms, R.sub.2 is a substituted ethylene group of the formula --CH.sub.2 CH.sub.2 R.sub.4 wherein R.sub.4 is selected from hydrogen, methyl, ethyl or mixtures thereof, and n is a number from 0 to about 40 provided that when R.sub.1 is phenyl or alkyl substituted phenyl n is at least one, and X is any compatible cation.
- 27. The method of claim 25 wherein water is present in said cement composition in an amount in the range of from about 22% to about 95% by weight of cement therein.
- 28. The method of claim 25 wherein said hydraulic cement in said cement composition is Portland cement.
- 29. The method of claim 25 wherein said aqueous rubber latex in said composition is an aqueous styrene/butadiene latex.
- 30. The method of claim 29 wherein said aqueous styrene/butadiene latex contains water in an amount of about 50% by weight of said latex, and the weight ratio of styrene to butadiene in said latex is about 25%:75%.
- 31. The method of claim 29 wherein said latex stabilizer is present in said cement composition in an amount in the range of from about 9% to about 35% by weight of said aqueous styrene/butadiene latex therein.
- 32. The method of claim 31 wherein said latex stabilizer in said composition is selected from the group consisting of surfactants of the general formula
- R.sub.5 --Ph(OR.sub.6).sub.o SO.sub.3 X
- wherein R.sub.5 is an alkyl group having in the range of from 1 to about 9 carbon atoms, R.sub.6 is the group --CH.sub.2 CH.sub.2 --, o is an integer from about 10 to about 20 and X is a compatible cation.
- 33. The method of claim 31 wherein said latex stabilizer in said composition is selected from the group consisting of surfactants of the general formula
- R.sub.7 (OR.sub.8).sub.p SO.sub.3 X
- wherein R.sub.7 is an alkyl group having in the range of from about 5 to about 20 carbon atoms, R.sub.8 is the group --CH.sub.2 CH.sub.2 --, p is an integer in the range of from about 10 to about 40 and X is a compatible cation.
- 34. The method of claim 31 wherein said latex stabilizer in said composition is selected from the group consisting of nonylphenol ethoxylated with in the range of from about 15 to about 40 moles of ethylene oxide and the sodium salt of a sulfonated and ethoxylated compound having the formula H (CH.sub.2).sub.12-15 (CH.sub.2 CH.sub.2 O).sub.15 SO.sub.3 Na.
- 35. The method of claim 25 wherein said composition further comprises a defoaming agent comprised of polydimethylsiloxane present in said composition in an amount in the range of from about 0.1% to about 0.9% by weight of hydraulic cement in said composition.
- 36. A method of cementing in a subterranean well whereby the set cement can withstand impacts, shocks and cemented pipe movements subsequently generated by drilling and other well operations without cracking, shattering or otherwise failing comprising the steps of:
- introducing a cement composition which sets into a high strength solid mass having elasticity and ductility into said well, said cement composition comprising:
- a hydraulic cement,
- fumed silica present in an amount in the range of from about 5% to about 30% by weight of hydraulic cement in said composition,
- an aqueous rubber latex present in an amount in the range of from about 2.5% to about 45% by weight of hydraulic cement in said composition,
- an effective amount of a latex stabilizer,
- a defoaming agent comprised of polydimethyl-siloxane present in an amount in the range of from about 0.1% to about 0.9% by weight of hydraulic cement in said composition,
- a gas present in an amount sufficient to foam said cement composition and produce a cement composition density in the range of from about 8 to about 16 pounds per gallon,
- an effective amount of a foaming agent, and
- an effective amount of a foam stabilizer; and
- allowing said cement composition to set in said well.
- 37. The method of claim 36 wherein the latex stabilizer in said cement composition is selected from the group consisting of surfactants having the formula
- R--Ph--O(OCH.sub.2 CH.sub.2).sub.m OH
- wherein R is an alkyl group having from about 5 to about 30 carbon atoms, Ph is phenyl and m is an integer in the range of from about 5 to about 50, and surfactants of the general formula
- R.sub.1 (OR.sub.2).sub.n SO.sub.3 X
- wherein R.sub.1 is selected from the group consisting of alkyl groups having from 1 to about 30 carbon atoms, cycloalkyl groups having 5 or 6 carbon atoms, C.sub.1 -C.sub.4 alkyl substituted cycloalkyl groups, phenyl, alkyl substituted phenyl of the general formula (R.sub.3).sub.a Ph-- wherein Ph is phenyl, R.sub.3 is an alkyl group having from 1 to about 18 carbon atoms and a is an integer of from 1 to 3, and phenyl-alkyl groups wherein the alkyl groups have from 1 to about 18 carbon atoms and the phenyl-alkyl groups have a total of from about 8 to about 28 carbon atoms, R.sub.2 is a substituted ethylene group of the formula --CH.sub.2 CH.sub.2 R.sub.4 wherein R.sub.4 is selected from hydrogen, methyl, ethyl or mixtures thereof, and n is a number from 0 to about 40 provided that when R.sub.1 is phenyl or alkyl substituted phenyl n is at least one, and X is any compatible cation.
- 38. The method of claim 36 wherein said foaming agent in said composition is comprised of the sodium salt of alpha-olefinic sulfonic acid and is present in an amount in the range of from about 4% to about 9.5% by weight of water in said composition.
- 39. The method of claim 36 wherein said foam stabilizer in said composition is comprised of an amidopropylbetaine of the formula:
- R--CONHCH.sub.2 CH.sub.2 CH.sub.2 N.sup.+ (CH.sub.3).sub.2 CH.sub.2 CO.sub.2.sup.-
- wherein R is a cocoyl group and is present in an amount in the range of from about 2% to about 5% by weight of water in said composition.
- 40. The method of claim 36 wherein water is present in said cement composition in an amount in the range of from about 22% to about 95% by weight of cement therein.
- 41. The method of claim 36 wherein said hydraulic cement in said composition is Portland cement.
- 42. The method of claim 36 wherein said aqueous rubber latex in said composition is an aqueous styrene/butadiene latex.
- 43. The method of claim 42 wherein said aqueous styrene/butadiene latex contains water in an amount of about 50% by weight of said latex, and the weight ratio of styrene to butadiene in said latex is about 25%:75%.
- 44. The method of claim 42 wherein said latex stabilizer is present in said cement composition in an amount in the range of from about 9% to about 35% by weight of said aqueous styrene/butadiene latex therein.
- 45. The method of claim 44 wherein said latex stabilizer in said composition is selected from the group consisting of nonylphenol ethoxylated with in the range of from about 15 to about 40 moles of ethylene oxide and a sodium salt of a 5 sulfonated and ethoxylated compound having the formula H (CH.sub.2).sub.12-15 (CH.sub.2 CH.sub.2 O).sub.15 SO.sub.3 Na.
Parent Case Info
This application is a continuation of application Ser. No. 08/673,987, filed Jul. 1, 1996 now abandoned.
US Referenced Citations (20)
Foreign Referenced Citations (4)
Number |
Date |
Country |
0 431 600 A1 |
Jun 1991 |
EPX |
0 572 857 A2 |
Dec 1993 |
EPX |
0 592 217 A2 |
Apr 1994 |
EPX |
WO 9223187 |
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WOX |
Non-Patent Literature Citations (2)
Entry |
Paper entitled "Light, strong foamed cement: A new well tool for problem wells" by Terry Smith; World Oil; May 1984. |
Chemical Abstract entitled "Fire-resistant lightweight building maerials" by Kiichi Suzuki; May 1988. |
Continuations (1)
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Number |
Date |
Country |
Parent |
673987 |
Jul 1996 |
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