Composition for well cementing comprising a compounded elastomer swelling additive

• US 9,382,159 B2
• Filed: 04/11/2011
• Issued: 07/05/2016
• Est. Priority Date: 04/20/2010
• Status: Active Grant

• Current Assignee: Schlumberger Technology Corporation (SLB)
• Original Assignee: Schlumberger Technology Corporation (SLB)
• Inventors: Khalfallah, Ines, Loizzo, Matteo, Dennis, Katia, de la Mothe, Loic Regnault, Le Roy-Delage, Sylvaine
• Primary Examiner(s): DiTrani, Angela M
• Assistant Examiner(s): Varma, Ashish
• Application Number:
  US13/640,480
• Publication Number:
  US 20130075096A1
• Time in Patent Office: 1,912 Days
• Field of Search: 166/294
• US Class Current: 1/1
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: C04B 14/08 Diatomaceous earth
• CPC Class Codes: C04B 18/22 Rubber , e.g. ground waste tires
• CPC Class Codes: C04B 20/008 Micro- or nanosized fillers, e.g. micronised fillers with particle size smaller than that of the hydraulic binder colloidal silica C04B14/062 ; silica fume C04B18/146
• CPC Class Codes: C04B 2103/0045 Polymers chosen for their physico-chemical characteristics
• CPC Class Codes: C04B 2103/0051 Water-absorbing polymers, hydrophilic polymers
• CPC Class Codes: C04B 2103/10 Accelerators; Activators
• CPC Class Codes: C04B 2103/20 Retarders
• CPC Class Codes: C04B 2103/408 Dispersants
• CPC Class Codes: C04B 2103/46 Water-loss or fluid-loss reducers, hygroscopic or hydrophilic agents, water retention agents
• CPC Class Codes: C04B 22/0026 Salt water, e.g. seawater
• CPC Class Codes: C04B 24/2611 Polyalkenes
• CPC Class Codes: C04B 24/2641 Polyacrylates; Polymethacrylates
• CPC Class Codes: C04B 24/2652 Nitrogen containing polymers, e.g. polyacrylamides, polyacrylonitriles
• CPC Class Codes: C04B 24/2676 Polystyrenes
• CPC Class Codes: C04B 28/02 containing hydraulic cements other than calcium sulfates
• CPC Class Codes: C09K 8/467 containing additives for specific purposes
• CPC Class Codes: E21B 33/14 for cementing casings into boreholes
• CPC Class Codes: Y02W 30/91 Use of waste materials as fillers for mortars or concrete
• CPC Class Codes: Y10S 977/773 Nanoparticle, i.e. structure having three dimensions of 100 nm or less

Abstract

Compositions for well cementing comprise a pumpable slurry of cement, water and at least one additive that swells in contact with an underground fluid (hydrocarbon, water or brines or mixtures thereof). In case of failure of the cement matrix after setting, the additive swells when contacted by the underground fluid and restores zonal isolation. The swelling additive is an elastomer compounded with an aqueous inverse emulsion of particles of a polymer comprising a betaine group.

Claims

1. A composition for well cementing in a subterranean formation comprising a pumpable slurry of an inorganic settable material, water and at least one additive that swells in contact with a fluid that contains CO₂, wherein said additive is an elastomer compounded with an aqueous inverse emulsion of particles of a polymer comprising a betaine group,

wherein the settable material comprises portland cement, microcement, geopolymer, mixtures of cement and geopolymer, plaster, phosphomagnesium cement or chemically bonded phosphate ceramics or combinations thereof.

2. The composition according to claim 1, wherein the well is an oil well, a gas well or both.

3. The composition of claim 1, further comprising dispersing additives, retarder additives, accelerating agents, fluid loss control agents, or weighting agents or combinations thereof.

4. The composition of claim 1, wherein the additive is present at a concentration between 5% and 20% by volume of solid blend.

5. The composition of claim 1, wherein the particles of polymer have a particle size between 10 nm and 1,000,000 nm.

6. The composition of claim 1, further comprising a swellable compound comprising a rubber, poly 2,2,2-bicyclo-heptene, alkylstyrene, crosslinked substituted vinyl-acetate copolymers an elastic terpolymer of ethylene, propylene and non-conjugated diene monomer or diatomaceous earth or mixtures thereof.

7. The composition of claim 1, further comprising a super-absorbent polymer.

8. The composition of claim 1, wherein OH functions are incorporated as grafting sites of the polymer.

9. The composition according to claim 8, wherein 1% to 10% of the grafting sites of the polymer incorporate OH functions.

10. The composition of claim 1, wherein the polymer comprising a betaine group is prepared by inverse emulsion polymerization of monomers A_b comprising a betaine group, monovalent monomers B_a and polyvalent monomers C_a, wherein the emulsion is in the form of an aqueous phase dispersed in a hydrophobic external phase comprising hydrophobic surfactants, the molar ratio of the monomers A_b to the monomers B_a being between 4/96 and 40/60.

11. The composition of claim 10, wherein the quantity of polyvalent monomers C_a is between 0.001 mol % and 0.1 mol %.

12. The composition of claim 1, wherein 1% to 49% by weight of the aqueous inverse emulsion is compounded with 99% to 51% by weight of elastomer.

13. A method for cementing a well in a subterranean formation comprising:

compounding an elastomer with an aqueous inverse emulsion of particles of a polymer comprising a betaine group;

providing a pumpable slurry of cement, water and at least one additive that swells in contact with an aqueous saline fluid in case of failure of the cement matrix, said swelling additive being the compounded elastomer;

pumping the cement slurry down the well;

allowing the cement slurry to set; and

in the event of set cement failure, allowing the swelling additive to swell in contact with a fluid that contains CO₂.

14. The method of claim 13, wherein the polymer comprising a betaine group is prepared by inverse emulsion polymerization of monomers A_b comprising a betaine group, monovalent monomers B_a and polyvalent monomers C_a, wherein the emulsion is in the form of an aqueous phase dispersed in a hydrophobic external phase comprising hydrophobic surfactants, the molar ratio of the monomers A_b to the monomers B_a being between 4/96 and 40/60.

15. The method of claim 13, wherein the cement slurry further comprises dispersing additives, retarder additives, accelerating agents, fluid loss control agents, or weighting agents or combinations thereof.

16. The method of claim 13, wherein the additive is present at a concentration between 5% and 20% by volume of solid blend.

17. The method of claim 13, wherein the particles of polymer have a particle size between 10 nm and 1,000,000 nm.

18. The method of claim 13, wherein the cement slurry further comprises a swellable compound comprising a rubber, poly 2,2,2-bicyclo-heptene, alkylstyrene, crosslinked substituted vinyl-acetate copolymers, an elastic terpolymer of ethylene, propylene and non-conjugated diene monomer or diatomaceous earth or mixtures thereof.