Accelerating agents for resin cement composite systems for oil well cementing

1. A method of cementing comprising:

providing a bulk dry cement, wherein the bulk dry cement comprises a dry blend of cement and a solid resin accelerator, wherein the solid resin accelerator comprises a liquid resin accelerator on a solid particle;

preparing a cement slurry comprising:

the bulk dry cement;

water; and

a liquid hardenable resin component;

introducing the cement slurry into a wellbore;

hardening the cement by reacting the cement with water; and

hardening the liquid hardenable resin component by reacting with the liquid resin accelerator.

2. The method of claim 1 wherein the cement comprises at least one cement selected from the group consisting of Portland cement, pozzolan cement, gypsum cement, alumina cement, slag cement, high magnesia content cement, shale cement, acid/base cement, fly ash cement, zeolite cement, kiln dust cement system, metakaolin cement, pumice/lime cement, and combinations thereof.

3. The method of claim 1 wherein the liquid hardenable resin component comprises at least one liquid resin selected from the group consisting of epoxy-based resins, novolak resins, polyepoxide resins, phenol-aldehyde resins, urea-aldehyde resins, urethane resins, phenolic resins, furan resins, furan and furfuryl alcohol resins, phenolic/latex resins, phenol formaldehyde resins, bisphenol A diglycidyl ether resins, butoxymethyl butyl glycidyl ether resins, bisphenol A-epichlorohydrin resins, bisphenol F resins, diglycidyl ether bisphenol F resin, cyclohexane dimethanol diglycidyl ether, glycidyl ether resins, polyester resins and hybrids and copolymers thereof, polyurethane resins and hybrids and copolymers thereof, acrylate resins, and combinations thereof and wherein the liquid resin accelerator comprises at least one liquid resin accelerator selected form the group consisting of aliphatic amines, aliphatic tertiary amines, aromatic amines, cycloaliphatic amines, heterocyclic amines, amido amines, polyamides, polyethyl amines, polyether amines, polyoxyalkylene amines, carboxylic anhydrides, triethylenetetraamine, ethylene diamine, N-cocoalkyltrimethylene, isophorone diamine, N-aminophenyl piperazine, imidazoline, 1,2-diaminocyclohexane, polyetheramine, diethyltoluenediamine, 4,4′-diaminodiphenyl methane, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, maleic anhydride, polyazelaic polyanhydride, phthalic anhydride, 6-Methyl-2,4-bis(methylthio)phenylene-1,3-diamine; 2-methyl-4,6-bis(methylthio) phenylene-1,3-diamine, 2,4,6-tris(dimethylaminomethyl)phenol, and combinations thereof.

4. The method of claim 1 wherein the liquid resin accelerator comprises 2,4,6-tris(dimethylaminomethyl)phenol, wherein the solid particle comprises halloysite, and wherein the liquid hardenable resin comprises diglycidyl ether of bisphenol A and butyl glycidyl ether.

5. The method of claim 1 wherein the solid particle comprises at least one solid selected from the group consisting of halloysite, halloysite nanotubes, silica dust, silica flour, fumed silica, silica fume, porous silica, cement kiln dust (CKD), Portland cement, calcium silicate, pumice, perlite, metakaolin, kaolinite, natural glasses, synthetic glass, biomass ash, diatomaceous earth, iron oxide, manganese oxide, barite, calcium carbonate, slag and hollow glass spheres.

6. The method of claim 1 wherein the step of preparing comprises:

blending the bulk dry cement and the water to form a resin-free cement slurry; and

combining the liquid hardenable resin component and the resin-free cement slurry in a pump to form the cement slurry.

7. The method of claim 1 wherein the step of preparing comprises:

blending the bulk dry cement, the liquid hardenable resin component and the water in a blender to form the cement slurry.

8. The method of claim 1 wherein the step of preparing comprises:

combining the liquid hardenable resin component and the water to form a resin water mixture; and

blending the bulk dry cement and the resin water mixture to form the cement slurry.

9. The method of claim 1 , wherein the solid resin accelerator is present in an amount of 0.1 vol. % to 10 vol. % of the cement slurry.

10. A system comprising:

a cement blender;

a source of water coupled to the cement blender;

a source of cement coupled to the cement blender;

a pump fluidically coupled to the cement blender and a wellbore; and

a liquid additive pump coupled to a source of liquid hardenable resin and at least one of the source of water, the cement blender, or the pump,

wherein the source of cement comprises bulk dry cement comprising a dry blend of cement and a solid resin accelerator, wherein the solid resin accelerator comprises a liquid resin accelerator on a solid particle.

11. The system of claim 10 wherein the cement comprises at least one cement selected from the group consisting of Portland cement, pozzolan cement, gypsum cement, alumina cement, slag cement, high magnesia content cement, shale cement, acid/base cement, fly ash cement, zeolite cement, kiln dust cement system, metakaolin cement, pumice/lime cement, and combinations thereof.

12. The system of claim 10 wherein the solid resin accelerator comprises a liquid resin accelerator adsorbed and/or absorbed on the solid particle.

13. The system of claim 12 wherein the liquid resin accelerator comprises at least one liquid resin accelerator selected form the group consisting of aliphatic amines, aliphatic tertiary amines, aromatic amines, cycloaliphatic amines, heterocyclic amines, amido amines, polyamides, polyethyl amines, polyether amines, polyoxyalkylene amines, carboxylic anhydrides, triethylenetetraamine, ethylene diamine, N-cocoalkyltrimethylene, isophorone diamine, N-aminophenyl piperazine, imidazoline, 1,2-diaminocyclohexane, polyetheramine, diethyltoluenediamine, 4,4′-diaminodiphenyl methane, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, maleic anhydride, polyazelaic polyanhydride, phthalic anhydride, 6-Methyl-2,4-bis(methylthio)phenylene-1,3-diamine; 2-methyl-4,6-bis(methylthio) phenylene-1,3-diamine, 2,4,6-tris(dimethylaminomethyl)phenol, and combinations thereof.

14. The system of claim 12 wherein the solid particle comprises at least one solid selected from the group consisting of halloysite, halloysite nanotubes, silica dust, silica flour, fumed silica, silica fume, porous silica, cement kiln dust (CKD), Portland cement, calcium silicate, pumice, perlite, metakaolin, kaolinite, natural glasses, synthetic glass, biomass ash, diatomaceous earth, iron oxide, manganese oxide, barite, calcium carbonate, slag and hollow glass spheres.

15. The system of claim 10 further comprising a control system configured to control the liquid additive pump.

16. A method of cementing comprising:

providing a bulk dry cement, wherein the bulk dry cement comprises a dry blend of cement and a solid resin accelerator, wherein the solid resin accelerator comprises a liquid resin accelerator on a solid particle, and wherein the solid resin accelerator is capable of reacting with a liquid hardenable resin component to form a solid mass;

preparing a cement slurry comprising:

the bulk dry cement; and

water;

pumping the cement slurry using a pump while introducing the liquid hardenable resin component into a suction header on the pump, thereby mixing the cement slurry and the liquid hardenable resin component to form a resin containing cement slurry; and

introducing the resin containing cement slurry into a wellbore, and reacting the liquid resin accelerator with the liquid hardenable resin component to form a solid mass.

17. The method of claim 16 wherein the cement comprises at least one cement selected from the group consisting of Portland cement, pozzolan cement, gypsum cement, alumina cement, slag cement, high magnesia content cement, shale cement, acid/base cement, fly ash cement, zeolite cement, kiln dust cement system, metakaolin cement, pumice/lime cement, and combinations thereof.

18. The method of claim 16 wherein the liquid hardenable resin component comprises at least one liquid resin selected from the group consisting of epoxy-based resins, novolak resins, polyepoxide resins, phenol-aldehyde resins, urea-aldehyde resins, urethane resins, phenolic resins, furan resins, furan and furfuryl alcohol resins, phenolic/latex resins, phenol formaldehyde resins, bisphenol A diglycidyl ether resins, butoxymethyl butyl glycidyl ether resins, bisphenol A-epichlorohydrin resins, bisphenol F resins, diglycidyl ether bisphenol F resin, cyclohexane dimethanol diglycidyl ether, glycidyl ether resins, polyester resins and hybrids and copolymers thereof, polyurethane resins and hybrids and copolymers thereof, acrylate resins, and combinations thereof and wherein the liquid resin accelerator comprises at least one liquid resin accelerator selected form the group consisting of aliphatic amines, aliphatic tertiary amines, aromatic amines, cycloaliphatic amines, heterocyclic amines, amido amines, polyamides, polyethyl amines, polyether amines, polyoxyalkylene amines, carboxylic anhydrides, triethylenetetraamine, ethylene diamine, N-cocoalkyltrimethylene, isophorone diamine, N-aminophenyl piperazine, imidazoline, 1,2-diaminocyclohexane, polyetheramine, diethyltoluenediamine, 4,4′-diaminodiphenyl methane, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, maleic anhydride, polyazelaic polyanhydride, phthalic anhydride, 6-Methyl-2,4-bis(methylthio)phenylene-1,3-diamine; 2-methyl-4,6-bis(methylthio) phenylene-1,3-diamine, 2,4,6-tris(dimethylaminomethyl)phenol, and combinations thereof.

19. The method of claim 16 wherein the liquid resin accelerator comprises 2,4,6-tris(dimethylaminomethyl)phenol, wherein the solid particle comprises halloysite, and wherein the liquid hardenable resin comprises diglycidyl ether of bisphenol A and butyl glycidyl ether.

20. The method of claim 16 wherein the solid particle comprises at least one solid selected from the group consisting of halloysite, halloysite nanotubes, silica dust, silica flour, fumed silica, silica fume, porous silica, cement kiln dust (CKD), Portland cement, calcium silicate, pumice, perlite, metakaolin, kaolinite, natural glasses, synthetic glass, biomass ash, diatomaceous earth, iron oxide, manganese oxide, barite, calcium carbonate, slag and hollow glass spheres.