Use of graphene as a cement retarder

Patent metadata

Field	Value
Publication number	US-12359111-B2
Application number	US-202217892781-A
Country	US
Kind code	B2
Filing date	Aug 22, 2022
Priority date	Aug 22, 2022
Publication date	Jul 15, 2025
Grant date	Jul 15, 2025

Abstract

A cement slurry includes a set retarder comprising graphene, a cementitious material, and water; the graphene comprises bioderived renewable graphene (BRG). The cement slurry has from about 0.01 to about 20, from about 0.1 to about 15, or from about 0.5 to about 5 percent graphene by weight of cementitious material (% graphene bwoc). The cement slurry has an increased thickening time relative to a same cement slurry absent the graphene.

First claim

What is claimed is:

1. A method comprising:
increasing a thickening time of a cement slurry produced by combining a mix water with a cementitious material by combining a set retarder consisting of graphene with the mix water, wherein the graphene comprises bioderived renewable graphene (BRG), and wherein the cement slurry having the increased thickening time comprises from greater than 3 to about 20 percent BRG by weight of cementitious material (% BRG bwoc);
wherein the cement slurry has an increased thickening time at 70 Beardon Consistency Units (Bc), as measured according to API 10B-2, relative to the cement slurry absent the graphene; and
pumping the cement slurry with the increased thickening time into a workspace.

2. The method of claim 1 , wherein the cementitious material comprises a cement selected from the group consisting of Type I, IA, II, IIA, III, IIIA, IV, V, VI, VII Portland cements, and combinations thereof.

3. The method of claim 1 , wherein the cementitious material comprises an API grade cement.

4. The method of claim 1 , wherein the BRG comprises graphene with a fused sheet-like morphology.

5. The method of claim 1 , wherein the BRG comprises graphene derived from a plant.

6. The method of claim 5 , wherein the plant comprises cassava.

7. The method of claim 1 , wherein the thickening time is increased by at least 10 percent relative to the same cement slurry absent the graphene.

8. The method of claim 1 , wherein the BRG comprises graphene nanosheets.

9. The method of claim 1 further comprising allowing the cement slurry to set to form a hardened cement, wherein the hardened cement has a tensile strength, a Young's modulus, a Poisson's ratio, or a combination thereof that is at least as high as a tensile strength, a Young's modulus, a Poisson's ratio, or a combination thereof of a hardened cement produced from a same cement slurry absent the BRG and optionally comprising a different set retarder.

10. The method of claim 1 , wherein the workspace comprises an oilwell workspace.

11. The method of claim 1 , wherein the workspace has a temperature of greater than or equal to about 100° F.

12. The method of claim 1 , wherein the cement slurry comprises from greater than 5 to about 20 percent BRG by weight of cementitious material (% BRG bwoc).

13. The method of claim 1 , wherein the cement slurry comprises from about 4 to about 20 percent BRG by weight of cementitious material (% BRG bwoc).

14. The method of claim 1 , wherein the BRG comprises nanosheets comprising greater than 90 weight percent carbon.

15. The method of claim 14 , wherein the nanosheets have a surface area of at least 2000 m 2 /g, a pore volume of at least 3 cc/g, or a combination thereof.

16. The method of claim 1 , wherein the BRG is produced by:
combining a renewable carbohydrate material with a dehydration solvent to aid hydrolysis;
removing glycosidic linkages and water via chemical and/or thermal activation to provide an intermediate fused carbon material;
thermochemically activating the intermediate fused carbon material to exfoliate intercalated carbon layers of the intermediate fused carbon material and to initiate chemical bonding of carbon atoms to form the BRG, wherein the BRG comprises a network of high surface area and pore volume sp2 bonded carbon nanosheets.

17. The method of claim 16 , wherein the dehydration solvent comprises water, ethylene glycol, ethanol, or a combination thereof.

18. The method of claim 16 , wherein the chemical activation comprises activation with sodium hydroxide, hydrochloric acid, phosphoric acid, phosphorous acid, nitric acid, or a combination thereof.

19. The method of claim 16 , wherein removing glycosidic linkages is effected in the presence of a catalyst selected from yeast, aluminum-nickel alloy, cobalt, B 2 H 6 , zinc, copper, or a combination thereof.

20. The method of claim 16 , wherein removing glycosidic linkages comprises exposing a mixture of the carbonaceous material, a chemical, and optionally a catalyst to a temperature in a range of from about 45° C. to about 1050° C., in air or inert atmosphere to aid formation of the intermediate fused carbon material, wherein the intermediate fused carbon material comprises a fused carbon network with a sheet-like morphology.

21. The method of claim 16 , wherein the thermochemically activating comprising heating to a temperature in a range of from about 500 to about 1500° C., in an inert gas containing hydrogen gas.

22. The method of claim 21 , wherein the thermochemically activating further comprises treating the intermediate fused carbon product with a chemical selected from hydrazine, LiAlH 4 , B 2 H 6 , and/or NaBH 4 , or a combination thereof.

23. The method of claim 16 , wherein thermochemically activating comprises direct heating of the intermediate fused carbon material to exfoliate and remove water from the intermediate fused carbon material to form the BRG.

24. The method of claim 1 , wherein the thickening time can be increased by at least 50 percent relative to the same cement absent the set retarder.

25. A method comprising:
increasing a thickening time of a cement slurry produced by combining a mix water with a cementitious material by combining a set retarder consisting of graphene with the mix water, wherein the graphene comprises a bioderived renewable graphene (BRG); wherein the cement slurry having the increased thickening time comprises from greater than 3 to about 20 percent BRG by weight of cementitious material (% BRG bwoc);
placing the cement slurry having the increased thickening time in a workspace; and
allowing the cement slurry having the increased thickening time to set to form the hardened cement,
wherein the cement slurry having the increased thickening time has an increased thickening time at 70 Beardon Consistency Units (Bc), as measured according to API 10B-2, relative to the cement slurry absent the graphene.

26. The method of claim 25 , wherein the hardened cement has a tensile strength, a Young's modulus, a Poisson's ratio, or a combination thereof that is at least as high as a tensile strength, a Young's modulus, a Poisson's ratio, or a combination thereof of a hardened cement produced from a same cement slurry absent the BRG and optionally comprising a different set retarder.

27. The method of claim 25 , wherein the workspace comprises an oilwell workspace.

28. The method of claim 25 , wherein the workspace comprises a non-oilwell workspace.

29. The method of claim 25 , wherein the cementitious material comprises a cement selected from the group consisting of Type I, IA, II, IIA, III, IIIA, IV, V, VI, VII Portland cements, and combinations thereof.

30. The method of claim 25 , wherein the cementitious material comprises an API grade cement.

31. The method of claim 25 , wherein the BRG comprises a graphene with a fused sheet-like morphology.

32. The method of claim 25 , wherein the BRG comprises graphene derived from a plant.

33. The method of claim 32 , wherein the plant comprises cassava.

34. The method of claim 25 , wherein the cement slurry comprises from about 4 to about 20 percent BRG by weight of cementitious material (% BRG bwoc).

Assignees

• Halliburton Energy Services Inc

Inventors

• Pisklak Thomas Jason
• Lewis Samuel J
• Pineda Claudia

Classifications

• C04B28/02

  containing hydraulic cements other than calcium sulfates · CPC title

• C04B2103/0028

  according to API · CPC title

• C04B2103/22

  Set retarders · CPC title

• C09K8/467 Primary

  containing additives for specific purposes · CPC title

• C04B14/024 Primary

  Graphite · CPC title