Cement slurries, cured cement and methods of making and use of these

Patent metadata

Field	Value
Publication number	US-12006261-B2
Application number	US-202117523295-A
Country	US
Kind code	B2
Filing date	Nov 10, 2021
Priority date	Nov 11, 2020
Publication date	Jun 11, 2024
Grant date	Jun 11, 2024

Abstract

Cement slurries, cured cements, and methods of making cured cement and methods of using cement slurries are provided. The cement slurries have, among other attributes, improved expanding capabilities and may be used, for instance, in the oil and gas drilling industry. The cement slurry comprises water, a cement precursor material, and an expanding agent. The expanding agent comprising at least a poly(acrylic acid)-metal oxide nanocomposite, where the metal oxide comprises MgO, CaO, or both, and the poly(acrylic acid) comprises a t-butyl terminal group, an isobornyl terminal group, or both.

First claim

What is claimed is:

1. A cement slurry comprising:
water;
a cement precursor material; and
an expanding agent comprising at least a poly(acrylic acid) block copolymer-metal oxide nanocomposite, where the metal oxide comprises MgO, CaO, or both, and the poly(acrylic acid) block copolymer comprises a t-butyl terminal group, an isobornyl terminal group, or both.

2. The cement slurry of claim 1 , further comprising from 15 to 100 mol. % acid catalyst relative to combined moles of the t-butyl terminal group and the isobornyl terminal group.

3. The cement slurry of claim 2 , in which the acid catalyst comprises sulfonic acid, para-toluene sulfonic acid, hydrochloric acid, trifluoroacetic acid, aqueous phosphoric acid, molecular iodine, zinc bromide, or combinations thereof.

4. The cement slurry of claim 1 , in which the expanding agent has a structure of:

where XO is MgO, CaO, or both; a ranges from 1 to 100; and b ranges from 1 to 100.

5. The cement slurry of claim 1 , in which the expanding agent has a structure of:

where XO is MgO, CaO, or both; a ranges from 1 to 100; and b ranges from 1 to 100.

6. The cement slurry of claim 1 , in which:
the cement precursor material comprises calcium hydroxide, silicates, belite (Ca 2 SiO 5 ), alite (Ca 3 SiO 4 ), tricalcium aluminate (Ca 3 Al 2 O 6 ), tetracalcium aluminoferrite (Ca 4 Al 2 Fe 2 O 10 ), brownmillerite (4CaO·Al 2 O 3 ·Fe 2 O 3 ), gypsum (CaSO 4 ·2H 2 O), Portland cement precursor, siliceous fly ash, calcareous fly ash, slag cement, or combinations of these;
the cement slurry optionally comprises sodium oxide, potassium oxide, limestone, lime (calcium oxide), hexavalent chromium, trivalent chromium, calcium aluminate, quartz, silica fume, or combinations of these; and
the cement slurry contains from 0.1 to 10 wt. % BWOC of one or more additives selected from the group consisting of accelerators, retarders, extenders, suspending agents, weighting agents, fluid loss control agents, lost circulation control agents, surfactants, antifoaming agents, or combinations of these.

7. A method of cementing a casing in a wellbore, the method comprising:
pumping a cement slurry into an annulus between the casing and the wellbore, where the cement slurry comprises:
water; a cement precursor material; and an expanding agent comprising at least a poly(acrylic acid) block copolymer-metal oxide nanocomposite, where the metal oxide comprises MgO, CaO, or both, and the poly(acrylic acid) block copolymer comprises a t-butyl terminal group, an isobornyl terminal group, or both; and

curing the cement slurry to cement the casing in the wellbore.

8. The method of claim 7 , in which the cement slurry further comprises from 15 to 100 mol. % acid catalyst relative to combined moles of the t-butyl terminal group and the isobornyl terminal group.

9. The method of claim 8 , further comprising:
allowing the poly(acrylic acid) block copolymer to deprotect when in contact with the acid catalyst at a temperature of greater than 100° C. after pumping the cement slurry into the annulus, thereby removing the t-butyl terminal group, an isobornyl terminal group, or both, and thereby forming a hydrophilic homopolymer of poly(acrylic acid);
allowing the hydrophilic homopolymer of poly(acrylic acid) to degrade when in contact with water at a temperature of greater than 100° C. after curing the cement slurry; and
allowing the metal oxide to contact water after allowing the hydrophilic homopolymer poly(acrylic acid) to degrade after curing the cement slurry, thereby expanding the metal oxide, in which the metal oxide expands after contact with water by forming a Mg(OH) 2 crystal, a Ca(OH) 2 crystal, or both.

10. The method of claim 8 , in which:
the acid catalyst comprises sulfonic acid, para-toluene sulfonic acid, hydrochloric acid, trifluoroacetic acid, aqueous phosphoric acid, molecular iodine, zinc bromide, or combinations thereof; and
the sulfonic acid comprises para-toluenesulfonic acid.

11. The method of claim 7 , in which the expanding agent has a structure of:

where XO is MgO, CaO, or both; a ranges from 1 to 100; and b ranges from 1 to 100.

12. The method of claim 7 , in which the expanding agent has a structure of:

where XO is MgO, CaO, or both; a ranges from 1 to 100; and b ranges from 1 to 100.

13. The method of claim 7 , in which:
the cement precursor material comprises calcium hydroxide, silicates, belite (Ca 2 SiO 5 ), alite (Ca 3 SiO 4 ), tricalcium aluminate (Ca 3 Al 2 O 6 ), tetracalcium aluminoferrite (Ca 4 Al 2 Fe 2 O 10 ), brownmillerite (4CaO·Al 2 O 3 ·Fe 2 O 3 ), gypsum (CaSO 4 ·2H 2 O), Portland cement precursor, siliceous fly ash, calcareous fly ash, slag cement, or combinations of these;
the cement slurry optionally comprises sodium oxide, potassium oxide, limestone, lime (calcium oxide), hexavalent chromium, trivalent chromium, calcium aluminate, quartz, silica fume, or combinations of these; and
the cement slurry contains from 0.1 to 10 wt. % BWOC of one or more additives selected from the group consisting of accelerators, retarders, extenders, suspending agents, weighting agents, fluid loss control agents, lost circulation control agents, surfactants, antifoaming agents, or combinations of these.

Assignees

• Saudi Arabian Oil Co

Inventors

• Musso Simone
• Shanmugam Sivaprakash

Classifications

• C09K8/473

  Density reducing additives, e.g. for obtaining foamed cement compositions · CPC title

• C08L51/10

  grafted on to inorganic materials · CPC title

• C08F220/06

  Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof · CPC title

• C04B2103/0061

  Block (co-)polymers · CPC title

• C04B2103/0059

  Graft (co-)polymers · CPC title