Geopolymer composition and application in oilfield industry

• US 7,794,537 B2
• Filed: 08/07/2006
• Issued: 09/14/2010
• Est. Priority Date: 08/07/2006
• Status: Active Grant

• Current Assignee: Schlumberger Technology Corporation (SLB)
• Original Assignee: Schlumberger Technology Corporation (SLB)
• Inventors: Porcherie, Olivier, Barlet-Gouedard, Veronique, Zusatz-Ayache, Benedicte
• Primary Examiner(s): MARCANTONI, PAUL D
• Application Number:
  US11/462,724
• Publication Number:
  US 20080028994A1
• Time in Patent Office: 1,499 Days
• Field of Search: 106/713, 106/737, 106/600, 106/672, 106/676, 106/677, 106/678, 106/679, 106/716, 106/DIG.1
• US Class Current: 106/672
• CPC Class Codes: C04B 14/047 Zeolites
• CPC Class Codes: C04B 14/10 Clay sepiolite C04B14/042; grog C04B18/025
• CPC Class Codes: C04B 14/22 Glass ; Devitrified glass
• CPC Class Codes: C04B 14/301 porous or hollow
• CPC Class Codes: C04B 14/305 Titanium oxide, e.g. titanates
• CPC Class Codes: C04B 14/365 Gypsum synthetic gypsum C04B18/0445, C04B18/064
• CPC Class Codes: C04B 18/023 Fired or melted materials
• CPC Class Codes: C04B 18/082 Cenospheres
• CPC Class Codes: C04B 18/141 Slags
• CPC Class Codes: C04B 18/146 Silica fume
• CPC Class Codes: C04B 20/002 Hollow or porous granular materials
• CPC Class Codes: C04B 2103/0008 Li
• CPC Class Codes: C04B 2103/10 Accelerators; Activators
• CPC Class Codes: C04B 2103/20 Retarders
• CPC Class Codes: C04B 2103/34 Flow improvers
• 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 2103/50 Defoamers, air detrainers
• CPC Class Codes: C04B 2111/00146 Sprayable or pumpable mixtures
• CPC Class Codes: C04B 2111/00215 Mortar or concrete mixtures defined by their oxide composition
• CPC Class Codes: C04B 22/0013 : Boron compounds
• CPC Class Codes: C04B 22/062 : of the alkali or alkaline-earth metals
• CPC Class Codes: C04B 22/16 : containing phosphorus in the anion, e.g. phosphates
• CPC Class Codes: C04B 24/06 : containing hydroxy groups
• CPC Class Codes: C04B 24/18 : Lignin sulfonic acid or derivatives thereof, e.g. sulfite lye
• CPC Class Codes: C04B 28/006 : containing mineral polymers, e.g. geopolymers of the Davidovits type
• CPC Class Codes: C04B 38/10 : by using foaming agents C04B38/02 takes precedenceor by using mechanical means, e.g. adding preformed foam
• CPC Class Codes: C04B 38/103 : the foaming being obtained by the introduction of a gas other than untreated air, e.g. nitrogen
• CPC Class Codes: C04B 40/0633 : Chemical separation of ingredients, e.g. slowly soluble activator
• CPC Class Codes: C09K 8/467 : containing additives for specific purposes
• CPC Class Codes: Y02P 40/10 : Production of cement, e.g. improving or optimising the production methods; Cement grinding
• CPC Class Codes: Y02W 30/91 : Use of waste materials as fillers for mortars or concrete
• CPC Class Codes: Y10S 106/01 : Fly ash

Abstract

The invention provides geopolymeric compositions, which have controllable thickening and setting times for a wide range of temperatures and a large range of geopolymer slurry densities. The geopolymer slurry compositions have good mixability and pumpability, while the set materials develop good compressive strength and permeability. The invention discloses a method for preparing geopolymer for oilfield cementing applications. The geopolymeric compositions according to the invention comprises a suspension comprising an aluminosilicate source, a metal silicate, an alkali activator, lightweight or heavyweight fillers and a carrier fluid wherein the suspension of said geopolymeric composition is pumped in a well and allowed to set.

Claims

1. A pumpable geopolymeric composition for use in oilfield industry formed from a suspension comprising an aluminosilicate source, a metal silicate, an alkali activator and a carrier fluid wherein the suspension has a viscosity lesser than or equal to 300 cP.

2. The geopolymeric composition of claim 1, further comprising a retarder to control the thickening and/or the setting times of the suspension of said geopolymeric composition.

3. The geopolymeric composition of claim 1, wherein the retarder is selected from the group constituted of boron containing compound, lignosulfate, sodium gluconate, sodium glucoheptonate, tartaric acid and phosphorus containing compound, or a mixture of them.

4. The geopolymeric composition of claim 1, wherein the retarder is efficient from 20°

C. to 120°

C.

5. The geopolymeric composition of claim 1, further comprising an accelerator to control the thickening and/or the setting times of the suspension of said geopolymeric composition.

6. The geopolymeric composition of claim 5, wherein the accelerator is a lithium containing compound.

7. The geopolymeric composition of claim 5, wherein the accelerator is efficient from 20°

C. to 120°

C.

8. The geopolymeric composition of claim 1, further comprising a lightweight particle selected from the group constituted of:

cenospheres, sodium-calcium-borosilicate glass, and silica-alumina microspheres.

9. The geopolymeric composition of claim 1, further comprising a heavy particle selected from the group constituted of manganese tetroxide, iron oxide, barium sulfate, silica and iron/titanium oxide.

10. The geopolymeric composition of claim 1, further comprising a gas phase.

11. The geopolymeric composition of claim 10, wherein the gas phase is introduced by foaming the suspension of said geopolymeric composition with air, nitrogen.

12. The geopolymeric composition of claim 10, further comprising a gas generating additive and wherein the gas phase is introduced by the use of said gas generating additive.

13. The geopolymeric composition of claim 1, further comprising a water-immiscible phase.

14. The geopolymeric composition of claim 13, wherein the water-immiscible phase is an oil-based phase.

15. The geopolymeric composition of claim 1, wherein the density of the suspension of said geopolymeric composition varies between 1 gram per cubic centimeter and 2.5 grams per cubic centimeter.

16. The geopolymeric composition of claim 1, further comprising an additive selected from the group constituted of:

an activator, an antifoam, a defoamer, silica, a fluid loss control additive, a flow enhancing agent, a dispersant, a rheology modifier, a foaming agent, a surfactant and an anti-settling additive.

17. A pumpable geopolymeric composition formed from a suspension comprising an aluminosilicate source, a metal silicate, an alkali activator, a retarder and/or an accelerator and a carrier fluid wherein the oxide molar ratio M₂O/SiO₂ is greater than 0.20 with M being an alkali metal and wherein said pumpable geopolymeric composition has a viscosity lesser than or equal to 300 cP.

18. The geopolymeric composition of claim 17, wherein the oxide molar ratio M₂O/SiO₂ is greater than or equal to 0.27.

19. The geopolymeric composition of claim 17, wherein the retarder is a boron containing compound and wherein the suspension of said geopolymeric composition has an oxide molar ratio B₂O₃/H₂O of less than 0.03.

20. The geopolymeric composition of claim 19, wherein the oxide molar ratio B₂O₃/H₂O is less than or equal to 0.02.

21. The geopolymeric composition of claim 17, wherein the accelerator is a lithium containing compound and wherein the suspension of said geopolymeric composition has an oxide molar ratio Li₂O/H₂O of less than 0.2.

22. The geopolymeric composition of claim 21, wherein the oxide molar ratio Li₂O/H₂O is less than or equal to 0.1.

23. The geopolymeric composition of claim 17, wherein the silicon to aluminum atomic ratio is between 1.8 and 2.2.

24. The geopolymeric composition of claim 23, wherein the silicon to aluminum atomic ratio is substantially equal to two.

25. The geopolymeric composition of claim 17, wherein the aluminosilicate source is selected from the group constituted of type C fly ash, type F fly ash, ground blast furnace slag, calcined clays, partially calcined clays, aluminium-containing silica fume, natural aluminosilicate, synthetic aluminosilicate glass powder, zeolite, scoria, allophone, bentonite and pumice.

26. The geopolymeric composition of claim 17, wherein the metal is selected from the group constituted of lithium, sodium, potassium, rubidium, and cesium.

27. The geopolymeric composition of claim 17, wherein the alkali activator is an alkali metal hydroxide.

28. The geopolymeric composition of claim 17, wherein the alkali activator and/or the carrier fluid is encapsulated.

29. The geopolymeric composition of claim 17, wherein the metal silicate and/or the carrier fluid is encapsulated.

30. A pumpable geopolymeric composition formed from a suspension within water comprising an aluminosilicate source, a metal silicate, an alkali activator, and a retarder and/or an accelerator wherein the oxide molar ratio M₂O/SiO₂ is greater than 0.20 with M being an alkali metal and wherein said pumpable geopolymeric composition has a viscosity lesser than or equal to 300 cP.

31. The geopolymeric composition of claim 30, wherein the oxide molar ratio M₂O/SiO₂ is greater than or equal to 0.27.

32. The geopolymeric composition of claim 30, wherein the retarder is a boron containing compound and wherein the suspension of said geopolymeric composition has an oxide molar ratio B₂O₃/H₂O of less than 0.03.

33. The geopolymeric composition of claim 32, wherein the oxide molar ratio B₂O₃/H₂O is less than or equal to 0.02.

34. The geopolymeric composition of claim 30, wherein the accelerator is a lithium containing compound and wherein the suspension of said geopolymeric composition has an oxide molar ratio Li₂O/H₂O of less than 0.2.

35. The geopolymeric composition of claim 34, wherein the oxide molar ratio Li₂O/H₂O is less than or equal to 0.1.

36. The geopolymeric composition of claim 30, wherein the silicon to aluminum atomic ratio is between 1.8 and 2.2.

37. The geopolymeric composition of claim 36, wherein the silicon to aluminum atomic ratio is substantially equal to two.

38. The geopolymeric composition of claim 30, wherein the aluminosilicate source is selected from the group constituted of type C fly ash, type F fly ash, ground blast furnace slag, calcined clays, partially calcined clays, aluminium-containing silica fume, natural aluminosilicate, synthetic aluminosilicate glass powder, zeolite, scoria, allophone, bentonite and pumice.

39. The geopolymeric composition of claim 30, wherein the metal is selected from the group constituted of lithium, sodium, potassium, rubidium, and cesium.

40. The geopolymeric composition of claim 30, wherein the alkali activator is an alkali metal hydroxide.

41. The geopolymeric composition of claim 30, wherein the alkali activator and/or the alkali activator within water is encapsulated.

42. The geopolymeric composition of claim 30, wherein the metal silicate and/or the metal silicate within water is encapsulated.

43. A pumpable geopolymeric composition formed from a suspension within water comprising an aluminosilicate source, a metal silicate, an alkali activator, and a retarder and/or an accelerator wherein the geopolymer composition is in majority a poly(sialate-siloxo) geopolymer and wherein the oxide molar ratio M₂O/SiO₂ is greater than 0.20 with M being an alkali metal and wherein said pumpable geopolymeric composition has a viscosity lesser than or equal to 300 cP.

44. The geopolymeric composition of claim 43, wherein the oxide molar ratio M₂O/SiO₂ is greater than or equal to 0.27.

45. The geopolymeric composition of claim 43, wherein the retarder is a boron containing compound.

46. The geopolymeric composition of claim 43, wherein the accelerator is a lithium containing compound.

47. The geopolymeric composition of claim 43, wherein the silicon to aluminum atomic ratio is between 1.8 and 2.2.

48. The geopolymeric composition of claim 47, wherein the silicon to aluminum atomic ratio is substantially equal to two.

49. The geopolymeric composition of claim 43, wherein the aluminosilicate source is selected from the group constituted of type C fly ash, type F fly ash, ground blast furnace slag, calcined clays, partially calcined clays, aluminium-containing silica fume, natural aluminosilicate, synthetic aluminosilicate glass powder, zeolite, scoria, allophone, bentonite and pumice.

50. The geopolymeric composition of claim 43, wherein the metal is selected from the group constituted of lithium, sodium, potassium, rubidium, and cesium.

51. The geopolymeric composition of claim 43, wherein the alkali activator is an alkali metal hydroxide.

52. The geopolymeric composition of claim 43, wherein the alkali activator and/or the alkali activator within water is encapsulated.

53. The geopolymeric composition of claim 43, wherein the metal silicate and/or the metal silicate within water is encapsulated.

54. A method to control the setting time and/or the thickening time of a pumpable geopolymeric composition having a viscosity less than or equal to 300 cP, comprising the step of providing a suspension of said geopolymeric composition within a carrier fluid by adding:

(i) a retarder and/or an accelerator;

(ii) an aluminosilicate source;

(iii) an alkali activator; and

(iv) a metal silicate.

55. The method of claim 54, wherein the method applies for temperature ranges from 20°

C. to 120°

C.

56. The method of claim 54, wherein the alkali activator is selected from the group constituted of:

sodium hydroxide and potassium hydroxide, whether encapsulated or not.

57. The method of claim 54, wherein the retarder is selected from the group constituted of boron containing compound, lignosulfate, sodium gluconate, sodium glucoheptonate, tartaric acid and phosphorus containing compounds, or a mixture of them.

58. The method of claim 54, wherein the accelerator is a lithium containing compound.

59. The method of claim 54, wherein the retarder and/or the accelerator is encapsulated.

60. The method of claim 54, wherein the thickening and/or the setting times are controlled by changing the nature and/or the concentration of the retarder and/or accelerator.

61. The method of claim 54, wherein the thickening and/or the setting times are controlled by changing the pH and/or the concentration of the alkali activator.

62. A method to control the setting time and/or the thickening time of a pumpable geopolymeric composition having a viscosity less than or equal to 300 cP, comprising the step of providing a suspension of said geopolymeric composition within a carrier fluid by adding:

(i) an aluminosilicate source;

(ii) an alkali activator; and

(iii) a metal silicate.

63. The method of claim 62, wherein the thickening and/or the setting times are controlled by changing the pH and/or the concentration of the alkali activator.

64. The method of claim 62, wherein the alkali activator and/or the alkali activator within a carrier fluid is encapsulated.

65. A method to control the density of a pumpable geopolymeric composition having a viscosity less than or equal to 300 cP, comprising the step of providing a suspension of said geopolymeric composition within a carrier fluid by adding:

(i) lightweight particles and/or heavy particles;

(ii) an aluminosilicate source;

(iii) an alkali activator; and

(iv) a metal silicate.

66. The method of claim 65, further comprising the step of adding a retarder and/or an accelerator.

67. The method of claim 65, further comprising the step of foaming the suspension of said geopolymeric composition.

68. The method of claim 65, wherein the density range varies between 1 gram per cubic centimeter and 2.5 grams per cubic centimeter.

69. A method to control the density of a pumpable geopolymeric composition having a viscosity less than or equal to 300 cP, comprising the step of:

(i) providing a suspension of said geopolymeric composition within a carrier fluid by mixing an aluminosilicate source, a metal silicate, and an alkali activator, and

(ii) foaming the suspension of said geopolymeric composition.

70. The method of claim 69, wherein the density range varies between 1 gram per cubic centimeter and 2.5 grams per cubic centimeter.

71. A method to place a pumpable geopolymeric composition, having a viscosity less than or equal to 300 cP, in a borehole in a formation comprising the step of:

(i) providing a suspension of said geopolymeric composition within a carrier fluid by mixing an aluminosilicate source, a metal silicate and an alkali activator to said suspension,

(ii) pumping the suspension of said geopolymeric composition into the borehole, and

(iii) allowing the suspension of said geopolymeric composition to set and thereby form the geopolymeric composition.

72. The method of claim 71, wherein the step of providing a suspension of said geopolymeric composition further comprises adding a retarder.

73. The method of claim 71, wherein the step of providing a suspension of said geopolymeric composition further comprises adding an accelerator.

74. The method of claim 71, wherein the step of providing a suspension of said geopolymeric composition further comprises adding a retarder and an accelerator.

75. The method of claim 71, further comprising the step of activating in situ the suspension of said geopolymeric composition.

76. The method of claim 71, wherein the step of pumping the suspension of said geopolymeric composition is made with conventional tools of wellbore cementing.

77. The method of claim 71, wherein the method applies to the placement of the geopolymeric composition in an annular space between a casing and the borehole.

78. The method of claim 71, wherein the method applies to the placement of the geopolymeric composition through a hole made in a casing.

79. The method of claim 71, wherein the method applies to the placement of the geopolymeric composition to plug a zone of the borehole.

80. A method to place a pumpable geopolymeric composition, having a viscosity less than or equal to 300 cP, in a borehole in a formation comprising the step of:

(i) providing a suspension of said geopolymeric composition within a carrier fluid by mixing an aluminosilicate source, a retarder, a metal silicate and an alkali activator to said suspension,

(ii) pumping the suspension of said geopolymeric composition into the borehole,

(iii) activating in situ the suspension of said geopolymeric composition by releasing an accelerator within the suspension of said geopolymeric composition, and

(iv) allowing the suspension of said geopolymeric composition to set and thereby form the geopolymeric composition.

81. The method of claim 80, wherein the accelerator and/or the accelerator within the carrier fluid is encapsulated before activating and is de-capsulated for activating.

82. The method of claim 80, wherein the step of pumping the suspension of said geopolymeric composition is made with conventional tools of wellbore cementing.

83. The method of claim 80, wherein the method applies to the placement of the geopolymeric composition in an annular space between a casing and the borehole.

84. The method of claim 80, wherein the method applies to the placement of the geopolymeric composition through a hole made in a casing.

85. The method of claim 80, wherein the method applies to the placement of the geopolymeric composition to plug a zone of the borehole.

86. A method to place a pumpable geopolymeric composition, having a viscosity less than or equal to 300 cP, in a borehole in a formation comprising the step of:

(i) providing a stable suspension of said geopolymeric composition within a carrier fluid by mixing an aluminosilicate source, a retarder, a metal silicate and an alkali activator to said suspension,

(ii) storing during a given time said stable suspension of said geopolymeric composition,

(iii) activating the suspension of said geopolymeric composition by releasing an accelerator within the suspension of said geopolymeric composition,

(iv) pumping the suspension of said geopolymeric composition into the borehole, and

(v) allowing the suspension of said geopolymeric composition to set and thereby form the geopolymeric composition.

87. The method of claim 86, wherein the accelerator and/or the accelerator within the carrier fluid is encapsulated before activating and is de-capsulated for activating.

88. The method of claim 86, wherein the step of pumping the suspension of said geopolymeric composition is made with conventional tools of wellbore cementing.

89. The method of claim 86, wherein the method applies to the placement of the geopolymeric composition in an annular space between a casing and the borehole.

90. The method of claim 86, wherein the method applies to the placement of the geopolymeric composition through a hole made in a casing.

91. The method of claim 86, wherein the method applies to the placement of the geopolymeric composition to plug a zone of the borehole.

92. A method to place a pumpable geopolymeric composition, having a viscosity less than or equal to 300 cP, in a borehole in a formation comprising the step of:

(i) providing a stable suspension of said geopolymeric composition within a carrier fluid by mixing an aluminosilicate source, a retarder, a metal silicate and an alkali activator to said suspension,

(ii) storing during a given time said stable suspension of said geopolymeric composition,

(iii) pumping the suspension of said geopolymeric composition into the borehole,

(iv) activating in situ the suspension of said geopolymeric composition by releasing an accelerator within the suspension of said geopolymeric composition,

(v) allowing the suspension of said geopolymeric composition to set and thereby form the geopolymeric composition.

93. The method of claim 92, wherein the accelerator and/or the accelerator within the carrier fluid is encapsulated before activating and is de-capsulated for activating.

94. The method of claim 92, wherein the step of pumping the suspension of said geopolymeric composition is made with conventional tools of wellbore cementing.

95. The method of claim 92, wherein the method applies to the placement of the geopolymeric composition in an annular space between a casing and the borehole.

96. The method of claim 92, wherein the method applies to the placement of the geopolymeric composition through a hole made in a casing.

97. The method of claim 92, wherein the method applies to the placement of the geopolymeric composition to plug a zone of the borehole.