CA2575212A1 - Cement-free zeolite and fly ash settable fluids and methods therefor - Google Patents

Cement-free zeolite and fly ash settable fluids and methods therefor Download PDF

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Publication number
CA2575212A1
CA2575212A1 CA002575212A CA2575212A CA2575212A1 CA 2575212 A1 CA2575212 A1 CA 2575212A1 CA 002575212 A CA002575212 A CA 002575212A CA 2575212 A CA2575212 A CA 2575212A CA 2575212 A1 CA2575212 A1 CA 2575212A1
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fluid
cement
zeolite
sodium
calcium
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CA002575212A
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French (fr)
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CA2575212C (en
Inventor
Ashok K. Santra
Karen Luke
B. Raghava Reddy
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Halliburton Energy Services Inc
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/02—Well-drilling compositions
    • C09K8/04—Aqueous well-drilling compositions
    • C09K8/14—Clay-containing compositions
    • C09K8/16—Clay-containing compositions characterised by the inorganic compounds other than clay
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/91—Use of waste materials as fillers for mortars or concrete

Abstract

Zeolite and Class F fly ash compositions are provided for use as cement-free settable fluids such as settable spotting fluids and cementitious compositions.

Claims (95)

1. A method of treating a subterranean zone, comprising: introducing a cement-free settable fluid into the zone, the fluid comprising: a zeolite, Class F fly ash, a source of calcium ion, and a carrier fluid; and allowing the fluid to set therein.
2. The method of Claim 1 wherein the cement-free settable fluid further comprises a retarder.
3. The method of Claim 2 wherein the cement-free settable fluid further comprises an activator.
4. The method of Claim 3 further comprising: introducing a subsequent composition into the zone to displace all but a remaining portion of the cement-free settable fluid from the zone prior to allowing the fluid to set therein.
5. The method of Claim 4 wherein the remaining portion of the cement-free settable fluid is in one or more of a filter cake, fissure, fracture, cavern, vug, thief zone, low pressure subterranean zone, and high pressure subterranean zone.
6. The method of Claim 3 wherein the introduction of the cement-free settable fluid at least partially displaces mud from the zone.
7. The method of Claim 3 wherein the activator comprises calcium hydroxide, sodium silicate, sodium fluoride, sodium silicofluoride, magnesium silicofluoride, zinc silicofluoride, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, sodium sulfate, or mixtures thereof.
8. The method of Claim 3 wherein the source of calcium ion is a carbonate, carboxylate, silicate, nitrate, nitrite, phosphate, sulfate, sulfite, or halide salt of calcium, or an oxide or hydroxide of calcium.
9. The method of Claim 3 wherein the source of calcium ion is the activator.
10. The method of Claim 3 wherein the zeolite is represented by the formula:
M a/n[(A1O2),(SiO2)b] = x H2O
where M represents one or more cations selected from the group consisting of Na, K, Mg, Ca, Sr, Li, Ba,NH4, CH3NH3, (CH3)3NH, (CH3)4N, Ga, Ge and P;
n represents the cation valence;

b:a ratio is in a range from greater than or equal to 1 and less than or equal to 5;
and x represents number of moles of water entrained into the zeolite.
11. The method of Claim 3 wherein the zeolite comprises analcime, bikitaite, brewsterite, chabazite, clinoptilolite, faujasite, harmotome, heulandite, laumontite, mesolite, natrolite, paulingite, phillipsite, scolecite, stellerite, stilbite, or thomsonite.
12. The method of Claim 3 wherein the carrier fluid comprises a water-based carrier fluid in an amount of from about 20 to about 200 percent by weight of the zeolite.
13. The method of Claim 3 wherein the carrier fluid comprises fresh water, unsaturated salt solution, brine, seawater, or saturated salt solution.
14. The method of Claim 3 wherein the retarder comprises a lignosulfonate, an organic acid having an a-hydroxy group, a salt of an organic acid having an a-hydroxy group, or a combination thereof.
15. The method of Claim 3 wherein the subterranean zone is treated by removing drilling fluid or spacer fluid from a wellbore within the subterranean zone.
16. The method of Claim 3 wherein the subterranean zone is treated by preparing a wellbore for cementing, and the method further comprises: displacing a fluid with the cement-free settable fluid, running a casing into the wellbore, placing a cement composition behind the casing, and allowing the cement composition to set.
17. The method of Claim 4 wherein an activator is present in the subsequent composition.
18. The method of Claim 17 wherein the activator comprises calcium hydroxide, sodium silicate, sodium fluoride, sodium silicofluoride, magnesium silicofluoride, zinc silicofluoride, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, sodium sulfate, or mixtures thereof.
19. The method of Claim 1 wherein the settable fluid further comprises an activator.
20. The method of Claim 19 wherein the activator comprises calcium hydroxide, sodium silicate, sodium fluoride, sodium silicofluoride, magnesium silicofluoride, calcium chloride, zinc silicofluoride, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, sodium sulfate, or mixtures thereof.
21. The method of Claim 19 wherein the zeolite is represented by the formula:
M a/n[(A1Oz)a(SiO2)b] = x H2O
where M represents one or more cations selected from the group consisting of Na, K, Mg, Ca, Sr, Li, Ba,NH4, CH3NH3, (CH3)3NH, (CH3)4N, Ga, Ge and P;
n represents the cation valence;
b:a ratio is in a range from greater than or equal to 1 and less than or equal to 5;
and x represents number of moles of water entrained into the zeolite.
22. The method of Claim 19 wherein the zeolite comprises analcime, bikitaite, brewsterite, chabazite, clinoptilolite, faujasite, harmotome, heulandite, laumontite, mesolite, natrolite, paulingite, phillipsite, scolecite, stellerite, stilbite, or thomsonite.
23. The method of Claim 19 wherein the zeolite and Class F fly ash form a base mix and the carrier fluid comprises a water-based carrier fluid in an amount of from about 100 to about 200 percent by weight of the base mix.
24. The method of Claim 19 wherein the settable fluid further comprises an accelerator.
25. The method of Claim 24 wherein the fluid is allowed to set at a temperature of less than about 140 °F.
26. The method of Claim 24 wherein the accelerator comprises sodium sulfate, sodium carbonate, calcium sulfate, calcium carbonate, potassium sulfate, or potassium carbonate.
27. The method of Claim 25 wherein the accelerator comprises sodium sulfate.
28. The method of Claim 19 wherein the source of calcium ion is the activator.
29. The method of Claim 19 wherein the source of calcium ion is a carbonate, carboxylate, silicate, nitrate, nitrite, phosphate, sulfate, sulfite, or halide salt of calcium, or an oxide or hydroxide of calcium.
30. The method of Claim 24 wherein the fluid is allowed to set at a temperature of 80 F to 100 °F.
31. The method of Claim 19 wherein the composition has a density of equal to or greater than 12 ppg.
32. The method of Claim 19 wherein the subterranean zone is treated by sealing the subterranean zone penetrated by a wellbore.
33. The method of Claim 1 wherein the cement-free settable fluid is a drilling fluid, spacer fluid, settable spotting fluid, cementitious fluid, completion fluid, stimulation fluid, remedial fluid, well cleanup fluid, workover fluid, gravel pack fluid, acidizing fluid, fracturing fluid, conformance fluid, or a combination thereof.
34. A method of preparing a cement-free settable fluid, comprising: combining a zeolite, Class F fly ash, a source of calcium ion, and a carrier fluid.
35. The method of Claim 34 wherein the cement-free settable fluid further comprises a retarder.
36. The method of Claim 35 wherein the cement-free settable fluid further comprises an activator.
37. The method of Claim 36 wherein the zeolite is represented by the formula:
M a/n[(A1O2)a(SiO2)b] = x H2O
where M represents one or more cations selected from the group consisting of Na, K, Mg, Ca, Sr, Li, Ba,NH4, CH3NH3, (CH3)3NH, (CH3)4N, Ga, Ge and P;
n represents the cation valence;
b:a ratio is in a range from greater than or equal to 1 and less than or equal to 5;
and x represents number of moles of water entrained into the zeolite.
38. The method of Claim 36 wherein the zeolite comprises analcime, bikitaite, brewsterite, chabazite, clinoptilolite, faujasite, harmotome, heulandite, laumontite, mesolite, natrolite, paulingite, phillipsite, scolecite, stellerite, stilbite, or thomsonite.
39. The method of Claim 36 wherein the activator comprises calcium hydroxide, sodium silicate, sodium fluoride, sodium silicofluoride, magnesium silicofluoride, zinc silicofluoride, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, sodium sulfate, or mixtures thereof.
40. The method of Claim 36 wherein the carrier fluid comprises a water-based carrier fluid in an amount of from about 100 to about 200 percent by weight of the zeolite.
41. The method of Claim 36 wherein the retarder comprises a lignosulfonate/tartaric acid solution, an organic acid having an a-hydroxy group, a salt of an organic acid having an a-hydroxy group, or a combination thereof.
42. The method of Claim 36 wherein the source of calcium ion is the activator.
43. The method of Claim 36 wherein the source of calcium ion is a carbonate, carboxylate, silicate, nitrate, nitrite, phosphate, sulfate, sulfite, or halide salt of calcium, or an oxide or hydroxide of calcium.
44. The method of Claim 34 further comprising combining an activator in the settable fluid.
45. The method of Claim 44 wherein the activator comprises calcium hydroxide, sodium silicate, sodium fluoride, sodium silicofluoride, magnesium silicofluoride, zinc silicofluoride, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, sodium sulfate, or mixtures thereof.
46. The method of Claim 44 further comprising allowing the settable fluid to set.
47. The method of Claim 44 wherein the zeolite is represented by the formula:
M a/n[(A1O2)a(SiO2)b] = x H2O
where M represents one or more cations selected from the group consisting of Na, K, Mg, Ca, Sr, Li, Ba,NH4, CH3NH3, (CH3)3NH, (CH3)4N, Ga, Ge and P;
n represents the cation valence;
b:a ratio is in a range from greater than or equal to 1 and less than or equal to 5;
and x represents number of moles of water entrained into the zeolite.
48. The method of Claim 44 wherein the zeolite comprises analcime, bikitaite, brewsterite, chabazite, clinoptilolite, faujasite, harmotome, heulandite, laumontite, mesolite, natrolite, paulingite, phillipsite, scolecite, stellerite, stilbite, or thomsonite.
49. The method of Claim 44 wherein the settable fluid further comprises an accelerator.
50. The method of Claim 49 further comprising allowing the settable fluid to set.
51. The method of Claim 50 wherein the settable fluid is allowed to set at a temperature of less than about 140 °F.
52. The method of Claim 51 wherein the accelerator comprises sodium sulfate, sodium carbonate, calcium sulfate, calcium carbonate, potassium sulfate, or potassium carbonate.
53. The method of Claim 52 wherein the accelerator comprises sodium sulfate.
54. The method of Claim 44 further comprising foaming the composition to form a foamed composition.
55. The method of Claim 44 wherein the carrier fluid comprises a water-based carrier fluid.
56. The method of Claim 44 wherein the source of calcium ion is the activator.
57. The method of Claim 44 wherein the source of calcium ion is a carbonate, carboxylate, silicate, nitrate, nitrite, phosphate, sulfate, sulfite, or halide salt of calcium, or an oxide or hydroxide of calcium.
58. The method of Claim 34 wherein the cement-free settable fluid is a drilling fluid, spacer fluid, settable spotting fluid, cementitious fluid, completion fluid, stimulation fluid, remedial fluid, well cleanup fluid, workover fluid, gravel pack fluid, acidizing fluid, fracturing fluid, conformance fluid, or a combination thereof.
59. A cement-free settable fluid comprising: a zeolite, Class F fly ash, a source of calcium ion, and a carrier fluid.
60. The cement-free settable fluid of Claim 59 further comprising a retarder.
61. The cement-free settable fluid of Claim 60 further comprising an activator.
62. The cement-free settable fluid of Claim 61 wherein the zeolite is represented by the formula:

M a/n[(A1O2)a(SiO2)b] = x H2O
where M represents one or more cations selected from the group consisting of Na, K, Mg, Ca, Sr, Li, Ba,NH4, CH3NH3, (CH3)3NH, (CH3)4N, Ga, Ge and P;
n represents the cation valence;
b:a ratio is in a range from greater than or equal to I and less than or equal to 5;
and x represents number of moles of water entrained into the zeolite.
63. The cement-free settable fluid of Claim 61 wherein the zeolite comprises analcime, bikitaite, brewsterite, chabazite, clinoptilolite, faujasite, harmotome, heulandite, laumontite, mesolite, natrolite, paulingite, phillipsite, scolecite, stellerite, stilbite, or thomsonite.
64. The cement-free settable fluid of Claim 61 wherein the Class F fly ash is present in an amount of from greater than 0% to about 600% by weight of zeolite.
65. The cement-free settable fluid of Claim 61 wherein the Class F fly ash is present in an amount of equal to the amount of zeolite by weight.
66. The cement-free settable fluid of Claim 61 wherein the activator comprises calcium hydroxide, sodium silicate, sodium fluoride, sodium silicofluoride, magnesium silicofluoride, zinc silicofluoride, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, sodium sulfate, or mixtures thereof.
67. The cement-free settable fluid of Claim 61 wherein the activator is present in an amount of from about 5% to about 50% by weight of zeolite.
68. The cement-free settable fluid of Claim 61 wherein the activator is calcium hydroxide.
69. The cement-free settable fluid of Claim 61 wherein the carrier fluid comprises a water-based carrier fluid in an amount of from about 20% to about 200% by weight of the zeolite.
70. The cement-free settable fluid of Claim 61 wherein the carrier fluid comprises a water-based carrier fluid in an amount of from 100% to 125% by weight of the zeolite.
71. The cement-free settable fluid.of Claim 61 wherein the carrier fluid comprises an oil-based carrier fluid in an amount of from about 50% to about 150% by weight of the zeolite.
72. The cement-free settable fluid of Claim 61 wherein the carrier fluid comprises an oil-based carrier fluid in an amount of from about 100% to about 125% by weight of the zeolite.
73. The cement-free settable fluid of Claim 61 wherein the retarder comprises a lignosulfonate, an organic acid having an a-hydroxy group, a salt of an organic acid having an a-hydroxy group, or a combination thereof.
74. The cement-free settable fluid of Claim 61 wherein the retarder is present in an amount of from about 1.0% to about 5.0% by weight of zeolite.
75. The cement-free settable fluid of Claim 61 wherein the source of calcium ion is the activator.
76. The cement-free settable fluid of Claim 61 wherein the source of calcium ion is a carbonate, carboxylate, silicate, nitrate, nitrite, phosphate, sulfate, sulfite, or halide salt of calcium, or an oxide or hydroxide of calcium.
77. The cement-free settable fluid of Claim 61 wherein the zeolite is represented by the formula:
M a/n[(A1O2)a(SiO2)b] = x H2O
where M represents one or more cations selected from the group consisting of Na, K, Mg, Ca, Sr, Li, Ba,NH4, CH3NH3, (CH3)3NH, (CH3)4N, Ga, Ge and P;

n represents the cation valence;
b:a ratio is in a range from greater than or equal to 1 and less than or equal to 5;
and x represents number of moles of water entrained into the zeolite.
78. The cement-free settable fluid of Claim 61 wherein the zeolite comprises analcime, bikitaite, brewsterite, chabazite, clinoptilolite, faujasite, harmotome, heulandite, laumontite, mesolite, natrolite, paulingite, phillipsite, scolecite, stellerite, stilbite, or thomsonite.
79. The cement-free settable fluid of Claim 61 wherein the zeolite and Class F
fly ash form a base mix and the Class F fly ash is present in an amount of from about 30% to about 90% by weight of the base mix.
80. The cement-free settable fluid of Claim 79 wherein the Class F fly ash is present in an amount of from about 70% to about 85% by weight of the base mix.
81. The cement-free settable fluid of Claim 59 further comprising an activator.
82. The cement-free settable fluid of Claim 81 wherein the activator comprises calcium hydroxide, sodium silicate, sodium fluoride, sodium silicofluoride, magnesium silicofluoride, zinc silicofluoride, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, sodium sulfate, or mixtures thereof.
83. The cement-free settable fluid of Claim 81 wherein the activator is calcium hydroxide.
84. The cement-free settable fluid of Claim 81 wherein the zeolite and the Class F fly ash form a base mix and the activator is present in an amount of 10% to 25% by weight of base mix.
85. The cement-free settable fluid of Claim 81 further comprising an accelerator.
86. The cement-free settable fluid of Claim 85 wherein the accelerator comprises sodium sulfate, sodium carbonate, calcium sulfate, calcium carbonate, potassium sulfate, or potassium carbonate.
87. The cement-free settable fluid of Claim 85 wherein the accelerator comprises sodium sulfate.
88. The cement-free settable fluid of Claim 85 wherein the zeolite and Class F
fly ash form a base mix and wherein the accelerator is present in an amount of from about 2.0%
to about 4.0% by weight of the base mix.
89. The cement-free settable fluid of Claim 81 wherein the zeolite and Class F
fly ash form a base mix and the carrier fluid comprises a water-based carrier fluid in an amount of from about 50% to about 150% by weight of the base mix.
90. The cement-free settable fluid of Claim 81 wherein the zeolite and Class F
fly ash form a base mix and the carrier fluid comprises a water-based carrier fluid in an amount of from 100% to 125% by weight of the base mix.
91. The cement-free settable fluid of Claim 81 wherein the zeolite and Class F
fly ash form a base mix and the carrier fluid comprises an oil-based carrier fluid in an amount of from about 50% to about 150% by weight of the base mix.
92. The cement-free settable fluid of Claim 81 wherein the zeolite and Class F
fly ash form a base mix and the carrier fluid comprises an oil-based carrier fluid in an amount of from 100% to 125% by weight of the base mix.
93. The cement-free settable fluid of Claim 81 wherein the source of calcium ion is the activator.
94. The cement-free settable fluid of Claim 81 wherein the source of calcium ion is a carbonate, carboxylate, silicate, nitrate, nitrite, phosphate, sulfate, sulfite, or halide salt of calcium, or an oxide or hydroxide of calcium.
95. The cement-free settable fluid of Claim 59 wherein the cement-free settable fluid is a drilling fluid, spacer fluid, settable spotting fluid, cementitious fluid, completion fluid, stimulation fluid, remedial fluid, well cleanup fluid, workover fluid, gravel pack fluid, acidizing fluid, fracturing fluid, conformance fluid, or a combination thereof.
CA2575212A 2004-07-28 2005-07-01 Cement-free zeolite and fly ash settable fluids and methods therefor Expired - Fee Related CA2575212C (en)

Applications Claiming Priority (3)

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US10/901,507 US7297664B2 (en) 2004-07-28 2004-07-28 Cement-free zeolite and fly ash settable fluids and methods therefor
US10/901,507 2004-07-28
PCT/GB2005/002615 WO2006010879A1 (en) 2004-07-28 2005-07-01 Cement-free zeolite and fly ash settable fluids and methods therefor

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CA2575212C CA2575212C (en) 2012-05-01

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