MEADE MARK (US)
FISCHER NATHAN (US)
NENJERAMA YEUKAYI (US)
TERCERO RANDY (US)
PARTON CHRISTOPHER (US)
MCDONALD VERONICA RICHTER (US)
PERNITES RODERICK (US)
LAFITTE VALERIE GISELE HELENE (US)
SCHLUMBERGER CA LTD (CA)
SERVICES PETROLIERS SCHLUMBERGER (FR)
SCHLUMBERGER TECHNOLOGY BV (NL)
WO2018210418A1 | 2018-11-22 | |||
WO2020092754A1 | 2020-05-07 |
US20120260829A1 | 2012-10-18 | |||
US20080028994A1 | 2008-02-07 | |||
US20120260594A1 | 2012-10-18 |
CLAIMS We claim: 1. A method of cementing a subterranean well, comprising: mixing a dry geopolymer precursor, comprising an aluminosilicate source and an activator, with a non-activating water material to form a geopolymer slurry; pumping the geopolymer slurry into a subterranean well; and hardening the geopolymer slurry into a solid geopolymer within the subterranean well. 2. The method of claim 1, wherein the activator is a solid alkali metal silicate M2xSiyO2y+x, wherein x is 1, 2, or 3 and y is 1 or 2, and where M is Li, Na, K, Rb, Cs or a combination of thereof. 3. The method of claim 1, wherein the activator comprises a mixture of an alkaline earth metal hydroxide, an alkaline earth metal oxide, an alkaline metal peroxide, or a combination thereof, with an alkali metal salt selected from the group consisting of M2CO3, M2SO4, M2SO3, M3PO4, M2C2O4, M2xSiyO2y+x where x is 1, 2, or 3 and y is 1 or 2, MF, M2SiF6, MIO3, M2MoO4, where M is Li, Na, K, Rb, or Cs, or a combination thereof. 4. The method of claim 3, wherein the activator further comprises Portland cement, cement kiln dust, cement by-pass dust or a combination thereof. 5. The method of claim 1, wherein the aluminosilicate source is fly ash, volcanic ash, ground blast furnace slag, calcined or partially calcined clay, aluminum- containing silica fume, natural aluminosilicate, synthetic aluminosilicate glass powder, zeolite, scoria, allophone, bentonite, red mud, calcined red mud, pumice, or a combination thereof. 6. The method of claim 1, wherein the dry geopolymer precursor further comprises soda-lime glass dust, borosilicate glass dust, microsilica, fumed silica, precipitated silica, nanosilica, silica fume, rice husk ash, or a combination thereof. 7. The method of claim 1, wherein the dry geopolymer precursor further comprises a retarder selected from the group consisting of boric acid, glucoheptonic acid and soluble salts thereof, gluconic acid and soluble salts thereof, tartaric acid and soluble salts thereof, citric acid and soluble salts thereof, phosphoric acid and soluble salts thereof, sodium pentaborate decahydrate, borax, sucrose, lignosulphonates, and combinations thereof. 8. The method of claim 1, wherein the dry geopolymer precursor further comprises a viscosifier selected from the group consisting diutan gum, welan gum, a polyanionic cellulose (PAC), a carboxymethylcellulose (CMC), and combinations thereof. 9. The method of claim 1, wherein the dry geopolymer precursor further comprises one or more accelerators, density modifiers, antifoam agents, viscosifiers, defoamers, silica, fluid-loss control additives, dispersants, expanding agents, anti- settling additives or combinations thereof. 10. The method of claim 1, wherein the non-activating water material is added as an incremental activator solution. 11. The method of claim 10, wherein the activator comprises an alkali metal hydroxide MOH, an alkaline earth metal oxide, hydroxide, or peroxide, or an alkali metal salt selected from the group consisting of M2CO3, M2SO4, M2SO3, M3PO4, M2C2O4, M2xSiyO2y+x where x is 1, 2, or 3 and y is 1 or 2, MF, M2SiF6, MIO3, M2MoO4, where M is Li, Na, K, Rb, or Cs, or a combination thereof. 12. The method of claim 1, further comprising adding a retarder to the water to control a setting time of the geopolymer slurry. 13. A method of cementing, comprising: adding activator-free water to a dry geopolymer precursor composition comprising an aluminosilicate source and an activator to form a geopolymer slurry; pumping the geopolymer slurry to a cementing destination; and hardening the geopolymer slurry into a solid geopolymer at the cementing destination. 14. The method of claim 13, wherein the cementing destination is at an underground or under water location. 15. The method of claim 13, wherein the cementing destination is a subterranean well, a pipeline location, or an electrical installation. 16. The method of claim 13, further comprising adding to the geopolymer slurry one or more materials selected from the group consisting of gluconic acid, glucoheptonic acid, tartaric acid, citric acid, glycolic acid, lactic acid, formic acid, acetic acid, proprionic acid, oxalic acid, malonic acid, succinic acid, adipic acid, malic acid, nicotinic acid, benzoic acid, ethylenediamine tetraacetic acid, and salts thereof. 17. The method of claim 13, wherein the activator is present in a concentration of 2 to 40 parts per hundred based weight of the dry geopolymer precursor. 18. The method of claim 17, further comprising adding to the geopolymer slurry a polysaccharide material. 19. A method of cementing a subterranean well, comprising: mixing a dry geopolymer precursor, comprising an aluminosilicate source and an activator, with a non-activating water material to form a geopolymer slurry; pumping the geopolymer slurry into a subterranean well; and hardening the geopolymer slurry into a solid geopolymer within the subterranean well, wherein the aluminosilicate source is fly ash, volcanic ash, ground blast furnace slag, calcined or partially calcined clay, aluminum-containing silica fume, natural aluminosilicate, synthetic aluminosilicate glass powder, zeolite, scoria, allophone, bentonite, red mud, calcined red mud, pumice, or a combination thereof, and wherein the activator is a solid alkali metal silicate M2xSiyO2y+x where x is 1, 2, or 3 and y is 1 or 2, or a combination of thereof, or the activator is a mixture of an alkaline earth metal hydroxide, an alkaline earth metal oxide, an alkaline earth metal peroxide, or a combination of thereof with an alkali metal salt selected from the group consisting of M2CO3, M2SO4, M2SO3, M3PO4, M2C2O4, M2xSiyO2y+x where x is 1, 2, or 3 and y is 1 or 2, MF, M2SiF6, MIO3, M2MoO4, where M is, Li, Na, K, Rb, or Cs, or a combination thereof. 20. The method of claim 19-, further comprising adding to the dry geopolymer precursor one or more density modifiers from the group consisting of cenospheres, plastic particles, rubber particles, uintaite, vitrified shale, petroleum coke or coal, hematite, barite, ilmenite, silica, crushed granite, manganese tetroxide, or combinations thereof. 21. The method of claim 20, further comprising adding a viscosifier, a retarder agent, an antifoam agent, or a combination thereof to the dry geopolymer precursor, the geopolymer slurry, or both. 22. The method of any of claims 1, 13, and 19, wherein the geopolymer slurry has a thickening time of at least about 2 hours. 23. A method, comprising: mixing a dry geopolymer precursor, comprising an aluminosilicate source that is at least 18% by weight calcium oxide and a hydroxide-free activator, with a non- activating water material to form a geopolymer slurry; disposing the geopolymer slurry at a setting location; and hardening the geopolymer slurry into a solid geopolymer at the setting location. 24. The method of claim 23, wherein the setting location is a subterranean well. 25. The method of claim 23, wherein the hydroxide-free activator is soda ash, sodium metasilicate, or a combination thereof. 26. The method of claim 25, wherein the aluminosilicate source is ground granulated blast furnace slag, ASTM Class C fly ash, or a mixture thereof. 27. The method of claim 23, wherein the hydroxide-free activator is selected from the group consisting of M2CO3, M2SO4, M2SO3, M3PO4, M2C2O4, M2xSiyO2y+x where x is 1, 2, or 3 and y is 1 or 2, MF, M2SiF6, MIO3, M2MoO4, where M is Li, Na, K, Rb, or Cs, or a combination thereof 28. The method of claim 23, further comprising adding to the geopolymer precursor a retarder, an accelerator, an antifoam agent, a defoamer, silica, a fluid- loss control additive, a viscosifier, a dispersant, an expanding agent, an anti-settling additive, a density modifier, or a combination thereof. 29. The method of claim 23, wherein the hydroxide-free activator is present in the dry geopolymer precursor at a concentration of 4 to 40 parts per hundred based on the weight of the dry geopolymer precursor. 30. The method of claim 23, further comprising adding to the dry geopolymer precursor one or more density modifiers from the group consisting of cenospheres, plastic particles, rubber particles, uintaite, vitrified shale, petroleum coke or coal, hematite, barite, ilmenite, silica, crushed granite, manganese tetroxide, or combinations thereof 31. A dry geopolymer precursor that reacts with a non-activating water material to form a geopolymer material, the dry geopolymer precursor comprising an aluminosilicate source and a solid activator. 32. The dry geopolymer precursor of claim 31, wherein the dry geopolymer precursor is hydroxide-free. 33. The dry geopolymer precursor of claim 31, further comprising a retarder, an accelerator, an antifoam agent, a defoamer, silica, a fluid-loss control additive, a viscosifier, a dispersant, an expanding agent, an anti-settling additive, a density modifier, or a combination thereof. 34. The dry geopolymer precursor of claim 31, wherein the solid activator is present at a concentration of 4 to 40 parts per hundred based on the weight of the dry geopolymer precursor. 35. The dry geopolymer precursor of claim 31, wherein the solid activator consists of soda ash. 36. The dry geopolymer precursor of claim 31, wherein the aluminosilicate source is ground granulated blast furnace slag, ASTM Class C fly ash, or a mixture thereof. 37. The dry geopolymer precursor of claim 31, wherein the solid activator is soda ash, sodium metasilicate, or a combination thereof. 38. The dry geopolymer precursor of claim 31, wherein the aluminosilicate source is GGBS and the solid activator is soda ash. 39. The dry geopolymer precursor of claim 38, wherein the soda ash is present in a concentration of 4 to 40 parts per hundred based on the weight of the dry geopolymer precursor. 40. The dry geopolymer precursor of claim 39, further comprising a defoamer, a viscosifier, and a dispersant. 41. A method, comprising: obtaining a dry geopolymer precursor comprising an aluminosilicate source and an activator; mixing the dry geopolymer precursor with a non-activating water material to form a geopolymer slurry; disposing the geopolymer slurry at a setting location; and hardening the geopolymer slurry into a solid geopolymer at the setting location. 42. The method of claim 41, wherein the dry geopolymer precursor is hydroxide- free. 43. The method of claim 41, wherein the aluminosilicate source is GGBS and the activator is soda ash, and the dry geopolymer precursor further comprises a defoamer, a viscosifier, and a dispersant. 44. The method of claim 41, wherein the activator is selected from the group consisting of M2CO3, M2SO4, M2SO3, M3PO4, M2C2O4, M2xSiyO2y+x where x is 1, 2, or 3 and y is 1 or 2, MF, M2SiF6, MIO3, M2MoO4, where M is Li, Na, K, Rb, or Cs, or a combination thereof. 45. The method of claim 44, wherein the aluminosilicate source is at least 15% by weight calcium oxide. |
[0037] Table 3 shows preparation of Examples A4-A8. These examples were prepared by blending fly ash, soda ash, glass bubbles, retarder, viscosifier, hydrated lime, silicate (e.g. sodium silicate or sodium metasilicate), soda-lime glass dust, and/or cement by-pass dust to form different dry mixtures, and then adding water containing anti-foam to the dry mixtures. The anti-foam is the only component added to the water prior to mixing the slurry. Table 3 The compositions shown in Table 3 can be prepared by mixing the dry ingredients together, and then adding water to complete the composition. While the anti-foam was added to Examples A4-A8 by adding the anti-foam to the water prior to mixing, the anti-foam can also be added to the dry mixture as a dry ingredient. The mixed dry ingredients can be stored, shipped, and otherwise handled in dry form, and then water can be added at the time the composition is to be deployed to make a geopolymer precursor slurry. The slurry is pumpable for deployment in a hydrocarbon well. In some cases, a geopolymer slurry is pumpable where the slurry has a slurry consistency lower than about 70 Bc as measured by a high-temperature, high- pressure consistometer, a yield value (Ty) lower than about 50 lbj/100ft 2 , or both. [0038] Rheology of examples A4-A8 was measured after conditioning the mixtures at 48.9˚C (BHCT; 120˚F) according to API procedure RP 10B-2. Thickening time and ultrasonic cement analyzer (“UCA”) measurements were performed at 48.9˚C (120˚F) and 3000 psi, and compressive strength was measured utilizing non- destructive UCA methodology according to API procedure RP 10B-2. The results are summarized in Table 4. Table 4 [0039] The examples above show that one-sack geopolymer precursor compositions can be made using solid activator materials that are safe to store, transport, and mix with water. The precursor compositions can be prepared at a well site to suitable density and rheology for pumping into a subterranean well such as a hydrocarbon well. The compositions then set in a suitable time period for use in cementing subterranean wells. Additionally, mixing water with these geopolymer precursor compositions generates only modest heat that will not adversely affect pumpability of the slurry by accelerating setting. [0040] In some cases, a dry geopolymer precursor can have an aluminosilicate source and one or more activators that are hydroxide-free. The metal silicates mentioned above can be used as activators alone, without any other alkaline materials. Other materials that can be used as activators alone, without any other alkaline materials, include metal carbonates M 2 CO 3 , where M is Li, Na, K, Rb, or Cs. Soda ash and sodium metasilicate are materials that can be used to activate geopolymer slurries without adding hydroxide to the mixture. In some cases, a single hydroxide-free material, as described above, can be used to activate a geopolymer slurry. For example, soda ash can be used as a single hydroxide-free activator for a geopolymer slurry comprising GGBS. Although not wishing to be limited by theory, it is believed that the dry, hydroxide-free activators used herein in some cases, react in water to form hydroxide species that can polymerize the geopolymer slurry. [0041] Fig. 1 is a graph 100 showing compression strength of various geopolymers made using GGBS and ASTM Class C fly ash as aluminosilicate sources and soda ash as the only activator. These geopolymers were each made using 0.04% by weight of diutan gum viscosifier, based on the weight of the aluminosilicate source, and 0.15% by weight of polynaphthalene sulfonate dispersant, based on the weight of the aluminosilicate source. The dry ingredients, including aluminosilicate source and dry activator, were blended, and the slurries were made by adding activator-free water and mixing. At 102, an axis of the graph 100 shows quantity of calcium oxide in the aluminosilicate source, with axis markings at 106. At 104, a second axis of the graph 100 shows compression strength in pounds per square inch. The data points showing results for ASTM Class C fly ash as the aluminosilicate source are grouped at 110 and the data points showing results for GGBS as the aluminosilicate source are grouped at 112. The fly ash used to make the geopolymers represented by the grouping 110 of data points contained 30.08 % calcium oxide, and 59.59% calcium oxide plus silica, by weight. The GGBS used to make the geopolymers represented by the grouping 112 of data points contained 39.93 % calcium oxide, and 72.23% calcium oxide plus silica, by weight. The geopolymers represented by the data points at 110 were made by subjecting a precursor based on ASTM Class C fly ash to curing at 81 °C for 168 hours, and the geopolymers represented by the data points at 112 were made by subjecting a GGBS-based precursor to curing at 81 °C for 24 hours, with two exceptions. The data points labeled 122 are for geopolymers made by subjecting a GGBS-based precursor to curing at 44 °C for 24 hours. [0042] The geopolymers represented by the data points in Fig.1 were made by compiling all the dry ingredients into a hydroxide-free dry mixture and adding water to the dry mixture to make the precursor slurry. For all these precursors, 0.02 gallons per sack of propylene glycol was added as a defoamer. The dry mixtures use different amounts of soda ash activator. The data points 114 represent geopolymers made using 2% by weight soda ash activator, based on the weight of the aluminosilicate source. The data points 116 represent geopolymers made using 4% by weight soda ash activator, based on the weight of the aluminosilicate source. The data points 120 represent geopolymers made using 6% by weight soda ash activator, based on the weight of the aluminosilicate source. The data points 118 represent geopolymers made using 8% by weight soda ash activator, based on the weight of the aluminosilicate source. All the geopolymer precursor slurries that produced the geopolymers of Fig.1 were made to a density of 15.2 pounds per gallon. [0043] The data of Fig.1 shows that soda ash can be used as the sole activator for geopolymer precursors using GGBS and/or ASTM Class C fly ash as aluminosilicate sources. With these two aluminosilicate sources, using sufficient soda ash as a single hydroxide-free activator can result in a geopolymer having suitable compression strength for some applications. As shown in Fig.1, using more activator generally results in a geopolymer having higher compression strength, up to a point. As also shown in Fig.1, GGBS generally develops higher compression strength than ASTM Class C fly ash for a given activator concentration. Generally speaking, the data of Fig.1 shows that using soda ash as a single activator for a dry hydroxide-free geopolymer precursor that reacts with water to form a geopolymer, where the soda ash is present in the dry geopolymer precursor at a concentration of 4% by weight or more, based on the total weight of the aluminosilicate source in the dry hydroxide- free geopolymer precursor, provides a geopolymer having suitable compression strength for some applications. With some aluminosilicate sources having higher calcium oxide content, for example at least 40% by weight of the aluminosilicate source, as little as 2% by weight soda ash, based on the weight of the aluminosilicate source, can provide a geopolymer having suitable compression strength for some applications. [0044] Fig. 2 is a graph 200 showing compression strength of various geopolymers made using the same GGBS and ASTM Class C fly ash materials from Fig.1 as aluminosilicate sources and sodium metasilicate as the only activator. These geopolymers were each made using 0.04% by weight of diutan gum viscosifier, based on the weight of the GGBS, and 0.15% by weight of polynaphthalene sulfonate dispersant, based on the weight of the GGBS. The graph 200 has the same axes 102 and 104 as the graph 100, with the same label group 106, and the same data groupings 110 and 112. The geopolymers represented by the data points in the graph 200 were all cured at 81 °C for 24 hours. [0045] As with Fig.1, the geopolymers represented by the data points in Fig. 2 were made by compiling all the dry ingredients into a hydroxide-free dry mixture and adding activator-free water to the dry mixture to make the precursor slurry. For all these precursors, 0.02 gallons per sack of propylene glycol was added as a defoamer. The dry mixtures use different amounts of ASTM Class C fly ash activator. The data points 202 represent geopolymers made using 7.31% by weight sodium metasilicate activator, based on the weight of the aluminosilicate source. The data points 204 represent geopolymers made using 11% by weight sodium metasilicate activator, based on the weight of the aluminosilicate source. The data points 206 represent geopolymers made using 15% by weight sodium metasilicate activator, based on the weight of the aluminosilicate source. All the geopolymer precursor slurries that formed the geopolymers of Fig.2 were made to a density of 15.2 pounds per gallon. [0046] The data of Fig.2 shows that sodium metasilicate can be used as the sole added activator for geopolymer precursors using GGBS and/or ASTM Class C fly ash as aluminosilicate sources. With these two aluminosilicate sources, using sufficient sodium metasilicate in a dry blend as a single hydroxide-free activator, to mix with activator-free water to form a geopolymer slurry, can result in a geopolymer having suitable compression strength for some applications. As shown in Fig.2, using more activator generally results in a geopolymer having higher compression strength, up to a point. As also shown in Fig.2, in contrast to the result in Fig.1, GGBS and ASTM Class C fly ash generally develop similar compression strength for a given activator concentration. Generally speaking, the data of Fig. 2 shows that using sodium metasilicate as a single activator for a dry hydroxide-free geopolymer precursor that reacts with water to form a geopolymer, where the sodium metasilicate is present in the dry geopolymer precursor at a concentration of 7% by weight or more, based on the total weight of the aluminosilicate source in the dry hydroxide-free geopolymer precursor, provides a geopolymer having suitable compression strength for some applications. [0047] The dry, hydroxide-free geopolymer precursors described above can be mixed with any of the additives described herein prior to adding water, or any of the additives described herein can be added to the geopolymer slurry formed by adding water after the water is added. Upon adding water, a geopolymer slurry is formed that can be deployed at a setting location by any suitable means, for example by pumping in certain embodiments, and allowed to harden into a geopolymer.
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