USE OF A COMPOSITION FOR STABILIZING A GEOLOGICAL FORMATION IN OIL FIELDS, GAS FIELDS, WATER PUMPING FIELDS, MINING OR TUNNEL CONSTRUCTIONS

Abstract

The present invention relates to the use of a composition for stabilizing a geological formation in oil fields, gas fields, water pumping fields, mining or tunnel constructions. The composition has a hardening temperature in the range from about 40 C. to about 120 C. and can therefore be used to stabilize a geological formation in oil fields, gas fields, water pumping fields as well as in mining or tunnel constructions.

Claims

1.-22. (canceled)

23. A composition comprising (a) a polyisocyanate, (b) a mixture obtained by mixing a salt selected from an alkali metal halide, cyanide, nitrate, sulfate, hydrogen sulfate, sulfite, hydrogen sulfite, carbonate, hydrogen carbonate, phosphate, hydrogen phosphate, dihydrogen phosphate, carboxylate, sulfonate, or amidosulfonate or from an alkaline earth metal halide, hydrogen sulfate, or nitrate, with a compound obtained by reacting a polyisocyanate (a1) with a compound having one or more hydroxy groups and (c) an epoxy group containing compound; wherein the composition is a composition for stabilizing a geological formation in oil fields, gas fields, water pumping fields, mining or tunnel constructions.

24. The composition according to claim 23 wherein the composition is a composition for stabilizing an oil well, a gas well or a water well.

25. The composition according to claim 23 in drilling muds, wherein the composition is a composition for enhancing oil recovery, for avoiding or reducing loss circulation, for soil stabilization, as a dust suppressant or as a water retainer.

26. The composition according to claim 23, wherein the amount of the components (b) and (c) together is 0.1 to 3 wt.-%, based on the total weight of components (a) to (c) of the composition.

27. The composition according to claim 23, wherein the amount of the components (b) and (c) together is 0.1 to 15 wt.-%, based on the total weight of components (a) to (c) of the composition.

28. The composition according to claim 23, wherein the composition additionally comprises a compound (d) selected from the group consisting of monools, polyols, alkoxylated monools and alkoxylated polyols, wherein compound (d) is different from the compound having one or more hydroxy groups used in step (b).

29. The composition according to claim 23, wherein polyisocyanate (a1) is reacted with the compound having one hydroxy group.

30. The composition according to claim 23, wherein the compound having one or more hydroxy groups is used in a stoichiometric amount or in a stoichiometric excess.

31. The composition according to claim 23, wherein the composition is essentially free of polyols.

32. The composition according to claim 23, wherein polyisocyanate (a1) is selected from the group consisting of diphenyl methane diisocyanate, polymeric diphenyl methane diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, tetramethylxylylene diisocyanate, methylcyclohexane diisocyanate, isomers, homologs, prepolymers and mixtures thereof.

33. The composition according to claim 23, wherein polyisocyanate (a) and polyisocyanate (a1) are the same.

34. The composition according to claim 23, wherein compound (c) contains one or more epoxy groups per molecule.

35. The composition according to claim 23, wherein the salt is an alkali metal halide.

36. The composition according to claim 23, wherein the equivalent ratio of epoxy groups to isocyanate groups in the composition is from 0.1 to 2.0.

37. The composition according to claim 23, wherein the composition additionally comprises one or more additives, selected from the group consisting of chain extenders, cross linkers, fillers, additives for water adsorption, weighting agents and flame retardants.

38. The composition according to claim 37, wherein the weighting agent is barium sulfate.

39. The composition according to claim 23, wherein the composition is in the form of a kit-of-parts, wherein component (a) is contained in a first part and components (b) and (c) together are contained in a second part or each of the components (a), (b) and (c) is contained in a separate part.

40. A method for stabilizing a geological formation in oil fields, gas fields, water pumping fields, mining or tunnel constructions, which comprises providing a composition as defined in claim 23, introducing the composition into the formation and allowing the composition to cure.

41. The method according to claim 40, wherein the composition has a hardening temperature of 40 to 150 C.

42. The method according to claim 41, wherein the composition is introduced into the formation by pumping or injecting.

43. A composition comprising (a) a polyisocyanate, (b) a mixture obtained by mixing a salt selected from an alkali metal halide, cyanide, nitrate, sulfate, hydrogen sulfate, sulfite, hydrogen sulfite, carbonate, hydrogen carbonate, phosphate, hydrogen phosphate, dihydrogen phosphate, carboxylate, sulfonate, or amidosulfonate or from an alkaline earth metal halide, hydrogen sulfate, or nitrate, with a compound obtained by reacting 50 to 150 mol-%, of polyisocyanate (a1) with an alcohol having one hydroxy group, and (c) an epoxy group containing compound, wherein the mixture is essentially free of polyols.

44. The composition according to claim 41 further comprising a weighting agent, preferably BaSO.sub.4.

45. The composition according to claim 23, wherein the amount of the components (b) and (c) together is 1 to 2 wt.-%, based on the total weight of components (a) to (c) of the composition.

46. The composition according to claim 23, wherein the amount of the components (b) and (c) together is 5 to 13 wt.-%, based on the total weight of components (a) to (c) of the composition.

Description

[0127] The present invention will be further illustrated by the following figures and examples.

[0128] FIG. 1A) shows a diagram, wherein the compressive force applied to the material obtained in Example 27 and the resulting deformation are correlated.

[0129] FIG. 1B) shows a diagram, wherein the compressive force applied to the material obtained in Example 28 and the resulting deformation are correlated.

[0130] FIG. 2A) shows a diagram, wherein the bending force applied to the material obtained in Example 27 and the resulting deformation are correlated.

[0131] FIG. 2B) shows a diagram, wherein the bending force applied to the material obtained in Example 28 and the resulting deformation are correlated.

EXAMPLES

Starting Materials:

[0132] Polyol 1 Castor oil [0133] Polyol 2 Glycerol-started polypropylene oxide, OH-functionality=3, OHZ=400 mg KOH/g [0134] Polyol 3 Polyester, based on adipic acid, OH-functionality=2, OHZ=56 mg KOH/g [0135] GDE 1 Trimethylolpropane triglycidyl ether [0136] GDE 2 Bisphenol A based diglycidylether, e.g. Araldite GY 250 of Huntsman [0137] ZM1 triisopropylorthoformate [0138] ZM 2 Reaction product of ethanol and Iso 1 [0139] ZM3 Reaction product of Iso 1 and a monofunctional polyethylene oxide having a number average molecular weight of 500 g/mol, available as Pluriol A 500 E by BASF [0140] Kat 1 Mixture of LiCl and ZM3, 0.50 eq. LiCl with respect to the number of urethane groups in ZM 3 [0141] Kat 2 Mixture of LiBr and ZM 2, 0.65 eq. LiBr with respect to the number of urethane groups in ZM2 [0142] Kat 3 Mixture of MgCl.sub.2 and ZM 2, 0.65 eq. MgCl.sub.2 with respect to the number of urethane groups in ZM2 [0143] Kat 4 Saturated LiCl solution in ethanol, concentration=0.67 mol/L, mathematically determined according to Knovel Critical Tables (2nd Edition) [0144] Iso 1 Carbodiimide-modified 4,4-Diphenylmethandiisocyanat (MDI), e.g. Lupranat MM 103 by BASF, NCO-content 29.5% [0145] Iso 2 Diphenylmethane diisocyanate (MDI) with higher homologues thereof, e.g. Lupranat M20 by BASF, NCO-content 31.5% [0146] Iso 3 prepolymer, obtainable by conversion of diphenylmethane diisocyante, higher homologues of diphenylmethane diisocyanate and a polyetherol, NCO-functionality 2.4, NCO-content 28.5% (Lupranat MP 105 by BASF)

[0147] Preparation of ZM 2 and 3: A glass flask was charged with the monool and the isocyanate was added under vigorous stirring. The mixture was heated to 70 C., until the reaction started. In the case the reaction started without heating, the mixture was cooled with ice/water mixture. In the case of a rather slow reaction, temperature was further increased to 90 C. and stirred for additional 30 min. After completion of the reaction, the reaction mixture was cooled to room temperature. During the whole procedure temperature was monitored by a temperature sensor. Depending on the molecular weight of the monool, the product was obtained as a solid or viscous oil.

[0148] Preparation of Kat 1-3: ZM 2 or 3 was admixed to a suitable amount of LiCl dissolved in ethanol and heated to 70 C. and stirred for 30 min at this temperature. Then the reaction mixture was cooled and excess ethanol was removed at reduced pressure. Depending on the molecular weight of the ZM, the product was obtained as a solid or viscous oil.

[0149] According to Table 1 the components 1 and 2 were in a speed mixer at 1950 rpm for 1 min at room temperature in the depicted weight ratios. Then the complete mixture with an index of 700 was mixed, using component 1 and 2. Mixing was carried out with a speed mixer at 1950 rpm for 1 min. Gelling time was determined by a Shyodu Gel timer, Type 100, Version 2012 at 25 C. and at 130 C.

TABLE-US-00001 TABLE 1 Component 1 Component 2 Open time Polyol 1 GDE 1 Kat 1 Iso 1 Iso 1 Kat 1 GDE 1 Index RT 130 C. 16.31 3.84 79.45 0.4 700 Several hours <10 min 16.31 79.45 0.4 3.84 700 Several hours <10 min 16.31 79.45 0.4 3.84 700 Several hours <10 min 16.31 3.84 79.45 0.4 700 Several hours <10 min 16.31 0.4 79.45 3.84 700 Several hours <10 min 16.31 79.45 0.4 3.84 700 Several hours <10 min 16.31 0.4 79.45 3.84 700 Several hours <10 min 16.31 79.45 0.4 3.84 700 Several hours <10 min 16.31 3.84 0.4 79.45 700 Several hours <10 min 16.31 0.4 79.45 3.84 700 Several hours <10 min 16.31 3.84 0.4 79.45 700 Several hours <10 min 16.31 0.4 79.45 3.84 700 Several hours <10 min 16.31 3.84 0.4 79.45 700 Several hours <10 min 16.31 3.84 79.45 0.4 700 Several hours <10 min 16.31 3.84 0.4 79.45 700 Several hours <10 min

[0150] Table 1 shows that the order of admixing the specific compounds does not have an effect on the latent reaction.

[0151] According to Table 2 the depicted compounds were mixed in a speed mixer at 1950 rpm for 1 min at room temperature in the stated weight ratios. Then gelling time was determined by a

[0152] Shyodu Gel timer, Type 100, Version 2012. Unless otherwise stated it is referred to percent by weight values.

TABLE-US-00002 TABLE 2 Compara- Compara- Compara- Compara- Example Example Example tive 1 tive 2 tive 3 tive 4 1 2 3 Polyol 1 77.0 77.0 77.0 100.0 77.0 77.0 77.0 Polyol 2 Polyol 3 GDE 1 20.0 20.0 20.0 20.0 20.0 20.0 GDE 2 ZM1 3.0 3.0 3.0 3.0 3.0 3.0 A component 100.0 100.0 100.0 100.0 100.0 100.0 100.0 ZM 2 5.0 Kat 1 0.5 0.5 0.5 0.5 Kat 2 Kat 3 Kat 4 2.3 Iso 1 95.0 97.7 99.5 99.5 99.5 99.5 Iso 2 Iso 3 100.0 B component 100.0 100.0 100.0 100.0 100.0 100.0 100.0 Index 420 410 420 500 100 500 1700 Mixing ratio 100:245 100:243 100:242 100:515 100:57 100:283 100:962 Open time (RT) 1) 1) 1 min 1) Several >1 week >1 week hours Open time 1) 1) 1 min 1) 3 min 6 min 10 min (130 C.) Difference in Not meas- Not meas- Not meas- Not meas- Several >1 week >1 week open time (RT urable urable urable urable hours vs 130 C.) 1) Hardly a reaction, viscosity increase over hours Exam- Exam- Exam- Exam- Exam- Exam- Example ple 4 ple 5 ple 6 ple 7 ple 8 ple 9 10 Polyol 1 77.0 77.0 77.0 77.0 Polyol 2 79.0 Polyol 3 77.0 GDE 1 20.0 20.0 20.0 21.0 20.0 100.0 GDE 2 20.0 ZM1 3.0 3.0 3.0 3.0 3.0 A component 100.0 100.0 100.0 100.0 100.0 100.0 100.0 ZM 2 Kat 1 0.5 0.5 0.5 0.5 Kat 2 5.0 Kat 3 5.0 Kat 4 0.5 Iso 1 95.0 95.0 99.5 99.5 99.5 99.5 Iso 2 Iso 3 99.5 B component 100.0 100.0 100.0 100.0 100.0 100.0 100.0 Index 410 410 410 500 500 700 500 Mixing ratio 100:293 100:307 100:307 100:312 100:265 100:263 100:1102 Open time (RT) 20 min Several Several Several Several Several Several hours hours hours hours hours hours Open time 2 min 10 min 40 min 10 min 10 min 10 min 10 min (130 C.) Difference in 18 min Several Several Several Several Several Several open time (RT hours hours hours hours hours hours vs 130 C.)

[0153] Table 2 shows that without the addition of mixture (b) of the invention no reaction or a retarded reaction at room temperature is observable. Without the addition of Kat 1, 2, 3 or 4, the reaction does not start (Comparative 1 and 2). When LiCl is added, open time is about 1 min for room temperature and 130 C. (Comparative 3), the reaction is not retarded. It is also essential that a sufficient amount of urethane groups is present (Example 4). Examples 1 to 10 show that long open times at room temperature and a quick setting at 130 C. can be achieved for various isocyanate indices, different compounds with isocyanate groups and different alkali or earth alkali salts.

[0154] Table 3a shows mixtures with different indices that were obtained by using mixture (b) of the invention. Table 3b shows additional mixtures, wherein besides the index also additional mixing ratios were varied.

[0155] For that purpose the depicted components were mixed in a speed mixer at 1950 rpm for 1 min at room temperature in the stated weight ratios. Then the mixture was transferred into an aluminum mould (open on top, dimensions 30200.2) and reacted in an oven at 130 C. The characteristic values of Tables 3a and 3b were determined according to the norms as given in Tables 3a and 3b.

TABLE-US-00003 TABLE 3a Example Exam- Example 1 Exam- Exam- Example 11 ple 12 [Tab 1] ple 13 ple 14 2 [Tab 2] Polyol 1 77 77 77 77 77 77 GDE1 20 20 20 20 20 20 ZM1 3 3 3 3 3 3 A compo- 100 100 100 100 100 100 nent Iso 1 99.5 99.5 99.5 99.5 99.5 99.5 Kat 1 0.5 0.5 0.5 0.5 0.5 0.5 B compo- 100 100 100 100 100 100 nent Index 50 90 100 150 250 500 Mixing ratio 100:28 100:51 100:57 100:85 100:142 100:283 hardness DIN 26 A 52 A 67 A 82 A 77 D 87 D 53505 Tensile DIN EN Not 8.6 16.3 26.7 61.7 Not strength ISO 527 measura- measura- [MPa] ble ble Elongation DIN EN Not 104 85 53 9 Not at break ISO 527 measura- measura- [%] ble ble E-modulus DIN EN Not 20 13.9 267 1158 Not [MPa] ISO 527 measura- measura- ble ble Tear re- DIN ISO 2.1 6.6 24.4 51.2 19.2 Not sistance 34-1b measura- [N/mm] B(b) ble

TABLE-US-00004 TABLE 3b Example Example Example Example Example 15 16 17 18 19 Polyol 1 79 79 79 79 79 GDE1 21 21 21 21 21 ZM1 0 0 0 0 0 A component 100 100 100 100 100 Iso 1 95 95 95 95 95 Iso 2 0 0 0 0 0 Kat 1 5 5 5 5 5 B component 100 100 100 100 100 Index 50 90 100 150 250 Mixing ratio 100:34 100:59 100:65 100:98 100:164 hardness DIN 53505 22A 86D/35A 92D/44A 72 D 75 D Tensile strength DIN EN Not meas- 11.2 12.7 39 42 [MPa] ISO 527 urable Elongation at DIN EN Not meas- 80 55 8 3 break [%] ISO 527 urable E-modulus [MPa] DIN EN Not meas- 24.9 34.8 1085.4 1440.5 ISO 527 urable Tear resistance DIN ISO 1.3 26.8 36.6 43.2 18.8 [N/mm] 34-1b B(b) Exam- Exam- Example Exam- Example Example Example ple 20 ple 21 22 ple 23 24 25 26 Polyol 1 77 77 77 77 77 77 77 GDE1 20 20 20 20 20 20 20 ZM1 3 3 3 3 3 3 3 A component 100 100 100 100 100 100 100 Iso 1 0 0 0 0 0 0 0 Iso 2 99.5 99.5 99.5 99.5 99.5 99.5 99.5 Kat 1 0.5 0.5 0.5 0.5 0.5 0.5 0.5 B component 100 100 100 100 100 100 100 Index 260 365 470 575 680 1500 1700 Mixing ratio 100:178 100:248 100:319 100:390 100:461 100:1018 100:1154 hardness 78 D 81 D 82 D 85 D 85 D 85 D 85 D Tensile strength 43.3 56.5 69.9 76.4 80.7 6.7 7.1 [MPa] Elongation at 7 7 5 5 5 0 0 break [%] E-modulus 1535 2027 2664 2997 3139 2417 2619.7 [MPa] Tear resistance Not Not Not Not Not Not Not [N/mm] measur- measur- measura- measur- measur- measura- measura- able able ble able able ble ble

Example 27

[0156] Lupranat MP 102, Lupranat M10R and a mixture (I) of Araldit GY 250 and a composition (II) were mixed at room temperature and heated to 80 C. for 16 h. Said mixture (I) was applied in an amount of 2 wt.-%, Lupranat MP 102 and Lupranat M10R were applied in 49 wt.-% each.

[0157] The ratio of Araldit GY 250 and composition (II) was 2:0.5. Composition (II) was obtained by mixing Lupranat MM103 (200 g), Pluriol A 500 E (800 g) and lithium chloride (17 g).

Reagents:

[0158] Lupranat MP 102: Modified 4,4-diphenyl methane diisocyanate (MDI). The average NCO-functionality is about 2.05.

[0159] Lupranat M10R: Solvent-free product on basis of 4,4-diphenyl methane diisocyanate (MDI) with isomers and oligomers of higher NCO-functionality. The average NCO-functionality is about 2.6. Araldit GY 250: Bisphenol A-epoxy resin.

[0160] Lupranat MM103: Carbodiimide-modified 4,4-diphenyl methane diisocyanate (MDI). The average NCO-functionality is about 2.2.

[0161] Pluriol A 500 E: Methyl-endcapped polyethylene glycol with an average molecular weight of 500 g/mol.

[0162] The initial viscosity before heating was below 200 mPas at 25 C. A pot life of 3 h was observed at 80 C. No curing occurred below 50 C. After 3 h at 80 C. curing started with practically no foaming.

[0163] Example 27 offered a bending strength of 5 MPa and a compressive strength of 51 MPa. A prism of 4416 cm was used for the determination of the bending strength, a 444 cube was used for the determination of the compressive strength. For a graphical illustration of the compressive force experiment see FIG. 1A). For a graphical illustration of the bending force experiment see FIG. 2A)

[0164] The material of Example 27 is therefore suitable for stabilizing geological material in boreholes, where the temperature is about 80 to 100 C.

Example 27a

[0165] During the preparation of Example 27 an additional amount of BaSO.sub.4 (25% based on the total weight of the composition) was added. After heating to 80 C. for 16 h Example 27a provided a bending strength of 26 N/mm.sup.2 and a compressive strength of 89 N/mm.sup.2.

Example 28

[0166] Lupranat MP 102 and a mixture (I) of Araldit GY 250 and a composition (II) were mixed at room temperature and heated to 80 C. for 16 h. Said mixture (I) was applied in an amount of 2 wt.-%, Lupranat MP 102 was applied in 98 wt.-%. The ratio of Araldit GY 250 and composition (II) was 2:0.5. Composition (II) was obtained by mixing Lupranat MM103 (200 g), Pluriol A 500 E (800 g) and lithium chloride (17 g).

[0167] The initial viscosity before heating was below 200 mPas at 25 C. A pot life of more than 3 h was observed at 80 C. No curing occurred below 50 C. Example 28 offered a bending strength of 16 MPa and a compressive strength of 100 MPa. A prism of 4416 cm was used for the determination of the bending strength, a 444 cube was used for the determination of the compressive strength. For a graphical illustration of the compressive force experiment, see FIG. 1B). For a graphical illustration of the bending force experiment, see FIG. 2B).

[0168] The material of Example 28 is therefore suitable for stabilizing geological material in boreholes, where the temperature is about 80 to 100 C.

[0169] Example 28 further provided adhesion values to marble of greater than 3.2 N/mm.sup.2 and to concrete of 5.5 N/mm.sup.2.

Example 28a

[0170] During the preparation of Example 28 an additional amount of BaSO.sub.4 (25% based on the total weight of the composition) was added. After heating to 80 C. for 16 h Example 28a provided a bending strength of 34 N/mm.sup.2 and a compressive strength of 84 N/mm.sup.2.

Example 28b

[0171] During the preparation of Example 28 an additional amount of BaSO.sub.4 (50% based on the total weight of the composition) was added. After heating to 80 C. for 16 h Example 28b provided a bending strength of 19 N/mm.sup.2 and a compressive strength of 34 N/mm.sup.2.

Example 29

[0172] Lupranat MP 102 (87.75 g), Lupranat M10R (87.75 g) and a mixture (I) of Araldit GY 250 (7 g) and a composition (II) (7 g) were mixed at room temperature. Composition (II) was obtained by mixing Lupranat MM103 (200 g), Pluriol A 500 E (800 g) and lithium chloride (17 g). After a short mixing period BaSO.sub.4 (API grade, 164.5 g) was admixed and the material was cured at 80 C. for 16 h.

[0173] The material of Example 3 is suitable for stabilizing geological material in boreholes, where the temperature is about 80 to 100 C.

Comparative Example 1

[0174] Example 27 was repeated using DBU (1,8-diazabicyclo[5.4.0]undec-7-ene) instead of composition (II). With this catalyst no curing at 80 C. could be observed. Rather, the temperature had to be increased to 150 C. to achieve curing. Moreover, curing occurred with undesired foaming.

Comparative Example 2

[0175] Example 27 was repeated using a polyisocyanate composition comprising a polyisocyanate, lithium chloride and an urea compound (Vitrox catalyst of Huntsman Corp., WO 2010/121898) instead of composition (II). With this catalyst slow curing was observed after 300 min. at 80 C. with undesired foaming.