EP0448646A1 - Utilisation d'huiles-esters selectionnees dans des lavages de sondage, en particulier pour la reconnaissance en mer de gisements de petrole ou de gaz naturel (ii) - Google Patents
Utilisation d'huiles-esters selectionnees dans des lavages de sondage, en particulier pour la reconnaissance en mer de gisements de petrole ou de gaz naturel (ii)Info
- Publication number
- EP0448646A1 EP0448646A1 EP90901766A EP90901766A EP0448646A1 EP 0448646 A1 EP0448646 A1 EP 0448646A1 EP 90901766 A EP90901766 A EP 90901766A EP 90901766 A EP90901766 A EP 90901766A EP 0448646 A1 EP0448646 A1 EP 0448646A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- oil
- esters
- ester
- drilling
- drilling fluids
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000005553 drilling Methods 0.000 title claims abstract description 80
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 239000003345 natural gas Substances 0.000 title claims abstract description 6
- 239000003921 oil Substances 0.000 title claims description 67
- 239000012530 fluid Substances 0.000 title claims description 59
- 239000003209 petroleum derivative Substances 0.000 title description 2
- 150000005690 diesters Chemical class 0.000 title 1
- 150000002148 esters Chemical class 0.000 claims abstract description 46
- 239000012071 phase Substances 0.000 claims abstract description 38
- 150000002763 monocarboxylic acids Chemical class 0.000 claims abstract description 22
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 20
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 17
- 150000001298 alcohols Chemical class 0.000 claims abstract description 16
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 16
- 239000000654 additive Substances 0.000 claims abstract description 15
- 239000008346 aqueous phase Substances 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- 235000019198 oils Nutrition 0.000 claims description 64
- 239000010696 ester oil Substances 0.000 claims description 55
- 239000000203 mixture Substances 0.000 claims description 40
- 150000001735 carboxylic acids Chemical class 0.000 claims description 31
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 24
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 24
- 239000004571 lime Substances 0.000 claims description 24
- 239000003513 alkali Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 10
- 239000004033 plastic Substances 0.000 claims description 9
- 125000001931 aliphatic group Chemical group 0.000 claims description 8
- 241001465754 Metazoa Species 0.000 claims description 6
- 230000009969 flowable effect Effects 0.000 claims description 6
- 150000003626 triacylglycerols Chemical class 0.000 claims description 6
- 238000011161 development Methods 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 235000013311 vegetables Nutrition 0.000 claims description 5
- 239000011787 zinc oxide Substances 0.000 claims description 5
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 4
- 150000001733 carboxylic acid esters Chemical class 0.000 claims description 4
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims description 4
- 150000004706 metal oxides Chemical class 0.000 claims description 4
- 239000002585 base Substances 0.000 claims description 3
- 238000007711 solidification Methods 0.000 claims description 3
- 230000008023 solidification Effects 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 125000003158 alcohol group Chemical group 0.000 claims description 2
- 229910001854 alkali hydroxide Inorganic materials 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 239000010480 babassu oil Substances 0.000 claims description 2
- 239000003240 coconut oil Substances 0.000 claims description 2
- 235000019864 coconut oil Nutrition 0.000 claims description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 2
- 239000011707 mineral Substances 0.000 claims description 2
- 239000003346 palm kernel oil Substances 0.000 claims description 2
- 235000019865 palm kernel oil Nutrition 0.000 claims description 2
- 230000002829 reductive effect Effects 0.000 claims description 2
- 238000005984 hydrogenation reaction Methods 0.000 claims 1
- 239000002562 thickening agent Substances 0.000 claims 1
- 239000003208 petroleum Substances 0.000 abstract description 3
- 238000005086 pumping Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 24
- 239000002253 acid Substances 0.000 description 13
- 235000014113 dietary fatty acids Nutrition 0.000 description 9
- 239000000194 fatty acid Substances 0.000 description 9
- 229930195729 fatty acid Natural products 0.000 description 9
- -1 Isooctyl monoalcohol ester Chemical class 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 150000004665 fatty acids Chemical class 0.000 description 7
- 229930195733 hydrocarbon Natural products 0.000 description 7
- 150000002430 hydrocarbons Chemical class 0.000 description 7
- 239000004215 Carbon black (E152) Substances 0.000 description 6
- 150000007513 acids Chemical class 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 230000009471 action Effects 0.000 description 5
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 5
- 239000010428 baryte Substances 0.000 description 5
- 229910052601 baryte Inorganic materials 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 239000002480 mineral oil Substances 0.000 description 5
- 239000000440 bentonite Substances 0.000 description 4
- 229910000278 bentonite Inorganic materials 0.000 description 4
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 239000003077 lignite Substances 0.000 description 4
- 235000010446 mineral oil Nutrition 0.000 description 4
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 4
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 3
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 3
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 3
- DPUOLQHDNGRHBS-UHFFFAOYSA-N Brassidinsaeure Natural products CCCCCCCCC=CCCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-UHFFFAOYSA-N 0.000 description 3
- URXZXNYJPAJJOQ-UHFFFAOYSA-N Erucic acid Natural products CCCCCCC=CCCCCCCCCCCCC(O)=O URXZXNYJPAJJOQ-UHFFFAOYSA-N 0.000 description 3
- 239000005642 Oleic acid Substances 0.000 description 3
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- DPUOLQHDNGRHBS-KTKRTIGZSA-N erucic acid Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-KTKRTIGZSA-N 0.000 description 3
- 238000011010 flushing procedure Methods 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 150000007530 organic bases Chemical class 0.000 description 3
- 239000010499 rapseed oil Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000007762 w/o emulsion Substances 0.000 description 3
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- 235000019483 Peanut oil Nutrition 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 239000008186 active pharmaceutical agent Substances 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- SECPZKHBENQXJG-UHFFFAOYSA-N cis-palmitoleic acid Natural products CCCCCCC=CCCCCCCCC(O)=O SECPZKHBENQXJG-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 239000003925 fat Substances 0.000 description 2
- 235000019197 fats Nutrition 0.000 description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 description 2
- 150000007529 inorganic bases Chemical class 0.000 description 2
- 239000000944 linseed oil Substances 0.000 description 2
- 235000021388 linseed oil Nutrition 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- SECPZKHBENQXJG-FPLPWBNLSA-N palmitoleic acid Chemical compound CCCCCC\C=C/CCCCCCCC(O)=O SECPZKHBENQXJG-FPLPWBNLSA-N 0.000 description 2
- 239000000312 peanut oil Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000000518 rheometry Methods 0.000 description 2
- 239000003549 soybean oil Substances 0.000 description 2
- 235000012424 soybean oil Nutrition 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000003784 tall oil Substances 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 235000015112 vegetable and seed oil Nutrition 0.000 description 2
- 239000008158 vegetable oil Substances 0.000 description 2
- 150000003752 zinc compounds Chemical class 0.000 description 2
- XCHBJTJFTCUURB-QXMHVHEDSA-N (z)-2-(2-methylpropyl)octadec-9-enoic acid Chemical compound CCCCCCCC\C=C/CCCCCCC(C(O)=O)CC(C)C XCHBJTJFTCUURB-QXMHVHEDSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000252203 Clupea harengus Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical class NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- 101500021084 Locusta migratoria 5 kDa peptide Proteins 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 241000283903 Ovis aries Species 0.000 description 1
- 239000004435 Oxo alcohol Substances 0.000 description 1
- 235000019482 Palm oil Nutrition 0.000 description 1
- 235000021319 Palmitoleic acid Nutrition 0.000 description 1
- SCKXCAADGDQQCS-UHFFFAOYSA-N Performic acid Chemical compound OOC=O SCKXCAADGDQQCS-UHFFFAOYSA-N 0.000 description 1
- 206010063493 Premature ageing Diseases 0.000 description 1
- 208000032038 Premature aging Diseases 0.000 description 1
- 235000019486 Sunflower oil Nutrition 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000003113 alkalizing effect Effects 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000002199 base oil Substances 0.000 description 1
- 229910001038 basic metal oxide Inorganic materials 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 235000005687 corn oil Nutrition 0.000 description 1
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- 235000012343 cottonseed oil Nutrition 0.000 description 1
- 239000002385 cottonseed oil Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000010931 ester hydrolysis Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 235000021323 fish oil Nutrition 0.000 description 1
- 235000021588 free fatty acids Nutrition 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 235000019514 herring Nutrition 0.000 description 1
- 150000002462 imidazolines Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 235000020778 linoleic acid Nutrition 0.000 description 1
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 description 1
- OYHQOLUKZRVURQ-HZJYTTRNSA-N linoleic acid group Chemical group C(CCCCCCC\C=C/C\C=C/CCCCC)(=O)O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
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- 239000000047 product Substances 0.000 description 1
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- 235000009566 rice Nutrition 0.000 description 1
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- NNNVXFKZMRGJPM-KHPPLWFESA-N sapienic acid Chemical compound CCCCCCCCC\C=C/CCCCC(O)=O NNNVXFKZMRGJPM-KHPPLWFESA-N 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
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- 230000008719 thickening Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
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Classifications
-
- 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
- C09K8/32—Non-aqueous well-drilling compositions, e.g. oil-based
- C09K8/34—Organic liquids
Definitions
- the invention describes new drilling fluids based on ester oils and invert drilling fluids based thereon, which are characterized by high ecological compatibility and, at the same time, good standing and usage properties.
- An important area of application for the new drilling fluid systems is offshore drilling for the development of oil and / or natural gas deposits, whereby the invention in particular aims to provide technically usable drilling fluids with high ecological compatibility.
- the use of the new drilling fluid systems is particularly important in the marine area, but is not limited to this.
- the new flushing systems can also be used in general for land-based drilling, for example in geothermal drilling, water drilling, in the execution of geoscientific drilling and in drilling in the mining sector. In principle, it also applies here that the ecotoxic problem area is substantially simplified by the ester-based drilling oil fluids selected according to the invention.
- oil flushing systems for producing rock boreholes while applying the detached cuttings are thickened, flowable, water-based or oil-based systems. These last-mentioned oil-based systems are of increasing importance in practice and here in particular in the area of offshore drilling or when penetrating water-sensitive layers.
- Oil-based drilling fluids are generally used as so-called invert emulsion muds, which consist of a three-phase system: oil, water and finely divided solids. These are preparations of the W / O emulsions type, ie the aqueous phase is heterogeneously finely dispersed in the closed oil phase.
- a plurality of additives are provided to stabilize the overall system and to set the desired performance properties, in particular emulsifiers or emulsifier systems, weighting agents, fluid loss additives, alkali reserves, viscosity regulators and the like.
- emulsifiers or emulsifier systems weighting agents, fluid loss additives, alkali reserves, viscosity regulators and the like.
- Oil-based drilling fluids were initially based on diesel oil fractions containing aromatics.
- aromatic-free hydrocarbon fractions now also referred to as "nonpolluting oils” - as a closed oil phase, see the literature cited above. If, in this way, certain progress has also been achieved by excluding the aromatic compounds, a further reduction in the environmental problem appears - triggered by drilling fluid. of the type concerned here - urgently required. This is particularly true when drilling offshore wells to develop oil or natural gas deposits, because the marine ecosystem is particularly sensitive to the introduction of toxic and difficult-to-decompose substances. The relevant technology has for some time recognized the importance of ester-based oil phases for solving this problem.
- esters of monofunctional carboxylic acids with monofunctional alcohols derived from these oils or fats can be used.
- the second essential finding is that ester oils of the type in question do not behave in practice in the same way as the mineral oil fractions based on pure hydrocarbons previously used.
- the ester oils from monofunctional components concerned are subject to partial hydrolysis in practical use. Free fatty acids are thereby formed. These in turn react with the alkaline constituents which are always present in drilling fluid systems of the type concerned here - e.g. B. with the alkali reserve used for corrosion protection - to the corresponding ones Salt. Salts from strongly hydrophilic bases and those in fats or. Oils of natural origin predominantly encountered acids of a chain length up to about C ⁇ - and here in particular the longer-chain acids from about C i C to C_ "- are however
- the invention relates in a first embodiment to the use of selected esters which are flowable and pumpable in the temperature range from 0 to 5 C and consist of mono-functional alcohols with 2 to 12, in particular 4 to 12, C atoms and aliphatic saturated monocarboxylic acids with 12 to 16 carbon atoms or their mixtures with at most approximately the same amounts of other monocarboxylic acids as the oil phase or at least a substantial proportion of the oil phase of invert drilling muds, which in a closed oil phase form a disperse aqueous phase together with emulsifiers, weighting agents, fluid loss additives and, if desired, further conventional additives.
- selected esters which are flowable and pumpable in the temperature range from 0 to 5 C and consist of mono-functional alcohols with 2 to 12, in particular 4 to 12, C atoms and aliphatic saturated monocarboxylic acids with 12 to 16 carbon atoms or their mixtures with at most approximately the same amounts of other monocarboxylic acids as the oil phase or at least a substantial
- the invention relates to mineral-oil-free invert drilling fluids which are suitable for the off-shore development of petroleum or natural gas deposits and, in a closed oil phase based on ester oils, a disperse aqueous phase together with emulsifiers, Thickening, contain agents, fluid-ioss additives and, if desired, further customary additives, the characteristic of the invention being that the oil phase consists at least substantially of esters of monofunctional alcohols with 2 to 12 carbon atoms and aliphatic saturated monocarboxylic acids with 12 up to 16 carbon atoms is formed.
- these closed oil phase ester oils have a Brookfield (RVT) viscosity not above 50 mPas in the temperature range from 0 to 5 ° C.
- ester oils are used in a particularly preferred embodiment which are at least predominantly, ie at least about 50 to 51%, based on aliphatic C 1 __ 1 ⁇ monocarboxylic acids, such ester oils being particularly suitable can be at least about 60 wt .-% - based on the carboxylic acid mixture present - esters of such aliphatic C. _. “Monocarboxylic acids are.
- the ester oil contains exclusively saturated aliphatic monocarboxylic acids of the stated broader range of C, _. _. , but especially the range i - 1 o
- esters of other carboxylic acids in at most approximately the same amount and preferably in minor amounts can be advantageous.
- shorter-chain aliphatic monocarboxylic acids or their esters and / or esters of long-chain carboxylic acids are suitable here.
- the at least partial use of corresponding mono- and / or polyolefinically unsaturated long-chain carboxylic acid derivatives is preferred.
- ester oils defined here when used, substantial quantities of strong hydrophilic bases such as alkali hydroxide and / or diethanolamine are not used in the finished invert drilling fluid.
- invert drilling fluids with a closed oil phase of the prior art always contain an alkali reserve, in particular for protection against ingress of CO_ and / or H_S into the drilling fluid and thus for protection against corrosion on the metal parts of the drill pipe.
- a useful alkali reserve in the context of the inventive action is the addition of lime (calcium hydroxide or lime) or the concomitant use of weaker-based metal oxides, for example of the type of zinc oxide and / or other zinc compounds. Details of these elements of the teaching according to the invention are presented in more detail below. First, the ester oils selected according to the invention, which are intended exclusively or at least predominantly to form the closed oil phase of the invert drilling mud, are dealt with.
- the ester oils of monofunctional alcohols and selected monocarboxylic acids used according to the invention can be derived from unbranched or branched hydrocarbon chains.
- the esters of corresponding straight-chain acids are of particular importance.
- Saturated monocarboxylic acids the range of _ C., fi, and in particular the range of C 2 _ l ü can with monofunctional alcohols of the carbon number in the present invention defined bi lden Esteröle, the adequate rheological Show properties even down to temperatures in the range of 0 to 5 C and are particularly flowable and pumpable in this temperature range.
- Preferred esters for the oil phase of drilling muds are saturated components in the sense of the action according to the invention which have a Brookfield (RVT) viscosity in the temperature range from 0 to 5 C in the range not above 50 mPas and preferably not above 40 Pas.
- RVT Brookfield
- the ester oils used according to the invention on the basis of selected individual components or on the basis of ester mixtures have solidification values (pour point and pour point) below ⁇ 10 ° C. and in particular below ⁇ 15 ° C.
- Molecule size of the ester oil ensures that its flash points have sufficiently high values. They are at least 80 ° C, but generally exceed the temperature limit of about 100 ° C.
- Ester oils having flash points above 150 ° C. to 160 ° C. are preferred, ester oils of the type described being able to be produced, the flash points of which are 185 ° C. or higher.
- ester oils of the range required according to the invention for the saturated monocarboxylic acids C .. _,. on materials of predominantly vegetable origin Carboxylic acids or carboxylic acid mixtures with a predominant content of saturated monocarboxylic acids specified range can be obtained, for example, from renewable triglycerides such as coconut oil, palm kernel oil and / or babassu oil.
- Fatty acid mixtures of this origin usually contain a limited amount of lower fatty acids (C ß , Q ), which is generally a maximum of about 15%.
- the mixture components likewise of natural origin are, in particular, monofunctional ester oils, as described in the parallel patent application. . . (D 8523 "Use of selected ester oils in drilling fluids (I)"). In the sense of the teaching according to the invention affected here, however, these mixture components are then preferably used in minor amounts (maximum about 49% based on the ester oil mixture). To complete the description of the invention, this class of possible mixture components is briefly described. Further details can be found in the parallel application mentioned.
- carboxylic acids can be derived from unbranched or branched hydrocarbon chains, with the straight-chain acids again being of particular importance.
- Esters of the higher affected here Chain lengths are flowable and pumpable down to temperatures in the range from 0 " to 5 C if a sufficient degree of olefinically unsaturated ester constituents is ensured.
- esters of this type are accordingly used as a mixture component, which add up to more than 70 wt .-% and derived preferably more than 80 wt .-% of olefinically unsaturated carboxylic acids, the range of C 6 __ tt.
- Important natural starting materials provide Car ⁇ bonklaregemische, at least 90 wt unge ⁇ olefinically saturated carboxylic acids of the mentioned C.
- the unsaturated carboxylic acids can be mono- and / or poly-olefinically unsaturated
- carboxylic acids or carboxylic acid mixtures of natural origin in addition to a simple ethylenic double bond in the molecule, the double and, to a lesser extent, a triple ethyienic plays in particular
- Dop pel bond plays a certain role per carboxylic acid molecule.
- esters of unsaturated monocarboxylic acids of higher C chain number used as the mixture component preferably have solidification values (pour point and pour point) below - 10 ° C. and in particular below - 15 ° C. Because of their molecular size, the flash points of these mixture components are also in the desired range, ie. H. at least above 80 ° C., preferably above 100 ° C. and in particular above 160 C. In the preferred embodiment, mixed components of this type in the temperature range from 0 to 5 ° C. Brookfield (RVT) viscosities should not exceed 55 mPas and preferably values of at most 45 mPas exhibit.
- RVT Brookfield
- the first of these subclasses is based on unsaturated C 1 ß monocarboxylic acids which are not more than about 35% by weight of 2-and optionally multiply olefinically unsaturated.
- unsaturated C 1 ß monocarboxylic acids which are not more than about 35% by weight of 2-and optionally multiply olefinically unsaturated.
- the content of polyunsaturated carboxylic acid residues in the ester oil is comparatively limited.
- it is preferred that at least about 60% by weight of the carboxylic acid residues are simply olefinically unsaturated.
- I 0-24 acid mixtures from which more than 45 wt. "-% while vor ⁇ preferably more than 55 wt -.% Of 2- and / or poly-unsaturated acids ole ⁇ finisch of said C number range can be derived.
- C. - 1 0 ionic acid
- C__ erucic acid
- the most important diunsaturated carboxylic acid of the range in question here is linoleic acid (C-fi) and the most important three-ethylenically un ⁇ saturated carboxylic acid, the linolenic (1 8).
- Selected individuals of the ester type unsaturated monocarboxylic acid / monoalcohol can be used as the mixture component.
- An example of this are the esters of oleic acid, for example of the isobutyl oleic acid type.
- esters of oleic acid for example of the isobutyl oleic acid type.
- Vegetable oils of natural origin which, when saponified or transesterified, provide mixtures of carboxylic acids or carboxylic acid esters of the first subclass specified above for example palm oil, peanut oil, castor oil and in particular rape oil. Both types of rape oil with a high erucic acid content and more modern rape oil varieties with a reduced erucic acid content and therefore an increased oleic acid content are considered.
- Carboxylic acid mixtures of the aforementioned second subclass are widely accessible in the context of natural fatty substances of plant and / or animal origin.
- Classic examples of oils with a high content of carboxylic acids in the range of C. g, "or C 1 6 _ 2 - and at the same time at least about 45% of at least twice ethylenically unsaturated carboxylic acids are cottonseed oil, soybean oil, sunflower oil and linseed oil.
- the tall oil fatty acids isolated in the pulp production also fall into this range.
- a typical animal feed for obtaining corresponding carboxylic acid mixtures is fish oil, especially herring oil.
- saturated ester oils used in the context of the present invention and in particular also the last-mentioned ester oil mixtures, it should be taken into account that saturated carboxylic acid esters in the C. fi and higher C number range can have comparatively high melting points and thus easily rheological difficulties prepare. According to the invention it may accordingly be preferred that saturated carboxylic acid residues in the range of C 1 g ,. 8 and higher C number not more than about 20 wt .-% and in particular not more than about 10 wt .-%.
- ester oil phases selected according to the invention can be present here.
- Their esters are just as little under the practical conditions of use susceptible to oxidation, such as the saturated main components of the range in particular C 12 / l ü provided according to the invention.
- the theological properties of the lower fatty acid esters favor the objective according to the invention, the pure hydrocarbon oils previously used alone in practice, at least in part, preferably predominantly or even completely, by ester oils or. To replace ester oil fractions.
- the alcohol residues of the esters or ester mixtures in the sense of the teaching according to the invention are preferably derived from straight-chain and / or branched-chain saturated alcohols, alcohols with at least 4 carbon atoms and in particular alcohols in the range up to about C being particularly important. comes to.
- the alcohols can also be of natural origin and are then usually obtained from the corresponding carboxylic acids or their esters by hydrogenative reduction.
- the invention is by no means restricted to feedstocks of natural origin.
- components of synthetic origin can be used in part or in full or in full.
- Typical examples of alcohols are the corresponding oxo alcohols (branched) or the linear alcohols obtained by the Ziegler process.
- monocarboxylic acid components present in carboxylic acid mixtures in particular can be derived from petrochemical synthesis.
- there is an advantage in the raw materials of natural origin especially in the proven low toxicological values, the easy degradability and the easy accessibility. For the ultimately desired destruction of the used oil rinse in a natural way, it is from Meaning that ester oils of the type described here can be broken down both by aerobic and anaerobic routes.
- Invert drilling muds of the type concerned here usually contain, together with the closed oil phase, the finely disperse aqueous phase in amounts of about 5 to 45% by weight and preferably in amounts of about 5 to 25% by weight.
- the range from about 10 to 25% by weight of disperse aqueous phase can be of particular importance.
- drilling fluids of the type in question always contain an alkali reserve in practice.
- This alkali reserve has an important meaning as corrosion protection against unexpected ingress of acid gases, in particular C0 2 and / or H 2 S.
- the problem of corrosion on the drill pipe requires the safe adjustment of pH values at least in the weakly alkaline range, for example to pH 8.5 to 9 and higher values.
- oil rinses based on pure hydrocarbon fractions as the oil phase generally use strongly alkaline and strongly hydrophilic additives of an inorganic or organic type without hesitation.
- the alkali metal hydroxides and here in particular the sodium hydroxide on the one hand or strongly hydrophilic organic bases can be of particular importance, diethanolamine and / or triethanolamine being particularly common additives for trapping H 2 S impurities.
- lime calcium hydroxide or lime
- weaker-based metal oxides in particular zinc oxide and other zinc compounds
- Lime in particular is widely used as a cheap alkalizing agent. Relatively high amounts are safely used, for example 5 to 10 lb / bbl (lime / oil rinse) or even higher values.
- ester rinses of the type described here may require a departure from previous practice in the variables discussed here.
- the pH of the drilling fluid is kept in the at least weakly alkaline range and that a sufficient amount of alkali reserve is available for unexpected break-ins, especially of acidic gases.
- care is taken to ensure that the ester hydrolysis is not undesirably promoted and / or accelerated by such an alkali content.
- the invention dispenses with the use of alkali metal hydroxides or highly hydrophilic amines of the diethanolamine and / or triethanolamine type.
- Lime can be used effectively as an alkali reserve.
- other known alkali reserves can be used.
- esters defined according to the invention which are flowable and pumpable in the temperature range from 0 to 5 C, based on the saturated monocarboxylic acids having 12 to 16 C atoms, generally make up at least approximately in the closed oil phase of the drilling mud.
- those oil phases, the esters are preferred of the type according to the invention to a large extent and, in a very particularly important embodiment of the invention, consist practically of such ester oils.
- Suitable mixture components for blending with the ester oils defined according to the invention are those in the parallel patent application. , , (D 8523 "Selected ester oils in drilling fluids I") described compounds.
- the invention also includes blends with such selected other ester oils.
- Emulsifiers that can be used in practice are systems that are suitable for forming the required W / O emulsions.
- Selected oleophilic fatty acid salts for example those based on amidoamine compounds, are particularly suitable. Examples of this are described in the already cited US Pat. No. 4,374,737 and the literature cited there.
- a particularly suitable type of emulsifier is that of the applicant BAROID DRI LLING FLUIDS, INC. Product sold under the trade name "EZ-mul".
- Emulsifiers of the type concerned here are sold commercially as highly concentrated active ingredient preparations and can be used, for example, in amounts of about 2.5 to 5% by weight, in particular in amounts of about 3 to 4% by weight, based in each case on the ester oil phase Find.
- organophilic lignite is used in particular as a fluid loss additive and thus in particular to form a dense covering of the drilling walls with a largely liquid-impermeable film.
- Suitable amounts are, for example, in the range from about 15 to 20 lb / bbl or in the range from about 5 to 7% by weight, based on the ester oil phase.
- the viscosity former usually used is a cationically modified organophilic finely divided bentonite which can be used in particular in amounts of about 8 to 10 lb / bbl or in the range of about 2 to 4% by weight, based on the ester oil phase .
- the weighting agent usually used in the relevant practice for setting the required pressure equalization is barite, the additional amounts of which are adapted to the respectively expected conditions of the bore. For example, by adding barite it is possible to increase the specific weight of the drilling fluid to values in the range up to approximately 2.5 and preferably in the range from approximately 1.3 to 1.6.
- the disperse aqueous phase is loaded with soluble salts in invert drilling fluids of the type concerned here.
- Calcium chloride and / or potassium chloride are predominantly used here, saturation of the aqueous phase at room temperature with the soluble salt is preferred.
- emulsifiers or emulsifier systems may also serve to improve the oil wettability of the inorganic weighting materials.
- further examples are alkylbenzenesulfonates and imidazoline compounds. Additional information on the relevant prior art can be found in the following references: GB 2 158 437, EP 229 912 and DE 32 47 123.
- the drilling fluids which are based on the use of ester oils of the type described are also distinguished by a significantly improved lubricity. This is particularly important if the passage of the drill pipe and thus also the borehole have deviations from the vertical when drilling, for example at greater depths. The rotating drill pipe easily comes into contact with the borehole wall and digs into it during operation. Ester oils of the type used as an oil phase according to the invention have a significantly better lubricating effect than the mineral oils used hitherto. This is another important advantage for the action according to the invention.
- distilled lauric acid / n-hexyl ester is used as the ester oil for the formation of the closed oil phase. It is a whitish-yellow liquid with a flash point above 165 C, a pour point below
- the measurements are carried out both on the unaged material and on the aged material, the aging taking place by treatment for a period of 16 h at 125 ° C. in an autoclave - in the so-called roller oven.
- the following composition of the drilling fluid is selected: 230 ml ester oil
- BAROID DRILLING FLUIDS, INC. 6 g organopnile lignite (DURATONE from Fa.
- Example 1 The invert drilling fluid of Example 1 is put together in equal proportions. Now, however, the lime content increased to three times the amount (3 g).
- a particularly heavily weighted invert drilling fluid is put together using the same ester oil according to the following recipe:
- Example 2 The heavily weighted recipe of Example 2 is put together again. However, the lime content is now being doubled (2 g).
- ester oil for the formation of the closed oil phase, the majority of which is based on C 12 , ⁇ fatty acids and corresponds to the following specification :
- the ester mixture is a light yellow liquid with a flash point above 165 C, a pour point below - 10 ° C, a density (20 C) of 0.86 and an acid number below 0.3. In the low temperature range, the ester mixture shows the following viscosity data (Brookfield mPas):
- a W / O invert drilling fluid is put together from the components listed below and the viscosity parameters are then determined on the unaged and aged material.
- the following composition of the drilling fluid is selected:
- a W / O invert drilling fluid containing 40% water is put together using the last-described ester oil according to the following recipe: 350 ml ester oil 20 g emulsifier (EZ-MUL) 8 g organophilic lignite (DURATONE) 4 g lime
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- General Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Lubricants (AREA)
- Earth Drilling (AREA)
- Treatment Of Sludge (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
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Abstract
Utilisation d'esters pompables sélectionnés, coulants dans la fourchette de température de 0 à 5°C, à base d'alcools monofonctionnels avec entre 2 et 12, en particulier entre 4 et 12, atomes de C et d'acides monocarboxyliques aliphatiquement saturés avec entre 12 et 16 atomes de C, en tant que phase huileuse de boues de pompage de forage inverses. Grâce à ces produits, qui contiennent dans une phase huileuse bloquée une phase aqueuse dispersée, ainsi que des émulsifiants, des agents alourdissants, des additifs de perte de fluide et, au besoin, d'autres additifs habituels, la reconnaissance des gisements de pétrole ou de gaz naturel en mer peut se faire de manière écologique.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3842703 | 1988-12-19 | ||
| DE3842703A DE3842703A1 (de) | 1988-12-19 | 1988-12-19 | Verwendung ausgewaehlter esteroele in bohrspuelungen insbesondere zur off-shore-erschliessung von erdoel- bzw. erdgasvorkommen (ii) |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP0448646A1 true EP0448646A1 (fr) | 1991-10-02 |
Family
ID=6369522
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP89122820A Expired - Lifetime EP0374672B1 (fr) | 1988-12-19 | 1989-12-11 | Utilisation d'esters gras sélectionnés dans les fluides de forage, en particulier pour l'exploitation off-shore du pétrole ou du gaz naturel |
| EP90901766A Pending EP0448646A1 (fr) | 1988-12-19 | 1989-12-11 | Utilisation d'huiles-esters selectionnees dans des lavages de sondage, en particulier pour la reconnaissance en mer de gisements de petrole ou de gaz naturel (ii) |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP89122820A Expired - Lifetime EP0374672B1 (fr) | 1988-12-19 | 1989-12-11 | Utilisation d'esters gras sélectionnés dans les fluides de forage, en particulier pour l'exploitation off-shore du pétrole ou du gaz naturel |
Country Status (17)
| Country | Link |
|---|---|
| EP (2) | EP0374672B1 (fr) |
| AR (1) | AR247756A1 (fr) |
| AT (1) | ATE86646T1 (fr) |
| BR (1) | BR8907836A (fr) |
| CA (1) | CA2006009C (fr) |
| DE (2) | DE3842703A1 (fr) |
| DK (1) | DK170979B2 (fr) |
| ES (1) | ES2041956T3 (fr) |
| IE (1) | IE63862B1 (fr) |
| MX (1) | MX174331B (fr) |
| NZ (1) | NZ231826A (fr) |
| PT (1) | PT92598B (fr) |
| RO (1) | RO111580B1 (fr) |
| TR (1) | TR24166A (fr) |
| UA (1) | UA26405C2 (fr) |
| WO (1) | WO1990006981A1 (fr) |
| ZA (1) | ZA899696B (fr) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10294401B2 (en) | 2015-05-14 | 2019-05-21 | Halliburton Energy Services, Inc. | Downhole fluids with high dielectric constant and high dielectric strength |
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| DE102009060865A1 (de) | 2009-12-30 | 2011-07-07 | Emery Oleochemicals GmbH, 40589 | Ester aus festen Polyolen und ungesättigten Carbonsäuren |
| US20130233623A1 (en) | 2010-11-25 | 2013-09-12 | Bp Exploration Operating Company Limited | Consolidation |
| EA201301252A1 (ru) | 2011-05-12 | 2014-05-30 | Бп Эксплорейшн Оперейтинг Компани Лимитед | Способ осуществления работы скважины |
| CA2881747C (fr) | 2012-07-26 | 2019-04-09 | Amril Ag | Esters pour emulsions de forage et fluides de traitement des metaux |
| US9238783B2 (en) | 2012-11-20 | 2016-01-19 | Chevron U.S.A. Inc. | Monoester-based lubricants and methods of making same |
| US9115556B2 (en) | 2012-11-20 | 2015-08-25 | Chevron U.S.A. Inc. | Method of using biologically-derived monoesters as drilling fluids |
| US9115326B2 (en) | 2012-11-20 | 2015-08-25 | Chevron U.S.A. Inc. | Monoester-based lubricants and methods of making same |
| US9115303B2 (en) | 2012-11-20 | 2015-08-25 | Chevron U.S.A. Inc. | Biologically-derived monoesters as drilling fluids |
| CN105492569A (zh) * | 2013-08-22 | 2016-04-13 | 雪佛龙美国公司 | 生物衍生的单酯作为钻井液 |
| CA2918645A1 (fr) * | 2013-08-22 | 2015-02-26 | Chevron U.S.A. Inc. | Procede d'utilisation de monoesters d'origine biologique en tant que fluides de forage |
| EP2848720B1 (fr) | 2013-09-12 | 2016-03-02 | 3M Innovative Properties Company | Utilisation de lubrifiant dans un tapis de montage et procédé de fabrication d'un tel tapis |
| WO2019147515A1 (fr) | 2018-01-29 | 2019-08-01 | Exxonmobil Chemical Patents Inc. | Fluides biodégradables par voie anaérobie pour des applications de forage |
| EP3763922B1 (fr) | 2019-07-09 | 2025-07-02 | 3M Innovative Properties Company | Mat de montage à utiliser dans des dispositifs antipollution |
| EP4379197A1 (fr) | 2022-11-30 | 2024-06-05 | 3M Innovative Properties Company | Mat de montage polycristallin sans liant à production améliorée |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2843473A1 (de) * | 1978-10-05 | 1980-04-17 | Bayer Ag | Lactonmodifizierte esteroele |
| US4631136A (en) * | 1985-02-15 | 1986-12-23 | Jones Iii Reed W | Non-polluting non-toxic drilling fluid compositions and method of preparation |
-
1988
- 1988-12-19 DE DE3842703A patent/DE3842703A1/de not_active Withdrawn
-
1989
- 1989-12-11 AT AT89122820T patent/ATE86646T1/de not_active IP Right Cessation
- 1989-12-11 WO PCT/EP1989/001513 patent/WO1990006981A1/fr not_active Ceased
- 1989-12-11 ES ES198989122820T patent/ES2041956T3/es not_active Expired - Lifetime
- 1989-12-11 DE DE8989122820T patent/DE58903735D1/de not_active Expired - Lifetime
- 1989-12-11 UA UA93004579A patent/UA26405C2/uk unknown
- 1989-12-11 BR BR898907836A patent/BR8907836A/pt not_active IP Right Cessation
- 1989-12-11 RO RO147838A patent/RO111580B1/ro unknown
- 1989-12-11 EP EP89122820A patent/EP0374672B1/fr not_active Expired - Lifetime
- 1989-12-11 EP EP90901766A patent/EP0448646A1/fr active Pending
- 1989-12-15 PT PT92598A patent/PT92598B/pt not_active IP Right Cessation
- 1989-12-18 ZA ZA899696A patent/ZA899696B/xx unknown
- 1989-12-18 IE IE405789A patent/IE63862B1/en not_active IP Right Cessation
- 1989-12-18 MX MX018754A patent/MX174331B/es unknown
- 1989-12-18 NZ NZ231826A patent/NZ231826A/xx unknown
- 1989-12-19 AR AR89315715A patent/AR247756A1/es active
- 1989-12-19 CA CA002006009A patent/CA2006009C/fr not_active Expired - Lifetime
-
1990
- 1990-01-02 TR TR90/0004A patent/TR24166A/xx unknown
-
1991
- 1991-06-18 DK DK199101176A patent/DK170979B2/da not_active IP Right Cessation
Non-Patent Citations (1)
| Title |
|---|
| See references of WO9006981A1 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10294401B2 (en) | 2015-05-14 | 2019-05-21 | Halliburton Energy Services, Inc. | Downhole fluids with high dielectric constant and high dielectric strength |
| US11136485B2 (en) | 2015-05-14 | 2021-10-05 | Halliburton Energy Services, Inc. | Downhole fluids with high dielectric constant and high dielectric strength |
| US11624017B2 (en) | 2015-05-14 | 2023-04-11 | Halliburton Energy Services, Inc. | Downhole fluids with high dielectric constant and high dielectric strength |
Also Published As
| Publication number | Publication date |
|---|---|
| ZA899696B (en) | 1990-08-29 |
| EP0374672A1 (fr) | 1990-06-27 |
| ES2041956T3 (es) | 1993-12-01 |
| DK117691D0 (da) | 1991-06-18 |
| IE63862B1 (en) | 1995-06-14 |
| UA26405C2 (uk) | 1999-08-30 |
| DK117691A (da) | 1991-08-13 |
| DE58903735D1 (de) | 1993-04-15 |
| DE3842703A1 (de) | 1990-06-21 |
| NZ231826A (en) | 1991-08-27 |
| MX174331B (es) | 1994-05-09 |
| RO111580B1 (ro) | 1996-11-29 |
| TR24166A (tr) | 1991-05-01 |
| PT92598A (pt) | 1990-06-29 |
| PT92598B (pt) | 2001-04-30 |
| DK170979B2 (da) | 2005-03-29 |
| ATE86646T1 (de) | 1993-03-15 |
| AU4954990A (en) | 1990-07-10 |
| DK170979B1 (da) | 1996-04-09 |
| IE894057L (en) | 1990-06-19 |
| CA2006009C (fr) | 2001-07-03 |
| BR8907836A (pt) | 1991-10-22 |
| EP0374672B1 (fr) | 1993-03-10 |
| WO1990006981A1 (fr) | 1990-06-28 |
| AU634207B2 (en) | 1993-02-18 |
| AR247756A1 (es) | 1995-03-31 |
| CA2006009A1 (fr) | 1990-06-19 |
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