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 muds 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 for Ceothermal drilling, water drilling, drilling geosciences and mining. 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 drilling rock bores while applying the detached cuttings are thickened, flowable, water-based or oil-based systems.
• 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 substance fractions now also referred to as "nonpolluting oils” - as a closed oil phase - see the literature cited above for this. If, in this way, certain progress has also been achieved by excluding the aromatic compounds, a further reduction in the environmental problem - triggered by drilling fluid of the type concerned here - appears to be urgently required. This is particularly valid when drilling offshore boreholes to develop oil or natural gas deposits, because the marine ecosystem is particularly sensitive to the introduction of toxic and difficult-to-decompose substances.
• 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 type W / O emissions, i.e. H. 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 viscosity regulators and the like.
• Oil-based drilling fluids were initially based on diesel oil fractions containing aromatics. To detoxify and reduce the ecological problems thus created, it has been proposed to use largely 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 - triggered by drilling fluid of the type concerned here - appears to be urgently required. This is particularly valid when drilling offshore boreholes to develop oil or natural gas deposits, because the marine ecosystem is particularly sensitive to the introduction of toxic and difficult-to-decompose substances.
• Acids in the range from about C 16 to 24 frequently encountered in oils or oils of natural origin are known to be compounds with comparatively high HLB values, which in particular lead to the setting and stabilization of O / W emulsions.
• the washing and cleaning technology makes known use of this to the greatest extent.
• the formation of undesirably large amounts of such O / W emulsifier systems must, however, interfere with the W / O emulsions required in the sense of the objective according to the invention and thus lead to faults.
• the teaching of the invention described in the following describes how, in spite of these difficulties inherent in the system, invert drilling fluids based on ester oils which can be used in practice can be used.
• 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., from monofunctional alcohols having 2 to 12 carbon atoms and olefinically mono- and / or polyunsaturated monocarboxylic acids containing 16 up to 24 carbon atoms or their mixtures with minor amounts of other, in particular saturated, monocarboxylic acids as the oil phase or at least a substantial proportion of the oil phase of invert drilling muds containing a disperse aqueous phase and emulsifiers, weighting agents, fluid loss additives in a closed oil phase and if desired contain further customary additives together with an alkali reserve with the proviso that the use of substantial amounts of strong hydrophilic bases such as alkali hydroxide and / or diethanolamine is dispensed with.
• monofunctional alcohols having 2 to 12 carbon atoms and olefinically mono- and / or polyunsaturated monocarboxy
• lime calcium hydroxide or lime
• the addition of lime is often provided as an alkali reserve, in particular for protection against the ingress of CO_ and / or H_S into the drilling fluid and thus for protection against corrosion.
• the use of such a lime additive as an alkali reserve is possible within the scope of the invention. However, care is only taken here to mix in comparatively limited amounts of this alkaline component.
• the maximum amount for the lime addition in the preferred embodiment according to the invention is about 2 lb / bbl (lime / oil rinse) and thus significantly below the values that are usually used in practice in oil-based invert rinses.
• the invention relates to mineral oil-free invert drilling fluids which are suitable for the offshore shooting of oil or natural gas deposits and, in a closed oil phase based on ester oils, to a disperse aqueous phase together with emulsifiers and thickeners , Weighting agents, fluid-ioss additives and, if desired, further conventional additives.
• the new drilling fluid systems are characterized in that the oil phase is formed at least substantially from esters of monofunctional alcohols with 2 to 12 C atoms and olefinically 1- and / or polyunsaturated monocarboxylic acids with 16 to 24 C atoms, that the W / O emulsion is weakly alkaline conditioned and when adding lime this alkali reserve preferably does not exceed amounts of about 2 lb / bbl (lime / oil rinse). It may be preferred that the lime content is slightly below this limit.
• ester oils selected according to the invention are first discussed which, as intended, exclusively or at least as a substantial proportion form the closed oil phase of the invert drilling mud.
• esters which is to be assigned to the class of reaction products from monofunctional carboxylic acids with onofunctional alcohols.
• the invention also provides for carboxylic acids within this class the specified range of 16 to 24 carbon atoms exclusively or at least predominantly.
• the carboxylic acids can be derived from unbranched or branched hydrocarbon chains, the straight-chain ones being of particular importance.
• Monocarboxylic acids of this type and the range of 16 to 24 carbon atoms or their esters affected here are unsuitable as predominantly saturated hydrocarbon compounds because of their comparatively high solidification values.
• esters of the type concerned here are flowable and pumpable down to temperatures in the range from 0 to 5 ° C.
• esters of the type described here are used in the preferred embodiment of the invention, which are more than 70% by weight and preferably more than 80% by weight of olefinically unsaturated carboxylic acids in the range from C 16 __ ⁇ deduce.
• Important natural starting materials provide carboxylic acid mixtures which contain at least 90% by weight of olefinically unsaturated carboxylic acids of the C range mentioned here.
• the unsaturated carboxylic acids can be mono- and / or poly-olefinically unsaturated.
• the maximum amount for the lime addition in the preferred embodiment according to the invention is about 2 lb / bbl (lime / oil rinse) and thus significantly below the values that are usually used in practice in oil-based invert rinses.
• 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, to a disperse aqueous phase together with emulsifiers and thickeners , Weighting agents, fluid loss additives and, if desired, further conventional additives.
• the new drilling fluid systems are characterized in that the oil phase is formed at least substantially from esters of monofunctional alcohols with 2 to 12 C atoms and olefinically 1 - and / or polyunsaturated monocarboxylic acids with 16 to 24 C atoms, that the W / O emulsion is weakly alkaline conditioned and when added to lime this alkali reserve preferably does not exceed amounts of about 2 lb / bbl [lime / oil rinse). It may be preferred that the lime content is slightly below this limit.
• ester oils selected according to the invention are first discussed, which, as intended, form the closed oil phase of the invert drilling mud exclusively or at least as a substantial proportion.
• esters which is to be assigned to the class of reaction products from monofunctional carboxylic acids with monofunctional alcohols.
• the invention also provides for carboxylic acids within this class Comparatively limited ester oil. In this subclass, however, it is preferred that at least about 60% by weight of the carboxylic acid residues are simply olefinically unsaturated.
• the second subclass of ester oils which is important in practice, is derived from such C_. g_ 2Z , -monocarboxylic acid mixtures derived from more than 45% by weight and preferably more than 55% by weight of 2- and / or poly-olefinically unsaturated acids of the C number range mentioned.
• the most important ethylenically monounsaturated carboxylic acids in the area concerned are hexadecenoic acid (palmitoleic acid, C 1 ß ), oleic acid (C_. G), its related ricinoleic acid (C_. _) And erucic acid (C__).
• the most important diunsaturated carboxylic acid of the range in question here is linoleic acid (C j and the most important three-ethylenically un ⁇ saturated carboxylic acid, the linoleic acid (C 8).
• ester oil selected individuals of the ester type unsaturated monocarboxylic acid / mono alcohol can be used as ester oil.
• esters of oleic acid for example of the type of oleic acid isobutyl ester.
• acid mixtures For the rheology of the system and / or for reasons of accessibility, it is often desirable to use acid mixtures. This is important for the fulfillment of the previously given specifications of the two subclasses for preferred ester oils.
• the first of these two subclasses is distinguished by the fact that its content of 2- and polyunsaturated acids is limited and does not exceed about 35%.
• Vegetable oils of natural origin which, when saponified or transesterified, provide mixtures of carboxylic acids or carboxylic acid esters of the type required here are, for example, palm oil, peanut oil, Castor oil and especially rape oil. Both types of rape oil with a high erucic acid content and modern rape oil varieties with a reduced erucic acid content and therefore an increased oleic acid content come into consideration.
• Ester oils based on this definition of the first subclass can be of particular importance if only problems that may arise from the oxidation instability in practical operation are alleviated.
• the drilling fluid is pumped continuously in the circuit and is constantly brought into contact with atmospheric oxygen - often with a large surface area and at least slightly elevated temperatures - in order to separate the carried-up cuttings, for example by sieving.
• carboxylic acid mixtures of the aforementioned second subclass are also of considerable practical importance for use in the sense according to the invention. Last but not least, this is due to their wide accessibility 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 1 fi __. a or C_. g_ 2 _ and at least about 45% of at least double ethylenically unsaturated carboxylic acids are cottonseed oil, soybean oil, sunflower oil and linseed oil.
• the tall oil acids isolated in the pulp production also fall into this range.
• feedstocks of this last-mentioned origin are generally distinguished by more or less large additional contents of resin components.
• a typical animal feed for the production of corresponding carboxylic acid mixtures is fish oil, especially herring oil.
• ester oils used according to the invention can be selected individually determined esters of the specified ones Definition. Usually, however, mixtures of esters from corresponding monocarboxylic acids and monoalcohols are present. In the context of the invention, in particular those mixtures are those which, on the one hand, correspond to the viscosity condition required according to the invention, particularly also at low temperatures, and on the other hand to at least 50 to 51% of the monofunctional esters of olefinically mono- and / or polyunsaturated carboxylic acids with 16 have up to 24 carbon atoms.
• Ester constituents and in particular carboxylic acid esters of monofunctional alcohols and monofunctional carboxylic acids of other constitution are permissible as subordinate mixture constituents, provided the requirement profile for the properties of the substance mixture is fulfilled. This is important for the use of carboxylic acid mixtures of natural origin. As a rule, such natural feedstocks also contain more or less large amounts of saturated carboxylic acids and frequently also straight carboxylic acids in the range C 1 ß __. ". Saturated fatty acids of this type or their esters easily cause theological difficulties because of their comparatively high melting points.
• Castor oil and especially rape oil Castor oil and especially rape oil. Both types of rape oil with a high erucic acid content and modern rape oil varieties with a reduced erucic acid content and therefore an increased oleic acid content come into consideration.
• Ester oils based on this definition of the first subclass can be of particular importance if only problems that may arise from the oxidation instability in practical operation are alleviated.
• the drilling fluid is pumped continuously in the circuit and is constantly brought into contact with atmospheric oxygen - often with a large surface area and at least slightly elevated temperatures - in order to separate the carried-up cuttings, for example by sieving.
• carboxylic acid mixtures of the aforementioned second subclass are also of considerable practical importance for use in the sense according to the invention. Last but not least, this is due to their wide accessibility 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. fi , fi or C_.g_- 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 acids isolated in the pulp production also fall into this range.
• feedstocks of this last-mentioned origin are generally distinguished by more or less large additional contents of resin components.
• a typical animal use material for the extraction of corresponding carbons uregemische is fish oil, especially the herring oil.
• ester oils used according to the invention can be selected individually determined esters of the specified ones described the difficulty that the carboxylic acid esters are in principle susceptible to hydrolysis and must accordingly behave differently than the pure hydrocarbon oils used hitherto.
• 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.
• strongly alkaline and strongly hydrophilic additives of an inorganic or organic type are generally used in oil rinses based on pure hydrocarbon fractions as the oil phase.
• the alkali metal hydroxides and in particular the sodium hydroxide on the one hand or strongly hydrophilic organic bases diethanolamine and / or triethanolamine being particularly common additives for trapping H_S impurities.
• the strongly hydrophilic mentioned here Lime (lime) or even weaker-based metal oxides, in particular zinc oxide or comparable zinc compounds, are of considerable importance as an alkali reserve as inorganic and organic bases. Lime in particular is widely used as a cheap alkalizing agent. Comparatively 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 requires a departure from previous practice with regard to these variables.
• 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.
• care is taken not to use any significant amounts of strongly hydrophilic bases of an inorganic and / or organic type in the oil rinse.
• the invention dispenses with the use of alkali metal hydroxides or highly hydrophilic amines of the type of diethanolamine and / or triethanolamine.
• Lime can be used effectively as an alkali reserve.
• esters defined according to the invention which are flowable and pumpable in the temperature range from 0 to 5 ° C., based on the olefinically unsaturated monocarboxylic acids with 16 to 24 carbon atoms generally make up at least about half of the oil phase in the closed oil phase of the drilling mud .
• Suitable mixture components for blending with the ester oils defined according to the invention are, in particular, selected other ester oil fractions which are described in the parallel patent application. , , (D 8524 "Selected ester oils in drilling fluids II").
• 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 therein.
• a particularly suitable type of emulsifier is that of the applicant BAROID DRILLING 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, finely divided organophilic 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, the saturation of the aqueous phase at room temperature with the soluble salt being 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 based on the use of ester oils of the type described are also characterized 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.
• 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.
• An invert drilling fluid based on an undistilled isobutyl rapeseed oil ester is produced as a closed oil phase.
• This rape oil ester is based on a mixture of predominantly unsaturated straight-chain carboxylic acids, which correspond approximately to the following distribution: 60% oleic acid, 20% linoleic acid, 9 to 10% linolenic acid, olefinically unsaturated C-. , --- Monocarboxylic acids about 4%, the rest saturated monocarboxylic acids predominantly in the range
• the rapeseed oil ester used also has the following characteristics: density (20 ° C.) 0.872 g / cm 3 ; Pour point below - 15 ° C; Flash point (DIN 51584) above 180 ° C; Acid number (DGF-CV 2) 1.2; Viscosity at 0 ° C 32 mPas, viscosity at 5 ° C 24 mPas; no aromatic content.
• An invert drilling fluid is made in a conventional manner using the following ingredients:
• BAROID DRILLING FLUIDS, INC. First, by measuring the viscosity at 50 C on the unleaved material, the plastic viscosity (PV), the yield point (YP) and the gel strength after 10 sec. And 10 min. certainly.
• the invert drilling fluid is then aged for 16 hours at 125 ° C. in an autoclave in a so-called "roller oven” in order to check the influence of temperature on the stability of the emulsion. Then the viscosity values at 50 C are determined again.
• Invert drilling fluid is again compiled in accordance with the information in Example 1. Now, however, the amount of lime is raised to the value of 4 g and thus increased drastically above the limit value of about 2 Ib / bbl.
• Plastic viscosity (PV) 41 cannot be determined
• Distilled oleic acid isobutyl ester which has the following characteristics, is used as the oil phase: density (20 ° C.), 86 g / cm; Viscosity (20 ° C) 8 to 10 mPas; Pour point below 25 ° C .; Flash point (DIN 51584) above 185 ° C; Acid number
• a drilling fluid of the following composition is formulated:
• BAROID DRILLING FLUIDS, INC. 13 g organophilic lignite (DURATONE from Fa.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Life Sciences & Earth Sciences (AREA)
• 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)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Medicines Containing Material From Animals Or Micro-Organisms (AREA)
• Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)

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• 1988
  • 1988-12-19 DE DE3842659A patent/DE3842659A1/de not_active Withdrawn
• 1989
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