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 " 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 development of oil and / or natural gas deposits, the present invention being particularly concerned with providing technically usable drilling fluids with high ecological compatibility.
• the use of the new drilling fluid systems is of particular importance in the marine field, but is not restricted to this New flushing systems can also be used in general for land-based drilling, for example for geothermal drilling, for water drilling, for carrying out geoscientific drilling and for drilling in the mining sector.
• the selection according to the invention also applies here Since drilling oil fluids simplify the ecotoxic problem area substantially.
• 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 of W / O emulsions, i.e. H . the aqueous phase is heterogeneously finely dispersed in the closed oil phase.
• a plurality of additives are provided, in particular emulsifiers or emulsifier systems, weighting agents, fluid loss additives, alkali reserves, viscosity regulators and the like.
• ester oils of the type concerned do not behave in the same way as the mineral oil fractions based on pure hydrocarbons used to date.
• ester oils are also subject to partial hydrolysis, especially in W / O invert drilling muds. In this way free carboxylic acids are formed.
• the older applications P 38 42 659.5 and P 38 42 703.6 (D 8523 and D 8524) describe the problems that are triggered by this and give suggestions for their solution. Further modifications of usable ester oils are described in the earlier patent applications P 39 07 391 .2 and P 39 07 392.0 (D 8606 and D 8607).
• the subject of these earlier applications is the use of ester oils based on selected monocarboxylic acids or. Monocarboxylic acid mixtures and monofunctional and optionally multifunctional alcohols.
• the older applications show that the esters or ester mixtures disclosed therein can be used to set not only satisfactory rheological properties in the fresh drilling fluid, but that it is also possible to work in the drilling fluid using selected known alkali reserves and in this way retain unwanted corrosion.
• the alkali reserve - especially when using ester oils based on carboxylic acids with at least 6 carbon atoms - is the addition of lime (calcium hydroxide or urn) and / or the use of zinc oxide or comparable zinc compounds. However, an additional restriction is advisable.
• the amount of the alkalizing additive and in particular the amount of lime is increased limit.
• the maximum amount envisaged is about 2 lb / bbl oil rinse.
• the oleophilic amine compounds can at the same time be used at least partially as an alkali reserve of invert drilling fluid, but they can also be used in combination with conventional alkali reserves, in particular together with lime. Preferred is the use of oleophilic amine compounds which are at least largely free of aromatic constituents len ⁇ tei is.
• olefinically unsaturated aliphatic, cycloaliphatic and / or heterocyclic oleophilic basic amine compounds, which one or more of which are capable of forming salts with carboxylic acids, are particularly suitable N groupings included.
• the room temperature of these amine compounds is at most about 5% by weight and is advantageously below 1% by weight. -.
• Typical examples of such amine compounds are at least largely water-insoluble primary, secondary and / or tertiary amines, which can also be alkoxylated to a limited extent and / or substituted with, in particular, hydroxyl groups. Further examples are corresponding aminoamides and / or heterocycles containing nitrogen as a ring component. Suitable are, for example, basic amine compounds which have at least one long-chain hydrocarbon residue with preferably 8 to 36 C atoms, in particular with 1 0 to 24 C atoms, which can also be 1 - or polyolefinically unsaturated.
• the oleophilic basic amine compounds can be added to the drilling fluid in amounts up to about 10 Ib / bbI, preferably in amounts up to about 5 Ib / bbI and in particular in the range from about 0.1 to 2 ib / bbl.
• the present invention is based on the object of further developing systems of the type concerned and in particular drilling fluids of high ecological compatibility.
• the invention wants oils or. Provide oil mixtures for the construction of drilling fluids based on W / O emulsions that are technically usable and easily accessible and at the same time have a high ecological value award.
• the invention intends to make additives available for the above-described systems of the type concerned here, which impart valuable additional properties to drilling fluids based on W / O emulsions without adversely affecting their ecological compatibility.
• the technical solution to the problems according to the invention is based on the knowledge that selected ethers which are adapted to the respective application can lead to new and improved drilling fluids of the type specified.
• These ethers are water-insoluble or essentially water-insoluble components, in particular therefore corresponding compounds with a pronounced oleophilic character, but which differ from the pure hydrocarbon compounds in the presence of the functional ether group. This makes important technological improvements accessible, while at the same time ensuring high ecological compatibility.
• the invention relates in a first embodiment to the use of water-insoluble and flashpoints above 80 ° C ethers of monohydric alcohols of natural and / or synthetic origin with at least 4 C atoms, preferably at least 6 C atoms in the alcohol residues as an oil phase or as a component of Oil phase of invert drilling fluids, which are in the form of W / O emulsions, have a disperse aqueous phase in the closed oil phase which is flowable and pumpable in the temperature range from 0 to 5 C and, if desired, further customary additives and for the environmentally friendly development of, for example, petroleum respectively . Natural gas deposits are suitable.
• the invention relates to invert drilling fluids of the type described, which thereby are characterized in that they contain, as a closed oil phase or dissolved in ecologically compatible oils, an addition of at least largely water-insoluble ethers of monohydric alcohols, the respective oil phase being flowable and pumpable in the temperature range from 0 to 5 ° C. and having flash points above 80 ° C. .
• the closed oil phase of the invert drilling fluids is formed exclusively or largely by the essentially water-insoluble and preferably pronounced oleophilic ethers. Understandably, the rheology of the ethers used must be adapted to the technical requirements of the drilling fluids. Slight theological corrections are possible by using the small amounts of diluents provided in this embodiment.
• oil phases are particularly considered which are formed by more than 70% by weight, preferably by more than 80% by weight and, if desired, exclusively by the ethers as such. The general technical knowledge applies to the theological requirements of such oils for the field of use of drilling fluids, which will be discussed again below.
• suitable ethers includes, in general, symmetrical ethers, each based on a selected alcohol, mixed ethers of different alcohols and / or ether mixtures of the two aforementioned ether types. From the wide range of suitable individual ethers or. Mixed ethers and / or ether mixtures are particularly suitable representatives, the at least partially corresponding derivatives of monofunctional alcohols with at least 6 or 7 carbon atoms, preferably with at least 8 Are carbon atoms, the possible upper limit of the C number being strongly influenced by the structure of the hydrocarbon radical.
• the known influence of branched-chain and / or unsaturated structure of the hydrocarbon radicals in corresponding alcohols also has an effect on the rheology of the ethers formed therefrom.
• the rheology of branched-chain and / or unsaturated ethers of the type concerned here is known to meet the requirements for flowability and pumpability even at low temperatures more easily than the straight-chain saturated hydrocarbon skeleton.
• Saturated straight-chain fatty alcohol ethers in the range C 1 f . / 1 fl are known to have high solidification ranges.
• branched ethers of the same C number range can represent usable flowable and pumpable oil phases in the sense of the invention.
• the range of low carbon numbers is particularly suitable, in particular the range of about C__...
• Theological advantages can also come from the ethers from branched-chain alcohols.
• oil mixture components optionally used in small amounts in this embodiment can be pure, in particular aromatic-free hydrocarbon compounds, but in particular selected ester oils of the type described in the above-mentioned earlier applications by the applicant.
• a second embodiment of the invention accordingly relates to the use of oil phases in systems of the type concerned, which nevertheless already considerable or even predominant.
• the content of ethers selected according to the invention is generally above 10% by weight. -% to about 70 wt .-% - each based on the liquid oil phase - with ether fractions in amounts of at least about 35 wt. -% and preferably at least about 50 wt. -
• the oil phase may be preferred.
• Mixture components for this second embodiment of the invention are in turn both pure, in particular aromatic-free, hydrocarbon oils and, above all, ester oils of the type described in the earlier applications of the applicant. Mixtures of these types also fall within the scope of the invention, it being possible for mixtures of ester oils with pure hydrocarbon compounds and also mixtures of different types of ester oils to be mixture components for use together with the oleophilic ethers.
• the pure hydrocarbon oils which have no functional groups are used in the oil phase in amounts of at most 50% by weight. %, preferably of at most about 35% by weight and in particular in amounts of at most about 25% by weight. -% - each based on the oil phase.
• mixtures of the ethers and ester oils defined according to the invention are used as the oil phase without the addition of pure hydrocarbon compounds.
• the invention relates to the use of the practically water-insoluble ether as an additive in the oil phase of drilling fluids based on W / O emulsions.
• the amount of the ethers used according to the invention is usually in the range from about 0.1 to a maximum 10% by weight, preferably in the range from about 1 to 5% by weight, of the oil phase.
• the range of suitable water-insoluble ethers can understandably be expanded substantially in this embodiment.
• the rheology of the overall system is no longer determined by the theological values of the ether.
• important improvements in the behavior of drilling fluids of the type described above are achieved.
• the main component of the closed oil phase is formed exclusively or predominantly by ester oils of the type described in the above-mentioned older applications of the applicant.
• the main components for the oil phase are accordingly at least 25% by weight, preferably at least 50% by weight and in particular at least about 75 to 80% by weight of the oil phase as ester oil.
• pure hydrocarbon oils of the prior art can also be used, but it is expedient to dispense with them entirely.
• water-insoluble ethers defined according to the invention By adding the water-insoluble ethers defined according to the invention to invert systems, important improvements for the practical use of the drilling fluids can be set. The following four aspects are particularly affected: reduction of the fluid loss values, the facilitation and improvement of the emulsification of the disperse aqueous phase, a possibly significantly improved lubricating effect of the drilling fluid and possibly a significant improvement in the theological properties of invert drilling fluids based on ester oil.
• the ethers used according to the invention are particularly affected: reduction of the fluid loss values, the facilitation and improvement of the emulsification of the disperse aqueous phase, a possibly significantly improved lubricating effect of the drilling fluid and possibly a significant improvement in the theological properties of invert drilling fluids based on ester oil.
• the water solubility of suitable ethers is preferably below 5% by weight, in particular below 1% by weight and preferably not more than about 0.1% by weight.
• the selection of suitable ethers or. Ether mixtures first of all determined by the corresponding basic theological data.
• the ether or. the ether mixtures used in the temperature range from 0 to 5 C have a Brookfield (RVT) viscosity not above 50 mPas, preferably not above 40 mPas and in particular not more than about 30 mPas.
• RVT Brookfield
• the setting values (pour point and pour point) of the or. the ether is below 0 C.
• ether or. Ether mixtures with solidification values below - 5 ° C and in particular below - 10 C are used.
• the flash points of the or. the ether used the more expedient as not below 90 C and preferably above 100 C.
• Significantly higher flash points for example those above 130 ° C. and in particular above 150 ° C., can be particularly expedient.
• An important element of the invention is the use of comparably, non-toxic components, so that thus for example the use of aromatic ether is eliminated in particular the "Phenolethertyps practical.
• Aliphatic, optionally mono- and / or polyolefinically unsaturated alcohols having straight-chain and / or branched hydrocarbon structure and, if appropriate, cycioaliphatic alcohols are the most important ether-forming components in the sense of the action according to the invention.
• the lower limit of the carbon number of such alcohols is C, preferably C fi and in particular C_.
• the upper limit of the carbon number in the ether-forming alcohols can vary depending on the rheological requirements also be selected very high and is for example about C- fi, preferably at about C__.
• I n consideration are in particular monofunctional alcohols the range of about C fi _ 2 U, preferably C fi _.. "ethers of C" _ 1 6 and especially C.
• Alcohols are suitable components in the sense of the teaching
• the ether-forming alcohols can in each case be wholly or at least partly straight-chain and / or branched-chain, even-numbered and / or odd-numbered, saturated and / or unsaturated.
• the ether-forming alcohols can in turn be whole or partly natural and / or synthetic origin.
• Oil components suitable for blending in the context of the invention are the mineral oils used in the practice of drilling fluids today, and preferably essentially aromatic-free al-ipatic and / or cycloal-ipatic hydrocarbon fractions of the required flow properties. Reference is made to the relevant printed state of the art and the hand ice cream products on the market.
• ester oils such as those in particular in the earlier applications mentioned P 38 42 659.5, P 38 42 703.6, P 39 07 391 .2 and P 39 07 392 .0 (D 8523, D 8524 , D 8606 and D 8607) are described. To complete the disclosure of the invention, in The following essential characteristics of such esters or ester mixtures are briefly summarized.
• flowable and pumpable esters of monofunctional alcohols with 2 to 12, in particular with 6 to 12 C atoms and aliphatic saturated monocarboxylic acids with 12 to 16 C atoms or their mixture with at most in the temperature range from 0 to 5 C. approximately the same amounts of other monocarboxylic acids are also used as the oil phase.
• ester oils which are at least about 60% by weight, based on the respective carboxylic acid mixture, of esters of aliphatic C.-, “-monocarboxylic acids and, if desired, the remainder to minor amounts of short-chain aliphatic and / or longer-chain, then in particular 1- and / or polyolefinically unsaturated monocarboxylic acids.
• Esters are preferably used which have a Brookfield (RVT) viscosity in the temperature range from 0 to 5 C in the range not above 50 mPas, preferably not above 40 mPas and in particular of at most about 30 mPas.
• the esters used in the drilling mud show solidification values (pour point and pour point) below - 10 C, preferably below - 15 C and in particular have flash points above 100 C, preferably above 150 ° C.
• the carboxylic acids present in the ester or ester mixture are straight-chain and / or branched and are of vegetable and / or synthetic origin. They can be derived from appropriate triglycerides such as coconut oil, palm kernel oil and / or babassu oil.
• the alcohol residues of the esters used are derived in particular from straight-chain and / or branched saturated alcohols having preferably 6 to 10 carbon atoms. These alcohol components can also be of vegetable and / or animal origin and have been obtained by reductive hydrogenation of corresponding carboxylic acid esters.
• Another class of particularly suitable ester oils is derived from olefinically 1- and / or polyunsaturated monocarboxylic acids with 16 to 24 carbon atoms or their mixtures with subordinate amounts of other, in particular saturated monocarboxylic acids and monofunctional alcohols with preferably 6 to 12 carbon atoms . These ester oils are also flowable and pumpable in the temperature range from 0 to 5 C.
• esters of this type which are more than 70% by weight, preferably more than 80% by weight and in particular more than 90% by weight.
• the solidification values are below - 10 C, preferably below - 15 ° C, while the flash points are above 100 C and preferably above 160 ° C.
• the esters used in the drilling mud show a Brookfield (RVT) viscosity of not more than 55 mPas, preferably not more than 45 mPas, in the temperature range from 0 to 5 C.
• ester oils of the type concerned here two subclasses can be defined.
• the unsaturated C ... - "- monocarboxylic acid residues present in the ester are not derived to more than 35% by weight. -% of 2- and poly-olefinically unsaturated acids, preferably at least about 60 wt. -% of the acid residues are simply olefinically unsaturated.
• the C, c - "- monocarboxylic acids present in the ester mixture are derived to more than 45% by weight. -%, preferably i o -__ 4 more than 55% by weight of 2- and / or poly-olefinically unsaturated acids.
• Saturated carboxylic acids in the range C .. -, .. - present in the ester mixture expediently make up no more than about 20% by weight and in particular no more than about 10% by weight.
• Saturated carboxylic acid esters are preferably in the range of lower C numbers for the acid residues.
• the carboxylic acid residues in front can be vegetable and / or be of animal origin. Vegetable starting materials are, for example, palm oil, peanut oil, castor oil and in particular rape oil.
• Carboxylic acids of animal origin are, in particular, corresponding mixtures of fish oils such as herring oil.
• esters of C, - monocarboxylic acids and mono- and / or polyfunctional alcohols which are flowable at room temperature and have flash points above 80 C, which are preferably also in the temperature range are flowable and pumpable from 0 to 5 ° C.
• esters of these lower carboxylic acids with monofunctional alcohols with at least 8 carbon atoms and / or esters of these acids with 2 to 4-valent alcohols with preferably 2 to 6 carbon atoms are particularly suitable.
• acetic acid is particularly suitable as the ester-forming acid component of this class. Measurements of the rheology and volatility or the solidification values of preferred esters in this subclass correspond to the values mentioned above.
• the chain length in Vor ⁇ are predominantly aliphatic saturated alcohols in the range of C ", 5, in case 1 - and polyolefinically unsaturated alcohols, but also in higher C numbers, for example up to about C 2 ". Details can be found in the applicant's older patent application P 39 07 391 .2 (D 8606).
• esters described in the parallel application P 39 07 392.0 (D8607) from synthetic and / or natural monocarboxylic acids with 6 to 11 carbon atoms and 1- and / or polyfunctional ones Alcohols, which are preferably flowable and pumpable even in the temperature range from 0 to 5 C.
• Suitable mixture components are at least largely water-insoluble alcohols of pronounced oleophilic character, such as those in the form of an oil phase or at least as a component of the closed oil phase of such W / O invert emulsions in the applicant's parallel application. . . (D 851 1/8512).
• water-insoluble alcohols of pronounced oleophilic character such as those in the form of an oil phase or at least as a component of the closed oil phase of such W / O invert emulsions in the applicant's parallel application. . . (D 851 1/8512).
• Multi-component mixtures fall within the scope of the invention, which together with the ethers defined according to the invention can contain one or more of the mixture components listed in detail here.
• any mixes can be used, provided they meet the basic theological requirements for invert drilling fluids of the type concerned here.
• Examples of such multi-component mixtures include materials based on different types of ester oils or mixtures of substances additionally containing mineral oil.
• oleophilic basic amine compounds are used as an additive together with ester oils, which are described in detail in applicant's earlier application P 39 03 785.1 (D 8543) mentioned at the beginning. For details, reference is made to the disclosure of this earlier application described at the outset.
• ester oils are also used as mixture components in the context of the invention - and in particular ester oils based on carboxylic acids with at least 6 C atoms - are used, it may be expedient not to use significant amounts of highly hydrophilic bases of inorganic and / or organic in the oil rinse Way to share.
• Lime can be used effectively as an alkali reserve. However, it is then expedient to limit the maximum amount of lime to be used with about 2 lb / bbI, it being preferred to work with drilling mud loads on lime that are slightly below this, for example in the range from about 1 to 1.8 Ib / bbI (lime / drilling fluid) lie.
• other known alkali reserves can be used.
• 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 wt. -%.
• the range from about 10 to 25% by weight of disperse aqueous phase can be of particular importance.
• 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. Nos. 4,374,737 and the literature cited therein.
• a particularly suitable type of emulsifier is the product sold by NL Baroid 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, in each case based on the oil phase.
• hydrophobicized 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 Ib / bbI or in the range from about 5 to 7% by weight, based on the oil phase.
• the viscosity former usually used is a cationically modified, finely divided bentonite, which can be used in particular in amounts of about 8 to 10 lb / bbI or in the range of about 2 to 4% by weight, based on the 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 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 plastic viscosity (PV), the yield point (YP) and the strength of the spirit are determined after 10 seconds and after 10 minutes on the invert drilling fluid by viscosity measurement at 50 ° C. on the unaged material.
• the invert drilling fluid is then aged for 16 hours at 125 ° C. in an autoclave in a “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.
• the values determined on the unaged and aged material are the following:
• the viscosity values measured on the unaged and aged drilling fluid are as follows: unaged aged
• invert drilling fluids are produced at an O / W ratio of 90/10 according to the following recipe: 230 ml ether (see the following identification in the
• Example 3 C -O-Cg
• Example 4 c ⁇ o- ° - c ⁇ o
• Example 5 Di-isotridecyl ether The viscosity values measured on the unaged and the aged drilling fluid are summarized below. The aging is determined once after 16 hours at 125 ° C and in another test after 72 hours at 125 ° C.
• test batches of this example are additionally modified in the following manner: For aging over a period of 72 hours, a drilling fluid of the recipe given is used, to which an additional 2 g of a pronounced oleophilic amine (hand ice product "Araphen G2D" from the applicant) have been added was. The following values are determined:
• Plastic viscos 63 63 63 act PV

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• Chemical & Material Sciences (AREA)
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• Life Sciences & Earth Sciences (AREA)
• General Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Organic Chemistry (AREA)
• Lubricants (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Earth Drilling (AREA)
• Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
• Treatment Of Sludge (AREA)
• Drilling Tools (AREA)
• Electrical Discharge Machining, Electrochemical Machining, And Combined Machining (AREA)
• Detergent Compositions (AREA)
• Materials For Medical Uses (AREA)

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• 1989
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