CA2047697C - Use of selected ester oils of low carboxylic acids in drilling fluids - Google Patents
Use of selected ester oils of low carboxylic acids in drilling fluids Download PDFInfo
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- CA2047697C CA2047697C CA002047697A CA2047697A CA2047697C CA 2047697 C CA2047697 C CA 2047697C CA 002047697 A CA002047697 A CA 002047697A CA 2047697 A CA2047697 A CA 2047697A CA 2047697 C CA2047697 C CA 2047697C
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- 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
- C09K8/36—Water-in-oil emulsions
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- 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
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Abstract
The invention describes the use of selected esters, fluid at room temperature and with flash points above 80°C, of C1-5-monocarboxylic acids and mono- and/or polyfunctional alcohols as the oil phase, or a component of the oil phase of invert drilling muds which are suitable for environment-friendly development of petroleum or natural gas deposits and contain in a continuous oil phase a dispersed aqueous phase together with emulsifiers, weighting agents, fluid-loss additives and preferably further conventional additives. In a further embodiment the invention relates to invert drilling fluids of the type described, which are characterized in that the oil phase contains esters from C1-5-monocarboxylic acids with mono-and/or polyfunctional alcohols preferably in admixture with other components from the class of ecologically acceptable compounds.
Description
"The use of selected ester oils of low carboxylic acids in drilling fluids"
The invention discloses new drilling fluids based on ester oils and invert drilling mulls muilt up thereon, which are distinguished by high ecological acceptability and at the same time good keeping and application properties. An imQortant area of application for the new drilling fluid systems ~s in off-shore web s for the develognent of ' petroleum and/or natural gas deposits, the aim of the invention being particularly to make available technically usable drilling fluids with high ecological acceptability. The use of the new drilling fluid syst~ns has particular significance in the marine environment, but is not limited thereto. The new mud systems can be put to quite general use e~:en in land-based drilling, for example, in geothermal wells, water boreholes, in the drilling of geoscientific bores and in drilling for the mining indiatry. Here too it is essentially true that associated ecotoxic problems are substantially simplified by the ester-base drilling oil fluids selected according to the invention.
Oil-base drilling fluids are generally used as so-called invert-emulsion mulls, which consist of a three-phase system: oil, water and finely particulate solids. These are preparations of the W/O enulsion type, i.e. the aqueous phase is distributed as a heterogeneous fine dispersion in the continuous oil phase. A number of additives can be used to stabilize the system as a whole and to adjust the desired ~~oplication properties, particularly emulsifiers or emulsifier systems, weighting agents, f laid=loss additives, alkali reserves, viscosity regulators and the like. For details, refer, e.g., to the publication by P.A. Boyd et al. "New Base Oil Used in Laa-Zbxicity Oil Mulls"
Journal of Petroleum Technology, 1985, 137 to 142, and R.B. Hennett, "New Drilling Fluid Technology - Mineral Oil Mud" Journal of Petroleum Technology, 1984, 975 to 981 and the literature cited therein.
The relevant technology has for some time re ognized the importance of - 2 - __ ester-base oil phases in reducing the problems caused by such oil-base mulls. For example, US Patent Specifications 4,374,737 and 4,481,121 disclose oil-base drilling fluids in which non-polluting oils are to be used. 'The following are mentioned as non-polluting oils of equal value - mineral oil fractions free from arrxnatic hydrocarbons and vegetable oils such as peanut oil, soybean oil, linseed oil, corn oil, rice oil or even oils of animal origin, such as whale oil. Without exception, these named ester oils of vegetable and animal origin are triglycerides of natural fatty acids, which are lmawn to have a high environmental acceptability, and- are clearly superior from the ecological viewpoint when oayared with hydrocarbon fractions - even Interestingly enough, however, none of the examples in the aforementioned US Patent Specifications describes the use of such natural ester oils in invert-drilling fluids such as those in question here. In all cases, mineral oil fractions are used as the continuous oil phase. Oils of vegetable and/or animal origin are not considered for reasons of practicality. The Theological properties of such oil phases cannot be controlled for the wide temperature range reaching from 0 to 5°C on the one hand up to 250°C on the other hand, which is widely required in the industry.
In use, ester oils of the type in question do not in fact behave in the same way as the mineral oil fractions based on pure hydrocarbons which were previously used. Est a r oils are subject to partial hydrolysis in practical use also and particularly in W/0 invert drilling raids. Fee carboxylic acids are formed as a result. The publications DE 38 42 659 and DE 38 42 703 describe the problems caused thereby and give suggestions for their solution.
The subject of these publications is the use of ester oils based on selected monocarboxylic acids or monocarboxylic acid mixtures and monofunctional alcohols with at least 2, and preferably with at least 4 carbon atoms. The publications show that with the esters and ester mixtures they disclose, monofunctional reactants can r not only be given satisfactory theological properties in fresh drilling fluid, but that by using selected known alkali reserves it is possible to work with the drilling fluid and in this way to inhibit undesirable corrosion. For the alkali reserve, one can add calcium hydroxide or lime and/or use zinc oxide or comparable zinc compounds.
However, in this case an additional restriction is advisable. If undesired thickening of the oil-base invert-mud system is to be prevented in practical use, the arount of alkalizing additive and in particular the amount of lime must be limited. The tnaxitrnun amount provided is set at about 2 lb/bbl oil-base mud in the disclosure of the aforementioned publications.
' The teaching of the present invention intends to avoid the problems described above by using in the drilling fluids of the afor~nentioned type a class of ester oils which forms non-problematical carboxylic acids and carboxylic-acid salts during the limited ester hydrolysis which always occurs. This idea can be technically realized by the selection of estar oils which are based on lower carboxylic acids with 1 to 5 carbon atcens. The corresponding esters from acetic acid are particularly significant here. The acetate salts which form during the partial hydrolysis of the ester oil do not have the emulsifying properties which could substantially disturb the W/O system.
The subject of the invention is accordingly, in a first embodiment, the use of esters, fluid at roots tgtperature and having flash points above 80oC, frcen Cl_5-tronocarboxylic acids and tmno- and/or polyfunctional alo~hols as the oil phase or as a catponent of the oil phase of invert-drilling mulls, which are suitable for an environment-frietxlly development of petroleum or natural gas deposits, and in a continuous oil phase contain a dispersed aqueous phase together with emulsifiers, weighting agents, fluid-loss additives and preferably further vonventional additives.
In a further gtibodiment the invention relates to invert-drilling fluids which are suitable far the purpose itxLicated and vont,ain, in a continuous oil phase, - a dispersed aqueous phase together with the additives mentioned, and which are characterized in that the oil phase vonsists at least partly of the above esters of C1_5-tmonocarboxylic acids with mono- and/or polyfunctional alcohols.
The substance properties of the monocarboxylic acid esters of the type referred to in the invention can be so controlled by the selection of the alcohol ocer~onents used for the esterification, that it is possible to use them as described in the invention. Corresponding esters or ester mixtures are preferably used which are fluid and pumpable even in the temperature range of 0 to 5°C. It is also preferred to use as the oil phase C1-5-monocarboxylic acid esters or their admixtures with ecologically acceptable ooa~onents frcm the class of so-called non-polluting oils, which in the temperature range of 0 to 5°C possess a Brc~~kfield (RVT) viscosity of not above 50 mPas and preferably not above 40 mPas. The viscosity of the oil phase is preferably at most about 30 mPas.
The C1_5-carboxylic-acid esters used in the drilling mud of the invention usefully have solidification values (pour~and setting point) below 0°C, preferably below -5°C and particularly below -10°C. At the same time, particularly for safety reasons, the flash points of these esters are to be selected as high as possible so that preferred limit values for the flash point lie at about 90°C and preferably above 100oC.
The esters of the lower carboxylic acids suitable according to the invention can be divided into two sub-classes. In a first class the lower monocarboxylic acids are reaction products of monofunctional aloohols. In this case the carbon number of the alcohol is at least 6, but is preferably higher, i.e. at least 8 to 10 carbon atoms. The second sub-class of the ester oils referred to here uses polyfunctional aloohols as the ester-forming ax~ponents. Particularly to be~
considered here are di- to tetra-hydric alcohols, lower alcohols of this type, preferably with 2 to 6 carbon atcans, being particularly suitable. Typical exar~les of such poly-hydric aloohols are glycol and/or propanediols. Both ethylene glycol and 1,2-propanediol and/or 1,3-propanediol are particularly important. In the case described here of esters of polyhydric alcohols, completely esterified reaction products are preferred, even though the invention - in particular in the case of the polyfunctional aloohols - is not limited thereto. In 20476~J7 the latter case in particular, the use of partial esters of such hiker valency polyfunctional alcohols with the lower carboxylic acids mentioned can be considered.
The most in~ortant esters for the teaching of the invention are derived from monocarboxylic acids with 2 to 4 carbon atoms, with acetic acid, already mentioned, being of particular importance as the ester-forming c~r~onent.
When selecting the appropriate aloohols it is important tc~ take account of the following additional considerations: When the ester oil is used in practice, as a rule it is not possible to exclude paotial saponification of the ester. Free alcohols form, in addition to the free carboxylic acids thus formed or carboxylic acid salts forming together with the alkali reserves. They should be selected such that even after partial hydrolysis operational conditions are ensured which are ecologically and toxicologically harmless, with inhalation-toxioological considerations in particular being taken into account.
The alcohols used for the ester formation should in particular possess such a low volatility that in the free state under conditions to be exQected in practice, they dp not result in any nuisance on the working platform. For the class of ester oils based on very short-chain monocarboxylic acids which are selected in the invention, it is necessary from the outset to use oc~aratively long-chain monofunctional alcohols, so as to reduce sufficiently the volatility of the ester oil. The considerations discussed here are therefore particularly important in cases in which ester oils of the type defined in the invention are used in blends with other mixture oa~Onents, in particular other carboxylic acid esters. In the invention it is regarded as particularly i.~ortant in the preferred embodiment that even after partial hydrolysis in use, the drilling fluids are ecologically and toxicologically harmless, particularly inhalation-toxicologically harmless under working conditions.
Suitable aloohols, particularly suitable monofunctional alcohols can be of natural and/or synthetic origin. Straight-chain and/or branched aloohols can be used here. The chain length in the presence of predominantly aliphatic-saturated alcohol is preferably from 8 to 15 .. 2047697 carbon atcgns. In any case olefin mono- and/or poly-unsaturated aloohols are also suitable, such as can be obtained, for example, by the selective reduction of naturally occurring unsaturated fatty acids or fatty acid mixtures. Olefin-mono- and/or poly-unsaturated alcohols such as this can also have higher carbon numbers in the ester oils according to the invention, for example, up to 24 carbon atoms.
Ester oils of the type mentioned here can form the whole of the continuous oil phase of the W/O invert mud. On the other hand there is an industrial process in the scope of the invention in which the carboxylic-acid esters defined in the invention only constitute a mixture oampor~ent of the oil phase. Practically any of the oil ~onents previously known and/or previously described in the relevant area of application are suitable as further oil ~rponents.
Particularly suitable mixture oaiponents will be discussed below.
The ester oils according to the invention are as a rule harogeneously miscible with the mixture ~onents in any desired mixture ratios. ~It is useful in the framework of the invention for at least about 25 % and particularly at least about a third of the oil phase to be in the form of the C1_5-ester oils. In important embodiments of the invention these ester oils form the main part of the oil phase.
Mixture oallQonents in the oil phase Suitable oil oo~ponents for admixture with the monocarboxylic acid esters of the invention are the mineral oils currently used in practice in drilling fluids, and preferably the aliphatic and/or cycloaliphatic hydrocarbon fractions essentially free frail amnatic hydrocarbons and which the required rheological properties. Refer here to the prior-art publications cited and the available commercial products.
Particularly important mixture axiponents are, however, ester oils with are ecologically acveptable _when used acoordi~g to the invention, as -described, for example, in the above publications DE 38 42 659 and DE 38 42 703.. To complete the invention disclosure, essential characteristics of these esters or ester mixtures '~' ; are briefly summarized below.
_ , _ __ As the oil phase, in a first embodiment, esters are used of monofunctional alcohols with 2 to 12, particularly with 6 to 12 carbon atoms and aliphatic-saturated monocarboxylic acids with 12 to 16 carbon at~xns, which esters are fluid and pu~able in the temperature range of 0 to 5°C, or an admixture thereof with at rrost about the same amounts of other monocarboxylic acids. E st a r oils are preferred which at least to about 60 % by weight - referred to the respective carW xylic acid mixture - are esters of aliphatic C12-1~-monocarboxylic acids and preferably for the remaining percentage are based on lower amounts of shorter-chain aliphatic and/or longer chain, and in particular olefin mono- or poly-unsaturated monocarboxylic acids.
. Esters are preferably used which in the temperature range of 0 to 5°C
have a Brookfield (RVT) viscosity of not above 50 mPas, preferably not above 40 mPas and particularly of a ma~curnun of about 30 mPas. The esters used in the drilling mud have solidification values (pour and setting point) below -10°C, preferably below -15°C and have at the same time 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 fratn corresponding triglycerides such as coconut oil, palm kernel oil and/or babassu oil. The alcohol radicals of the esters used are derived in particular from straight-chain and/or branched saturated alcohols preferably with 6 to 10 carbon atoms. These alcohol oa~onents can also be of vegetable and/or animal origin and can thus be obtained by reductive hydration of corresponding carboxylic acid esters.
A further class of particularly suitable ester oils is derived from olefin mono- and/or poly-unsaturated monocarboxylic acids with 16 to 24 carbon atoHns or their admixtures with lager amounts of other particularly saturated monocarboxylic acids and monofunctional aloohols with preferably 6 to 12 carbon atans. These ester oils are also fluid and pumpable in the terperature range of 0 to 5°C. Particularly suitable are such esters derived to more than 70 % by weight, preferably to more than 80 % by weight and in particular to more than 90 % by weight from olefin-unsaturated carboxylic acids with between 16 and 24 carbon atoms. _ - 8 - __ Here too the solidification values (pour and setting point) lie below -lOoC, preferably below -15°C while the flash points lie above 100oC and preferably above 160°C. In the ter~erature range of 0 to 5°C the esters used in the drilling mud have a Brookfield (RVT) vis<_rosity of not rrore than 55 mPas, preferably not more than 45 mPas.
~o subclasses can be defined for the ester oils of the type in question. In the first, the unsaturated C16-24-m°n~°xYlic acid radicals present in the ester are derived tc~ not more than 35 % by weight frcm olefin di- and poly-unsaturated acids, with preferably at least about 60 % by weight of the arid radicals being olefin mono-unsaturated. In the second gnbodiment the C16-24-~~~X1'lic acids present in the ester mixture are derived at more than 45 % by weight, preferably at mire than 55 % by weight fran olefin di- and/or poly-unsaturated acids. It is useful if the saturated carboxylic acids with between 16 to 18 carbon at~ns which are present in the ester mixture do :got amount to more than about 20 % by weight and in particular not more than about 10 % by weic~t. Preferably, saturated carboxylic acid esters, however, have lower carbon numbers in the acid radicals. The cari~oxylic acid radicals present can be of vegetable and/or animal origin. Vegetable starting materials are, for. exanple, palm oil, peanut oil, castor oil and in particular rapeseed oil. The carboxylic acids of animal origin are particularly corresporxiing mixtures of fish oils, such as herring oil.
Suitable mixture catponents are finally however the esters from mc~nocarboxylic acids of synthetic and/or natural origin with 6 to 11 carbon atoms and mono- and/or polyfunctional alcohols, described in the co-pending Canadian Application 2,047,706, filed March 1, 1990 (DE 39 07 392), which are preferably also fluid and pumpable in the temperature range of 0 to 5 °C .
E
204~69~
- __ Further mixture oorr~onents of the invert drillinq fluid All the usual constituents of mixtures for conditioning and for the practical uses of invert drilling roods can be considered here, that are currently used with mineral oils as the continuous oil phase. In addition to the dispersed aqueous phase, emulsifiers, weighting agents, fluid-loss additives, viscosifiers and alkali reserves can be considered here.
Use is also made in a particularly important embodiment of the invention, of the further development of these ester oil-base invert drilling fluids which is the subject of the Applicant's co-pending Canadian Application 2,009,689, filed February 9, 1990 (DE 39 03 785).
The teaching of this co-pending Application is based on the concept of using a further additive in ester oil-base invert-drilling fluids, which is suited to keeping the desired rheological properties of the drilling fluid in the required range even when, in use, increasingly large amounts of free carboxylic acids are formed by partial ester hydrolysis. These liberated carboxylic acids should not only be trapped in a harmless form, it should moreover be possible to reform these free carboxylic acids, preferably into valuable oarponents with stabilizing or emulsifying properties for the whole system. According to this teaching, alkaline amine oa~ounds of marked oleophilic nature and at best limited water solubility, which are capable of forming salts with carboxylic acids, can be used as additives in the oil phase. The oleophilic amine compounds can at the same time be used at least in part as alkali reserves in the invert drilling fluid, they can however also be used in combination with vonventional alkali reserves, particularly together with lime. The use of oleophilic amine varpounds which are at least largely free from aromatic constituents is preferred. In particular, optionally olefin unsaturated aliphatic, cycloaliphatic and/or heterocyclic oleophilic basic amine oa~OUnds~
can be considered, which contain one or tmre N-groups capable of forming salts with carboxylic acids. In a preferred embodiment the water-solubility of these amine oa~unds at roan temperature is at most about 5 % by weight and is most preferably below 1 % by weight.
_ to _ _. 2047697 Typical exiles of such amine ax~ounds are primary, secondary and/or tertiary amines, which are at least predominantly water-insoluble, and which can also to a limited extent be alkoxylated and/or substituted particularly with hydroxyl groups. Further examples are corresponding aminoamides and/or heterocycles containing nitrogen as ring constituent. For example, basic amine oorrpounds are suitable which have at least one long-chain hydrocar!~on radical with preferably 8 to 36 carbon atcans, particularly with 10 to 24 carbon atoms, which can also be olefin mono- or poly-unsaturated. The oleophilic basic amine compounds can be added to the drilling fluid -in amounts of up to about lb/bbl, preferably in arrounts up to about 5 lb/bbl and particularly in the range of about 0.1 to 2 lb/bbl.
It has emerged that the use of such oleophilic basic amine o~rø~ounds can effectively prevent thickening of the mud system, which presumably can be attributed to a disturbance in the W/O invert system and also to the formation of free carboxylic acids by ester hydrolysis. '' If in the context of the invention teaching, esters of longer-chain carboxylic acids are used as mixture cocrponents, which on hydrolytic cleavage yield fatty acids or fatty-acid salts with a pronounced O/W-emulsifying effect, then in the method according to the invention the measures regarding the alkali reserves should also be taken into consideration as described in detail in the aforementioned publications DE 38 42 659 and DE 38 42 703 in association with such problems. When such ester mixtures are used the following applies:
In a preferred embodiment of the use according to the invention, care is taken not to use considerable amounts of strongly hydrophilic bases of inorganic and/or organic nature in the oil-base mud. In particular the invention refrains fran using alkali hydroxides or strongly hydrbphilic amines such as diethanolamine and/or triethanolamine. Lime can be also used effectively as an alkali reserve. It is then useful to limit the maximum amount of lime to be used to about 2 lb/bbl, and it may be preferred to work with lime contents in the drilling tn~d slightly below this, e.g., therefore, frrm about 1 to 1.8 lb/bbl (lime/drilling fluid). Other known alkali reserves can be used in _ _ addition to or in place of the lime. The less basic metal oxides, such as zinc oxide, should particularly be mentioned here. E~ren when these acid traps are used, care is still taken that the amounts used are not too large, so as to prevent undesired premature ageing of the drilling fluid, associated with an increase in viscosity and therefore a deterioration in the rheological properties. The special features discussed here of the process according to the invention prevent, or at least restrict, the formation of undesirable amounts of highly active O/W-~nulsifiers, so that the good r!~eological properties are maintained for a sufficiently long time in use, even when there is thern~al ageing.
The following also applies:
Invert-drilling mulls of the type in question here usually contain, together with the continuous oil phase, the finely dispersed aqueous phase in amounts of about 5 to 45 % by weight and preferably in amounts of about 5 to 25 % by weight. A dispersed aqueous phase from about 10 to 25 % by weight can be regarded as particularly useful.
The following rheological data apply to the rheology of preferred invert drilling mulls according to the invention: Plastic viscosity (PV) frown about 10 to 60 mPas, preferably about 15 to 40 mPas. Yield point (YP) from about 5 to 40 lb/100 ft2, preferably about 10 to 25 lb/100 ft2 - each measured at 50oC. For the measurement of these parameters, for the measuring methods used and for the rest of the conventional oce~osition of the invert drilling fluids described here, refer in detail to the specifications in the prior art which were cited above and are, for example, described fully in the handbook "Manual of Drilling Fluids Technology" of NL-Baroid Co., London, GB, particularly in the chapters "Mud Testing - Tools and Techniques" and "Oil Mud Technology", which is freely accessible to interested experts. In su~y, for the purposes of oarpleting the invention disclosure the following can be said:
The emulsifiers which can be used in practice are systems which are suitable for the formation of the required W/O emulsions. In particular, selected oleophilic fatty acid salts, for example, those based on amidoamine oortpounds can be considered. Examples of these are -. 2p47697 described in the already cited US-PS 4,374,737 and the literature cited there. A particularly suitable type of emulsifier is the product sold by NLrBaroid Co. under the trade-mark "EZ-mul" .
Emulsifiers of the type in question are sold a~mercially as highly concentrated active-substance preparations and can, for example, be used in amounts of about 2.5 to 5 % by weight, particularly in amounts of about 3 to 4 % by weight - each based on the ester oil phase.
In pracrice, hydrophobized lignite in particular is used as the fluid-loss additive and therefore particularly for forming a dense coating on the- bore-hole walls of a largely liquid-impermeable film. Suitable amounts are, fob example, from about l5 to 20 lb/bbl or frcan about 5 to 7 % by weight, based on the ester oil phase .
The visoosifier conventionally used in drilling fluids of the type in question here, is a ration-modified finely particulate bentonite, which can be used particularly in amounts of about 8 to 10 lb/bbl or frnm about 2 to 4 % by weight, based on the ester oil phase. The weighting material conventionally used in relevant applications to establish the necessary pressure vompensation is barite, and the amounts added are varied according to the drilling conditions anticipated in each case. It i$, for exanple, possible by adding barite to raise the specific gravity of the drilling fluid to values up to 2.5 and preferably from about 1.3 to 1.6.
The dispersed aqueous phase in these invert drilling fluids, is loaded with soluble salts. Calcium chloride and/or potassi,.un chloride are mainly used here, and saturation of the aqueous phase with the soluble salt at room tatperature is preferred.
The aforementioned emulsifiers or emulsifier systems can optionally also be used to improve the oil wettability of the inorganic weighting materials. In addition to the aminoamides already mentioned, further exanples are alkylbenzene sulfonates and imidazoline compounds.
Additional inforn~ation regarding the relevant prior art can be found in the following publications: CB 2 158 437, EP 229 912 and DE 32 47 123.
The drilling fluids synthesized according to the invention using ester oils of the type described are distinguished, in addition to the advantages already described, by a notably i~roved lubricity. This is particularly important when in very deep wells, for example, the path of the drill rod and therefore the borehole deviates frcen the vertical.
The rotating drill rod oo~nes slightly into contact with the borehole wall and when operating buries itself into it. Ester oils of the type used as the oil phase according to the invention have a notably better lubricity than the mineral oils previously used. This ~s another imQortant advantage of the method according to the invention.
E~~es In the following examples invert drilling fluids are prepared in the conventional manner using the following basic fornlulation:
230 ml ester oil 26 ml water TM
6 g organophilic bentonite (Geltone II of NL Baroid Co.) TM
12 g organophilic lignite (Duratone of NL Baroid Co.) x g lime (x = 1 or 2) 6 g W/O emulsifier (EZ-mul NT of NL Baroid Co.) 346 g barite 9.2 g , CaCl2 x 2 H20 In this formulation about 1.35 g of lime corresponds to 2 lb/bbl.
After a W/O invert drilling fluid has been prepared in a lmc~m manner from the components used, with variation of the ester oil phase, the viscosities of the unaged and then the aged material arA determined !as follows:
TM
Measurement of the viscosity at 50°C in a Fann-35-viscosimeter supplied by NL Baroid Co. The plastic viscosity (PV), the yield point (YP) and the gel strengths (lb/100 ft2) are determined in a Imown manner after sec. and 10 min.
Ageing is carried out by treatment in autoclaves - in the so-called roller-oven - for a period of 16 hours at 125°C.
Isotridecyl acetate which has the following rheological characteristics is used as the ester oil: viscosity at 20oC 5 mPas; viscosity at 50oC
2.1 mPas; setting point below -lOoC.
In Exanple 1 below, the amount of lime used in the basic formulation is 2 g, in F~ple 2 this lime amount is reduced to 1 g.
The values determined for the unaged and aged material are listed in the following table.
W
_2A47697 unaged material aged material plastic viscosity (PV) 31 33 yield point (YP) 11 13 gel strengths (lb/100 ft2) 1C sec. 6 7 min. 9 9 Example 2 unaged material aged material plastic viscosity (PV) 24 25 yield point (YP) 14 12 gel strengths (lb/100 ft2) 10 sec. 5 5 10 min. 8 7 The basic formulation in Exa~les 1 and 2 has a value of 90/10 for the oil phase/water weight ratio. In further tests the the ester oil/water ratio is changed to 80/20.
In Examples 3 and 4 below, invert drilling fluids are prepared using the ester oil based on isotridecyl acetate, according to the following basic forniulation:
210 m1 ester oil 48.2 g water TM
6 g organophilic bentonite (Q~igel) 13 g or.ilic lignite (Duratone of I~ Bar~oid Co.) 2 g lime 8 g W/0-~ulsifier (EZ-mul NT of NL Baroid Co.) 270 g barite g CaCl2 x 2 H20 As in Exanples 1 and 2, the viscosities are determined first on the unaged, then on the aged material (16 hours at 125°C in the roller oven) (Exanple 3). .
2a47697 In a further test formulation (ale 4), 2 g of a strongly oleophilic amine is added to the basic formulation given for ale 3 TM
(Applicant's oonmercial product "Araphen G2D" - the reaction product of an epoxidized C12/14-alpha-olefin and diethanolamine). The viscosity characteristics are then determined as above first on the unaged and then on the aged material.
ale 3 unaged material aged material plastic viscosity (PV) 34 36 yield point (YP) 52 51.
gel strengths (lb/100 ft2) sec. 25 23 10 min. 37 35 F~cample 4 unaged material aged material plastic visvosity (Ptl) 31 34 yield point (YP) 36 32 gel strengths (lb/100 ft2) 10 sec. 14 13 10 min. 17 15 E~cample 5 The ester-mixture fran acetic acid and a C6_10'aloohol cut (Applicant's TM
ocmmercial product "Lorol'technisch"), prepared by the reduction of the corresponding pre-fatty-acid cut of natural origin, is used as the ester oil. The basic forn~ulation for the ester mud corresponds to the fornailation given for ~anple 2.
The visvosity data are determined and the ageing is carried out as indicated in the previous acanples. The following visoosities are determined. 2 ~ 4 7 6 9 7 unaged material aged material plastic visvosity (PV) 28 29 yield point (YP) 17 20 gel strengths (lb/100 ft2) sec. g g 10 min. 24 14 ~~~les 6 to 8 In parallel formulations, three drilling fluids based on isotridecyl acetate are produced according to the basic formulation in Exanples 1 and 2 (oil phase/water = 90/10). As in the preceding ales, their rheological data was determined im~iately after preparation and after ageing in the roller oven at 125oC for a period of 16 hours.
In a first mud, no lime is added (ale 6), in a second mud (ale 7) 2 g of lime is used, while in the parallel third mud (ale 8) 2 g of lime is used together with 1 g of the strongly oleophilic amine "Araphen G2D".
The rheological data determined in each case are as follows:
~1e6 2047697 unaged material aged material plastic viscosity (PV) 28 30 yield point (YP) 15 9 gel strengths (lb/100 ft2) sec. y 10 min. 10 8 ale 7 unaged material aged material plastic viscosity (PV) 30 29 yield point (YP) 13 17 gel strengths (lb/100 ft2) 10 sec. g g 10 min. 10 12 F~cample 8 unaged material aged material plastic viscosity (PV) 25 25 yield point (YP) 12 8 gel strengths (lb/100 ft2) 10 sec. g 10 min. 11 9 les 9 to 11 In a further oca~arative series of tests, drilling fluids based on isotridecyl acetate are vombined in the basic formulation of E~camples 6 to 8 as follows: bcanple 9 addition of 1 g of lime; ale 10 addition of 2 g of lime; Ele 11 addition of 2 g of lime + 1 g of "Araphen G2D".
2o4~ss~
These mulls are then aged, however, in the roller oven at 125°C
for a period of 72 hours. The rheological data determined on the unaged and aged material in each case are as follows:
Example 9 unaged material aged material plastic viscosity (PV) 30 37 yield point (YP) 15 16 gel strengths (lb/100 ft2) sec. 7 7 10 min. 11 10 Example 10 unaged material aged material plastic viscosity (PV) 28 34 yield point (YP) 16 13 gel strengths (lb/100 ft2) 10 sec. 6 6 10 min. 10 10 Example 11 unaged material aged material plastic viscosity (PV) 29 36 yield point (YP) 11 14 gel strengths (lb/100 ft2) 10 sec. 7 6 10 min. 10 10
The invention discloses new drilling fluids based on ester oils and invert drilling mulls muilt up thereon, which are distinguished by high ecological acceptability and at the same time good keeping and application properties. An imQortant area of application for the new drilling fluid systems ~s in off-shore web s for the develognent of ' petroleum and/or natural gas deposits, the aim of the invention being particularly to make available technically usable drilling fluids with high ecological acceptability. The use of the new drilling fluid syst~ns has particular significance in the marine environment, but is not limited thereto. The new mud systems can be put to quite general use e~:en in land-based drilling, for example, in geothermal wells, water boreholes, in the drilling of geoscientific bores and in drilling for the mining indiatry. Here too it is essentially true that associated ecotoxic problems are substantially simplified by the ester-base drilling oil fluids selected according to the invention.
Oil-base drilling fluids are generally used as so-called invert-emulsion mulls, which consist of a three-phase system: oil, water and finely particulate solids. These are preparations of the W/O enulsion type, i.e. the aqueous phase is distributed as a heterogeneous fine dispersion in the continuous oil phase. A number of additives can be used to stabilize the system as a whole and to adjust the desired ~~oplication properties, particularly emulsifiers or emulsifier systems, weighting agents, f laid=loss additives, alkali reserves, viscosity regulators and the like. For details, refer, e.g., to the publication by P.A. Boyd et al. "New Base Oil Used in Laa-Zbxicity Oil Mulls"
Journal of Petroleum Technology, 1985, 137 to 142, and R.B. Hennett, "New Drilling Fluid Technology - Mineral Oil Mud" Journal of Petroleum Technology, 1984, 975 to 981 and the literature cited therein.
The relevant technology has for some time re ognized the importance of - 2 - __ ester-base oil phases in reducing the problems caused by such oil-base mulls. For example, US Patent Specifications 4,374,737 and 4,481,121 disclose oil-base drilling fluids in which non-polluting oils are to be used. 'The following are mentioned as non-polluting oils of equal value - mineral oil fractions free from arrxnatic hydrocarbons and vegetable oils such as peanut oil, soybean oil, linseed oil, corn oil, rice oil or even oils of animal origin, such as whale oil. Without exception, these named ester oils of vegetable and animal origin are triglycerides of natural fatty acids, which are lmawn to have a high environmental acceptability, and- are clearly superior from the ecological viewpoint when oayared with hydrocarbon fractions - even Interestingly enough, however, none of the examples in the aforementioned US Patent Specifications describes the use of such natural ester oils in invert-drilling fluids such as those in question here. In all cases, mineral oil fractions are used as the continuous oil phase. Oils of vegetable and/or animal origin are not considered for reasons of practicality. The Theological properties of such oil phases cannot be controlled for the wide temperature range reaching from 0 to 5°C on the one hand up to 250°C on the other hand, which is widely required in the industry.
In use, ester oils of the type in question do not in fact behave in the same way as the mineral oil fractions based on pure hydrocarbons which were previously used. Est a r oils are subject to partial hydrolysis in practical use also and particularly in W/0 invert drilling raids. Fee carboxylic acids are formed as a result. The publications DE 38 42 659 and DE 38 42 703 describe the problems caused thereby and give suggestions for their solution.
The subject of these publications is the use of ester oils based on selected monocarboxylic acids or monocarboxylic acid mixtures and monofunctional alcohols with at least 2, and preferably with at least 4 carbon atoms. The publications show that with the esters and ester mixtures they disclose, monofunctional reactants can r not only be given satisfactory theological properties in fresh drilling fluid, but that by using selected known alkali reserves it is possible to work with the drilling fluid and in this way to inhibit undesirable corrosion. For the alkali reserve, one can add calcium hydroxide or lime and/or use zinc oxide or comparable zinc compounds.
However, in this case an additional restriction is advisable. If undesired thickening of the oil-base invert-mud system is to be prevented in practical use, the arount of alkalizing additive and in particular the amount of lime must be limited. The tnaxitrnun amount provided is set at about 2 lb/bbl oil-base mud in the disclosure of the aforementioned publications.
' The teaching of the present invention intends to avoid the problems described above by using in the drilling fluids of the afor~nentioned type a class of ester oils which forms non-problematical carboxylic acids and carboxylic-acid salts during the limited ester hydrolysis which always occurs. This idea can be technically realized by the selection of estar oils which are based on lower carboxylic acids with 1 to 5 carbon atcens. The corresponding esters from acetic acid are particularly significant here. The acetate salts which form during the partial hydrolysis of the ester oil do not have the emulsifying properties which could substantially disturb the W/O system.
The subject of the invention is accordingly, in a first embodiment, the use of esters, fluid at roots tgtperature and having flash points above 80oC, frcen Cl_5-tronocarboxylic acids and tmno- and/or polyfunctional alo~hols as the oil phase or as a catponent of the oil phase of invert-drilling mulls, which are suitable for an environment-frietxlly development of petroleum or natural gas deposits, and in a continuous oil phase contain a dispersed aqueous phase together with emulsifiers, weighting agents, fluid-loss additives and preferably further vonventional additives.
In a further gtibodiment the invention relates to invert-drilling fluids which are suitable far the purpose itxLicated and vont,ain, in a continuous oil phase, - a dispersed aqueous phase together with the additives mentioned, and which are characterized in that the oil phase vonsists at least partly of the above esters of C1_5-tmonocarboxylic acids with mono- and/or polyfunctional alcohols.
The substance properties of the monocarboxylic acid esters of the type referred to in the invention can be so controlled by the selection of the alcohol ocer~onents used for the esterification, that it is possible to use them as described in the invention. Corresponding esters or ester mixtures are preferably used which are fluid and pumpable even in the temperature range of 0 to 5°C. It is also preferred to use as the oil phase C1-5-monocarboxylic acid esters or their admixtures with ecologically acceptable ooa~onents frcm the class of so-called non-polluting oils, which in the temperature range of 0 to 5°C possess a Brc~~kfield (RVT) viscosity of not above 50 mPas and preferably not above 40 mPas. The viscosity of the oil phase is preferably at most about 30 mPas.
The C1_5-carboxylic-acid esters used in the drilling mud of the invention usefully have solidification values (pour~and setting point) below 0°C, preferably below -5°C and particularly below -10°C. At the same time, particularly for safety reasons, the flash points of these esters are to be selected as high as possible so that preferred limit values for the flash point lie at about 90°C and preferably above 100oC.
The esters of the lower carboxylic acids suitable according to the invention can be divided into two sub-classes. In a first class the lower monocarboxylic acids are reaction products of monofunctional aloohols. In this case the carbon number of the alcohol is at least 6, but is preferably higher, i.e. at least 8 to 10 carbon atoms. The second sub-class of the ester oils referred to here uses polyfunctional aloohols as the ester-forming ax~ponents. Particularly to be~
considered here are di- to tetra-hydric alcohols, lower alcohols of this type, preferably with 2 to 6 carbon atcans, being particularly suitable. Typical exar~les of such poly-hydric aloohols are glycol and/or propanediols. Both ethylene glycol and 1,2-propanediol and/or 1,3-propanediol are particularly important. In the case described here of esters of polyhydric alcohols, completely esterified reaction products are preferred, even though the invention - in particular in the case of the polyfunctional aloohols - is not limited thereto. In 20476~J7 the latter case in particular, the use of partial esters of such hiker valency polyfunctional alcohols with the lower carboxylic acids mentioned can be considered.
The most in~ortant esters for the teaching of the invention are derived from monocarboxylic acids with 2 to 4 carbon atoms, with acetic acid, already mentioned, being of particular importance as the ester-forming c~r~onent.
When selecting the appropriate aloohols it is important tc~ take account of the following additional considerations: When the ester oil is used in practice, as a rule it is not possible to exclude paotial saponification of the ester. Free alcohols form, in addition to the free carboxylic acids thus formed or carboxylic acid salts forming together with the alkali reserves. They should be selected such that even after partial hydrolysis operational conditions are ensured which are ecologically and toxicologically harmless, with inhalation-toxioological considerations in particular being taken into account.
The alcohols used for the ester formation should in particular possess such a low volatility that in the free state under conditions to be exQected in practice, they dp not result in any nuisance on the working platform. For the class of ester oils based on very short-chain monocarboxylic acids which are selected in the invention, it is necessary from the outset to use oc~aratively long-chain monofunctional alcohols, so as to reduce sufficiently the volatility of the ester oil. The considerations discussed here are therefore particularly important in cases in which ester oils of the type defined in the invention are used in blends with other mixture oa~Onents, in particular other carboxylic acid esters. In the invention it is regarded as particularly i.~ortant in the preferred embodiment that even after partial hydrolysis in use, the drilling fluids are ecologically and toxicologically harmless, particularly inhalation-toxicologically harmless under working conditions.
Suitable aloohols, particularly suitable monofunctional alcohols can be of natural and/or synthetic origin. Straight-chain and/or branched aloohols can be used here. The chain length in the presence of predominantly aliphatic-saturated alcohol is preferably from 8 to 15 .. 2047697 carbon atcgns. In any case olefin mono- and/or poly-unsaturated aloohols are also suitable, such as can be obtained, for example, by the selective reduction of naturally occurring unsaturated fatty acids or fatty acid mixtures. Olefin-mono- and/or poly-unsaturated alcohols such as this can also have higher carbon numbers in the ester oils according to the invention, for example, up to 24 carbon atoms.
Ester oils of the type mentioned here can form the whole of the continuous oil phase of the W/O invert mud. On the other hand there is an industrial process in the scope of the invention in which the carboxylic-acid esters defined in the invention only constitute a mixture oampor~ent of the oil phase. Practically any of the oil ~onents previously known and/or previously described in the relevant area of application are suitable as further oil ~rponents.
Particularly suitable mixture oaiponents will be discussed below.
The ester oils according to the invention are as a rule harogeneously miscible with the mixture ~onents in any desired mixture ratios. ~It is useful in the framework of the invention for at least about 25 % and particularly at least about a third of the oil phase to be in the form of the C1_5-ester oils. In important embodiments of the invention these ester oils form the main part of the oil phase.
Mixture oallQonents in the oil phase Suitable oil oo~ponents for admixture with the monocarboxylic acid esters of the invention are the mineral oils currently used in practice in drilling fluids, and preferably the aliphatic and/or cycloaliphatic hydrocarbon fractions essentially free frail amnatic hydrocarbons and which the required rheological properties. Refer here to the prior-art publications cited and the available commercial products.
Particularly important mixture axiponents are, however, ester oils with are ecologically acveptable _when used acoordi~g to the invention, as -described, for example, in the above publications DE 38 42 659 and DE 38 42 703.. To complete the invention disclosure, essential characteristics of these esters or ester mixtures '~' ; are briefly summarized below.
_ , _ __ As the oil phase, in a first embodiment, esters are used of monofunctional alcohols with 2 to 12, particularly with 6 to 12 carbon atoms and aliphatic-saturated monocarboxylic acids with 12 to 16 carbon at~xns, which esters are fluid and pu~able in the temperature range of 0 to 5°C, or an admixture thereof with at rrost about the same amounts of other monocarboxylic acids. E st a r oils are preferred which at least to about 60 % by weight - referred to the respective carW xylic acid mixture - are esters of aliphatic C12-1~-monocarboxylic acids and preferably for the remaining percentage are based on lower amounts of shorter-chain aliphatic and/or longer chain, and in particular olefin mono- or poly-unsaturated monocarboxylic acids.
. Esters are preferably used which in the temperature range of 0 to 5°C
have a Brookfield (RVT) viscosity of not above 50 mPas, preferably not above 40 mPas and particularly of a ma~curnun of about 30 mPas. The esters used in the drilling mud have solidification values (pour and setting point) below -10°C, preferably below -15°C and have at the same time 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 fratn corresponding triglycerides such as coconut oil, palm kernel oil and/or babassu oil. The alcohol radicals of the esters used are derived in particular from straight-chain and/or branched saturated alcohols preferably with 6 to 10 carbon atoms. These alcohol oa~onents can also be of vegetable and/or animal origin and can thus be obtained by reductive hydration of corresponding carboxylic acid esters.
A further class of particularly suitable ester oils is derived from olefin mono- and/or poly-unsaturated monocarboxylic acids with 16 to 24 carbon atoHns or their admixtures with lager amounts of other particularly saturated monocarboxylic acids and monofunctional aloohols with preferably 6 to 12 carbon atans. These ester oils are also fluid and pumpable in the terperature range of 0 to 5°C. Particularly suitable are such esters derived to more than 70 % by weight, preferably to more than 80 % by weight and in particular to more than 90 % by weight from olefin-unsaturated carboxylic acids with between 16 and 24 carbon atoms. _ - 8 - __ Here too the solidification values (pour and setting point) lie below -lOoC, preferably below -15°C while the flash points lie above 100oC and preferably above 160°C. In the ter~erature range of 0 to 5°C the esters used in the drilling mud have a Brookfield (RVT) vis<_rosity of not rrore than 55 mPas, preferably not more than 45 mPas.
~o subclasses can be defined for the ester oils of the type in question. In the first, the unsaturated C16-24-m°n~°xYlic acid radicals present in the ester are derived tc~ not more than 35 % by weight frcm olefin di- and poly-unsaturated acids, with preferably at least about 60 % by weight of the arid radicals being olefin mono-unsaturated. In the second gnbodiment the C16-24-~~~X1'lic acids present in the ester mixture are derived at more than 45 % by weight, preferably at mire than 55 % by weight fran olefin di- and/or poly-unsaturated acids. It is useful if the saturated carboxylic acids with between 16 to 18 carbon at~ns which are present in the ester mixture do :got amount to more than about 20 % by weight and in particular not more than about 10 % by weic~t. Preferably, saturated carboxylic acid esters, however, have lower carbon numbers in the acid radicals. The cari~oxylic acid radicals present can be of vegetable and/or animal origin. Vegetable starting materials are, for. exanple, palm oil, peanut oil, castor oil and in particular rapeseed oil. The carboxylic acids of animal origin are particularly corresporxiing mixtures of fish oils, such as herring oil.
Suitable mixture catponents are finally however the esters from mc~nocarboxylic acids of synthetic and/or natural origin with 6 to 11 carbon atoms and mono- and/or polyfunctional alcohols, described in the co-pending Canadian Application 2,047,706, filed March 1, 1990 (DE 39 07 392), which are preferably also fluid and pumpable in the temperature range of 0 to 5 °C .
E
204~69~
- __ Further mixture oorr~onents of the invert drillinq fluid All the usual constituents of mixtures for conditioning and for the practical uses of invert drilling roods can be considered here, that are currently used with mineral oils as the continuous oil phase. In addition to the dispersed aqueous phase, emulsifiers, weighting agents, fluid-loss additives, viscosifiers and alkali reserves can be considered here.
Use is also made in a particularly important embodiment of the invention, of the further development of these ester oil-base invert drilling fluids which is the subject of the Applicant's co-pending Canadian Application 2,009,689, filed February 9, 1990 (DE 39 03 785).
The teaching of this co-pending Application is based on the concept of using a further additive in ester oil-base invert-drilling fluids, which is suited to keeping the desired rheological properties of the drilling fluid in the required range even when, in use, increasingly large amounts of free carboxylic acids are formed by partial ester hydrolysis. These liberated carboxylic acids should not only be trapped in a harmless form, it should moreover be possible to reform these free carboxylic acids, preferably into valuable oarponents with stabilizing or emulsifying properties for the whole system. According to this teaching, alkaline amine oa~ounds of marked oleophilic nature and at best limited water solubility, which are capable of forming salts with carboxylic acids, can be used as additives in the oil phase. The oleophilic amine compounds can at the same time be used at least in part as alkali reserves in the invert drilling fluid, they can however also be used in combination with vonventional alkali reserves, particularly together with lime. The use of oleophilic amine varpounds which are at least largely free from aromatic constituents is preferred. In particular, optionally olefin unsaturated aliphatic, cycloaliphatic and/or heterocyclic oleophilic basic amine oa~OUnds~
can be considered, which contain one or tmre N-groups capable of forming salts with carboxylic acids. In a preferred embodiment the water-solubility of these amine oa~unds at roan temperature is at most about 5 % by weight and is most preferably below 1 % by weight.
_ to _ _. 2047697 Typical exiles of such amine ax~ounds are primary, secondary and/or tertiary amines, which are at least predominantly water-insoluble, and which can also to a limited extent be alkoxylated and/or substituted particularly with hydroxyl groups. Further examples are corresponding aminoamides and/or heterocycles containing nitrogen as ring constituent. For example, basic amine oorrpounds are suitable which have at least one long-chain hydrocar!~on radical with preferably 8 to 36 carbon atcans, particularly with 10 to 24 carbon atoms, which can also be olefin mono- or poly-unsaturated. The oleophilic basic amine compounds can be added to the drilling fluid -in amounts of up to about lb/bbl, preferably in arrounts up to about 5 lb/bbl and particularly in the range of about 0.1 to 2 lb/bbl.
It has emerged that the use of such oleophilic basic amine o~rø~ounds can effectively prevent thickening of the mud system, which presumably can be attributed to a disturbance in the W/O invert system and also to the formation of free carboxylic acids by ester hydrolysis. '' If in the context of the invention teaching, esters of longer-chain carboxylic acids are used as mixture cocrponents, which on hydrolytic cleavage yield fatty acids or fatty-acid salts with a pronounced O/W-emulsifying effect, then in the method according to the invention the measures regarding the alkali reserves should also be taken into consideration as described in detail in the aforementioned publications DE 38 42 659 and DE 38 42 703 in association with such problems. When such ester mixtures are used the following applies:
In a preferred embodiment of the use according to the invention, care is taken not to use considerable amounts of strongly hydrophilic bases of inorganic and/or organic nature in the oil-base mud. In particular the invention refrains fran using alkali hydroxides or strongly hydrbphilic amines such as diethanolamine and/or triethanolamine. Lime can be also used effectively as an alkali reserve. It is then useful to limit the maximum amount of lime to be used to about 2 lb/bbl, and it may be preferred to work with lime contents in the drilling tn~d slightly below this, e.g., therefore, frrm about 1 to 1.8 lb/bbl (lime/drilling fluid). Other known alkali reserves can be used in _ _ addition to or in place of the lime. The less basic metal oxides, such as zinc oxide, should particularly be mentioned here. E~ren when these acid traps are used, care is still taken that the amounts used are not too large, so as to prevent undesired premature ageing of the drilling fluid, associated with an increase in viscosity and therefore a deterioration in the rheological properties. The special features discussed here of the process according to the invention prevent, or at least restrict, the formation of undesirable amounts of highly active O/W-~nulsifiers, so that the good r!~eological properties are maintained for a sufficiently long time in use, even when there is thern~al ageing.
The following also applies:
Invert-drilling mulls of the type in question here usually contain, together with the continuous oil phase, the finely dispersed aqueous phase in amounts of about 5 to 45 % by weight and preferably in amounts of about 5 to 25 % by weight. A dispersed aqueous phase from about 10 to 25 % by weight can be regarded as particularly useful.
The following rheological data apply to the rheology of preferred invert drilling mulls according to the invention: Plastic viscosity (PV) frown about 10 to 60 mPas, preferably about 15 to 40 mPas. Yield point (YP) from about 5 to 40 lb/100 ft2, preferably about 10 to 25 lb/100 ft2 - each measured at 50oC. For the measurement of these parameters, for the measuring methods used and for the rest of the conventional oce~osition of the invert drilling fluids described here, refer in detail to the specifications in the prior art which were cited above and are, for example, described fully in the handbook "Manual of Drilling Fluids Technology" of NL-Baroid Co., London, GB, particularly in the chapters "Mud Testing - Tools and Techniques" and "Oil Mud Technology", which is freely accessible to interested experts. In su~y, for the purposes of oarpleting the invention disclosure the following can be said:
The emulsifiers which can be used in practice are systems which are suitable for the formation of the required W/O emulsions. In particular, selected oleophilic fatty acid salts, for example, those based on amidoamine oortpounds can be considered. Examples of these are -. 2p47697 described in the already cited US-PS 4,374,737 and the literature cited there. A particularly suitable type of emulsifier is the product sold by NLrBaroid Co. under the trade-mark "EZ-mul" .
Emulsifiers of the type in question are sold a~mercially as highly concentrated active-substance preparations and can, for example, be used in amounts of about 2.5 to 5 % by weight, particularly in amounts of about 3 to 4 % by weight - each based on the ester oil phase.
In pracrice, hydrophobized lignite in particular is used as the fluid-loss additive and therefore particularly for forming a dense coating on the- bore-hole walls of a largely liquid-impermeable film. Suitable amounts are, fob example, from about l5 to 20 lb/bbl or frcan about 5 to 7 % by weight, based on the ester oil phase .
The visoosifier conventionally used in drilling fluids of the type in question here, is a ration-modified finely particulate bentonite, which can be used particularly in amounts of about 8 to 10 lb/bbl or frnm about 2 to 4 % by weight, based on the ester oil phase. The weighting material conventionally used in relevant applications to establish the necessary pressure vompensation is barite, and the amounts added are varied according to the drilling conditions anticipated in each case. It i$, for exanple, possible by adding barite to raise the specific gravity of the drilling fluid to values up to 2.5 and preferably from about 1.3 to 1.6.
The dispersed aqueous phase in these invert drilling fluids, is loaded with soluble salts. Calcium chloride and/or potassi,.un chloride are mainly used here, and saturation of the aqueous phase with the soluble salt at room tatperature is preferred.
The aforementioned emulsifiers or emulsifier systems can optionally also be used to improve the oil wettability of the inorganic weighting materials. In addition to the aminoamides already mentioned, further exanples are alkylbenzene sulfonates and imidazoline compounds.
Additional inforn~ation regarding the relevant prior art can be found in the following publications: CB 2 158 437, EP 229 912 and DE 32 47 123.
The drilling fluids synthesized according to the invention using ester oils of the type described are distinguished, in addition to the advantages already described, by a notably i~roved lubricity. This is particularly important when in very deep wells, for example, the path of the drill rod and therefore the borehole deviates frcen the vertical.
The rotating drill rod oo~nes slightly into contact with the borehole wall and when operating buries itself into it. Ester oils of the type used as the oil phase according to the invention have a notably better lubricity than the mineral oils previously used. This ~s another imQortant advantage of the method according to the invention.
E~~es In the following examples invert drilling fluids are prepared in the conventional manner using the following basic fornlulation:
230 ml ester oil 26 ml water TM
6 g organophilic bentonite (Geltone II of NL Baroid Co.) TM
12 g organophilic lignite (Duratone of NL Baroid Co.) x g lime (x = 1 or 2) 6 g W/O emulsifier (EZ-mul NT of NL Baroid Co.) 346 g barite 9.2 g , CaCl2 x 2 H20 In this formulation about 1.35 g of lime corresponds to 2 lb/bbl.
After a W/O invert drilling fluid has been prepared in a lmc~m manner from the components used, with variation of the ester oil phase, the viscosities of the unaged and then the aged material arA determined !as follows:
TM
Measurement of the viscosity at 50°C in a Fann-35-viscosimeter supplied by NL Baroid Co. The plastic viscosity (PV), the yield point (YP) and the gel strengths (lb/100 ft2) are determined in a Imown manner after sec. and 10 min.
Ageing is carried out by treatment in autoclaves - in the so-called roller-oven - for a period of 16 hours at 125°C.
Isotridecyl acetate which has the following rheological characteristics is used as the ester oil: viscosity at 20oC 5 mPas; viscosity at 50oC
2.1 mPas; setting point below -lOoC.
In Exanple 1 below, the amount of lime used in the basic formulation is 2 g, in F~ple 2 this lime amount is reduced to 1 g.
The values determined for the unaged and aged material are listed in the following table.
W
_2A47697 unaged material aged material plastic viscosity (PV) 31 33 yield point (YP) 11 13 gel strengths (lb/100 ft2) 1C sec. 6 7 min. 9 9 Example 2 unaged material aged material plastic viscosity (PV) 24 25 yield point (YP) 14 12 gel strengths (lb/100 ft2) 10 sec. 5 5 10 min. 8 7 The basic formulation in Exa~les 1 and 2 has a value of 90/10 for the oil phase/water weight ratio. In further tests the the ester oil/water ratio is changed to 80/20.
In Examples 3 and 4 below, invert drilling fluids are prepared using the ester oil based on isotridecyl acetate, according to the following basic forniulation:
210 m1 ester oil 48.2 g water TM
6 g organophilic bentonite (Q~igel) 13 g or.ilic lignite (Duratone of I~ Bar~oid Co.) 2 g lime 8 g W/0-~ulsifier (EZ-mul NT of NL Baroid Co.) 270 g barite g CaCl2 x 2 H20 As in Exanples 1 and 2, the viscosities are determined first on the unaged, then on the aged material (16 hours at 125°C in the roller oven) (Exanple 3). .
2a47697 In a further test formulation (ale 4), 2 g of a strongly oleophilic amine is added to the basic formulation given for ale 3 TM
(Applicant's oonmercial product "Araphen G2D" - the reaction product of an epoxidized C12/14-alpha-olefin and diethanolamine). The viscosity characteristics are then determined as above first on the unaged and then on the aged material.
ale 3 unaged material aged material plastic viscosity (PV) 34 36 yield point (YP) 52 51.
gel strengths (lb/100 ft2) sec. 25 23 10 min. 37 35 F~cample 4 unaged material aged material plastic visvosity (Ptl) 31 34 yield point (YP) 36 32 gel strengths (lb/100 ft2) 10 sec. 14 13 10 min. 17 15 E~cample 5 The ester-mixture fran acetic acid and a C6_10'aloohol cut (Applicant's TM
ocmmercial product "Lorol'technisch"), prepared by the reduction of the corresponding pre-fatty-acid cut of natural origin, is used as the ester oil. The basic forn~ulation for the ester mud corresponds to the fornailation given for ~anple 2.
The visvosity data are determined and the ageing is carried out as indicated in the previous acanples. The following visoosities are determined. 2 ~ 4 7 6 9 7 unaged material aged material plastic visvosity (PV) 28 29 yield point (YP) 17 20 gel strengths (lb/100 ft2) sec. g g 10 min. 24 14 ~~~les 6 to 8 In parallel formulations, three drilling fluids based on isotridecyl acetate are produced according to the basic formulation in Exanples 1 and 2 (oil phase/water = 90/10). As in the preceding ales, their rheological data was determined im~iately after preparation and after ageing in the roller oven at 125oC for a period of 16 hours.
In a first mud, no lime is added (ale 6), in a second mud (ale 7) 2 g of lime is used, while in the parallel third mud (ale 8) 2 g of lime is used together with 1 g of the strongly oleophilic amine "Araphen G2D".
The rheological data determined in each case are as follows:
~1e6 2047697 unaged material aged material plastic viscosity (PV) 28 30 yield point (YP) 15 9 gel strengths (lb/100 ft2) sec. y 10 min. 10 8 ale 7 unaged material aged material plastic viscosity (PV) 30 29 yield point (YP) 13 17 gel strengths (lb/100 ft2) 10 sec. g g 10 min. 10 12 F~cample 8 unaged material aged material plastic viscosity (PV) 25 25 yield point (YP) 12 8 gel strengths (lb/100 ft2) 10 sec. g 10 min. 11 9 les 9 to 11 In a further oca~arative series of tests, drilling fluids based on isotridecyl acetate are vombined in the basic formulation of E~camples 6 to 8 as follows: bcanple 9 addition of 1 g of lime; ale 10 addition of 2 g of lime; Ele 11 addition of 2 g of lime + 1 g of "Araphen G2D".
2o4~ss~
These mulls are then aged, however, in the roller oven at 125°C
for a period of 72 hours. The rheological data determined on the unaged and aged material in each case are as follows:
Example 9 unaged material aged material plastic viscosity (PV) 30 37 yield point (YP) 15 16 gel strengths (lb/100 ft2) sec. 7 7 10 min. 11 10 Example 10 unaged material aged material plastic viscosity (PV) 28 34 yield point (YP) 16 13 gel strengths (lb/100 ft2) 10 sec. 6 6 10 min. 10 10 Example 11 unaged material aged material plastic viscosity (PV) 29 36 yield point (YP) 11 14 gel strengths (lb/100 ft2) 10 sec. 7 6 10 min. 10 10
Claims (22)
1. A composition suitable for use in an invert emulsion drilling mud composition for the environmentally-compatible development of petroleum or natural gas deposits, said composition having an oil phase and an aqueous phase, said oil phase comprising an ester oil of a C1-C5 monocarboxylic acid and a mono- or polyfunctional alcohol, said ester oil being fluid at room temperature and having a flash point above 80° C, and said aqueous phase being dispersed in said oil phase.
2. The composition as in claim 1 wherein said ester oil comprises an ester of a C1-C5 monocarboxylic acid and a monofunctional alcohol having at least 8 carbon atoms.
3. The composition as in claim 2 wherein said monocarboxylic acid comprises acetic acid.
4. The composition as in claim 1 wherein said ester oil comprises an ester of a C1-C5 monocarboxylic acid and a polyfunctional alcohol having 2 to 6 carbon atoms.
5. The composition as in any one of claims 1 to 4 wherein said composition contains another ecologically acceptable oil selected from the group consisting of (a) a monocarboxylic acid ester of a C2-C12 monofunctional alkanol wherein the monocarboxylic acid contains from 12 to 16 carbon atoms and is aliphatically saturated, and (b) a monocarboxylic acid ester of a C2-C12 monofunctional alcohol wherein the monocarboxylic acid contains from 16 to 24 carbon atoms and is olefinically mono- or poly-unsaturated.
6. An invert emulsion drilling mud composition suitable for environmentally-compatible development of petroleum and natural gas deposits, comprising:
(a) a continuous oil phase containing an ester of a C1-C5 monocarboxylic acid and a mono- or polyfunctional alcohol, said ester being fluid at room temperature and having a flash point above 80° C, (b) an aqueous phase dispersed in said oil phase, (c) a water-in-oil emulsifier, (d) a weighting agent, (e) a viscosifier, (f) a fluid loss additive, and (g) an alkali reserve component.
(a) a continuous oil phase containing an ester of a C1-C5 monocarboxylic acid and a mono- or polyfunctional alcohol, said ester being fluid at room temperature and having a flash point above 80° C, (b) an aqueous phase dispersed in said oil phase, (c) a water-in-oil emulsifier, (d) a weighting agent, (e) a viscosifier, (f) a fluid loss additive, and (g) an alkali reserve component.
7. The invert emulsion drilling mud composition as in claim 6 wherein said ester has a Brookfield (RVT) viscosity of less than about 50 mPas at a temperature of about 0 to about 5°C.
8. The invert emulsion drilling mud composition as in claim 6 or 7 wherein said ester has a pour and setting value of below 0°C and a flash point above 90°C.
9. The invert emulsion drilling mud composition as in claim 6, 7 or 8 wherein said ester is prepared from a monofunctional alcohol having at least 6 carbon atoms, or from a di- to tetrahydric alcohol having from 2 to 6 carbon atoms.
10. The invert emulsion drilling mud composition as in any one of claims 6 to 9 wherein said ester of a C1-C5 monocarboxylic acid and a mono- or polyfunctional alcohol is present in an amount of at least about 50 percent by weight, based on the weight of said oil phase.
11. The invert emulsion drilling mud composition as in any one of claims 6 to 8 and 10 wherein said oil phase comprises an ester of a C1-C5 monocarboxylic acid and a monofunctional alcohol having at least 8 carbon atoms.
12. The invert emulsion drilling mud composition as in claim 11 wherein said monocarboxylic acid comprises acetic acid.
13. The invert emulsion drilling mud composition as in any one of claims 6 to 8 and 10 wherein said oil phase comprises an ester of a C1-C5 monocarboxylic acid and a polyfunctional alcohol having 2 to 6 carbon atoms.
14. The invert emulsion drilling mud composition as in claim 13 wherein said polyfunctional alcohol is selected from glycols and propanediols.
15. The invert emulsion drilling mud composition as in any one of claims 6 to 14 wherein said ester of a C1-C5 monocarboxylic acid and a mono- or polyfunctional alcohol is present in an amount of at least about 25 percent by weight, based on the weight of said oil phase.
16. The invert emulsion drilling mud composition as in any one of claims 6 to 15 wherein said oil phase contains another ecologically acceptable oil selected from the group consisting of (a) a monocarboxylic acid ester of a C2-C12 monofunctional alkanol wherein the monocarboxylic acid contains from 12 to 16 carbon atoms and is aliphatically saturated, and (b) a monocarboxylic acid ester of a C2-C12 monofunctional alcohol wherein the monocarboxylic acid contains from 16 to 24 carbon atoms and is olefinically mono- or poly-unsaturated.
17. The invert emulsion drilling mud composition as in any one of claims 6 to 16 wherein said alkali reserve component is substantially free from highly hydrophilic basic materials selected from the group consisting of alkali metal hydroxides, and amines selected from diethanolamine and triethanolamine.
18. The invert emulsion drilling mud composition as in any one of claims 6 to 17 wherein said alkali reserve component is selected from a mildly alkaline metal oxide, an oleophilic basic amine, and lime.
19. The invert emulsion drilling mud composition as in claim 18 wherein said lime is present in an amount of less than about 2 lbs/barrel of said drilling mud composition.
20. The invert emulsion drilling mud composition as in any one of claims 6 to 19 wherein said aqueous phase is present in an amount of from about 5 to about 45 percent by weight, based on the weight of said oil phase.
21. The invert emulsion drilling mud composition as in any one of claims 6 to 20 having a plastic viscosity of from about 10 to about 60 mPas, and a yield point of from about 5 to about 40 lbs/100 ft.2 each measured at about 50°C.
22. A process of developing sources of oil and gas by drilling using a drilling mud, comprising pumping the invert emulsion drilling mud composition of any one of claims 6 to 21 into said sources being drilled.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3907391.2 | 1989-03-08 | ||
| DE3907391A DE3907391A1 (en) | 1989-03-08 | 1989-03-08 | USE OF SELECTED ESTER OILS OF LOW CARBONIC ACIDS IN DRILL RINSING |
| PCT/EP1990/000342 WO1990010682A1 (en) | 1989-03-08 | 1990-03-01 | Use of selected low carboxylic acid ester oils in drilling muds |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2047697A1 CA2047697A1 (en) | 1990-09-09 |
| CA2047697C true CA2047697C (en) | 2001-07-31 |
Family
ID=6375780
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002047697A Expired - Lifetime CA2047697C (en) | 1989-03-08 | 1990-03-01 | Use of selected ester oils of low carboxylic acids in drilling fluids |
Country Status (15)
| Country | Link |
|---|---|
| EP (2) | EP0386638B2 (en) |
| JP (1) | JP2834319B2 (en) |
| AT (1) | ATE87020T1 (en) |
| AU (1) | AU624926B2 (en) |
| BR (1) | BR9007192A (en) |
| CA (1) | CA2047697C (en) |
| DE (2) | DE3907391A1 (en) |
| DK (1) | DK0386638T3 (en) |
| ES (1) | ES2042101T3 (en) |
| IE (1) | IE63931B1 (en) |
| MX (1) | MX174249B (en) |
| NO (1) | NO172501B (en) |
| TR (1) | TR24748A (en) |
| WO (1) | WO1990010682A1 (en) |
| ZA (1) | ZA901759B (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013124058A1 (en) * | 2012-02-20 | 2013-08-29 | Sasol Olefins & Surfactants Gmbh | Composition comprising an alkoxylated amine compound and a carboxylic acid compound, use thereof in water in oll emulsions and process using the composition as or as part of a drilling fluid |
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-
1989
- 1989-03-08 DE DE3907391A patent/DE3907391A1/en not_active Ceased
-
1990
- 1990-03-01 AU AU51823/90A patent/AU624926B2/en not_active Expired
- 1990-03-01 AT AT90104027T patent/ATE87020T1/en not_active IP Right Cessation
- 1990-03-01 CA CA002047697A patent/CA2047697C/en not_active Expired - Lifetime
- 1990-03-01 WO PCT/EP1990/000342 patent/WO1990010682A1/en not_active Application Discontinuation
- 1990-03-01 DE DE9090104027T patent/DE59001025D1/en not_active Expired - Lifetime
- 1990-03-01 EP EP90104027A patent/EP0386638B2/en not_active Expired - Lifetime
- 1990-03-01 DK DK90104027.9T patent/DK0386638T3/en active
- 1990-03-01 EP EP90904323A patent/EP0462160A1/en active Pending
- 1990-03-01 BR BR909007192A patent/BR9007192A/en not_active IP Right Cessation
- 1990-03-01 JP JP2504168A patent/JP2834319B2/en not_active Expired - Fee Related
- 1990-03-01 ES ES199090104027T patent/ES2042101T3/en not_active Expired - Lifetime
- 1990-03-06 MX MX019774A patent/MX174249B/en unknown
- 1990-03-06 TR TR90/0217A patent/TR24748A/en unknown
- 1990-03-07 ZA ZA901759A patent/ZA901759B/en unknown
- 1990-03-07 IE IE80290A patent/IE63931B1/en not_active IP Right Cessation
-
1991
- 1991-08-19 NO NO913239A patent/NO172501B/en unknown
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013124058A1 (en) * | 2012-02-20 | 2013-08-29 | Sasol Olefins & Surfactants Gmbh | Composition comprising an alkoxylated amine compound and a carboxylic acid compound, use thereof in water in oll emulsions and process using the composition as or as part of a drilling fluid |
Also Published As
| Publication number | Publication date |
|---|---|
| DE3907391A1 (en) | 1990-09-13 |
| JP2834319B2 (en) | 1998-12-09 |
| MX174249B (en) | 1994-05-02 |
| CA2047697A1 (en) | 1990-09-09 |
| NO913239L (en) | 1991-08-19 |
| ATE87020T1 (en) | 1993-04-15 |
| NO913239D0 (en) | 1991-08-19 |
| DK0386638T3 (en) | 1993-07-26 |
| WO1990010682A1 (en) | 1990-09-20 |
| ZA901759B (en) | 1990-11-28 |
| EP0386638B2 (en) | 2003-12-03 |
| ES2042101T3 (en) | 1993-12-01 |
| AU5182390A (en) | 1990-10-09 |
| BR9007192A (en) | 1991-12-10 |
| AU624926B2 (en) | 1992-06-25 |
| EP0386638A1 (en) | 1990-09-12 |
| EP0462160A1 (en) | 1991-12-27 |
| DE59001025D1 (en) | 1993-04-22 |
| NO172501B (en) | 1993-04-19 |
| IE63931B1 (en) | 1995-06-28 |
| IE900802L (en) | 1990-09-08 |
| EP0386638B1 (en) | 1993-03-17 |
| TR24748A (en) | 1992-03-01 |
| JPH04503965A (en) | 1992-07-16 |
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| Date | Code | Title | Description |
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| EEER | Examination request | ||
| MKEX | Expiry |