CA2050935C - Use of selected ethers of monofunctional alcohols in drilling fluids - Google Patents
Use of selected ethers of monofunctional alcohols in drilling fluids Download PDFInfo
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- CA2050935C CA2050935C CA002050935A CA2050935A CA2050935C CA 2050935 C CA2050935 C CA 2050935C CA 002050935 A CA002050935 A CA 002050935A CA 2050935 A CA2050935 A CA 2050935A CA 2050935 C CA2050935 C CA 2050935C
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- monocarboxylic acid
- drilling mud
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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
Abstract
The invention describes the use of water-insoluble ethers, with flash points above 80°C, from monohydric alcohols of natural and/or synthetic origin with at least 4 carbon atoms, preferably at least 6 carbon atoms in the alcohol radicals, as the oil phase, or a constituent of the oil phase of invert drilling fluids which exist as W/O-emulsions, have a dispersed aqueous phase and ideally also have further usual additives in the continuous oil phase, which is fluid and pumpable in the temperature range of 0 to 5°C, and which are suitable for the environment-friendly development of, e.g., petroleum and natural gas deposits. Drilling fluids of the above type are also described which are characterized in that they contain as the continuous oil phase, or dissolved in ecologically-acceptable water-insoluble oils, an additive of at least largely water-insoluble ethers from monohydric alcohols, the oil phase in each case being fluid and pumpable in the temperature range of 0 to 5°C and having flash points above 80°C.
Description
~05~1935 "The use of selected ethers of monofunctional alcohols in drilling fluids"
The invention discloses new drilling fluids and invert drilling mulls based thereon, which are distinguished by high ecological acceptability and at the same time good storage and application properties. An important area of application for the new drilling fluid systems is in off-shore wells for the development of petroleum and/or natural gas deposits, the aitn of the invention being particularly to make available industrially usable drilling fluids with high ecological acceptability.
The use of the new drilling fluid systems has particular significance in the marine environment, but is not limited thereto. The new mud systems can be put to quite general use even in land-based drilling, for example, in geothermal wells, water bore-holes, in the drilling of geoscientific bores and in drilling.for the mining industry. Here too it is essentially true that associated ecotoxic probleqns are substantially sircplified by the ester-based drilling-oil fluids selected aca>rding to the invention.
The Prior Art Oil-base drilling fluids are generally used in the form of 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-e~nulsion 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 syst~ as a whole and to confer on it the desired application properties, particularly emulsifiers or emulsifier systems, weighting agents, fluid-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 Iaw-Toxicity Oil Mulls" Journal of Petroleum Technology, 1985, 13? to 142, and R.B.
Bennett, "New Drilling Fluid Technology - Mineral Oil Mud" Journal of Petroleum Technology, 1984, 975 to 981 anti- the literature cited therein.
The i~ortance of ester-based oil phases in reducing the problems created by such oil-base muds has been recognized for scene time in the relevant field of technology. 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 follc7wing are of equal value as the non-polluting oils - mineral oil fractions which are free from araratic 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. These named ester oils of vegetable and animal origin are all, without exception, triglycerides of natural fatty acids, which are lmown to be of high environmental acceptability, and are clearly superior ecologically to hydrocarbon fractions- even when these do not contain aromatic hydrocarbons.
Interestingly enough, however, not one of the~exat~les in the above US
Patent Specifications describes the use of such natural ester oils in invert-drilling fluids of this type. In every case, mineral oil fractions are used as the continuous. oil phase. Oils of vegetable and/or animal origin are not vonsidered for practical reasons. The rheological properties of such oil phases cannot be controlled over the wide temperature range generally required in practice, fret 0 to 5°C on the one hand, up to 250°C on the other.
The Applicant's other proposals Ester oils of the type in question d4 not in fact behave in the 'same way in practice as the previously used mineral oil fractions based on pure hydrocarbons. Ester oils are subject to partial hydrolysis in practical use, particularly in w/O-invert drilling mode. Fret carboxylic acids are formed as a result. The Apphicant's co-pending Canadian Applications 2,006,009 and 2,006,010, filed December 19, 1989 describe the problems caused thereby and give proposals for their solution. Further types of usable ester oils are disclosed in ' the co-pending Canadian Patent Applications 2,047,697 and 2,047,206, filed March 1, 1990. -The subject of these co-pending Applications is the use of ester oils based on selected monocarboxylic acids or monocarboxylic acid mixtures and monofunctional, and optionally polyfunctional, alcohols. The co-pending Applications show that, with the esters and ester mixtures they disclose, it is not only possible to invest fresh drilling fluid with satisfactory rheological properties, but it is also possible to use selected ~a~m alkali reserves in the drilling fluid and in this way to retard undesirable corn~sion. As alkali reserves - particularly when ester oils based on carboxylic acids with at Least 6 carbon atoms are used - calcium hydroxide, or lime, can be added and/or can be used with zinc oxide or oa~arable zinc catpounds. In this case, however, an additional restriction is advisable. To prevent unwanted thickening of the oil-base invert mud system in practical use, the amount of alkalizing additive, and in particular the amount of lime, must be limited. The maxim~t amount permitted in the disclosure of the aforementioned co-pending Applications is about 2 lb/bbl (pounds/barrel) of oil-base muds.
An important further development of these invert-drilling fluids based on ester oils is the subject of the Applicant's co-pending Canadian Applications 2,009,689, filed February 9, 1990.
The teaching of this co-pending Application is based on the concept of using a further additive in the invert drilling fluids based on ester oils, which is suited to keeping the desired rheological properties of the drilling fluid within the required range, even when ever larger amounts of free carboxylic-acids are formed in use by partial ester hydrolysis. These liberated carboxylic acids should not only be caught in a harmless forth, it should m?reover be possible to convert these free carboxylic acids, preferably into valuable ;cxx~ponents with stabilizing or emulsifying properties for the whole system. According to this teaching, basic amine ocnpounds of marked oleophilic hature and at most limited water solubility, which are capable of forming salts with carboxylic acids, can be used as additives in the oil phase. The oleophilic amine ccarpounds 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 occ~ination with conventional alkali reserves, particularly together with lime. The use of oleophilic amine oc~pounds 4 _ which are at least largely free frcm arc~natic constituents is preferred. In particular, optionally olefin-unsaturated aliphatic, cycloaliphatic and/or heterocyclic oleophilic basic amine compounds, can be considered, which contain one or more N-groups capable of forming salts with carboxylic acids. In a preferred ~nbodiment the water-solubility of these amine compounds at room temperature is at most about 5 ~ by weight and is usefully below 1 ~ by weight.
Typical examples of such amine cc~ounds are primary, secondary and/or tertiary amines, which are at least largely water-insoluble, and which can also to a limited extent be alkoxylated and/or substituted, particularly with hydroxyl groups. Further examples are the corresponding aminoamides and/or heterocyclic compounds with nitrogen as a ring constituent. For example, basic amine compounds are suitable which have at least one long-chain hydrocarbon radical, preferably of from 8 to 36 carbon atoms, particularly with 10 to 24 carbon atoms, which can also be olefin mono- or poly-unsaturated. The oleophilic basic amine o~npounds can be added to the drilling fluid in amounts of up to about 10 lb/bbl, preferably in amounts up to about 5 lb/bbl and particularly in the range of about 0.1 to 2 lb/bbl.
It has been found that the use of such oleophilic basic amine ooa~ounds can effectively prevent thickening of the mud systean, which presumably can be attributed to a disturbance of the W/O invert systeqn and also to the formation of free carboxylic acids by ester hydrolysis.
The invention problegn and its technical solution The probleqn of the present invention is further to develop syst~ns of the type in question and in particular drilling fluids of high ecological acceptability. In a first embodiment the invention proposes to make available oils and oil mixtures for the production of drilling fluids based on W/O-emulsions, which can be used industrially and are easily accessible and at the same time are distinguished by high ecological acceptability. In a further eqnbodimPxit the invention intends to make available additives for the afor~entioned systems in question here, which confer valuable additive properties on drilling fluids based on W/O-e~milsions without having a disadvantageous effect - 5 _ .~a5a9~5 on their ecological acceptability.
The technical solution of the problems of the invention starts frown the Imowledge that selected ethers suited to this use can result in new and improved drilling fluids of the type described. These ethers are water-insoluble or essentially water-insoluble ~onents, in particular therefore oorrespondi.ng oampounds with a pronounced oleophilic nature, which differ, however, frown pure hydrocarbon c~ounds by the presence of the functional ether group. As a result important technological improvements can be made and at the same time high ecological acceptability is ensured.
The subject of the invention is accordingly, in a first embodiment, the use of water-insoluble ethers, with flash points above 80°C, of monohydric aloohols of natural and/or synthetic origin with at least 4 carbon atcms, preferably at least 6 carbon atcgns in the alcohol radicals, as the oil phase, or a constituent of the oil phase, of invert-drilling fluids, which exist as W/O-emulsions and which, in the continuous oil phase, which is fluid and pumpable in the temperature range of 0 to 5 °C, have a dispersed aqueous phase and preferably further usual additives and which are suitable for the environmentally acceptable develo~ent of, for e~le, petroleum or natural gas deposits.
In a further embodiment the invention relates to invert drilling fluids, as described above, which are characterized in that they contain, as a continuous oil phase or dissolved in ecologically acceptable oils, an additive which consists at least pred~i.nantly of water-insoluble ethers of monohydric alcohols, such that the respective oil phase is fluid and pumpable in the temperature range of 0 to 5°C
and has flash points above 80°C.
The various embodiments of the invention In a first embodiment the continuous oil phase of the invert drilling fluids i_s formed exclusively, or to by far the larc~st part, by the essentially water-insoluble and preferably markedly oleophilic ethers.
Understandably, the rheology of the ethers used here must be suited to ~~ 2050935 a. .. 6 ..
the technical requirements of the drilling fluids. Slight rheological adjustments are possible by adding small amounts of the diluents provided in this embodiment. In the case described here, in particular oil phases can be considered, which are forn~ed by more than 70 ~ by weight, preferably by more than 80 ~ by weight, and desirably exclusively, by the ethers themselves. The general subject lmowledge is applicable for the rheological requirements of such oils for use in drilling fluids, and this will be discussed again below.
The definition according to the invention of the term "suitable ethers"
includes quite common symmetrical ethers, derived fran a selected alcohol, mixed ethers from different alcohols and/or ether mixtures of the twr~ ether types mentioned above. From the broad range of suitable individual ethers or mixed ethers and/or ether mixtures, those agents can be considered in particular which are at least in part the corresponding derivatives of monofunctional alcohols with at least 6 to 7 carbon atoms, preferably with at least 8 carbon atoms, the possible upper limit of the carbon number being greatly influenced by the structure of the hydrocarbon radical. The lmown effect of branched-chain and/or un-saturated structure of a hydrocarbon radical in corresponding alcohols also influences the rheology of the ethers formed therefrcan.
The rheology of branched-chain and/or unsaturated ethers of the type in question here is lmoHm to meet the reduirements of flowability and pumpability, even at lower te~eratures, mare easily than the straight-chain saturated hydrocarbon structure. Saturated straight-cha;n fatty-aloohol-ethers with from 16-18 carbon atc~tis are imawn to have high setting ranges. Branched ethers of the same carbon-number range can -depending on the extent and degree of branching - constitute completely acceptable fluid and pumpable oil phases in the sense of the invention.
In the field of saturated ethers frcem monofunctional alcohols, the range with low numbers of carbon atoms is particularly suitable, particularly therefore the range of about 8 - 14 carbon atcens, here too the ethers from branched-chaW alcohols can have rheological advantages.
The oil-mixture vents optionally used in small amounts in this - ~ - 2~5~9~5 embodiment can be pure hydrocarbon ccxrpounds especially those free from aromatic hydrocarbons, in particular selected ester oils of the type described in the Applicant's co-pending Applications mentioned above.
The rheological properties of the ether oa~onents used according to the invention beoa~e less and less important, the greater the proportion of these mixture constituents in the ac~nixture with one or more oil ccmponents. A second embodiment of the invention relates accordingly to the use of oil phases in systems of the type in question which still have considerable or even predominant amounts of non-water-miscible oils, which are used in admixture with the ethers provided according to the invention. The ether content selected according to the invention in this embodiment is as a rule more than 10 % by weight and up to about 70 % by weight - each referred to the fluid oil phase -and ether fractions in amounts of at least about 35 % by weight and preferably at least about 50 % by weight of the oil phase may be pref erred .
As the mixture components for this second embodiment of the invention, there can again be considered both pure hydrocarbon oils, particularly those free frcm aromatic hydrocarbons, and especially ester oils of the type described in the co-pending Applications by the Applicant. Such admixtures also fall within the framework of the invention, with both admixtures of ester oils with pure hydrocarbon carpounds and mixtures of various ester oil types possible for use as mixture vents for general use with the oleophilic ethers. In preferred embodiments of the invention, the pure hydrocarbon oils with no functional groups at all are used in the oil phase in amounts of at most 50 % by weight, preferably of at mist about 35 % by weight and particularly in amounts of at most about 25 % by weight - each referred to the oil phase. In the most important ~diments of the variants described here, mixtures of the ethers and ester oils defined according to the invention are used as the oil phase without the addition of pure hydrocarbon ,..
The invention finally relates in a third variant to the use of practically water-insoluble=ethers as additives in the oil phase of the aforementioned drilling fluids based on w/O-emulsions. The amount of -a- 205095 ethers used according to the invention is usually in the range of about 0.1 to a maximnun of 10 % by weight; preferably in the range of about 1 to 5 % by weic~t of the oil phase. The range of suitable water-insoluble ethers can understandably be enlarged substantially in this ercibodiment. The rheology of the system as a whole is no longer determined here by the rheological values of the ether. It is in this embodiment that the use of the ethers defined according to the invention as additives achieves important improvements in the behaviour of drilling fluids of the aforementioned type.
This is true in particular for invert systems in which the main oa~ponent of the continuous oil phase is formed exclusively or primarily by ester oils of the type described in the above co-pending Applications of the Applicant. In the embodiment in question here, the oil phase is constituted accordingly by at least 25 % by weight, preferably by at least 50 % by weight and particularly by at least about 75 to 80 % by weight of the oil phase byvan ester oil as the main component. Pure hydrocarbon oils of the prior art can be used for the rest of the oil phase, it is however advantageous to dispense with them altogether. .
By adding to the invert systems the water-insoluble ethers defined according to the invention, important improveqnents can be achieved for the practical use of the drilling fluids. The following 4 aspects are particularly affected: reduction of the fluid-loss values, the facilitation and improvement of the emulsification of the dispersed aquebus phase, in some cases clearly improved lubrification by the drilling fluid and in sane cases a distinct improvement in the rheological properties of invert drilling fluids based on ester oils.
The ethers used acoordinct to the invention The use of the ethers as the oil phase, but also their oa~ination as a lesser or greater part in the oil phase, rern,?res these ethers to have adequate water-insolubility. The water-solubility of suitable ethers at roan temperature preferably lies below 5 % by weight, particularly under 1 % by weight and preferably not more than about 0.1 % by weight.
a, _ .~_,~
- 9 - ~a5n9~5 The following general rules apply for the cheqnical nature of the ethers:
The special structure of the ethers used in the method according to the invention is primarily determined by the embodiment selected in each case, in which the composition of the ether-containing oil phase is selected, see here the previous sub-section.
If the ethers form the oil phase exclusively or if the ethers are present at least as the major mixture ~onent in the application mixture forming the continuous oil phase, the selection of suitable ethers or ether mixtures is initially determined by the corresponding basic rheological data. In this case, in detail, the ether or the ether mixtures used in the temperature range of 0 to 5oC should have a Brookfield (RVT) viscosity not above 50 mPa.s, preferably not above 40 mPa.s and particularly at most of about 30 mPa.s. The solidification values (pour and setting point) of the ether or ethers should at the same time lie below 0°C. Preferably, ethers or ether mixtures are used with solidification values below -5°C and particularly below -l0oc.
Finally, the flash points of the ether or ethers used are important for practical use, these are advantageously not below 90°C and preferably above 100°C. Much higher flash points, for example, those above 130°C
and in particular above 150°C, can be particularly useful.
As already discussed in the preceding sub-section, the overall nature of the rheological properties and the flash point is greatly determined by the individual mr~lecular structure of the ether-forming alcohols.
These structural features are discussed below:
An important element of the invention is the use of c~aratively non-toxic components, as a result the use, for example, of aromatic ethers in particular of the phenol ether type is therefore practically excluded. Aliphatic, optionally olefin mono- and/or poly-unsaturated alcohols with a straight-chain and/or branched hydrocarbon structure and also optionally cycloaliphatic aloohols are the most important ether-forming c~ponents in the sense of the method according to the invention. The lower limit for the number of carbon atcgns in such "~,. , ~- to - 2050935 alcohols is 4 carbon atans, preferably 6 carbon atoms and particularly 8 carbon atans. The upper limit for the number of carbon atoms in the ether-forming alcohols can also be chosen quite high depending on the Theology requirements and lies, for exan~le, at about 36 carbon atcens, preferably at about 32 carbon atans. In particular, monofunctional aloohols can be considered with about 6-24 carbon atcens, preferably from 6-18 carbon atcens. Ethers of Cg_16-alcohols and in particular Cg-14-alcohols, are suitable components in the sense of the teaching of the invention.
The ether-forming alcohols can be oc~npletely or at least partly of straight-chain and/or branched-chain type, even and/or odd-numbered, saturated and/or unsaturated. The ether-forming alcohols here can again be ocarpletely or partly of natural and/or synthetic origin.
Within the limit conditions indicated, certain selected ethers or ethers frcsn certain selected alcohols, mixed ethers from certain selected aleohols and/or ether~mixtures are suitable. Since the ether function is inert, at least to a great extent, both to the constituents introduced with the: drilling fluid and to the chemical actions taking place when the drilling fluid is used - this is also true in particular for the alkalized invert W/O-based emulsions - there is almost no restriction of choice, and therefore the Theological data required in the drilling fluid can be set at an optina.un level and achieved. Secondary reactions when in~ use, such as are typical for the ester oils in alkalized W/O-invert emulsions, need not be seriously considered for ethers used as the oil phase-or as mixture v~nents of the oil phase.
The mixture ecar~onents in the oil phase Suitable oil components for the admixture according to the invention are the mineral oils currently used in drilling fluids, and preferably aliphatic and/or cycloaliphatic hydrocarbon fractions essentially free from arcmati.c hydrocarbons, with the required Theological properties.
Refer here to the prior-art publications cited above and the available vanrnxcial products .
Particularly important mixture oatponents, however, are ester oils .u .
rs:,:.~,~' n - I1- ~~50935 which are eoologica:lly acceptable as used in the invention, as described in particular in the aforementioned co-pending Applications 2,006,009; 2,006,010; 2,047,697 and 2,047,706. To complete the invention disclosure, the essential characteristics of these esters, or ester mixtures, are now briefly summarized.
In a first eqnbodiment, as the . oil phase, esters are used of monofunctional aloohols with from 2 to 12, particularly with frc~n 6 to 12, carbon atoms and aliphatic-saturated monocarboxylic acids with from 12 to 16 carbon atoms, which [esters] are fluid and pumpable in a te~erature range of 0 to 5°C, or an admixture thereof with at most about the same amounts of other monocarboxylic acids. Ester oils are preferred which are based, to at least about 60 % by weight - referred to the respective carboxylic acid mixture -, on esters of aliphatic X12-14-~~~xYlic acids, the remaining percentage preferably being based on smaller amounts of shorter-chain aliphatic and/or longer-chain, 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 mire than 50 mPa.s, preferably not above 40 mPa. s and particularly of a ma~ci,m~un of about 30 mPa.s. The esters used in the drilling mud have solidification values (pour and setting point) below -10°C, preferably below -15°C and at the same time have flash points above 100oC, preferably above I50°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 fran~the vorresponding triglycerides, such as coconut oil, palm kernel oil and/or babassu oil. The alcohol radicals of the esters used are derived i.n particular from straight-chain and/or branched saturated alvohols, preferably with fran 6 to l0 carbon atone.
These alcohol oa~onents can also be of vegetable and/or animal origin and can thus be obtained by the reductive hydrogenation of the corresponding carboxylic acid esters.
A further class of particularly suitable ester oils i.s derived from olefin mono- and/or poly-unsaturated monocarboxylic acids with 16 to 24 carbon atoms or their ac~nixtures with smaller amounts of other, particularly saturated, monocarboxylic acids and monofunctional v.~~:>
~:~r ~ -ahhols with preferably fran 6 to 12 carbon atans. These ester oils are also fluid and pumpable in the temperature range of 0 to 5°C. In particular those esters are suitable which are derived, by more than 70 % by weight, preferably by more than 80 % by weight and in particular by more than 90 % by weight, fran.olefin-unsaturated carboxylic acids with frcxn 16 to 24 carbon atoms.
Here too, the solidification values (pour and setting point) lie below -10°C, preferably below -15°C, while the flash points lie above 100oC
and preferably above 160°C. In the temperature range of 0 to 5°C, the esters used in the drilling mud have a Brookfield (RVT) viscosity of not more than 55 mPa.s, preferably not more than 45 mPa.s.
Two subclasses can be defined.for the ester oils of the type in question. In the first, the unsaturated C16_24-T~~'-~xYlic acid radicals present in the ester are derived by not more than 35 % by weight from olefin di- and poly-unsaturated acids, with preferably at least about 60 % by weight of the acid radicals being olefin mono-unsaturated. In the second embo~d.i,ment, the C16-24-~nxYlic acids present in the ester mixture are derived, by more than 45 % by weight, preferably by more than 55 % by meight, frcan olefin di- and/or poly-unsaturated acids. It is desirable for the saturated carboxylic acids with from 16 to 18 carbon atoms, which are present in the ester mixture, to amount' to not more than about 20 % by weight and in pa~icular not mare than about 10 % by weight. Preferably, saturated carboxylic acid esters, however, have lower numbers of carbon atoms in the acid radicals. The carboxylic acid radicals present can be of vegetable and/or animal origin. ~ples of vegetable raw materials are, for.example, palm oil, peanut oil, castor oil and in particular rapeseed oil. The carboxylic acids of animal origin are in particular the corresponding mixtures of fish oils, such as herring oil.
A further interesting class of ester oils which can be used as mixture oa~ponents for the use according to the invention, are esters which are fluid at roan temperature and have flash points above 80°C, fran C1_5-monocarboxylic acids and mono- and/or polyfunctional alcohols, which are preferably also fluid and punpable in the temperature range of 0 to 5°C. Particularly suitable are the corresponding esters of these lower -_ ~050~5 carboxylic acids with monofunctional aloohols with at least 8 carbon atoms and/or esters of these acids with di- to tetra-hydric alcohols with preferably 2 to 6 carbon atone. Acetic acid in particular ie suitable for practical reasons as the ester-forming acid-varponent of this class. T'he specifications for the rheology and volatility and the solidification values of the preferred esters in this sub-class correspond to the values given above.
Suitable mixture o~Onents from this sub-class are, in particular, esters fran monofunctional aloohols of natural and/or synthetic origin, the chain length of which in the presence of predominantly alip~hatic-unsaturated aloohols can be in the range of 8 to 15 carbon atoms, but in the case of olefin mono- and poly-unsaturated alcohols, can also consists of higher numbers of carbon atone, for example, up to,about 24 carbon atoms. Details can be found in the Applicant's co-pending Application 2,047,697.
Suitable mixture vocnQonents are finally, however, the esters, as described in the Applicant's co-pending Application 2,047,706, from monocarboxylic acids of synthetic and/or natural origin with from 6 to 1I carbon atoms and mono- and/or polyfunctional aloohols, which are preferably also fluid and piutpable in the te~erature range of 0 to 5 oC. 'Ib ooc~plete the invention disclosure, reference is made here to this extent to the above co-pending Application.
Suitable mixture ocnponents also for the teaching of the present invention are finally at least~largely water-insoluble alcohols of a marked oleophilic nature,-as described as the oil phase or at Least as a constituent of the eon~inuous oil phase of such W/O-invert, emulsions in the co-pending Canadian Application of the Applicant 2,051,624, filed March 29, 1990. For the purposes of the invention disclosure reference is expressly made to the details in this co-pending Application.
Multi-substance mixtures fall within the scope of the invention, which together with the ethers defined according to the invention, can vontain one or more of the mixture oatponents listed here individually.
Essentially any mixtures can be used provided that they fulfil the basic Theological requirements for invert drilling fluids of the type referred to here. E'~tamples of~ such multi-ca~onent mixtures are materials based on various types of ester oils or also substance mixtures additionally containing mineral oil.
Farther mixture oamponents of the invert drillinct fluid These may be any of the usual mixture oo~r~onents for conditioning and for the practical use of invert drilling mulls, such as are currently used when mineral oils provide the continuous oil phase. In addition to the dispersed aqueous phase, in particular emulsifiers, weighting agents, fluid-loss additives, viscosifiers and alkali reserves can be considered.
In an important eqnbodiment of the invention, oleophilic basic amine ocmpounds are used as additives together with the ester oils, these amine compounds are described in detail in,the aforementioned co-pending Application 2,009,689 of the Applicant. For details reference should be made to the disclosure of this co-pending Application, as described above.
If eater oils are used as mixture ocmponents in the scope of the invention - in particular ester oils based on carboxylic acids with at least 6 carbon atoms -, it can be advantageous not to etrploy significant amounts of strongly hydrophilic inorganic or organic bases in the oil-base fluid. Lime can be used effectively as an alkali reserve, in which case it is advantageous to limit the maxinuun amount of lime to be used to about 2 lb/bbl, and it may be preferred to work with a drilling-mud lime content slightly belc7w this figure, e.g. frcm about 1 to 1.8 lb/bbl (lime/drilling fluid). Other lmown alkali reserves can be used in addition to, or in place of, the lire. The less basic metal oxides, such as zinc oxide, should particularly. be mentioned. Even when these "acid traps" are used, care should still be taken to ensure that the amounts used are not too large, so as to prevent undesired premature ageing of the drilling fluid, which is associated with an~increase-in viscosity and therefore a deterioration in-the Theological properties. The special features discussed here of _ 15 _ 2050~~5 the use according to the invention prevent, or at least restrict, the formation of undesirable amounts of highly active O/W-emulsifiers so that good theological properties are maintained in practice for a sufficient period of time even when there is thermal ageing.
The following also applies:
Invert_drilling muds of the type being considered usually contain, together with the continuous oil phase, a finely dispersed aqueous phase in amounts from about 5 to 45 % by weight and preferably fran about 5 to 25 % by weight. A dispersed aqueous phase fran about 10 to 25 % by weight can be red as particularly useful.
The following theological data apply for the theology of the preferred invert drilling mode according to the invention: plastic viscosity (PV) from about 10 to 60 mPa.s, preferably fran about 15 to 40 mPa.s;
yield point (YP) in the range from about 5 to 40 1b/100 ft2, preferably from about 10 to 25 lb/100-ft2 - each measured at 50°C. Further details on the measurement of these,.parameters, the measuring methods used and the rest of the conventional composition of the invert drilling fluids described here, are given in the prior art as cited above and, for exatrple, described in full in the "Manual of Drilling Fluids Technology" of NIr-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 summary, to ca~lete the irnrention disclosure the following can be said:
The emulsifiers that can be used in practice are systems suitable for the formation of the required W/0-emulsions. In particular, selected oleophilic fatty acid salts, e.g. those based on amidoamine vc~ounds, can be considered. ~ples of these are described in the already cited US-PS 4,374,737 and the literature cited therein. A particularly suitable type of emulsifier is the product sold by NL-Bairoid Co. under the trade-mark "EZ-mul".
Such emulsifiers are sold oonmercially as highly concentrated active-substanoe preparations and can, for exaaQle, be used in amounts firm about 2.5 to 5 % by weight, particularly in amounts from about 3 to 4 %
t ~, _ t: v~-:
-16 - ~05~935 by weight - based on the ester oil phase.
Hydrophobized lignite in particular is used in practice as the fluid-loss additive and thus in particular to fozm a dense coating of a largely liquid-ir~ern~eable film on the bore-hole walls. Suitable amounts are, for.exa~ple, from about 15 to 20 lb/bbl or from about 5 to 7% by weight, based on the oil phase.
The viscosifier usually enployed in drilling fluids of the type in question is a ration-modified finely particulate bentonite, which can ~be used particularly in amounts from about 8 to 10 lb/bbl or fran about 2 to 4% by, weight, based on the oil phase. Barite is the weighting material generally used in relevant applications to establish the necessary pressure ocmpensation, the amounts added being varied according to the drilling conditions anticipated in each case. By adding barite, it is, for exanple, possible to raise the specific gravity of the drilling fluid to 2.5 and preferably to a value in the range from about 1.3 to~l.6.
The dispersed aqueous phase in these invert drilling fluids is loaded with soluble salts - calcium chloride and/or potassium chloride are mainly used. Saturation, at roan temperature, of the aqueous phase with the soluble salt is preferred.
The aforementioned emulsifiers, or emulsifier systems, optionally also serve to improve the oil wettability of the inorganic weighting materials. In addition to-the aminoamides already mentioned, further examples are alkylbenzene sulfonates and imidazoline ca~pounds.
Additional information regarding the relevant Prior Art can be found in the following published Patent Specifications: GB 2 158 437, EP 229 912 and DE ~32 47 123.
.i.-,~
17 _ F~canple 1 An invert-drilling fluid is prepared according to the following formulation with an O/W-ratio of 90/10:
239 ml dialkylether n-C 8 6 g gel former (oc~mercial product Omnigel ) 9 g W/O-emulsifier ("EZ-~ul NT of HI~ Baroid Co.) 20 g orgar~opd~ilic lignite ( Duratone~of HI~ Bamid Co. ) 28 g water 12 g CaCl2 x 2 H20 4g l~
255 g barite First of all, the plastic viscosity (PV), the.yield point (YP) and the gel strength of the invert drilling fluid are measured after l0 seconds and after l0 minutes by a visoosity,measurement at 50oC on the unaged material.
The invert drilling fluid is then aged for 16 hours at 125°C in the autoclave in the so-called "roller-oven", to test the effect of temperature on the stability of the emulsion. The viscosity values are then measured again at 50°C.
The following are the values dete~na~ined for the unaged and aged material:
unaged material aged material plastic viscosity (PV) 19 21 yield point (YP) 11 8 gel strengths (1b/100 ft2) 10'sec. 4 4 min. . 5 5 HTHP fluid-loss value after ageing 4 ml ~;, .~ -- X050935 Exanple 2 An invert-drilling fluid is prepared with an O/W-ratio of 80/20 acvording to the following-formulation:
210 ml di.alkylether as in ale 1 6 g gel former (canmercial product ~~4~nigel") 13 g organophilic lignite (~~Duratone" of NL Baroid Co.) 48.2 g water 20 g CaCl2 x 2 H20 8 g W/4-an~lsifier ( "EZ-~ul Nr" of I~ Baroid Co. ) 2 g lime 220 g barite T'he following are the values determined for the unaged and aged material:
unaged material aced material plastic viscosity (PV) 26 25 yield point (YP) I6 9 gel strengths (1b/100 ft2) sec. ~ 4 10 min . 9 6 . HTHP f laid-loss value of aged drilling f laid 1 ml F~cam~les 3 ~Go 5 In the following exanples, invert drilling fluids are prepared each with a O/W-ratio of 90/20 according to the following formulation:
230 ml ether (see the identification below in F~ples 3 to 5) 26 ml water 6 g gel fornsas ( oannercial product Geltone 12 g orc~ar~hilic lignite ( "Duratone" of Pff~ Baroid Co. ) 2 g 1~
6 g ~w/p-emulsifier ("EZ-mul Nr" of NL Baroid Co.) - -19 - 20509~~
346 g barite 9.2 g CaCl2 x 2 H2C?
The following ethers are used in each case as the oil phase:
Example 3: Ce-O-CB
Exanple 4: C10-O-C10 F~anple 5: di-isotridecylether The viscosity values measured for the unaged and aged drilling fluid are stBm~arized below. The ageing is measured once after 16 hours at 125oC and in a further test after 72 hours at 125oC.
Exanple 3 unaged aged ; - aged material material material 16 hrs/ 72 hrs/
125oC 125°C
plastic visvosity (PV) 21 24 ~ 29 yield point (YP) 10 7 6 gel strengths (1b/100 ft2) sec. 4 3 4 10 min. 6 5 6 ~ple 4 The test batches of this exanple are in addition modified in the following way: for the ageing over a period of 72 hours, a drilling fluid of the given formulation is used to which had also been added 2 g of a markedly oleophilic amine (Applicant's oomrercial product Araphen ~' G2D ~. The following values were measured:
unaged aged a~
material material material 16 hrs/ 72 hrs/
plastic viscosity (PV) 34 39 36 yield point (YP) 9 22 gel strengths (1b/100 ft2) sec. 6 10 7 10 min. 8 17 8 ale 5 age a~
material material material is hrs/ 72 hrs/
plastic viscosity (PV) 63 64 63 yield point (YP) 18 17 16 gel strengths (1b/100 ft2) 10 sec. 8 6 6 10 min. 11 9 9
The invention discloses new drilling fluids and invert drilling mulls based thereon, which are distinguished by high ecological acceptability and at the same time good storage and application properties. An important area of application for the new drilling fluid systems is in off-shore wells for the development of petroleum and/or natural gas deposits, the aitn of the invention being particularly to make available industrially usable drilling fluids with high ecological acceptability.
The use of the new drilling fluid systems has particular significance in the marine environment, but is not limited thereto. The new mud systems can be put to quite general use even in land-based drilling, for example, in geothermal wells, water bore-holes, in the drilling of geoscientific bores and in drilling.for the mining industry. Here too it is essentially true that associated ecotoxic probleqns are substantially sircplified by the ester-based drilling-oil fluids selected aca>rding to the invention.
The Prior Art Oil-base drilling fluids are generally used in the form of 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-e~nulsion 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 syst~ as a whole and to confer on it the desired application properties, particularly emulsifiers or emulsifier systems, weighting agents, fluid-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 Iaw-Toxicity Oil Mulls" Journal of Petroleum Technology, 1985, 13? to 142, and R.B.
Bennett, "New Drilling Fluid Technology - Mineral Oil Mud" Journal of Petroleum Technology, 1984, 975 to 981 anti- the literature cited therein.
The i~ortance of ester-based oil phases in reducing the problems created by such oil-base muds has been recognized for scene time in the relevant field of technology. 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 follc7wing are of equal value as the non-polluting oils - mineral oil fractions which are free from araratic 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. These named ester oils of vegetable and animal origin are all, without exception, triglycerides of natural fatty acids, which are lmown to be of high environmental acceptability, and are clearly superior ecologically to hydrocarbon fractions- even when these do not contain aromatic hydrocarbons.
Interestingly enough, however, not one of the~exat~les in the above US
Patent Specifications describes the use of such natural ester oils in invert-drilling fluids of this type. In every case, mineral oil fractions are used as the continuous. oil phase. Oils of vegetable and/or animal origin are not vonsidered for practical reasons. The rheological properties of such oil phases cannot be controlled over the wide temperature range generally required in practice, fret 0 to 5°C on the one hand, up to 250°C on the other.
The Applicant's other proposals Ester oils of the type in question d4 not in fact behave in the 'same way in practice as the previously used mineral oil fractions based on pure hydrocarbons. Ester oils are subject to partial hydrolysis in practical use, particularly in w/O-invert drilling mode. Fret carboxylic acids are formed as a result. The Apphicant's co-pending Canadian Applications 2,006,009 and 2,006,010, filed December 19, 1989 describe the problems caused thereby and give proposals for their solution. Further types of usable ester oils are disclosed in ' the co-pending Canadian Patent Applications 2,047,697 and 2,047,206, filed March 1, 1990. -The subject of these co-pending Applications is the use of ester oils based on selected monocarboxylic acids or monocarboxylic acid mixtures and monofunctional, and optionally polyfunctional, alcohols. The co-pending Applications show that, with the esters and ester mixtures they disclose, it is not only possible to invest fresh drilling fluid with satisfactory rheological properties, but it is also possible to use selected ~a~m alkali reserves in the drilling fluid and in this way to retard undesirable corn~sion. As alkali reserves - particularly when ester oils based on carboxylic acids with at Least 6 carbon atoms are used - calcium hydroxide, or lime, can be added and/or can be used with zinc oxide or oa~arable zinc catpounds. In this case, however, an additional restriction is advisable. To prevent unwanted thickening of the oil-base invert mud system in practical use, the amount of alkalizing additive, and in particular the amount of lime, must be limited. The maxim~t amount permitted in the disclosure of the aforementioned co-pending Applications is about 2 lb/bbl (pounds/barrel) of oil-base muds.
An important further development of these invert-drilling fluids based on ester oils is the subject of the Applicant's co-pending Canadian Applications 2,009,689, filed February 9, 1990.
The teaching of this co-pending Application is based on the concept of using a further additive in the invert drilling fluids based on ester oils, which is suited to keeping the desired rheological properties of the drilling fluid within the required range, even when ever larger amounts of free carboxylic-acids are formed in use by partial ester hydrolysis. These liberated carboxylic acids should not only be caught in a harmless forth, it should m?reover be possible to convert these free carboxylic acids, preferably into valuable ;cxx~ponents with stabilizing or emulsifying properties for the whole system. According to this teaching, basic amine ocnpounds of marked oleophilic hature and at most limited water solubility, which are capable of forming salts with carboxylic acids, can be used as additives in the oil phase. The oleophilic amine ccarpounds 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 occ~ination with conventional alkali reserves, particularly together with lime. The use of oleophilic amine oc~pounds 4 _ which are at least largely free frcm arc~natic constituents is preferred. In particular, optionally olefin-unsaturated aliphatic, cycloaliphatic and/or heterocyclic oleophilic basic amine compounds, can be considered, which contain one or more N-groups capable of forming salts with carboxylic acids. In a preferred ~nbodiment the water-solubility of these amine compounds at room temperature is at most about 5 ~ by weight and is usefully below 1 ~ by weight.
Typical examples of such amine cc~ounds are primary, secondary and/or tertiary amines, which are at least largely water-insoluble, and which can also to a limited extent be alkoxylated and/or substituted, particularly with hydroxyl groups. Further examples are the corresponding aminoamides and/or heterocyclic compounds with nitrogen as a ring constituent. For example, basic amine compounds are suitable which have at least one long-chain hydrocarbon radical, preferably of from 8 to 36 carbon atoms, particularly with 10 to 24 carbon atoms, which can also be olefin mono- or poly-unsaturated. The oleophilic basic amine o~npounds can be added to the drilling fluid in amounts of up to about 10 lb/bbl, preferably in amounts up to about 5 lb/bbl and particularly in the range of about 0.1 to 2 lb/bbl.
It has been found that the use of such oleophilic basic amine ooa~ounds can effectively prevent thickening of the mud systean, which presumably can be attributed to a disturbance of the W/O invert systeqn and also to the formation of free carboxylic acids by ester hydrolysis.
The invention problegn and its technical solution The probleqn of the present invention is further to develop syst~ns of the type in question and in particular drilling fluids of high ecological acceptability. In a first embodiment the invention proposes to make available oils and oil mixtures for the production of drilling fluids based on W/O-emulsions, which can be used industrially and are easily accessible and at the same time are distinguished by high ecological acceptability. In a further eqnbodimPxit the invention intends to make available additives for the afor~entioned systems in question here, which confer valuable additive properties on drilling fluids based on W/O-e~milsions without having a disadvantageous effect - 5 _ .~a5a9~5 on their ecological acceptability.
The technical solution of the problems of the invention starts frown the Imowledge that selected ethers suited to this use can result in new and improved drilling fluids of the type described. These ethers are water-insoluble or essentially water-insoluble ~onents, in particular therefore oorrespondi.ng oampounds with a pronounced oleophilic nature, which differ, however, frown pure hydrocarbon c~ounds by the presence of the functional ether group. As a result important technological improvements can be made and at the same time high ecological acceptability is ensured.
The subject of the invention is accordingly, in a first embodiment, the use of water-insoluble ethers, with flash points above 80°C, of monohydric aloohols of natural and/or synthetic origin with at least 4 carbon atcms, preferably at least 6 carbon atcgns in the alcohol radicals, as the oil phase, or a constituent of the oil phase, of invert-drilling fluids, which exist as W/O-emulsions and which, in the continuous oil phase, which is fluid and pumpable in the temperature range of 0 to 5 °C, have a dispersed aqueous phase and preferably further usual additives and which are suitable for the environmentally acceptable develo~ent of, for e~le, petroleum or natural gas deposits.
In a further embodiment the invention relates to invert drilling fluids, as described above, which are characterized in that they contain, as a continuous oil phase or dissolved in ecologically acceptable oils, an additive which consists at least pred~i.nantly of water-insoluble ethers of monohydric alcohols, such that the respective oil phase is fluid and pumpable in the temperature range of 0 to 5°C
and has flash points above 80°C.
The various embodiments of the invention In a first embodiment the continuous oil phase of the invert drilling fluids i_s formed exclusively, or to by far the larc~st part, by the essentially water-insoluble and preferably markedly oleophilic ethers.
Understandably, the rheology of the ethers used here must be suited to ~~ 2050935 a. .. 6 ..
the technical requirements of the drilling fluids. Slight rheological adjustments are possible by adding small amounts of the diluents provided in this embodiment. In the case described here, in particular oil phases can be considered, which are forn~ed by more than 70 ~ by weight, preferably by more than 80 ~ by weight, and desirably exclusively, by the ethers themselves. The general subject lmowledge is applicable for the rheological requirements of such oils for use in drilling fluids, and this will be discussed again below.
The definition according to the invention of the term "suitable ethers"
includes quite common symmetrical ethers, derived fran a selected alcohol, mixed ethers from different alcohols and/or ether mixtures of the twr~ ether types mentioned above. From the broad range of suitable individual ethers or mixed ethers and/or ether mixtures, those agents can be considered in particular which are at least in part the corresponding derivatives of monofunctional alcohols with at least 6 to 7 carbon atoms, preferably with at least 8 carbon atoms, the possible upper limit of the carbon number being greatly influenced by the structure of the hydrocarbon radical. The lmown effect of branched-chain and/or un-saturated structure of a hydrocarbon radical in corresponding alcohols also influences the rheology of the ethers formed therefrcan.
The rheology of branched-chain and/or unsaturated ethers of the type in question here is lmoHm to meet the reduirements of flowability and pumpability, even at lower te~eratures, mare easily than the straight-chain saturated hydrocarbon structure. Saturated straight-cha;n fatty-aloohol-ethers with from 16-18 carbon atc~tis are imawn to have high setting ranges. Branched ethers of the same carbon-number range can -depending on the extent and degree of branching - constitute completely acceptable fluid and pumpable oil phases in the sense of the invention.
In the field of saturated ethers frcem monofunctional alcohols, the range with low numbers of carbon atoms is particularly suitable, particularly therefore the range of about 8 - 14 carbon atcens, here too the ethers from branched-chaW alcohols can have rheological advantages.
The oil-mixture vents optionally used in small amounts in this - ~ - 2~5~9~5 embodiment can be pure hydrocarbon ccxrpounds especially those free from aromatic hydrocarbons, in particular selected ester oils of the type described in the Applicant's co-pending Applications mentioned above.
The rheological properties of the ether oa~onents used according to the invention beoa~e less and less important, the greater the proportion of these mixture constituents in the ac~nixture with one or more oil ccmponents. A second embodiment of the invention relates accordingly to the use of oil phases in systems of the type in question which still have considerable or even predominant amounts of non-water-miscible oils, which are used in admixture with the ethers provided according to the invention. The ether content selected according to the invention in this embodiment is as a rule more than 10 % by weight and up to about 70 % by weight - each referred to the fluid oil phase -and ether fractions in amounts of at least about 35 % by weight and preferably at least about 50 % by weight of the oil phase may be pref erred .
As the mixture components for this second embodiment of the invention, there can again be considered both pure hydrocarbon oils, particularly those free frcm aromatic hydrocarbons, and especially ester oils of the type described in the co-pending Applications by the Applicant. Such admixtures also fall within the framework of the invention, with both admixtures of ester oils with pure hydrocarbon carpounds and mixtures of various ester oil types possible for use as mixture vents for general use with the oleophilic ethers. In preferred embodiments of the invention, the pure hydrocarbon oils with no functional groups at all are used in the oil phase in amounts of at most 50 % by weight, preferably of at mist about 35 % by weight and particularly in amounts of at most about 25 % by weight - each referred to the oil phase. In the most important ~diments of the variants described here, mixtures of the ethers and ester oils defined according to the invention are used as the oil phase without the addition of pure hydrocarbon ,..
The invention finally relates in a third variant to the use of practically water-insoluble=ethers as additives in the oil phase of the aforementioned drilling fluids based on w/O-emulsions. The amount of -a- 205095 ethers used according to the invention is usually in the range of about 0.1 to a maximnun of 10 % by weight; preferably in the range of about 1 to 5 % by weic~t of the oil phase. The range of suitable water-insoluble ethers can understandably be enlarged substantially in this ercibodiment. The rheology of the system as a whole is no longer determined here by the rheological values of the ether. It is in this embodiment that the use of the ethers defined according to the invention as additives achieves important improvements in the behaviour of drilling fluids of the aforementioned type.
This is true in particular for invert systems in which the main oa~ponent of the continuous oil phase is formed exclusively or primarily by ester oils of the type described in the above co-pending Applications of the Applicant. In the embodiment in question here, the oil phase is constituted accordingly by at least 25 % by weight, preferably by at least 50 % by weight and particularly by at least about 75 to 80 % by weight of the oil phase byvan ester oil as the main component. Pure hydrocarbon oils of the prior art can be used for the rest of the oil phase, it is however advantageous to dispense with them altogether. .
By adding to the invert systems the water-insoluble ethers defined according to the invention, important improveqnents can be achieved for the practical use of the drilling fluids. The following 4 aspects are particularly affected: reduction of the fluid-loss values, the facilitation and improvement of the emulsification of the dispersed aquebus phase, in some cases clearly improved lubrification by the drilling fluid and in sane cases a distinct improvement in the rheological properties of invert drilling fluids based on ester oils.
The ethers used acoordinct to the invention The use of the ethers as the oil phase, but also their oa~ination as a lesser or greater part in the oil phase, rern,?res these ethers to have adequate water-insolubility. The water-solubility of suitable ethers at roan temperature preferably lies below 5 % by weight, particularly under 1 % by weight and preferably not more than about 0.1 % by weight.
a, _ .~_,~
- 9 - ~a5n9~5 The following general rules apply for the cheqnical nature of the ethers:
The special structure of the ethers used in the method according to the invention is primarily determined by the embodiment selected in each case, in which the composition of the ether-containing oil phase is selected, see here the previous sub-section.
If the ethers form the oil phase exclusively or if the ethers are present at least as the major mixture ~onent in the application mixture forming the continuous oil phase, the selection of suitable ethers or ether mixtures is initially determined by the corresponding basic rheological data. In this case, in detail, the ether or the ether mixtures used in the temperature range of 0 to 5oC should have a Brookfield (RVT) viscosity not above 50 mPa.s, preferably not above 40 mPa.s and particularly at most of about 30 mPa.s. The solidification values (pour and setting point) of the ether or ethers should at the same time lie below 0°C. Preferably, ethers or ether mixtures are used with solidification values below -5°C and particularly below -l0oc.
Finally, the flash points of the ether or ethers used are important for practical use, these are advantageously not below 90°C and preferably above 100°C. Much higher flash points, for example, those above 130°C
and in particular above 150°C, can be particularly useful.
As already discussed in the preceding sub-section, the overall nature of the rheological properties and the flash point is greatly determined by the individual mr~lecular structure of the ether-forming alcohols.
These structural features are discussed below:
An important element of the invention is the use of c~aratively non-toxic components, as a result the use, for example, of aromatic ethers in particular of the phenol ether type is therefore practically excluded. Aliphatic, optionally olefin mono- and/or poly-unsaturated alcohols with a straight-chain and/or branched hydrocarbon structure and also optionally cycloaliphatic aloohols are the most important ether-forming c~ponents in the sense of the method according to the invention. The lower limit for the number of carbon atcgns in such "~,. , ~- to - 2050935 alcohols is 4 carbon atans, preferably 6 carbon atoms and particularly 8 carbon atans. The upper limit for the number of carbon atoms in the ether-forming alcohols can also be chosen quite high depending on the Theology requirements and lies, for exan~le, at about 36 carbon atcens, preferably at about 32 carbon atans. In particular, monofunctional aloohols can be considered with about 6-24 carbon atcens, preferably from 6-18 carbon atcens. Ethers of Cg_16-alcohols and in particular Cg-14-alcohols, are suitable components in the sense of the teaching of the invention.
The ether-forming alcohols can be oc~npletely or at least partly of straight-chain and/or branched-chain type, even and/or odd-numbered, saturated and/or unsaturated. The ether-forming alcohols here can again be ocarpletely or partly of natural and/or synthetic origin.
Within the limit conditions indicated, certain selected ethers or ethers frcsn certain selected alcohols, mixed ethers from certain selected aleohols and/or ether~mixtures are suitable. Since the ether function is inert, at least to a great extent, both to the constituents introduced with the: drilling fluid and to the chemical actions taking place when the drilling fluid is used - this is also true in particular for the alkalized invert W/O-based emulsions - there is almost no restriction of choice, and therefore the Theological data required in the drilling fluid can be set at an optina.un level and achieved. Secondary reactions when in~ use, such as are typical for the ester oils in alkalized W/O-invert emulsions, need not be seriously considered for ethers used as the oil phase-or as mixture v~nents of the oil phase.
The mixture ecar~onents in the oil phase Suitable oil components for the admixture according to the invention are the mineral oils currently used in drilling fluids, and preferably aliphatic and/or cycloaliphatic hydrocarbon fractions essentially free from arcmati.c hydrocarbons, with the required Theological properties.
Refer here to the prior-art publications cited above and the available vanrnxcial products .
Particularly important mixture oatponents, however, are ester oils .u .
rs:,:.~,~' n - I1- ~~50935 which are eoologica:lly acceptable as used in the invention, as described in particular in the aforementioned co-pending Applications 2,006,009; 2,006,010; 2,047,697 and 2,047,706. To complete the invention disclosure, the essential characteristics of these esters, or ester mixtures, are now briefly summarized.
In a first eqnbodiment, as the . oil phase, esters are used of monofunctional aloohols with from 2 to 12, particularly with frc~n 6 to 12, carbon atoms and aliphatic-saturated monocarboxylic acids with from 12 to 16 carbon atoms, which [esters] are fluid and pumpable in a te~erature range of 0 to 5°C, or an admixture thereof with at most about the same amounts of other monocarboxylic acids. Ester oils are preferred which are based, to at least about 60 % by weight - referred to the respective carboxylic acid mixture -, on esters of aliphatic X12-14-~~~xYlic acids, the remaining percentage preferably being based on smaller amounts of shorter-chain aliphatic and/or longer-chain, 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 mire than 50 mPa.s, preferably not above 40 mPa. s and particularly of a ma~ci,m~un of about 30 mPa.s. The esters used in the drilling mud have solidification values (pour and setting point) below -10°C, preferably below -15°C and at the same time have flash points above 100oC, preferably above I50°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 fran~the vorresponding triglycerides, such as coconut oil, palm kernel oil and/or babassu oil. The alcohol radicals of the esters used are derived i.n particular from straight-chain and/or branched saturated alvohols, preferably with fran 6 to l0 carbon atone.
These alcohol oa~onents can also be of vegetable and/or animal origin and can thus be obtained by the reductive hydrogenation of the corresponding carboxylic acid esters.
A further class of particularly suitable ester oils i.s derived from olefin mono- and/or poly-unsaturated monocarboxylic acids with 16 to 24 carbon atoms or their ac~nixtures with smaller amounts of other, particularly saturated, monocarboxylic acids and monofunctional v.~~:>
~:~r ~ -ahhols with preferably fran 6 to 12 carbon atans. These ester oils are also fluid and pumpable in the temperature range of 0 to 5°C. In particular those esters are suitable which are derived, by more than 70 % by weight, preferably by more than 80 % by weight and in particular by more than 90 % by weight, fran.olefin-unsaturated carboxylic acids with frcxn 16 to 24 carbon atoms.
Here too, the solidification values (pour and setting point) lie below -10°C, preferably below -15°C, while the flash points lie above 100oC
and preferably above 160°C. In the temperature range of 0 to 5°C, the esters used in the drilling mud have a Brookfield (RVT) viscosity of not more than 55 mPa.s, preferably not more than 45 mPa.s.
Two subclasses can be defined.for the ester oils of the type in question. In the first, the unsaturated C16_24-T~~'-~xYlic acid radicals present in the ester are derived by not more than 35 % by weight from olefin di- and poly-unsaturated acids, with preferably at least about 60 % by weight of the acid radicals being olefin mono-unsaturated. In the second embo~d.i,ment, the C16-24-~nxYlic acids present in the ester mixture are derived, by more than 45 % by weight, preferably by more than 55 % by meight, frcan olefin di- and/or poly-unsaturated acids. It is desirable for the saturated carboxylic acids with from 16 to 18 carbon atoms, which are present in the ester mixture, to amount' to not more than about 20 % by weight and in pa~icular not mare than about 10 % by weight. Preferably, saturated carboxylic acid esters, however, have lower numbers of carbon atoms in the acid radicals. The carboxylic acid radicals present can be of vegetable and/or animal origin. ~ples of vegetable raw materials are, for.example, palm oil, peanut oil, castor oil and in particular rapeseed oil. The carboxylic acids of animal origin are in particular the corresponding mixtures of fish oils, such as herring oil.
A further interesting class of ester oils which can be used as mixture oa~ponents for the use according to the invention, are esters which are fluid at roan temperature and have flash points above 80°C, fran C1_5-monocarboxylic acids and mono- and/or polyfunctional alcohols, which are preferably also fluid and punpable in the temperature range of 0 to 5°C. Particularly suitable are the corresponding esters of these lower -_ ~050~5 carboxylic acids with monofunctional aloohols with at least 8 carbon atoms and/or esters of these acids with di- to tetra-hydric alcohols with preferably 2 to 6 carbon atone. Acetic acid in particular ie suitable for practical reasons as the ester-forming acid-varponent of this class. T'he specifications for the rheology and volatility and the solidification values of the preferred esters in this sub-class correspond to the values given above.
Suitable mixture o~Onents from this sub-class are, in particular, esters fran monofunctional aloohols of natural and/or synthetic origin, the chain length of which in the presence of predominantly alip~hatic-unsaturated aloohols can be in the range of 8 to 15 carbon atoms, but in the case of olefin mono- and poly-unsaturated alcohols, can also consists of higher numbers of carbon atone, for example, up to,about 24 carbon atoms. Details can be found in the Applicant's co-pending Application 2,047,697.
Suitable mixture vocnQonents are finally, however, the esters, as described in the Applicant's co-pending Application 2,047,706, from monocarboxylic acids of synthetic and/or natural origin with from 6 to 1I carbon atoms and mono- and/or polyfunctional aloohols, which are preferably also fluid and piutpable in the te~erature range of 0 to 5 oC. 'Ib ooc~plete the invention disclosure, reference is made here to this extent to the above co-pending Application.
Suitable mixture ocnponents also for the teaching of the present invention are finally at least~largely water-insoluble alcohols of a marked oleophilic nature,-as described as the oil phase or at Least as a constituent of the eon~inuous oil phase of such W/O-invert, emulsions in the co-pending Canadian Application of the Applicant 2,051,624, filed March 29, 1990. For the purposes of the invention disclosure reference is expressly made to the details in this co-pending Application.
Multi-substance mixtures fall within the scope of the invention, which together with the ethers defined according to the invention, can vontain one or more of the mixture oatponents listed here individually.
Essentially any mixtures can be used provided that they fulfil the basic Theological requirements for invert drilling fluids of the type referred to here. E'~tamples of~ such multi-ca~onent mixtures are materials based on various types of ester oils or also substance mixtures additionally containing mineral oil.
Farther mixture oamponents of the invert drillinct fluid These may be any of the usual mixture oo~r~onents for conditioning and for the practical use of invert drilling mulls, such as are currently used when mineral oils provide the continuous oil phase. In addition to the dispersed aqueous phase, in particular emulsifiers, weighting agents, fluid-loss additives, viscosifiers and alkali reserves can be considered.
In an important eqnbodiment of the invention, oleophilic basic amine ocmpounds are used as additives together with the ester oils, these amine compounds are described in detail in,the aforementioned co-pending Application 2,009,689 of the Applicant. For details reference should be made to the disclosure of this co-pending Application, as described above.
If eater oils are used as mixture ocmponents in the scope of the invention - in particular ester oils based on carboxylic acids with at least 6 carbon atoms -, it can be advantageous not to etrploy significant amounts of strongly hydrophilic inorganic or organic bases in the oil-base fluid. Lime can be used effectively as an alkali reserve, in which case it is advantageous to limit the maxinuun amount of lime to be used to about 2 lb/bbl, and it may be preferred to work with a drilling-mud lime content slightly belc7w this figure, e.g. frcm about 1 to 1.8 lb/bbl (lime/drilling fluid). Other lmown alkali reserves can be used in addition to, or in place of, the lire. The less basic metal oxides, such as zinc oxide, should particularly. be mentioned. Even when these "acid traps" are used, care should still be taken to ensure that the amounts used are not too large, so as to prevent undesired premature ageing of the drilling fluid, which is associated with an~increase-in viscosity and therefore a deterioration in-the Theological properties. The special features discussed here of _ 15 _ 2050~~5 the use according to the invention prevent, or at least restrict, the formation of undesirable amounts of highly active O/W-emulsifiers so that good theological properties are maintained in practice for a sufficient period of time even when there is thermal ageing.
The following also applies:
Invert_drilling muds of the type being considered usually contain, together with the continuous oil phase, a finely dispersed aqueous phase in amounts from about 5 to 45 % by weight and preferably fran about 5 to 25 % by weight. A dispersed aqueous phase fran about 10 to 25 % by weight can be red as particularly useful.
The following theological data apply for the theology of the preferred invert drilling mode according to the invention: plastic viscosity (PV) from about 10 to 60 mPa.s, preferably fran about 15 to 40 mPa.s;
yield point (YP) in the range from about 5 to 40 1b/100 ft2, preferably from about 10 to 25 lb/100-ft2 - each measured at 50°C. Further details on the measurement of these,.parameters, the measuring methods used and the rest of the conventional composition of the invert drilling fluids described here, are given in the prior art as cited above and, for exatrple, described in full in the "Manual of Drilling Fluids Technology" of NIr-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 summary, to ca~lete the irnrention disclosure the following can be said:
The emulsifiers that can be used in practice are systems suitable for the formation of the required W/0-emulsions. In particular, selected oleophilic fatty acid salts, e.g. those based on amidoamine vc~ounds, can be considered. ~ples of these are described in the already cited US-PS 4,374,737 and the literature cited therein. A particularly suitable type of emulsifier is the product sold by NL-Bairoid Co. under the trade-mark "EZ-mul".
Such emulsifiers are sold oonmercially as highly concentrated active-substanoe preparations and can, for exaaQle, be used in amounts firm about 2.5 to 5 % by weight, particularly in amounts from about 3 to 4 %
t ~, _ t: v~-:
-16 - ~05~935 by weight - based on the ester oil phase.
Hydrophobized lignite in particular is used in practice as the fluid-loss additive and thus in particular to fozm a dense coating of a largely liquid-ir~ern~eable film on the bore-hole walls. Suitable amounts are, for.exa~ple, from about 15 to 20 lb/bbl or from about 5 to 7% by weight, based on the oil phase.
The viscosifier usually enployed in drilling fluids of the type in question is a ration-modified finely particulate bentonite, which can ~be used particularly in amounts from about 8 to 10 lb/bbl or fran about 2 to 4% by, weight, based on the oil phase. Barite is the weighting material generally used in relevant applications to establish the necessary pressure ocmpensation, the amounts added being varied according to the drilling conditions anticipated in each case. By adding barite, it is, for exanple, possible to raise the specific gravity of the drilling fluid to 2.5 and preferably to a value in the range from about 1.3 to~l.6.
The dispersed aqueous phase in these invert drilling fluids is loaded with soluble salts - calcium chloride and/or potassium chloride are mainly used. Saturation, at roan temperature, of the aqueous phase with the soluble salt is preferred.
The aforementioned emulsifiers, or emulsifier systems, optionally also serve to improve the oil wettability of the inorganic weighting materials. In addition to-the aminoamides already mentioned, further examples are alkylbenzene sulfonates and imidazoline ca~pounds.
Additional information regarding the relevant Prior Art can be found in the following published Patent Specifications: GB 2 158 437, EP 229 912 and DE ~32 47 123.
.i.-,~
17 _ F~canple 1 An invert-drilling fluid is prepared according to the following formulation with an O/W-ratio of 90/10:
239 ml dialkylether n-C 8 6 g gel former (oc~mercial product Omnigel ) 9 g W/O-emulsifier ("EZ-~ul NT of HI~ Baroid Co.) 20 g orgar~opd~ilic lignite ( Duratone~of HI~ Bamid Co. ) 28 g water 12 g CaCl2 x 2 H20 4g l~
255 g barite First of all, the plastic viscosity (PV), the.yield point (YP) and the gel strength of the invert drilling fluid are measured after l0 seconds and after l0 minutes by a visoosity,measurement at 50oC on the unaged material.
The invert drilling fluid is then aged for 16 hours at 125°C in the autoclave in the so-called "roller-oven", to test the effect of temperature on the stability of the emulsion. The viscosity values are then measured again at 50°C.
The following are the values dete~na~ined for the unaged and aged material:
unaged material aged material plastic viscosity (PV) 19 21 yield point (YP) 11 8 gel strengths (1b/100 ft2) 10'sec. 4 4 min. . 5 5 HTHP fluid-loss value after ageing 4 ml ~;, .~ -- X050935 Exanple 2 An invert-drilling fluid is prepared with an O/W-ratio of 80/20 acvording to the following-formulation:
210 ml di.alkylether as in ale 1 6 g gel former (canmercial product ~~4~nigel") 13 g organophilic lignite (~~Duratone" of NL Baroid Co.) 48.2 g water 20 g CaCl2 x 2 H20 8 g W/4-an~lsifier ( "EZ-~ul Nr" of I~ Baroid Co. ) 2 g lime 220 g barite T'he following are the values determined for the unaged and aged material:
unaged material aced material plastic viscosity (PV) 26 25 yield point (YP) I6 9 gel strengths (1b/100 ft2) sec. ~ 4 10 min . 9 6 . HTHP f laid-loss value of aged drilling f laid 1 ml F~cam~les 3 ~Go 5 In the following exanples, invert drilling fluids are prepared each with a O/W-ratio of 90/20 according to the following formulation:
230 ml ether (see the identification below in F~ples 3 to 5) 26 ml water 6 g gel fornsas ( oannercial product Geltone 12 g orc~ar~hilic lignite ( "Duratone" of Pff~ Baroid Co. ) 2 g 1~
6 g ~w/p-emulsifier ("EZ-mul Nr" of NL Baroid Co.) - -19 - 20509~~
346 g barite 9.2 g CaCl2 x 2 H2C?
The following ethers are used in each case as the oil phase:
Example 3: Ce-O-CB
Exanple 4: C10-O-C10 F~anple 5: di-isotridecylether The viscosity values measured for the unaged and aged drilling fluid are stBm~arized below. The ageing is measured once after 16 hours at 125oC and in a further test after 72 hours at 125oC.
Exanple 3 unaged aged ; - aged material material material 16 hrs/ 72 hrs/
125oC 125°C
plastic visvosity (PV) 21 24 ~ 29 yield point (YP) 10 7 6 gel strengths (1b/100 ft2) sec. 4 3 4 10 min. 6 5 6 ~ple 4 The test batches of this exanple are in addition modified in the following way: for the ageing over a period of 72 hours, a drilling fluid of the given formulation is used to which had also been added 2 g of a markedly oleophilic amine (Applicant's oomrercial product Araphen ~' G2D ~. The following values were measured:
unaged aged a~
material material material 16 hrs/ 72 hrs/
plastic viscosity (PV) 34 39 36 yield point (YP) 9 22 gel strengths (1b/100 ft2) sec. 6 10 7 10 min. 8 17 8 ale 5 age a~
material material material is hrs/ 72 hrs/
plastic viscosity (PV) 63 64 63 yield point (YP) 18 17 16 gel strengths (1b/100 ft2) 10 sec. 8 6 6 10 min. 11 9 9
Claims (14)
1. An invert emulsion drilling mud composition suitable for environmentally-compatible development of petroleum and natural gas deposits, comprising:
(a) a continuous oil phase comprising a substantially water-insoluble ether of an monohydric alcohol having from 4 to 36 carbon atoms, said ether having a Brookfield (RVT) viscosity of less than about 50 mPas at a temperature of about 0 to about 5°C, said oil phase being fluid and pumpable at a temperature of about 0 to about 5°C, and having a flash point above 90°C and a pour and setting point of below about 0°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.
(a) a continuous oil phase comprising a substantially water-insoluble ether of an monohydric alcohol having from 4 to 36 carbon atoms, said ether having a Brookfield (RVT) viscosity of less than about 50 mPas at a temperature of about 0 to about 5°C, said oil phase being fluid and pumpable at a temperature of about 0 to about 5°C, and having a flash point above 90°C and a pour and setting point of below about 0°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.
2. The invert emulsion drilling mud composition as in claim 1 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.
3. The invert emulsion drilling mud composition as in claim 1 or 2 having a plastic viscosity of from about 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.
4. The invert emulsion drilling mud composition as in claim l, 2 or 3 wherein said ether is present in an amount of at least about 10 percent by weight, based on the weight of said oil phase.
5. The invert emulsion drilling mud composition as in any one of claims 1 to 4 wherein said ether is prepared from a monofunctional alcohol having from 6 to 24 carbon atoms.
6. The invert emulsion drilling mud composition as in claim 5 wherein said monofunctional alcohol comprises an aliphatic unsaturated alcohol having from 8 to 16 carbon atoms.
7. The invert emulsion drilling mud composition as in any one of claims 1 to 6 wherein said oil phase contains another ecologically acceptable oil.
8. The invert emulsion drilling mud composition as in claim 7 wherein said ecologically acceptable oil comprises a water-insoluble oil which is fluid and pumpable at a temperature of about 0 to about 5°C and is selected from (a) an ester of a C1-C5 monocarboxylic acid and a mono- or polyfunctional alcohol, (b) an ester of a C6-C11 monocarboxylic acid and a mono- or polyfunctional alcohol, (c) a monocarboxylic acid ester of a C6-C12 monofunctional alkanol, wherein the monocarboxylic acid contains from 12 to 16 carbon atoms and is aliphatically saturated, and (d) a monocarboxylic acid ester of a C6-C12 monofunctional alcohol, wherein the monocarboxylic acid contains from 16 to 24 carbon atoms and is olefinically mono- or poly-unsaturated.
9. The invert emulsion drilling mud composition as in any one of claims 1 to 8 wherein the alkali reserve comprises an oleophilic basic amine.
10. The invert emulsion drilling mud composition as in any one of claims 1 to 8 wherein the alkali reserve comprises lime present in an amount of less than about 2 lbs./bbl of said drilling mud composition.
11. A process of developing sources of oil and gas by drilling using a drilling mud, comprising the use therein of the invert emulsion drilling mud composition of any one of claims 1 to 10 as the drilling mud.
12. 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 comprising: a continuous oil phase comprising a substantially water-insoluble ether of a monohydric alcohol having from 4 to 36 carbon atoms, said ether having a Brookfield (RVT) viscosity of less than about 50 mPas at a temperature of about 0 to about 5°C, said ether being fluid and pumpable at a temperature of about 0 to about 5°C, and having a flash point above 90°C and a pour and setting point of below about 0°C; and an aqueous phase dispersed in said oil phase.
13. The composition as in claim 12 further comprising a water-insoluble oil which is fluid and pumpable at a temperature of about 0 to about 5°C and is selected from (a) an ester of a C1-C5 monocarboxylic acid and a mono- or polyfunctional alcohol, (b) an ester of a C6-C11 monocarboxylic acid and a mono- or polyfunctional alcohol, (c) a monocarboxylic acid ester of a C6-C12 monofunctional alkanol, wherein the monocarboxylic acid contains from 12 to 16 carbon atoms and is aliphatically saturated, and (d) a monocarboxylic acid ester of a C6-C12 monofunctional alcohol, wherein the monocarboxylic acid contains from 16 to 24 carbon atoms and is olefinically mono- or poly-unsaturated.
14. A process of improving the rheology, lubrication and fluid-loss properties of an invert emulsion drilling mud composition comprising a water-insoluble oil which is fluid and pumpable at a temperature of about 0 to about 5°C and is selected from (a) an ester of a C1-C5 monocarboxylic acid and a mono- or polyfunctional alcohol, (b) an ester of a C6-C11 monocarboxylic acid and a mono- or polyfunctional alcohol, (c) a monocarboxylic acid ester of a C6-C12 monofunctional alkanol, wherein the monocarboxylic acid contains from 12 to 16 carbon atoms and is aliphatically saturated, and (d) a monocarboxylic acid ester of a C6-C12 monofunctional alcohol, wherein the monocarboxylic acid contains from 16 to 24 carbon atoms and is olefinically mono- or poly-unsaturated, comprising adding to said drilling mud composition from about 0.1 to about 10% by weight of a substantially water-insoluble ether of a monohydric alcohol having from 4 to 36 carbon atoms, said ether having a Brookfield (RVT) viscosity of less than about 50 mPas at a temperature of about 0 to about 5°C, said ether being fluid and pumpable at a temperature of about 0 to about 5°C, and having a flash point above 90°C
and a pour and setting point of below about 0°C.
and a pour and setting point of below about 0°C.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3911299A DE3911299A1 (en) | 1989-04-07 | 1989-04-07 | USE SELECTED ETHER MONOFUNCTIONAL ALCOHOLS IN DRILLING |
| DEP3911299.3 | 1989-04-07 | ||
| PCT/EP1990/000498 WO1990012069A1 (en) | 1989-04-07 | 1990-03-29 | Use of selected ethers of monohydric alcohols in drilling-oil muds |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2050935A1 CA2050935A1 (en) | 1990-10-08 |
| CA2050935C true CA2050935C (en) | 2003-02-25 |
Family
ID=6378085
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002050935A Expired - Fee Related CA2050935C (en) | 1989-04-07 | 1990-03-29 | Use of selected ethers of monofunctional alcohols in drilling fluids |
Country Status (15)
| Country | Link |
|---|---|
| EP (2) | EP0391251B1 (en) |
| JP (1) | JPH04504434A (en) |
| AT (1) | ATE83499T1 (en) |
| AU (1) | AU625468B2 (en) |
| BR (1) | BR9007259A (en) |
| CA (1) | CA2050935C (en) |
| DE (2) | DE3911299A1 (en) |
| DK (1) | DK0391251T3 (en) |
| ES (1) | ES2037494T3 (en) |
| GR (1) | GR3007345T3 (en) |
| IE (1) | IE63846B1 (en) |
| MX (1) | MX174332B (en) |
| TR (1) | TR24953A (en) |
| WO (1) | WO1990012069A1 (en) |
| ZA (1) | ZA902665B (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5083622A (en) * | 1988-03-14 | 1992-01-28 | Shell Oil Company | Method for drilling wells |
| US5085282A (en) * | 1988-03-14 | 1992-02-04 | Shell Oil Company | Method for drilling a well with emulsion drilling fluids |
| US5072794A (en) * | 1988-09-30 | 1991-12-17 | Shell Oil Company | Alcohol-in-oil drilling fluid system |
| DE3916550A1 (en) * | 1989-05-20 | 1990-11-22 | Henkel Kgaa | USE OF SELECTED OLEOPHILER ETHERS IN WATER-BASED DRILLING RINSES OF THE O / W EMULSION TYPE AND CORRESPONDING DRILLING LIQUIDS WITH IMPROVED ECOLOGICAL COMPATIBILITY |
| US5260269A (en) * | 1989-10-12 | 1993-11-09 | Shell Oil Company | Method of drilling with shale stabilizing mud system comprising polycyclicpolyetherpolyol |
| US5058679A (en) * | 1991-01-16 | 1991-10-22 | Shell Oil Company | Solidification of water based muds |
| US5423379A (en) * | 1989-12-27 | 1995-06-13 | Shell Oil Company | Solidification of water based muds |
| US5076364A (en) * | 1990-03-30 | 1991-12-31 | Shell Oil Company | Gas hydrate inhibition |
| US5076373A (en) * | 1990-03-30 | 1991-12-31 | Shell Oil Company | Drilling fluids |
| DE4019266A1 (en) * | 1990-06-16 | 1992-01-23 | Henkel Kgaa | FLOW -ABLE BOHRLOCHANGE AGENTS BASED ON POLYCARBONIC ACID ESTERS |
| US5508258A (en) * | 1990-08-03 | 1996-04-16 | Henkel Kommanditgesellschaft Auf Aktien | Use of surface-active alpha-sulfo-fatty acid di-salts in water and oil based drilling fluids and other drill-hole treatment agents |
| GB2252993B (en) * | 1991-02-23 | 1994-09-28 | David Brankling | Drilling fluid composition |
| US5338870A (en) * | 1991-03-19 | 1994-08-16 | Shell Oil Company | Thermal condensation of polyhydric alcohols to form polyethercyclicpolyols |
| US5233055A (en) * | 1991-03-19 | 1993-08-03 | Shell Oil Company | Copolymerization of polyethercyclicpolyols with epoxy resins |
| US5371244A (en) * | 1991-03-19 | 1994-12-06 | Shell Oil Company | Polycondensation of dihydric alcohols and polyhydric alcohols and thermal condensation to form polyethercyclicpolyols |
| US5302728A (en) * | 1991-03-19 | 1994-04-12 | Shell Oil Company | Polycondensation of phenolic hydroxyl-containing compounds and polyhydric alcohols and thermal condensation to form polyethercyclipolyols |
| US5302695A (en) * | 1991-03-19 | 1994-04-12 | Shell Oil Company | Polycondensation of epoxy alcohols with polyhydric alcohols and thermal condensation to form polyethercyclicpolyols |
| EP0532128A1 (en) * | 1991-08-16 | 1993-03-17 | Exxon Chemical Patents Inc. | Load bearing fluid |
| MY108348A (en) * | 1991-08-16 | 1996-09-30 | Exxon Chemical Patents Inc | Ester free ethers. |
| DE4200502A1 (en) * | 1992-01-13 | 1993-07-15 | Henkel Kgaa | IMPROVED DISPOSAL OF CONTAMINATED DRILL SMALL FROM GEOLOGICAL HOLES WITH MINERAL OIL CONTAINING DRILL RINSING SYSTEMS |
| DE4218243C2 (en) * | 1992-06-03 | 1994-04-28 | Cognis Bio Umwelt | Improved nutrient mixtures for the bioremediation of polluted soils and waters |
| US5428178A (en) * | 1992-10-13 | 1995-06-27 | Shell Oil Company | Polyethercyclipolyols from epihalohydrins, polyhydric alcohols, and metal hydroxides or epoxy alcohols and optionally polyhydric alcohols with thermal condensation |
| US5371243A (en) * | 1992-10-13 | 1994-12-06 | Shell Oil Company | Polyethercyclicpolyols from epihalohydrins, polyhydric alcohols, and metal hydroxides |
| US5286882A (en) * | 1992-10-13 | 1994-02-15 | Shell Oil Company | Polyethercyclicpolyols from epihalohydrins, polyhydric alcohols and metal hydroxides or epoxy alcohol and optionally polyhydric alcohols with addition of epoxy resins |
| DE4420455A1 (en) * | 1994-06-13 | 1995-12-14 | Henkel Kgaa | Flowable borehole treatment compositions containing linear alpha-olefins, in particular corresponding drilling fluids |
| DE4432841A1 (en) | 1994-09-15 | 1996-03-21 | Hoechst Ag | Use of mixtures containing acetal |
| DE19546911A1 (en) | 1995-12-15 | 1997-06-19 | Henkel Kgaa | New aqueous-swellable preparations of guar and guar derivatives in oleophilic liquids and their use |
| US6022833A (en) * | 1996-10-30 | 2000-02-08 | Henkel Kommanditgesellschaft Auf Aktien | Multicomponent mixtures for use in geological exploration |
| TW354352B (en) * | 1996-10-30 | 1999-03-11 | Henkel Kgaa | A process for easier cleaning on the basis of water/oil inversion emulifier |
| CA2656289A1 (en) | 2006-06-26 | 2008-01-03 | Bp Exploration Operating Company Limited | Wellbore fluid |
| EP2154224A1 (en) | 2008-07-25 | 2010-02-17 | Bp Exploration Operating Company Limited | Method of carrying out a wellbore operation |
| WO2010141534A1 (en) | 2009-06-02 | 2010-12-09 | Chevron Phillips Chemical Company Lp | Wellbore fluid additives and methods of producing the same |
| AU2011333528A1 (en) | 2010-11-25 | 2013-05-30 | Bp Exploration Operating Company Limited | Consolidation |
| EP2707451B1 (en) | 2011-05-12 | 2015-03-25 | BP Exploration Operating Company Limited | Method of carrying out a wellbore operation |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE605264A (en) * | 1960-07-07 | |||
| FR1297556A (en) * | 1961-08-16 | 1962-06-29 | Huels Chemische Werke Ag | Lubricants free from mineral oil and used for shaping plastics |
| DE1218096B (en) * | 1961-07-26 | 1966-06-02 | Huels Chemische Werke Ag | Hydraulic fluid |
| US3630898A (en) * | 1970-01-09 | 1971-12-28 | Atlantic Richfield Co | Product and process |
| US4606833A (en) * | 1984-10-25 | 1986-08-19 | Phillips Petroleum Company | Mixture of dithiodiglycol and polyoxyalkylene glycol derivatives as a lubricating additive |
| ZW23786A1 (en) * | 1985-12-06 | 1987-04-29 | Lubrizol Corp | Water-in-oil-emulsions |
| DE3907392A1 (en) * | 1989-03-08 | 1990-09-13 | Henkel Kgaa | ESTER OF CARBONIC ACIDS, MEDIUM CHAIN LENGTH, AS THE BEST NEEDLE PART OF THE OIL PHASE IN INVERT DRILL RINSE |
| DE3907391A1 (en) * | 1989-03-08 | 1990-09-13 | Henkel Kgaa | USE OF SELECTED ESTER OILS OF LOW CARBONIC ACIDS IN DRILL RINSING |
-
1989
- 1989-04-07 DE DE3911299A patent/DE3911299A1/en not_active Ceased
-
1990
- 1990-03-29 CA CA002050935A patent/CA2050935C/en not_active Expired - Fee Related
- 1990-03-29 WO PCT/EP1990/000498 patent/WO1990012069A1/en not_active Application Discontinuation
- 1990-03-29 DE DE9090105991T patent/DE59000586D1/en not_active Expired - Fee Related
- 1990-03-29 JP JP2504936A patent/JPH04504434A/en active Pending
- 1990-03-29 EP EP90105991A patent/EP0391251B1/en not_active Expired - Lifetime
- 1990-03-29 BR BR909007259A patent/BR9007259A/en not_active Application Discontinuation
- 1990-03-29 DK DK90105991.5T patent/DK0391251T3/en active
- 1990-03-29 EP EP90904837A patent/EP0466724A1/en active Pending
- 1990-03-29 AT AT90105991T patent/ATE83499T1/en not_active IP Right Cessation
- 1990-03-29 ES ES199090105991T patent/ES2037494T3/en not_active Expired - Lifetime
- 1990-03-29 AU AU53308/90A patent/AU625468B2/en not_active Ceased
- 1990-04-05 ZA ZA902665A patent/ZA902665B/en unknown
- 1990-04-05 MX MX020187A patent/MX174332B/en unknown
- 1990-04-06 IE IE124490A patent/IE63846B1/en not_active IP Right Cessation
- 1990-04-06 TR TR90/0342A patent/TR24953A/en unknown
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1993
- 1993-03-15 GR GR930400543T patent/GR3007345T3/el unknown
Also Published As
| Publication number | Publication date |
|---|---|
| EP0466724A1 (en) | 1992-01-22 |
| EP0391251B1 (en) | 1992-12-16 |
| CA2050935A1 (en) | 1990-10-08 |
| MX174332B (en) | 1994-05-09 |
| EP0391251A1 (en) | 1990-10-10 |
| ES2037494T3 (en) | 1993-06-16 |
| DK0391251T3 (en) | 1993-02-01 |
| ATE83499T1 (en) | 1993-01-15 |
| DE3911299A1 (en) | 1990-10-11 |
| BR9007259A (en) | 1992-03-17 |
| GR3007345T3 (en) | 1993-07-30 |
| AU5330890A (en) | 1990-11-05 |
| IE63846B1 (en) | 1995-06-14 |
| JPH04504434A (en) | 1992-08-06 |
| AU625468B2 (en) | 1992-07-09 |
| ZA902665B (en) | 1990-12-28 |
| WO1990012069A1 (en) | 1990-10-18 |
| DE59000586D1 (en) | 1993-01-28 |
| TR24953A (en) | 1992-09-01 |
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