AU625468B2

AU625468B2 - Use of selected ethers of monohydric alcohols in drilling-oil muds

Info

Publication number: AU625468B2
Application number: AU53308/90A
Authority: AU
Inventors: Claus-Peter Herold; Heinz Muller; Gerhard Stoll; Stephan Von Tapavicza
Original assignee: Henkel AG and Co KGaA
Current assignee: BASF Personal Care and Nutrition GmbH
Priority date: 1989-04-07
Filing date: 1990-03-29
Publication date: 1992-07-09
Anticipated expiration: 2010-03-29
Also published as: ES2037494T3; DE3911299A1; EP0391251A1; JPH04504434A; TR24953A; ATE83499T1; DE59000586D1; AU5330890A; GR3007345T3; EP0466724A1; MX174332B; BR9007259A; IE63846B1; EP0391251B1; CA2050935A1; CA2050935C; WO1990012069A1; ZA902665B; DK0391251T3

Abstract

Described in the use of water-insoluble ethers, with a flash point above 80 DEG C, of monohydric alcohols, of natural and/or synthetic origin, with at least 4 C-atoms, preferably at least 6 C-atoms in the alcohol residues, as the oil phase or component of the oil phase in invert drilling-oil muds which are in the form of water/oil emulsions, which include in the closed oil phase, that can flow and be pumped in the temperature range 0 to 5 DEG C, a disperse aqueous phase plus, optionally, other commonly used additives, and which are suitable for use in prospecting for, for instance, oil and natural-gas deposits without polluting the environment. Also described are other drilling-oil muds of the kind described above, characterized by the fact that they have added to them as a closed oil phase, or dissolved in environmentally compatible water-insoluble oils, substantially water-insoluble ethers of monohydric alcohols, the oil phase being capable of flowing and being pumped in the temperature range 0 to 5 DEG C and having a flash point over 80 DEG C.

Description

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OPI DATE 05/11/90 APPLN. I D 53368 AOJP DATE 06/12/90 PL M ER P CT/EP90/00Li98

PCIT

I NTEIRNATIC OUSMFRJ D G INTERNATIONALE ZU RU Ul D G T DES PATENTWEShrNS (1J- r; (51) Internationale Patentklassifikation 5 (11) Internationale Ver~ffentlichungsnummer: WO 90/12069 C09K 7/06 Al (43) Internationales Ver~ffentlichungsdatum: 18, Oktober 1990 (18.10.90) (21) Internationales Aktcnzcichen: PCT/EP90/00498 (22) Internationales Annieldedatumn: 29, Mtirz 1990 (29.03.90) Prioritfitsdaten P 39 11 299.3 (81) Bestimmungsstaaten: AT (europtlisches Patent), AU, BE (europfiisches Patent), BR, CA, CH (europflisches Patent), DE (europilisches Patent), DK (europtiisches Patent), ES (europttisches Patent), FR (europfiisches Patent), GB (europflisches Patent), IT (europiiisches Patent), JP, LU (europiiisches Patent), NL (euiropfiiiches Patent), NO, SE (europiiisches Patent), US.

Vcr6ffentlicht A'it internationalent Reeherclhenberic,t.

7, April 1989 (07.04,89) (71) Anmelder (fib' tille Bestininningsseaalcn ausser US): H-EN- KEL KOMMANDITGESELLSCHAFT AUF AKTIEN [DE/DE]; TFP-Patentabteilun !-enkelstrage 67, D- 4000 D~sseldorf 13 (DE).

(72) Erflnrler; und Erfinder/Anelder (nor j 1 7r LIS) MOJLLER, Heinz [DE' DE]; Goldregenw,.g 4, U-4019 Monheirn STOLL, Gerhard [DE/DE]; Darziger Stra~e 69, D-4052 Korschenbroich I H_'ROLD, Claus-Peter [DE/DE]; Ostpreugenstrage 26, D-4020 Mettmann VON TA- PAVICZA, Stephan [DE/D Fl:. Thomas-Nlarn-Stra~e 12, D-4006 Erkrath 2 (DE).

(54)Tltle: USE OF SELECTED E'i HERS OF MONOHYDRIC ALCOHOLS IN DRILLING-OIL MUDS (54) Bezedchnung- VERWENDUNG AUSGEWA14LTER ETHER MONOFUNKTION ELLER ALKOHOLE IN BOHRSPC% LUNG EN (57) Abstract Described in the use of water-insoluble ethers, with a flash point above 80'C, of monohlydric alcohols, of natural and 'or ,,ynthetic origin, with at least 4 C-atonm, preferably at least 6 C-atoms in the alcohol residues, as the oil phase or component of the oil phase in invert drilling-oil muds which are in the Form or water/oil emulsions, wvhich include in the closed oil phase, that can flow and be pumped in the temperature range 0 to 5'C, a disperse aqueous phase plus, optionally, other commonly used additives, and which are suitable foi, use in prospecting for, for instance, oil and natural-gas deposits without pollutintg the envircn-.

ment. Also described are other drilling-oil muds of the kind described above, characterized by the fact that they have added to themn o a closed oil phase, or dissolved in environmentally compatible water-insolublb oils, substantially water-insoluble ethers of monohydric alcohols, the oil phase being capable of flowing and being pumped in the temperature range 0 to 5'C and having a flash point over (57) Zusaminenfassung Beschrieben wkrd die Verwendung von warserunlL~slichen und Flammpunkte oberhalb 801C aufweisenden Ethern einwerti.

ger Alkohole nattlrlichen und/oder synthetischtm Ursprungs mit wenigstens 4 C.Atomen, vorzugsweise wenigstens 6 C-Atomen in den Alkoholresten als Olphase oder Bestandieil der Olphase von InvertBohrspfllungen, die W/O-Emulsionen, vorliegen, in der geschlossenen und !im Temperaturbereich von, 0 bis 5 0 C Mleg- und pumpfttlhigen Olphase eine disperse wligrige Phase sowie gewilnschtenfalls weitere (Ibliche Zusatzstoffe aufweisen und fir die umweltsclionende Erschiliellung von beispielsweise Erd(Il.

bzw, Erdgasvorkommen geeignet sind. Dargestellt sind weiterhiri Bohrspfllungen der geniannten Art, die dadurch gekennzcichinet sind, Ma sic als geschlossene Olphase oder gel(Ist in (Ikologisch vertrtiglichenr wasserunlbslichen Olen elnen Zusatz von wenigstens weitgehend wlisserunl~slichen Ethern einwertiger Alkohiole enthalten, wobei die jew'ilige Olphase im Temperattirbereich von 0 bis 5'C filcO. und pumpflihig ist und Flammpunkte oberhalb 801C aufweist, Siche Rtlckselte -1- Patent Application D 8539 "The use of selected ethers of monofunctional alcohols in drilling fluids" S The invention discloses new drilling fluids and invert drilling muds based thereon which are distinguished by high ecological acceptability and at te same time good storage and application properties. An important area of application for the new drilling fluid systems is in S off-shore wells for the development of petroleum and/or natural gas deposits, the aim 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 problems are substantially simplified by the ester-based drilling-oil fluids selected according to the invention.

The Prior Art Oil-base drilling fluids are generally used in the form of so-called invert-emulsion muds, which consist of a three-phase system: oil, water and finely particulate solids. These are preparations of the W/Oemulsion type, i.e. the aqueous phase is distributed as a heterogeneous fine dispersion in the continuous oil phase. A number of additives can be used to stabilize the system as a whole and to 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, to the publication by P.A. Boyd et al. "New Base Oil Used in Low-Toxicity Oil Muds" Journal of Petroleum Technology, 1985, 137 to 142, and R.B.

Bennett, "New Drilling Fluid Technology Mineral Oil Mud" Journal of Petroleum Technology, 1984, 975 to 981 and the literature cited

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-2 therein.

The importance of ester-based oil phases in reducing the problems created by such oil-base muds has been recognized for some time in the relevant field of technology. For example, US Patent Specificati.ons 4,374,737 and 4,481,121 disclose oil-base drilling fluids in which nonpolluting oils are to be used. The following are of equal value a non-polluting oils mineral oil fractions which are free from aromatj hydrocarbons, and vegetable oils, such as groundnut 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 known 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 e:amples 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 S fractions are used as the con;tinuous oil phase, Oils of vegetable and/or animal origin are not considered for practical reasons. The rheological properties of such oil phases cannot be controlled over the wide temperature range generally required in practice, from 0 to 5 0 C on the one hand, up to 250 0 C on the other.

The Applicant's earlier proposals Ester oils of the type in question do 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 muds. Free carboxylic acids are formed as a result. The Aplicant's earlier rca\' ^n Fbre"-t P pp'\CoAons T- C 's L4bS551t -g U an 9ss 19.

describe the problems caused thereby and give proposals for their solution. Further adaptations of usable ester oils are disclosed in the Zealir Pae..t ,pliti. D 07 391.2 nd 3 07 92.0 (9 8606 the sir r r l 7-77- anmrrmn ii: -3- The subject of these earlier Applications is the use of ester oils based on selected monocarboxylic acids or monocarboxylic acid mixtures and monofunctional, and optionally polyfunctional, alcohols. The earlier 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 known alkali reserves in the drilling fluid and in this way to S retard undesirable corrosion. 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 comparable zinc compounds. 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 maximum amount permitted in the disclosure of the aforementioned earlier Applications is about 2 lb/bbl (pounds/barrel) of oil-base mud.

An important further development of these invert-drilling fluids based on ester oils is the subject of the Applicant's earlier Application 4- U.9519L qo The teaching of this earlier 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 form, it should moreover be possible to convert these free carboxylic acids, preferably into valuable components with stabilizing or emulsifying properties for the whole system. According to this teaching, basic amine compounds of marked oleophilic nature 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 compounds can at the same time be used at least in part as alkali reserves in the invert drilling fluid, they can, S ,however, also be used in combination with conventional alkali reserves, Sparticularly together with lime. The use of oleophilic air.ne compounds* L i r H ,T L r r- 4 -4which are at least largely free from aromatic 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 embodiment the Swater-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 compounds 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 besic amine compounds can be added to the drilling fluid in amounts of up to about 10 ib/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 compounds can effectively prevent thickening of the mud system, which presumably can be attributed to a disturbance of the W/O invert system and also to the formation of free carboxylic acids by ester hydrolysis.

SThe invention problem and its technical solution The problem of the present invention is further to develop systems 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 embodiment the invention intends to make available additives for the aforementioned systems in question here, which confer valuable additive properties on drilling fluids based on W/0-emulsions without having a disadvantageous effect 5 on their ecological acceptability.

The technical solution of the problems of the invention starts from the knowledge 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 components, in particular therefore corresponding compounds with a pronounced oleophilic nature, which differ, however, from pure hydrocarbon compounds 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.

According to a first embodiment of the present invention there is provided a process for preparing an invert drilling fluid which exists as a water in oil emulsion and is suitable for the environmentally friendly development of petroleum or natural gas deposits said process comprising 15 mixing an oil phase which is fluid and pumpable at 0 to 5°C and comprises °oo water-insoluble ethers having flash points above 80 0 C and derived from o monohydric alcohols of synthetic and/or natural origin having at least 4 o o carbon atoms or mixtures thereof with non-polluting oils together with a dispersed aqueous phase and optionally further additives.

o. 0 20 According to a second embodiment of the present invention there is provided an invert-drilling fluid, suitable for the environmentallyfriendly development of petroleum or natural gas deposits comprising In a 0 o continuous oil phase a dispersed aqueous phase, emulsifiers, weighting S agents, fluid-loss additives and alkali reserves, characterized in that S 25 said oil phase is fluid and pumpable at 0 to 5*C, has a flash point above 80°C and further comprises substantially water-insoluble ethers from monohydric alcohols having at least 4 carbon atoms or mixtures thereof with non-polluting water-insoluble oils.

Theyar I olu seibodi men t sof.te inyen.t 1on S 30 In a first embodiment the continuous oil phase of the invert drilling fluids is formed exclusively, or to by far the largest part, by the essentially water-insoluble and preferably markedly oleophilic ethers. Understandably, the rheology of the ethers used here must be suited to TMS/LMM/1807R 6the 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 formed by more than 70 by weight, preferably by more than 80 by weight, and desirably Sexclusively, by the ethers themselves. The general subject knowledge 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 from a selected alcohol, mixed ethers from different alcohols and/or ether mixtures of the two 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 known effect of branchedchain and/or un-saturated structure of a hydrocarbon radical in corresponding alcohols also influences the rheology of the ethere formed therefrom.

The rheology of branched-chain and/or unsaturated ethers of the type in question here is known to meet the requirements of flowability and pumpability, even at lower temperatures, more easily than the straightchain saturated hydrocarbon structure. Saturated straight-chain fattyalcohol-ethers with from 16-18 carbon atoms are known 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 puzrpable oil phases in the sense of the invention.

In the field of saturated ethers from monofunctional alcohols, the range with low numbers of carbon atoms is particularly suitable, particularly therefore the range of about 8 14 carbon atoms, here too the ethers from branched-chain alcohols can have rheological advantages.

SThe oil-mixture components optionally used in small amounts in this 7 embodiment can be pure hydrocarbon compounds especially those free from aromatic hydrocarbons, in particular selected ester oils of the type described in the Applicant's earlier Applications mentioned above.

The rheological properties of the ether components used according to the invention become less and less important, the greater the proportion of these mixture constituents in the admixture with one or more oil components. 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-watermiscible 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 preferred.

As the mixture components for this second embodiment of the invention, there can again be considered both pure hydrocarbon oils, particularly those free from aromatic hydrocarbons, and especially ester oils of the type described in earlier Applications by the Applicant. Such admixtures also fall within the framework of the invention, with both admixtures of ester oils with pure hydrocarbon compounds and mixtures of various ester oil types possible for use as mixture components 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 most 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 embc liments 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 compounds.

The invention finally relates in a third variant to the use of practically water-insoluble ethers as additives in the oil phase of the 2I aforementioned drilling fluids based on W/O-emulsions. The amount of

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-8 ethers used according to the invention is usually in the range of about 0.1 to a maximum of 10 by weight, preferably in the range of about 1 to 5 by weight of the oil phase. The range of suitable waterinsoluble ethers can understandably be enlarged substantially in this embodiment. The rheology of the system as a whole is no longer V 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 component of the continuous oil phase is formed exclusively or primarily by ester oils of the type described in the above earlier 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 by an 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 improvements 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 aqueous phase, in some cases clearly improved lubrification by the drilling fluid and in some cases a distinct improvement in the rheological properties of invert drilling fluids based on ester oils.

The etners used according to the invention The use of the ethers as the oil phase, but also their combination as a lesser or greater part in the oil phase, requires these ethers to have adequate water-insolubility. The water-solubility of suitable ethers at room temperature preferably lies below 5 by weight, particularly under 1 by weight and preferably not more than about 0.1 by weight.

9 The following general rules apply for the chemical 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 component 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 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 -50C and particularly below -10 0 c.

Finally, the flash points of the ether or ethers used are important for practical use, these are advantageously not below 90 0 C and preferably above 100 0 C. Much higher flash points, for example, those above 130 0

C

and in particular above 150 0 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 molecular structure of the ether-forming alcohols.

These structural features are discussed below: An important element of the invention is the use of comparatively nontoxic 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 alcohols are the most important ether-forming components in the sense of the method according to the i invention. The lower limit for the number of carbon atoms in such 10 alcohols is 4 carbon atoms, preferably 6 carbon atoms and particularly 8 carbon atoms. The upper limit for the number of carbon atoms in the ether-forming alcohols can also be chosen quite high depending on the rheology requirements and lies, for example, at about 36 carbon atoms, preferably at about 32 carbon atoms. In particular, monofunctional alcohols can be considered with about 6-24 carbon atoms, preferably from 6-18 carbon atoms. Ethers of C8- 1 6 -alcohols and in particular C 8 14 -alcohols, are suitable components in the sense of the teaching of the invention.

The ether-forming alcohols can be completely 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 completely or partly of natural and/or synthetic origin.

Within the limit conditions indicated, certain selected ethers or ethers from certain selected alcohos.s, mixed ethers from certain selected alcohols 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 freedom of choice, and therefore the rheological data required in the S drilling fluid can be set at an optimum 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 components of the oil phase.

The mixture components 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 aliphtic and/o ccloaliphatic /r c alipha hydrocarbon fractions essentially free from aromatic hydrocarbons, with the required rheological properties.

Refer here to the prior-art publications cited above and the available commercial products.

Particularly important mixture components, however, are ester oils

A

I

11 which are ecologically acceptable as used in the invention, as described in particular in the aforementiored earlier Australian Patent Application No's 46551/89, 491549/90, 51802/90 and 51802/90. To complete the invention disclosure, the essential characteristics of these esters, or ester mixtures, are now briefly summarized.

In a first,embodiment, as the oil phase, esters are used of monofunctional alcohols with from 2 to 12, particularly with from 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 temperature range of 0 to 5 0 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 0 C 12 14 -monocarboxylic acids, the remaining percentage preferably being 0o' 0 15 based on smaller amounts of shorter-chain aliphatic and/or longer-chain, o n particular olefin mono- or poly-uns tiurated, monocarboxylic acids.

o 4 Esters are preferably used which in the temperature range of 0 to o. o0 have a Brookfield (RVT) viscosity of not more than 50 mPa.s, preferably S0 0 not above 40 mPas and particularly of a maximum of about 30 mPa.s, The S 20 esters used in the drilling mud have solidification values (pour and setting point) below -10 0 C, preferably below -15 0 C and at the same time have flash points above 100°C, preferably above 150 0 C. The carboxylic acids present In the ester or ester mixture are straight-chain and/or S" branched, and are of vegetable and/or synthetic origin. They can be 0 25 derived from the corresponding triglycerides, such as coconut oil, palm kernel oil and/or babassu oil. The alcohol radicals of the esters used are derived in particular from straight-chain and/or branched saturated alcohols, preferably with from 6 to 10 carbon atoms. These alcohol components can also be of vegetable and/or animal origin and can thus be obtained by the .,ductive hydrogenation of the corresponding carboxylic acid esters.

A further class of particularly suitable ester oils is derived from olefin mono- and/or poly-unsaturated monocarboxylic acids Ith 16 to 24 carbon atoms or their admixtures with smaller amounts of other, particularly saturated, monocarboxylic acids and monofunctional TMS/LMM/1807R 4t 12 alcohols with preferably from 6 to 12 c -7b Atoms. These ester oils are also fluid and punpable in the temperature range of 0 to 5 0 C. In particular those esters are suitable which are derived, by more than by weight, preferably by more than 80 by weight and in particular by more than 90 by weight, from olefin-unsaturated carboxylic acids with from 16 to 24 carbon atoms.

Here too, the solidification values (pour and setting point) lie below 0 C, preferably below -15 0 C, while the flash points lie above 100 0

C

and preferably above 160 0 C. In the temperature range of 0 to 5 0 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 C 16 2 4 -monocarboxylic 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 monounsaturated. In the second embodiment, the C 16 2 4 -monocarboxylic acids present in the ester mixture are derived, by more than 45 by weight, preferably by more than 55 by weight, from olefin di- and/or polyunsaturated 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 wore than about 20 by weight and in particular not more than about 10 by weight. Preferab't.y ,turated 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. Examples of vegetable raw materials are, for example, paln oil, groundnut oil, castor oil and in particular colza 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 components for the use according to the invention, are esters which are fluid at room temperature and have flash points above 80 0 C, from CI_ 5 monocarboxylic acids and mono- and/or polyfunctional alcohols, which are preferably also fluid and pumpable in the temperature range of 0 to 0 C. Particularly suitable are the corresponding esters of these lower 13 carboxylic acids with monofunctional alcohols with at least 8 carbon atoms and/or esters of these acids with di- to tetra-hydric alcohols with preferably 2 to 6 carbon atoms. Acetic acid in particular is suitable for practical reasons as the ester-forming acid-component of this class.

The specification 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 components from this sub-cl? s are, in particular, esters from monofunctional alcohols of natural a /or synthetic origin, the chain length of which in the presence of predominantly aliphaticunsaturated alcohols can be in the range of 8 to 15 carbon atoms, but in the case of olefin mono- and poly-unsaturated alcohols, can also consist of higher numbers of carbon atoms, for example, up to about 24 carbon atoms. Details can be found In the Applicant's earlier Australian Patent o e 15 Application No 51823/90.

°0.,l Suitable mixture components are finally, however, the esters, as described in the Applicant's Parallel Australian Application No 51802/90, o0 o, from monocarboxylic acids of synthetic and/or natural origin with from 6 to 11 carbon atoms and mono- and/or polyfunctional alcohols, which are 20 preferably also fluid and pumpable in the temperature range of 0 to To complete the invention disclosure, reference is made here to this extent to the above Parallel Application, the contents of which are oo hereby also made subject of the present disclosure.

Suitable mixture components also for the teacing of the present so o 25 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 continuous oil phase of such W/0-invert emulsions in the Parallel Australian Application of the Applicant 53344/90. For the Spurposes of the invention disclosure reference is expressly made to the S 30 details in this Parallel Patent Application.

Multi-substance mixtures fall within the scope of the invention, which together with the ethers defined according to the invention, can contain one or more of the mixture components listed here individually,

MS/LMM/

S, f ,iFMS/LMM/1807R i. 14 Essentially any mixtures can be used provided that they fulfil the basic rheological requirements for invert drilling fluids of the type referred to here. Examples of such multi-component mixtures are materials based on various types of ester oils or also substance mixtures additionally containing mineral oil.

Further mixture components of the invert drilling fluid These may be any of the usual mixture components for conditioning and for the practical use of invert drilling muds, such as are currently Sused 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 embodiment of the invention, oleophilic basic amine compounds are used as additives together with the ester oils, these amine compounds are described in detail in the aforementioned earlier aLppi aLn .P 3 03 7-1 54) ot the Applicant. For details reference should be made to the disclosure of this earlier Application, as described above.

If ester oils are used as mixture component'. n 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 employ 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 maximum 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 below this figure, e.g. from about 1 to 1.8 lb/bbl (lime/drilling fluid). Other known alkali reserves can be used in addition to, or in place of, the lime. The less basic metal oxides, such as zinc oxide, should particularly be mentioned. 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 associatp with an increase in viscosity and therefore a deteriorationi in the xi.ological properties. The special features discussed here c.

L

15 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 rheological properties are iaintained 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 from S about 5 to 25 by weight. A dispersed aqueous phase from about 10 to 25 by weight can be regarded as particularly useful.

The following rheological data apply for the rheology of the preferred invert drilling muds according to the invention: plastic viscosity (PV) from about 10 to 60 mPa.s, preferably from about 15 to 40 mPa.s; yield point (YP) in the range from about 5 to 40 lb/100 ft 2 preferably from about 10 to 25 lb/100 ft 2 each measured at 50 0 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 example, described in full in the "Manual of Drilling Fluids Technology" of NL-Baroid Co., London, GB, particularly in the Schapters "Mud Testing Tools and Techniques" and "Oil Mud Technology", which is freely accessible to interested experts. In summary, to complete the invention disclosure the following can be said: The emulsifiers that can be used in practice are systems suitable for the formation of the required W/O-emulsions. In particular, selected oleophilic fatty acid salts, e.g. those based on amidoamine compounds, can be considered. Examples 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-Baroid Co. under the brand name "EZ-mul".

Such emulsifiers are sold conmercially as highly concentrated activei. substance preparations and can, for example, be used in amounts from about 2.5 to 5 by weight, particularly in amounts from about 3 to 4 L j- I a~-Tal-Y-- 16 by weight referred to the ester oil phase..

Hydrophobized lignite in particular is used in practice as the fluidloss additive and thus in particular to form a dense coating of a largely liquid-impermeable film on the bore-hole walls. Suitable amounts are, for example, from about 15 to 20 lb/bbl or from about 5 to 7 by weight, referred to the oil phase.

The viscosifier usually employed in drilling fluids of the type in question is a cation-modified finely particulate bentonite, which can be used particularly in amounts from about 8 to 10 lb/bbl or from about S2 to 4 by weight, referred to the oil phase. Barite is the weighting material generally used in relevant applications to establish the necessary pressure compensation, the amounts added being varied according to the drilling conditions anticipated in each case. By adding barite, it is, for example, possible to raise the specific weight of the drilling fluid to 2.5 and preferably to a value in the range from about 1.3 to 1.6.

The dispersed aqueous phase in these invert drilling fluids is loaded with soluble salts calcium chloride and/or potassium chloride are mainly used. Saturation, at room 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 compounds.

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.

el S.7__J 17 Emles Example 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 (comme:,cial product "Omnigel") 9 g W/0-emulsifier ("EZ-mul NT of NL Baroid Co.) i 20 g organophilic lignite ("Duratone" of NL Baroid Co.) 28 g water 12 g CaC12 x 2 H 2 0 4 g lime 255 g barite First of all, the plastic viscosity the yield point (YP) and the gel strength of the invert drilling fluid are measured after 10 seconds and after 10 minutes by a viscosity measurement at 50 0 C on the unaged material The invert drilling fluid is then aged for 16 hours at 125 0 C in the autoclave in the so-called "roller-oven", to test the effect of temperature on the stability of the enulsion. The viscosity values are then measured again at 50 0

C.

The following are the values determined for the unaged and aged material: unaged material aged material plastic viscosity (PV) 19 21 yield point (YP) 11 8 gel strengths (lb/100 ft 2 sec. 4 4 min. 5 T

H

P fluid-loss value after ageing 4 ml t 18 Example 2 An invert-drilling fluid is prepared with an O/W-ratio of 80/20 according to the following formulation: 210 ml dialkylether as in Example 1 6 g gel former (commercial product "Cmnigel") 13 g organophilic lignite ("Duratone" of NL Baroid Co.) 45.2 g water g CaCl2 x 2 8 g W/O--mulsifier ("EZ-mul NT" of NL Baroid Co.) 2 g lime 220 g barite The following are the values determined for the unaged and aged material: unaged material aged material plastic viscosity (PV) 26 yield point (YP) 16 9 gel strengths (lb/100 ft 2 sec. 7 4 min. 9 6 HTHP fluid-loss value of aged drilling fluid 1 ml Examples 3 to In the following examples. invert drilling fluids are prepared each with a O/W-ratio of 90/100 according to the following formulation: 230 ml ether (see the identification below in Examples 3 to 26 ml water 6 g gel former (comnercial product "Geltone") 12 g organophilic lignite ("Duratone" of NL Baroid Co.) 2 g lime i 6 g W/O-emulsifier ("EZ-mul NT" of NL Baroid Co.) ei 19 346 g barite 9.2 g CaCI2 x 2 H 2 0 The following ethers are used in each case as the oil phase: Example: Cg-O-Cg Example 4: C 1 0

-O-C

1 0 Example 5: di-isotridecylether The viscosity values measured for the unaged and aged drilling fluid are summnarized below. The ageing is measured once after 16 hours at 125 0 C and in a further test after 72 hours at 125 0

C.

Example 3 unaged material aged material 16 hrs/ 1250C aged material 72 hrs/ 125 0

C

0 plastic viscosity (PV) yield point (YP) gel strengths (lb/100 ft 2 10 sec.

min.

Ir The test batches of this example 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 commercial product "Araphen G2D"). The following values were measured: i i B ii'-TA 20 unaged material aged material :16 hrs/ 125 0

C

aged material 72 hrs/ 125 0

C

plastic viscosity (PV) yield point (YP) gel strengthis (lb/l00 ft 2 sec.

min.

Examp~le unaged material aged material 16 hrs/ 125 0

C

aged material 72 hrs/ 125 0

C

plastic viscosity (PV) yield point (YP) gel strengths (Lb/l00 ft 2 sec.

min.

mil-W 7<14

Claims

1. A process for preparing an invert drilling fluid which exists as a water in oil emulsion and is suitable for the environmentally friendly development of petroleum or natural gas deposits said process comprising mixing an oil phase which is fluid and pumpable at 0 to and comprises water-insoluble ethers having flash points above 80 0 C and derived from monohydric alcohols of synthetic and/or natural origin having at least 4 carbon atoms or mixtures thereof with non-polluting oils together with a dispersed aqueous phase and optionally further additives.

2. A process according to claim 1, characterized in that said oil phase has a Brookfield (RVT) viscosity of not more than 50 mPa.s at 0 to

3. A process according to claim 2, characterized In that said 15 viscosity is not more than 40 mPa.s. oo

4. A process according to claim 2, characterized in that said ao .o viscosity is at most about 30 mPa.s. o

5. A process according to any one of claims 1 to 4, characterized C in that said oil phase has solidification values (pour and setting point) o 0 20 below 0OC, and flash points not below 90 0 C.

6. A process according to claim 5, characterized in that said solidification values are below oo

7, A process according to claim 5, characterized in that said a° solidification values are below -10 0 C. 2 oo 25

8, A process according to any one of claims 5 to 7, characterized o in that said flash points are above 100 0 C. 0000

9, A process according to any one of cl-ims 1 to 8, characterized in that said ethers comprise from about 0,1 to about 10% by weight of 3 said oil phase. i 30

10. A process according to any one of claims 1 to 8, characterized in that said ethers comprise more than about 10% by weight of said oil phase.

11, A process according to claim 10, characterized In that said ethers comprise more than about 35% by weight of said oil phase.

12. A process according to claims 10 or 11, characterized In that said ethers comprise a substantial part of said oil phase, i

13. A process according to any one of claims 1 to 12, characterized in that said ethers Improve the rheology, the lubricating ability and/or the fluid-loss properties of said oil phase, TMS/LMM/1807R 22

14. A process according to any one of claims 1 to 13, characterized in that said alcohols have at least 6 carbon atoms.

I 1 A process according to any one of claims 1 to 14, characterized in that said alcohols have up to 24 carbon atoms.

16. A process according to claim 15, characterized in that said alcohols are partly olefin unsaturated.

17. A process according to any one of claims 1 to 16, characterized in that said alcohols have 8 to 18 carbon atoms and are of the straight-chain or branched-c' in type.

18. A process according to any one of claims 1 to 17, characterized in that said non-polluting oils comprise water-insoluble ester oils, which are fluid and pumpable at 0 to 5 0 C.

19. A process according to claim 18, characterized in that said ester oils are derived from mono- and/or polyfunctional alcohols. S 15

20. A process according to claim 19, characterized in that said 060( alcohols are non-toxic even after partial ester-saponification of said o0 ester oils.

21. A process according to claim 20, characterized in that said O a alcohols are non-toxic when inhaled. 20

22. A process according to any one of claims 18 to 21, characterized in that said ester oils comprise: esters from C 1 carboxylic acids and mono- and/or polyfunctional alcohols, esters from monocarboxylic acids of synthetic and/or natural origin with 6 to 11 o a o carbon atoms and mono- and/or polyfunctional alcohols, esters from aliphatic-saturated monocarboxylic acids with 12 to 16 carbon atoms and ooo monofunctional alcohols with 6 to 12 carbon atoms, esters from olefin mono- and/or poly-unsaturated carboxylic acids with 16 to 24 carbon atoms and monofunctional alcohols with 6 to 12 carbon atoms, or mixtures of two or more thereof.

23. A process according to any one of claims 18 to 22, characterized in that said non-polluting oils Include basic amine compounds of a markedly oleophilic nature, which can also be substituted with hydroxyl groups.

24. A process according to any one of claims 1 to 23, characterized in that said water in oil Invert-emulsion comprises the finely dispersed aqueous phase in amounts from about 5 to about 45% by weight, A process according to claim 24, characterized in that said l amounts are from about 5 to about 25% by weight.

TMS/LMM/1807R L s B 1. a 00 0 a 0 0 ar aO 00 0 00 0 00 0 0 oas o a a 4 a a 0o~ 0 oa a a 0004, 444,~ 23

26. A process according to any one of claims 1 to characterized in that alkali reserves are further added.

27. A process according to claim 26, characterized in that said alkali reserve is lime.

28. A process according to claim 27, characterized in that when said ester oils are based on carboxylic acids with at least 6 carbon atoms said lime is limited to a maximum of about 2 lb/bbl drilling fluid.

29. A process for preparing an invert drilling fluid suitable for the environmentally-friendly development of petroleum or gas deposits, substantially as hereinbefore defined with reference to the Examples.

An invert drilling fluid whenever prepared by the process according to any one of claims 1 to 29.

31. An invert-drilling fluid, suitable for the environmentally- friendly development of petroleum or natural gas deposits comprising in a 15 continuous oil phase a dispersed aqueous phase, emulsifiers, weighting agents, fluid-loss additives and alkali reserves, characterized in that said oil phase is fluid and pumpable at 0 to 5 0 C, has a flash point above 80°C and further comprises substantially water-insoluble ethers from monohydric alcohols having at least 4 carbon atoms or mixtures thereof with non-polluting water-insoluble oils.

32. An invert drilling fluid according to claim 31, characterized in that said fluid has a plastic viscosity (PV) of about 10 to about mPa.s and a yield point (YP) of about 5 to about 40 lb/100 ft 2 measured at 25

33. An Invert drilling fluid according to claims 31 or 32, characterized in that said dispersed aqueous phase comprises about 5 to about 45% by weight of said fluid.

34. An invert drilling fluid according to claim 33, characterized in that said dispersed aqueous phase comprises about 5 to about 25% by weight of said fluids.

An invert drilling fluid according to claim 33 or 34, characterized in that said aqueous phase comprises salts in solution.

36. An invert drIlling fluid according to claim 35, characterized in that said salts are CaCI 2 and/or KCI.

37. An invert drilling fluid according to any one of claims 31 to 36, characterized in that said oil phase has a Brookfield (RVT) viscosity below 50 mPa.s at 0 to 5 0 C.

38. An invert drilling fluid according to claim 37, characterized in that said viscosity is not above 40 mPa.s. i i-J ~'7p TMS/LMM/1807R 1 24

39. An invert drilling fluid according to any one of claims 31 to 38, characterized in that said non-polluting oils comprise at least some ester oils.

An invert drilling fluid according to claim 39, characterized in that said ester oils are derived from monocarboxylic acids and mono- and/or polyfunctional alcohols,

41. An invert drilling fluid according to any one of claims 31 to charactarized in that said ester oils constitute at least about one third of said non-polluting oils.

42. An invert drilling fluid according to claim 41, characterized in that said ester oils comprise the main part of said non-polluting oils.

43. An invert drilling fluid suitable for the environmentally friendly development of petroleum or gas deposits, substantially as hereinbefore described with reference to any one of Examples 1 to o o DATED this THIRTIETH day of MARCH 1992 So, Henkel Kommanditgesellschaft auf ',ktien 0 0 0 0 0 0 Patent Attorneys for the Applicant .S o° SPRUSON FERGUSON 0 0 0 0u Q 0 04 0 0600 0 TMS/LMM/1807R r '1 I 25 Abstract "Use of selected ethers of nmnofunctional alcohols in drilling fluids" The invention describes the use of water-insoluble esters, with flash points above 80 0 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 Sin the continuous oil phase, which is fluid and punpable in the temperature range of 0 to 5 0 C, and which are suitable for the environment-friendly development of, 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 p'uipable in the temperature range of 0 to 5°C and having flash points above 80 0 C. L A .1 ;.L L INTERNATIONAL SEARCH REPORT International Application No PCT/EP 90/00498 I. CLASSIFICATION OF SUBJECT MATTER (if several classification symbols apply, Indicate all) 6 According to International Patent Classification (IPC) or to both National Classification and IPC Int. Cl. C 09 K 7/06 II. FIELDS SEARCHED Minimum Documentation Searched 7 Classification System I Classification Symbols Int. Cl. C 09 K 7, C 10 M 173, C 10 M 101 Documentation Searched other than Minimum Documentation to the Extent that such Documents are Included In the Fields Searched 8 III, DOCUMENTS CONSIDERED TO BE RELEVANT 9 Category I Citation of Document, 11 with indication, where ppropriate, of the relevant passages 12 Relevant to Claim No. f Y WO, A, 87/03613 (LUBRIZOL) 18 June 1987 1,3,4,8,9, see page 10, lines 4-25; page 11, lines 17-18; page 12, lines 12-24 A 15-16 Y US, A. 3630898 TEETER) 28 December 1971 1,3,4,8, see column 1, lines 15-26, 52-67; 9,10,12 colume 2, lines 15 63-67 Y EP, A, 0183050 (PHILLIPS PETROLEUM CO.) 1,3,4,8,9, 4 June 1986, see page 1, lines 1-3; page 3, 10,12 lines 21-36; page 5, lines 11-27; example VI; claims 1,8,18,19,22 A FR, A, 1297556 (CHEMISCHE WERKE HULS) 1962 1,10 see right-hand column, lines 16-38; page 2, left-hand column, lines 35-42; abstract A DE, B, 1218096 (CHEMISCHE WERKE HULS) 2 June 1966 1,10 see column 1, lines 1-42; claims A DE, B, 1218645 (BAYER) 8 June 1966, see 1,10 column 1, lines 1-40 'pecial categories of cited documents: 0o later document pu..,ahed after the International filing date "A document defning the general state of the art which Is not or priority date and not in conflict with the application but considered to be of particular relevance cited to understand the principle or theory underlying the invention earlier document but published on or alter the international X" document of particular relevance; the claimed nvention iling de cannot be considered novel or cannot be considered to document which may throw doubts on priority claim(s) or involve an inventive step which is cited to establish the publication date of another document of particular relevance; the claimed Invention itation or other special reason (as specified) cannot be considered to Involve an Inventive step when the document referring to an oral disclosure, use, exhibition or document Is combined with one or more other such dncu- other means ments, such combination being obvious to a person sektle.; document published prior to the international filing date but In the art, later than the priority date claimed gocument member of the same patent family IV, CERTIFICATION Date of the Actual Completion of the International Search Date of Malling of this International Search Report 28 June 1990 (28.06.90) 26 July 1990 (26,07.90) International Searching Authority Signature of Authorized Offcer European Patent Office Form PCTIISA210O (second sheet) (January 1985) ANNEX TO THE INTERNATIONAL SEARCH REPORT ON INTERNATIONAL PATENT APPLICATION NO. EP 9000498 SA 35441 This annex lists the patent family members relating to the patent documents cited in the above-mentioned international search report. The members are as contained in the European Patent Office EDP file on 20/07/90 The European Patent Office is in no way liable for these particulars which are merely given for the purpose of information. Patent document Publication Patent family Publication cited in search report date member(s) date WO-A- 8703613 18-06-87 AU-A- 6738287 30-06-87 EP-A- 0285608 12-10-88 JP-T- 63502254 01-09-88 US-A- 4844756 04-07-89 US-A- 4708753 24-11-87 US-A- 3630898 28-12-71 None EP-A- 0183050 04-06-86 US-A- 4606833 19-08-86 JP-A- 61166891 28-07-86 FR-A- 1297556 DE-B- 1158696 DE-B- 1218096 FR-A- 1335195 GB-A- 1006940 DE-B- 1218645 BE-A- 605264 FR-A- 1292733 GB-A- 941496 For mo abutthisa ex see Of Jorl of the Eropen Ptent Offce 1282 otj[I 1 INTERNATIONALER RECHERCHENBERICHT Internationales Aktenzeichen PCT /EP 90 /00498 1. KLASSIFIKATION DES ANMELDUNGSGEGENSTANDS Wbei mehreren Klassifikaxionssymbolen sind alle Nach der Internationalen Patentklassifikation OPC) oder nach der nationalen Klassifikation und der IPC int.CI 5 C 09 K 7/06 11. RECHERCI-IERTE SACHGEBIETE Recherchierter MlndlesiprndStoff 7 Klassitikationstsystem K Iassifikationssymbale Int.CI 5 C 09 K 7, C 10 M 173, C 10 M 101 Recherchierte nicht zumn Mindestprufstoft gehorende Verbffentlichungen, soweit diese unter die recherchierten Sachgebiete fallen 8 III. EINSCHLAGIGE VEROFFENTLICHUNG3EN9 Art* Kennzeichnung der Veroffentlichun' 1 l,soweit erforderlich unter Angabe der ma~geblichen Teile1 2 FBetr. Anspruch Nr. 13 Y WO, A, 87/03613 (LUBRIZOL) 1,3,4,8,9, 18. Juni 1987 siehe Seite 10, Zeilen 4-25; Seite 11, Zeilen 17'-18; Seite 12, Zeilen 12-24 A 15-16 yUS, A, 3630898 TEE T rER) 1,3,4,8, 28. Dezemnber 1971 9,10,12 siehe Spalte 1, Zeilei 15-26,52-67; Spalte 2, Zeilen 15-35,63-67 Y EP, A, 0183050 (PHILLIPS PETROLEUM CO.) 1,3,4,8,9, 4. cruni 1986 10,12 siehe Seite 1, Zeilen 1-3; Seite 3 *Bosondere Kategorien von angegebenen Veroffentlichungen 10 Verdffentlichung, die den aligemeinon Stand der Technik Spatere VeroffentlichUng, die nach dam internationalon An- definier-t, aber nlcht als bosondors bedoeutsam anzusehen ast meldedatum odor dem Priorit~tsdlatumn verbffentlicht warden 5lteres Dokument, des jedloch erst am oder nach dem Interna- ist und mit der Anmeldung nicht kollidlert, sondern nur zurn tionalen Anmeldodatum verdf-fentllcht warden is Verstandnis des der Erfindung zugrundelILgenden Prinzips er~fenlichngdiegeeinetIst einn Piort~tsnspuch oder der Ihr zugrundelleganden Theorie ngegeben is% zwelfelhaft erscheinen zu lassen, oder dlurch die des Verdf- X rfenicugYnbsdrrBcltn;debaspch fentlichungsdatum elner andoren imh Recherchenbericht ge to Erfindung kann nlcht als neu odor auf orfinderischer Tfitig- namfoen 'Asrbffentllchung belegt werden soll odor die aus eier kalt beruhend betrachtet werden andoron bosonderon Grund angegeben ist IWe ausgeflihrt) Veroffenilichung von besonderer Bedeutung; die beanspruch- Verbffentlichung, die sich auf elite irUndlicho Offenbarung to Erfinnduny kann nlcht als auf erfinderls-cher Tatigkoit be- eino Benutzung, elne Ausstellung odor anderg Malnabmen ruhend betrarchtet warden, wenn die Verbffentllchung mit bez~et amer odor mehreren anderen Verdf-fentllchungen dieter Kate- bozlehtgoneo In Verbindung gebracht wird und diose Verbindung f~r Verbffentllchung, die vor dem Internatlonalen Anmeldeda- omnen Fachmann nahallegend 1st turn, aber nach dam beanspruchten Prioritattadatumn verofea dVrffentihndeMtle esle aetall s llcht warden IstV effnlcugdi iqeddrebnPttonleIs IV. BESCHEINIGULNG Datum des Abschlusses der internationalen Recherche Absendedatum In1ternationalen Recherchenberlchts 28. Juni 1990 2 6.07, Internationale Recherchonbohorde Unteritchrlft des bevolim~chtligton Belensteten Eueopgisches Patentamt-N.K PE 6,16iiij Formblatt PCT/ISA/210 (Blatt 2) (Januar 1985) Internationajes Akt ichen PCT/EP 90/00498,-t III.EINSCHLAGIGE VER6FFENTLICHUNGEN (Fortsetzung von Blatt 2) Art Kennzeichnung der Verdffentlichung, soweit erforderlich unter Angabe der maf~geblichen Teile Betr. Anspruch Nr. Zeilen 21-36; Seite 5, Zeilen 11-27; Beispiel VI; Anspr~che 1,8,18,19,22 FR, A, 1297556 (CHEMISCEE WERKE HULS) 1962 siehe rechte Spalte, Zeilen 16-38; Seite 2, linke Spalte, Zeilen 35-42; Zusamrnenfassung DE, B, 1218096 (CH-EMISCHE WERKE HULS) 2. Juni 1966 siehe Spalte 1, Zeilen 1-42; Patentansprache DE, B, 1218645 (BAYER) 8. Juni 1966 siehe Spalte 1, Zeilen 1-40 1,1.0 1,10 1,10 8116koo-I I Formblatt PCT/ISA/210 (Zusatzbogen) (Jonuar 1985) ENE" V. ANHANG ZUM INTERNATIONALEN RECHERCHENBERICHT OCBER DIE INTERNATIONALE PATENTANMIELDUNG NR. EP 9000498 SA 35441 In diesem Anhang sind die Mitglieder der Patentfamilien der im obengenarmten internationalen Recherchenbericht angefuhrteri Patentdokumente angegeben. Die Angaben fiber die Familienmitglieder entsprechen dem Stand der Datei des Europajeschen Patentamts am 20/07/90 Diese Angaben dienen nur zur Unterricbtung und erfolgen ohne GcwAhr. T.n Recherchenbericht Datum der Mitglied(er) der Datum der aVgefilhrtes Patentdokument Veroffentlichung Patentfamilic Veroffentlichung WO-A- 8703613 18-06-87 AU-A- 6738287 30-06-87 EP-A- 0285608 12-10-88 JP-T- 63502254 01-09-88 US-A- 4844756 04-07-89 US-A- 4708753 24-11-87 US-A- 3630898 28-12-71 Keine EP-A- 0183050 04-06-86 US-A- 4606833 19-08-86 JP-A- 61166891 28-07-86 FR-A- 1297556 DE-B- 1158696 DE-B- 1218096 FR-A- 1335195 GB-A- 1006940 OE-B- 1218645 BE-A- 605264 FR-A- 129273 GB-A- 941496 MM j For nfilcre Einzelheiten zu diesem Anhang :siehe Amtsblatt des ruropliischen Patentaints, Nr.12/82 h