EP0513041A1 - Utilisation d'emulsifiants selectionnes a base d'ether pour des emulsions inverties a base huileuse - Google Patents

Utilisation d'emulsifiants selectionnes a base d'ether pour des emulsions inverties a base huileuse

Info

Publication number
EP0513041A1
EP0513041A1 EP19910902405 EP91902405A EP0513041A1 EP 0513041 A1 EP0513041 A1 EP 0513041A1 EP 19910902405 EP19910902405 EP 19910902405 EP 91902405 A EP91902405 A EP 91902405A EP 0513041 A1 EP0513041 A1 EP 0513041A1
Authority
EP
European Patent Office
Prior art keywords
emulsifiers
invert
alcohols
ethers
embodiment according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP19910902405
Other languages
German (de)
English (en)
Inventor
Heinz Müller
Claus-Peter Dr. Herold
Fritz Dr. Lange
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP0513041A1 publication Critical patent/EP0513041A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C09K23/42—Ethers, e.g. polyglycol ethers of alcohols or phenols
    • 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
    • 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
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents

Definitions

  • the invention relates to the use of selected emulsifiers with increased ecological compatibility for the production of W / 0 invert emulsions and the technical use of such stabilized emulsion types in the context of drilling fluids and invert drilling fluids based thereon, which are characterized by high ecological compatibility and at the same time airszetrime ⁇ raft good standing and usage.
  • An important area of application for the new drilling mud systems is offshore drilling for the development of, for example, oil and / or natural gas deposits.
  • the use of the systems stabilized with the emulsifiers according to the invention is of particular importance in the marine field, but is not restricted to this. Drilling in permafrost areas should be mentioned as an important area of use
  • the new flushing systems according to the invention can also be used quite generally in land-based drilling, for example in geothermal drilling, in petroleum / natural gas, in carrying out geoscientific drilling and in drilling in the mining sector.
  • Oil-based drilling fluids are generally used as so-called invert emulsion muds, which consist of a three-phase system: oil, water and finely divided solids. These are preparations of the W / O emulsions type, ie the aqueous phase is heterogeneously finely dispersed in the closed oil phase.
  • additives in particular emulsifiers or emulsifier systems, weighting agents, thickeners, fluid loss additives, alkali reserves, viscosity regulators and the like.
  • additives in particular emulsifiers or emulsifier systems, weighting agents, thickeners, fluid loss additives, alkali reserves, viscosity regulators and the like.
  • the object of the present invention is to provide emulsifiers or emulsifier systems which are nitrogen-free and at the same time are ecologically compatible to a high degree.
  • emulsifiers or emulsifier systems which are nitrogen-free and at the same time are ecologically compatible to a high degree.
  • the technical requirements given by practice should be able to be met at least to the extent known to date by using the new emulsifiers.
  • the invention aims to create systems of the type described, which contribute to the further optimization of these tools, through the simultaneous use of the new environmentally compatible emulsifiers and, at the same time, of oil phases with increased environmental compatibility.
  • the teaching of the invention makes use of older proposals by the applicant regarding the nature of the closed oil phase in invert drilling fluids, which will be discussed in more detail below. Accordingly, the invention relates in a first embodiment to the use of partial ethers of lower polyfunctional alcohols with monofunctional alcohols containing at least 8 carbon atoms and / or their alkoxylates as nitrogen-free emulsifiers in oil-based invert emulsions.
  • the invention is based on the knowledge that selected, in particular oil-soluble partial ethers of the type described for the work area concerned here, with their varied requirements for the function of the emulsifier or the emulsifier system, surprisingly well for the exchange and replacement of the most effective emulsifiers to date Are based on nitrogen-containing compounds.
  • the invention relates to invert drilling fluids which, in a closed oil phase, contain a disperse aqueous phase together with customary other auxiliaries, for example emulsifiers, weighting agents, thickeners, fluid loss additives and alkali reserves, and are characterized thereby that they contain, as nitrogen-free W / O emulsifiers, at least some of the compounds of the type described above based on selected partial ethers of lower polyfunctional alcohols.
  • nitrogen-free partial ethers form the at least predominant proportion of the emulsifiers used in the invert rinse and, if additional emulsifier components are also used, nitrogen-free systems are preferably also used.
  • known nitrogen-containing emulsifiers can also be used together with the selected nitrogen-free partial ethers.
  • the selected partial ethers should also form the at least predominant portion of the emulsifiers used in the invert rinse.
  • the emulsifiers are used in invert drilling fluids, the closed oil phase of which is formed at least in part and preferably at least predominantly from oils which are more environmentally compatible.
  • Preferred oil phases here are ester oils, oil-soluble alcohols and / or oil-soluble ethers of the nature specified below.
  • the new nitrogen-free emulsifiers are, in particular, partial ethers of polyhydric alcohols having 2 to 6 carbon atoms and 2 to 6, preferably 2 to 4, hydroxyl groups.
  • partial ethers of ethylene glycol corresponding partial ethers of ethylene glycol, the
  • emulsifier systems which contain at least partially glycerol partial ethers of the type specified can be of particular importance in the context of the invention.
  • the monofunctional alcohols used to etherify a portion of the hydroxyl groups of the lower polyfunctional alcohols are oil-soluble compounds of this type or are derived from corresponding oil-soluble monofunctional alcohols having at least 8 carbon atoms. Suitable for partial etherification are in particular straight-chain and / or branched monofunctional alcohols with 8 to 36 C atoms and preferably those with 8 to 24 C atoms in the molecule. Corresponding monofunctional alcohols with 10 to 18 carbon atoms can be of particular importance. The alcohols themselves can be aliphatically saturated and / or mono- and / or poly-olefinically unsaturated. Corresponding alcohols of natural origin can be of particular importance in the context of the invention.
  • this class of substances are the so-called fatty alcohols, which are accessible on a large industrial scale, and which are reductive from fatty acids of natural origin or their derivatives. Partial ethers of this nature are characterized by their high ecological compatibility even with the particularly sensitive marine systems. However, the invention is not restricted to such components of natural origin. As is well known, synthetic chemistry is also able to provide comparable ecologically compatible components.
  • the partial etherification of the polyfunctional lower alcohols can also be carried out using alcohol alkoxylates, such as are obtained in particular by ethoxylation and / or propoxylation of the monofunctional alcohols.
  • the ethoxylated derivatives in particular can be of particular importance here as etherification components. If such alkoxylated fatty alcohols are used for ether formation, particular preference is given to corresponding alkoxylates with an average of up to 12 alkoxy radicals and in particular corresponding alcohol derivatives with an average of up to 8 alkoxy radicals in the alkoxylated monofunctional alcohol.
  • Partial ethers based on glycerol can be of particular importance both for reasons of ecological compatibility and for reasons of the required technical qualification.
  • monoethers of glycerol have proven to be effective emulsifiers and stabilizers of the invert system, but glycerol diethers can also be used at least in part in the systems.
  • these partial ethers of glycerol can also be present in a mixture with excess free glycerol. This means that there is no need to separate off an excess of glycerol caused by the preparation of the ethers.
  • Particularly suitable emulsifiers are ethers of the type described which have flash points above 100 ° C. and in particular above 120 ° C.
  • Compounds of this type can be safely used in drilling fluid based on invert emulsions. They are usually present in the multicomponent mixture in amounts below 10% by weight, preferably in amounts in the range from about 1 to 5% by weight, based in each case on invert rinsing.
  • R is a straight-chain and / or branched hydrocarbon residue with 8 to 36 C atoms and preferably a corresponding residue with 10 to 24 C atoms. If there are several etherifying residues of the type concerned here on the polyfunctional alcohol base molecule, the same, but also mixtures of different residues R of the given definition may be present. In the case of ethers based on monofunctional alcohols of natural origin, there are generally mixtures of homologous alcohol residues, the composition of which is derived in terms of the number of the respective carbon atoms and quantitative distribution of the alcohol residues of different chain lengths by the processes for isolating the alcohol mixtures based on natural products.
  • the radical Alk-0 from the general formula (I) denotes a lower alkylene oxide radical, ethylene oxide and / or propylene oxide radicals being preferred in particular.
  • the ethylene oxide residue is of particular importance here.
  • n denotes a number from 0 to 12 and preferably has a value from Q to 8.
  • y from the general formula (I) gives the number of hydroxyl groups of the lower polyfunctional alcohol R '- (0H) y used.
  • y preferably denotes a number from 2 to 6 and in particular a number from 2 to 4, where, in the case of glycerol, y assumes the value 3.
  • x from the general formula (I) is an integer or fractional number and preferably has the value of at least 1.
  • x is necessarily a number that is less than y.
  • x can have the value 1 and / or 2.
  • the balance between free and etherified hydroxyl groups of the lower polyfunctional alcohol is to be coordinated in a manner known per se in such a way that the compounds of the general formula (I) used are in fact W / 0 emulsifiers of the required type and thus in particular oil-soluble compounds are.
  • R 'from the general formula (I) means the radical of the lower polyfunctional alcohol used which is free of hydroxyl groups and has in particular 2 to 6, preferably 2 to 4, carbon atoms.
  • ethers used according to the invention as emulsifiers can be prepared in a manner known per se under conventional etherification conditions. Two types are particularly suitable driving types.
  • alcohols of the general formula (Ib) R-0- (Alk-0) n -H, in which R, Alk-0 and n have the meanings * indicated can be sulfated in a manner known per se. The sulfates formed are then reacted with the multifunctional lower alcohols in a known manner to give the partial ethers of the general formula (I).
  • the corresponding halide compounds in particular the corresponding chlorides, can be reacted with the lower polyfunctional alcohols in a manner known per se to give the ethers of the general formula (I).
  • this reaction component For the preparation of the partial ethers of lower polyfunctional alcohols, this reaction component latter is used in a preferred embodiment in a molar excess, with even more fold molar excess can be useful for example if, for example, 'monoether or predominantly monoether reaction mixtures containing required.
  • the resulting reaction mixtures which in addition to the partial ethers formed also contain free polyfunctional lower alcohols, can be used as such in the oil-based invert emulsions. If desired, however, the unreacted portion of the polyfunctional alcohol can also be withdrawn from the reaction mixture at least in part in a manner known per se.
  • the sulfate salts formed during the etherification in particular the corresponding sodium sulfate, may also remain in the reaction product, so that particularly inexpensive access to those used according to the invention can be obtained here
  • emulsifiers in industrial use.
  • the emulsifiers used according to the invention based on the partial ethers can be used in oil-based invert rinses of any desired oil phase. Accordingly, the diesel oil fractions still used on a large scale as well as the corresponding fractions of low-aromatic hydrocarbon compounds are suitable as a closed oil phase.
  • the invention provides for the use of selected oil phases as described in a number of older applications by the applicant.
  • a first class of particularly important oil components are ester oils in the sense of the inventive action, as described in particular in the earlier applications P 3842659.5, P 3842703.6, P 3907391.2 and P 3907392.0 (D 8523, D 8524, D 8606 and D 8607) .
  • the disclosure content of these named applications is hereby expressly made the subject of the present disclosure of the invention.
  • invert drilling fluids of the type concerned according to the invention regardless of the particular nature of the closed oil phase - that they are in preferred embodiments have a plastic viscosity (PV) in the range of about 10 to 60 Pas and a yield point (YP) in the range of about 24 to 190 dPa - each determined at 50 ° C.
  • PV plastic viscosity
  • YP yield point
  • the ester oils preferably ester oils from monocarboxylic acids and 1- and / or 2-functional alcohols - at least about a third, preferably the predominant ones Make up the proportion of these ecologically compatible oils.
  • the oil phase of the invert sludge should expediently have a Brookfield (RVT) viscosity below 50 mPas and preferably not above 40 mPas in the temperature range from 0 to 5 ° C.
  • RVT Brookfield
  • the disperse water content of the invert rinses is expediently 5 to 45% by weight, preferably approximately 10 to 25% by weight.
  • Salts for example of the type of CaCl2 and / or KC1, can be dissolved in the aqueous phase.
  • weighting agents There are weighting agents, fluid loss additives, viscosity formers and alkali reserves.
  • hydrophobicized lignite is used in particular as a fluid loss additive and thus in particular to form a dense covering of the drilling walls with a largely liquid-impermeable film.
  • Suitable amounts are for example in the range from about 15 to 20 lb / bbl or in the range from about 5 to 7% by weight, based on the oil phase.
  • the viscosity former usually used is a cationically modified, finely divided bentonite, which is present in particular in amounts of about 8 to 10 lb / bbl or in the range of about 2 to 4% by weight, based on the oil phase.
  • the weighting agent normally used in the relevant practice for setting the required pressure compensation is barite, the additional amounts of which are adapted to the respectively expected conditions of the bore. For example, by adding barite it is possible to increase the specific weight of the drilling fluid to values in the range up to about 2.5 and preferably in the range from about 1.3 to 1.6.
  • a characteristic parameter for the respective invert rinsing in the so-called HT / HP test under standard conditions is also described here.
  • the filtrate quantities determined here under standard conditions, which occur at high pressures and temperatures, are meaningful values, especially for the suitability of the emulsifiers used in each case.
  • emulsifiers are preferred according to the in the respective drilling fluid under standard conditions (HT / HP; 125 ° C) result in a fluid loss value in the range up to a maximum of 20 ml and preferably up to a maximum of 12 ml.
  • Particularly suitable values are in the range below 10 ml, for example in the range from 1 to 8 ml.
  • Drilling fluid I low aromatic oil
  • organophilic lignite (Duratone, NL Baroid)
  • the viscosity was measured at 50 ° C. in a Fann 35 viscometer from NL Baroid. Here were the plastic ones Viscosity, the yield point and the gel strength determined after 10 seconds and 10 minutes.
  • the oil rinse samples were then heated (aged) for 16 hours at 125 ° C. in small autoclaves, in a so-called “roller oven”, in order to check the influence of temperature on stability.
  • the viscosity was then determined again at 50 ° C.
  • the fluid loss at 125 ° C. was determined using an HT / HP filter cell (Baroid HT / HP cell No. 387).
  • Emulsifier A Emulsifier A

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)

Abstract

L'invention décrit de nouveaux émulsifiants sans N s'utilisant dans des émulsions inverties à base huileuse. Les émulsifiants objets de l'invention sont des éthers partiels d'alcools polyfonctionnels inférieurs comprenant des alcools monofonctionnels contenant au moins 8 atomes C et/ou leurs alkoxylats. Les éthers partiaux de glycérine correspondants sont particulièrement appropriés. On peut fabriquer avec les émulsifiants des fluides de forage invertis du type indiqué ci-dessus et améliorés sur le plan écologique, appropriés pour une exploitation de gisements géologiques qui ne nuise pas à l'environnement, et contenant une phase aqueuse dispersée à l'intérieur d'une phase huileuse fermée, avec d'autres adjuvants traditionnels, par exemple, des émulsifiants, des agents alourdissants, épaississants, des additifs fluid-loss et des réserves alcalines.
EP19910902405 1990-02-02 1991-01-24 Utilisation d'emulsifiants selectionnes a base d'ether pour des emulsions inverties a base huileuse Withdrawn EP0513041A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4003028A DE4003028A1 (de) 1990-02-02 1990-02-02 Verwendung ausgewaehlter emulgatoren auf etherbasis fuer oelbasierte invert-emulsionen
DE4003028 1990-02-02

Publications (1)

Publication Number Publication Date
EP0513041A1 true EP0513041A1 (fr) 1992-11-19

Family

ID=6399248

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19910902405 Withdrawn EP0513041A1 (fr) 1990-02-02 1991-01-24 Utilisation d'emulsifiants selectionnes a base d'ether pour des emulsions inverties a base huileuse

Country Status (6)

Country Link
EP (1) EP0513041A1 (fr)
JP (1) JPH05503955A (fr)
CA (1) CA2075208A1 (fr)
DE (1) DE4003028A1 (fr)
NO (1) NO922717L (fr)
WO (1) WO1991011254A1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
DE4200502A1 (de) * 1992-01-13 1993-07-15 Henkel Kgaa Verbesserte entsorgung von kontaminiertem bohrklein aus geologischen bohrungen mit mineraloel-enthaltenden bohrspuelsystemen
DE102004022252A1 (de) * 2004-05-04 2005-12-01 Cognis Ip Management Gmbh Glycerinethergemisch, dieses enthaltende kosmetische Zusammensetzung sowie Verfahren zu dessen Herstellung
US9376647B2 (en) * 2012-02-25 2016-06-28 Ethox Chemicals, Llc Natural oil based gels, applications and methods of preparation

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1794088A1 (de) * 1964-12-17 1971-07-08 Oreal Dispersionsvermittler
DE3070852D1 (en) * 1979-05-22 1985-08-14 Ici Plc Oil dispersants
DE3207612C2 (de) * 1982-03-03 1986-04-03 Akzo Gmbh, 5600 Wuppertal Polyätherderivate und deren Verwendung als Emulgatoren
GB8615478D0 (en) * 1986-06-25 1986-07-30 Bp Chem Int Ltd Low toxity oil composition
DE3916550A1 (de) * 1989-05-20 1990-11-22 Henkel Kgaa Verwendung ausgewaehlter oleophiler ether in wasser-basierten bohrspuelungen vom o/w-emulsionstyp sowie entsprechende bohrspuelfluessigkeiten mit verbesserter oekologischer vertraeglichkeit

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9111254A1 *

Also Published As

Publication number Publication date
CA2075208A1 (fr) 1991-08-03
NO922717D0 (no) 1992-07-09
NO922717L (no) 1992-07-09
DE4003028A1 (de) 1991-08-08
JPH05503955A (ja) 1993-06-24
WO1991011254A1 (fr) 1991-08-08

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