DE102008009368A1 - Producing organic composition, useful e.g. as additive in drilling fluid, comprises mixing n-nonyl ether obtained by reacting n-nonyl alcohol-component with e.g. polyether alcohol, functional component e.g. enzyme and further additive - Google Patents

Abstract

Producing an organic composition comprising a functional component comprising a thermoplastic polymer, enzyme, binder, paraffin, oil, colorant and a hair- or skin care substance, comprises: (i) providing (ia) a n-nonyl ether as additive, which is obtained by reacting a n-nonyl alcohol-component with a further component (iaa), which may be reacted with the n-nonyl alcohol component under formation of a n-nonyl ether, (ib) a functional component and optionally (ic) at least a further additive; and (ii) mixing the n-nonyl ether, the functional component and optionally the further additive. Independent claims are included for: (1) producing a molded body, comprising (I) providing a thermoplastic composition, (II) heating the thermoplastic composition to the glass transition temperature of the thermoplastic polymer or to a temperature above the glass transition temperature of the thermoplastic polymer and (III) producing a molded body from the heated thermoplastic composition produced in the step (II); (2) producing a packaged good comprising (a) providing a good and the molded body and (b) at least partially covering the good with the molded body; (3) a procedure for coating an edible substance, comprising (A) providing an edible substance and the n-nonyl ether and (B) at least covering the substance with the n-nonyl ether; (4) a procedure for cleaning the surfaces of bore holes, drilling attachments or drillings, comprising contacting the surfaces with a cleaning agent comprising n-nonyl ether and optionally washing the surfaces with water; (5) a procedure for producing a bore hole, comprising boring a bore hole in the earth by a drill head driven over a boring tool, introducing a casing in the bore holes, introducing cement in at least a sub-area of the gaps between the outer side of the casings and the walls of the bore holes, optionally introducing a feed pipe in the casing, optionally introducing a sealing liquid in the gaps between the outer side of the feed pipe and the inner side of the casings, where the surfaces of the bore holes, the guiding pipe, the boring tools or the drill head are contacted with the cleaning agent; and (6) a procedure for producing an oil or a gas, comprising boring a bore hole in the earth by a drill head driven over a boring tool, introducing a casing in the bore holes, introducing cement in at least a sub-area of the gaps between the outer side of the casings and the walls of the bore holes, optionally introducing a feed pipe in the casing, optionally introducing a sealing liquid in the gaps between the outer side of the feed pipe and the inner side of the casings, passing oil or gas through bore holes, and cleaning or rafinating the oil or gas, where the surfaces of the bore holes, the guiding pipe, the boring tools or the drill heads are treated with the cleaning agent or with the composition.

Description

The The present invention relates to the use of an n-nonyl ether, a method for cleaning the surfaces of boreholes, Drilling equipment or cuttings, method for producing a Borehole and method for producing an oil or a gas.

Medium chain linear fatty alcohols are now being used successfully as raw materials for surfactants, foam flow, solvents, bodying agents, lubricant additives and as etherification or esterification components in plastics processing. Available are either linear C ₈ - or C ₁₀ -alcohols or branched C ₉ -alcohols (i-nonanol). The linear alcohols are mostly of native origin and always even. C ₈ / C ₁₀ cuts with 40 to 48% by weight of C ₈ -alcohols and 51 to 59% by weight of C ₉ -alcohols are preferably used here.

Although pure C ₁₀ alcohol and its derivatives, such as, for example, ethers or esters, have a high boiling point and are thus comparatively less volatile, they have high solidification points. Pure C ₈ -alcohol and its derivatives are in turn characterized by low solidification points, but have low boiling points and are thus very volatile.

The branched i-nonanols are substance mixtures and become petrochemical produced. The branching of the alcohols leads to a poorer biodegradability. Disadvantageous in connection with the use in i-nonanols is still too high melting point or too low boiling range of the derivatives such as esters, ethoxylates, Sulfates, even if mixed alcohol mixtures are used. Due to the non-ideal viscosity behavior in particular at lower temperatures, this product group are therefore limits set.

Of the Present invention was based on the object resulting from the At least partially overcome the disadvantages of the prior art.

Especially the present invention has the object, a compound which is especially useful as an additive in drilling fluids or use cleaning agents for drilling equipment leaves.

a Contribute to the solution of at least one of the above Tasks perform the objects of the category-forming Claims, the dependent claims further embodiments of the invention represent.

The The present invention therefore particularly relates to the use an n-nonyl ether which is obtainable by reaction an n-nonyl alcohol component with another component which with the n-nonyl alcohol component to form an n-nonyl ether to react as an additive in drilling wells used compositions.

• ia1) das Bereitstellen einer n-Nonylalkohol-Komponente;
• ia2) das Bereitstellen einer weiteren Komponente, welche mit der n-Nonylalkohol-Komponente unter Bildung eines n-Nonylethers zu reagieren vermag;
• ia3) die Umsetzung der n-Nonylalkohol-Komponente mit der mindestens einen Komponente unter Bildung eines n-Nonylethers.

The n-nonyl ether is preferably provided by a process comprising preferably the following process steps:

• ia1) providing an n-nonyl alcohol component;
• ia2) providing a further component which is capable of reacting with the n-nonyl alcohol component to form an n-nonyl ether;
• ia3) the reaction of the n-nonyl alcohol component with the at least one component to form an n-nonyl ether.

In process step 1a1) of the process for providing an n-nonyl ether, an n-nonyl alcohol component is initially provided. According to a preferred embodiment of the method according to the invention for producing an organic composition, it is preferred that the n-nonyl alcohol component is at least 80% by weight, more preferably at least 90% by weight and most preferably at least 99% by weight. %, in each case based on the provided n-nonyl alcohol component, is obtained from pelargonic acid. In this context, it is further preferred that the provision of the n-nonyl alcohol component, the catalytic hydrogenation of pelargonic acid (octanecarboxylic acid, nonanoic acid), for example according to the in the WO-A-2006/021328 described method, or the catalytic hydrogenation of incurred in the ozonolysis of oleic acid Ölsäureozonids or both. Also conceivable is the catalytic hydrogenation of esters of pelargonic acid, for example the catalytic hydrogenation of the methyl, ethyl, propyl or butyl ester of pelargonic acid. If the n-nonyl alcohol component is obtained by the catalytic hydrogenation of pelargonic acid, the pelargonic acid itself can be obtained, for example, by ozonolysis of oleic acid and subsequent oxidative work-up of the oleic ozone or else by ozonolysis of erucic acid and subsequent oxidative work-up of the erucic acid ozone. Such a process is carried out industrially, for example, by Unilever, Emery and Henkel and is inter alia in "Ozonation of Alkenes in Alcohols as Solvents", dissertation by Eberhard Rischbieter, University of Carolo-Wilhelmina zu Braunschweig, 2000 or in US 2,813,113 described. The oxidation of the aldehydes obtained in the oxidative workup of ozonides to form the corresponding acid For example, in the DE-C-100 70 770 described. The production of the oleic acid can in turn be obtained from tallow or tall oils, as for example in US 6,498,261 is described. In addition to the ozonolysis of oleic acid or erucic acid, the pelargonic acid can also be obtained by isomerization of petrochemical raw materials. Also conceivable is the petrochemical production of pelargonic acid, such as by Harold A., Wittcoff, Bryan G., Reuben, Jeffrey S. Plotkin in "Fats and Oils", Industrial Organic Chemicals (Second Edition) (2004), John Wiley & Sons, Inc., pages 411-434 or the preparation of pelargonic acid from oleic acid according to the in the GB-A-813842 described method.

According to a particular embodiment of the process for providing the n-nonyl ether, the n-nonyl alcohol component used for the preparation of the n-nonyl ether contains, in addition to the n-nonyl alcohol, further alcohols, for example C ₈ and / or C ₁₀ alcohols, but in In this case, it is particularly preferred that the n-nonyl alcohol component is less than 10 wt .-%, more preferably less than 7.5 wt .-% and most preferably less 5 wt .-%, each based on the n-nonyl alcohol Component, C ₈ and C ₁₀ alcohols. The proportion of n-nonyl alcohol in the n-nonyl alcohol component is preferably at least 90 wt .-%, particularly preferably at least 92.5 wt .-% and most in the case of use of a mixture of n-nonyl alcohol and at least one other alcohol preferably at least 95 wt .-%, each based on the total weight of the n-nonyl alcohol component.

A according to the invention particularly preferred n-nonyl alcohol component is in particular that n-nonyl alcohol component prepared by catalytic hydrogenation under the under brand name EMERY ^® 1202 EMERY ^® 1203 and Emery ^® 1210 sold pelargonic acid or more than 10 wt .-%, preferably more than 25 wt .-%, each based on the Pelargonsäuremischung-containing, pelargonic Pelargonsäuremischungen., wherein EMERY ^® 1202 to less than 1 wt .-% of C ₆ monocarboxylic acids, to about 1 wt .-% of C ₇ monocarboxylic acids consists wt .-% of other by-products, in particular monocarboxylic acids having more than 9 carbon atoms to about 4 wt .-% of C ₈ monocarboxylic acids, to about 93 wt .-% of pelargonic acid and about 2, EMERY ^® 1203 about 0, 1 wt .-% of C ₆ -C ₈ monocarboxylic acids, to about 99 wt .-% of pelargonic acid and from about 0.9 wt .-% of other by-products, in particular monocarboxylic acids having more than 9 carbon atoms, while EMERY ^® 1210 to about 3 wt .-% of C ₅ monocarboxylic acids, about 27 wt .-% of C ₆ monocarboxylic acids, about 31 wt .-% of C ₇ monocarboxylic acids, about 12 wt .-% of C ₈ Monocarboxylic acids and about 27 wt .-% of pelargonic acid, but the use of EMERY ^® 1203 is particularly preferred because here the proportion of pelargonic acid is particularly high.

in the Process step ia2) of the process for providing an n-nonyl ether is at least one further component, which with the n-nonyl alcohol component provided to form an n-nonyl ether, wherein this further component is preferably a Alcohol to an epoxy, to a halogenated alkane or a mixture from at least two of them.

In the case of an alcohol as further component, it is preferred that this alcohol is selected from the group consisting of C ₁ - to C ₃₀ -alkanols, more preferably C ₁ - to C ₂₀ -alkanols, and most preferably C ₁ - to C ₁₀ -alkanols, such as, for example, methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol and nonanol, from C ₁ to C ₃₀ diols, more preferably from C ₁ to C ₂₀ diols, and most preferably C ₁ to C ₁₀ diols, such as, for example, glycol and propanediol, from C ₁ to C ₃₀ triols, more preferably from C ₁ to C ₂₀ triols, and most preferably C ₁ to C ₁₀ triols, such as, for example Glycerol, polyalcohols or polyether alcohols, such as diethylene glycol, dipropylene glycol, triethylene glycol, triethylene glycol, tetraethylene glycol, tetrapropylene glycol, polyethylene glycols having a molecular weight of more than 100 g / mol, polypropylene glycols having a molecular weight of more than 120 g / mol, poly ethylene glycol, polypropylene glycol, pentaerythritol, polyglycerides and saccharides, and mixtures of at least two of the aforementioned alcohols.

In the case of an epoxide as a further component, preference is given to using epoxides of C ₂ -C ₂₀ hydrocarbons and particularly preferably C ₂ -C ₁₄ hydrocarbons, with ethylene oxide, propylene oxide and glycidol being the most preferred epoxides and ethylene oxide and propylene oxide being the most preferred Epoxides are. Other suitable components are epoxystearic acid and diepoxylinoleic acid or derivatives thereof.

in the Fall of a halogen-alkane as a further component are in particular Chloroalkanes, such as 1-chloro-butane, 2-chloro-butane, 1-chloro-pentane, 2-chloro-pentane or 3-chloro-pentane into consideration.

In process step ia3) of the process for providing an n-nonyl ether, the n-nonyl alcohol component is reacted with the at least one component to form an n-nonyl ether puts.

If the n-nonyl ether is prepared by condensation reaction between the alcohols in the n-nonyl alcohol component and the alcohols used as further component, the condensation of the alcohols with dehydration is preferably carried out continuously, in particular in a fixed bed reactor charged with suitable catalysts, such as with alumina moldings, in particular with γ-alumina, preferably in the form of pellets, tablets, extrudates, spheres or granules, or with zeolite-based catalyst systems. The condensation is preferably carried out at temperatures of 200 ° C to 260 ° C, more preferably from 220 ° C to 260 ° C and at a pressure of 10 mbar to 60 bar. Depending on the temperature and pressure range, the condensation takes place in the gas and / or liquid phase. The optimum temperatures depend on the educt (s) used, the progress of the reaction, the type of catalyst and the catalyst concentration. They can easily be determined by experiment for each individual case. Higher temperatures increase the reaction rates and promote side reactions, such as dehydration from alcohols or formation of colored by-products. A suitable process for the preparation of an ether using haloalkanesulfonic acids as catalysts is described, for example, in US Pat DE-A-19511 668 described.

The crude product obtained in this way generally consists of a mixture of educt, olefins and dialkyl ethers, which can be separated, for example by distillation, wherein the unreacted alcohol is preferably recycled back into the process. The process for preparing the n-nonyl ethers is preferably carried out with an LHSV ("liquid hour space velocity" = m ³ alcohol / (h × m ³ Katalysatorschüttvolumen) of 0.2 to 1.4, optionally based on the entry of liquid starting materials. The preparation of dialkyl ethers by condensation of diols is for example in the DE-A-10 2004 056 786 or in the WO-A-97/035823 the disclosure of which is hereby incorporated by reference as part of the preparation of dialkyl ethers of alcohols and forms part of the disclosure of the present invention.

If the n-nonyl ether is prepared as a further component by substitution reaction between the alcohols in the n-nonyl alcohol component and an epoxide, for example ethylene oxide or propylene oxide, the reaction is preferably carried out in the presence of suitable catalysts, such as zeolites or hydrophobicized hydrotalcites , The reaction of ethylene oxide and propylene oxide with, for example, alcohols to give polyethoxylated or multiply propoxylated ethers is described, for example, in US Pat DE-A-40 10 606 is hereby incorporated by reference in the disclosure of the preparation of dialkyl ethers from alcohols and ethylene oxide or propylene oxide and forms part of the disclosure of the present invention.

Furthermore, it may be advantageous if the n-nonyl ether provided in process step i) is a polyether alcohol having 2 to 30 ether repeating units, more preferably having 4 to 20 ether repeat units, these ether repeating units preferably being a - [O-CH ₂ -CH ₂ ] unit, a - [O-CH ₂ -CH ₂ -CH ₂ ] unit or a mixture of these units. Such polyether alcohols can be obtained by reacting the n-nonyl alcohol component in a condensation reaction with a polyethylene glycol of corresponding chain length or by reacting the n-nonyl alcohol component in a substitution reaction with ethylene oxide, propylene oxide or a mixture of ethylene oxide and propylene oxide in such relative amounts is reacted, that 2 to 30 ether repeating units, more preferably 4 to 20 ether repeating units are bonded to the n-nonyl alcohol component.

• 1a4) Veresterung des im Verfahrensschritt 1a3) erhaltenen n-Nonylethers,

wobei eine solche Veresterung nur dann möglich ist, wenn als weitere Komponente im Verfahrensschritt 1a2) ein mehrwertiger Alkohol oder aber ein Epoxid eingesetzt wurde, da nur dann n-Nonylether erhalten werden, welche noch freie, veresterbare OH-Gruppen aufweisen.It may also be advantageous if the n-nonyl ether, especially the n-nonyl alcohol-based polyether alcohol described above, is used as a modified n-nonyl ether in the form of an organic or inorganic ester. In this case, the process for providing an n-nonyl ether comprises the further process step of

• 1a4) esterification of the n-nonyl ether obtained in process step 1a3),

wherein such esterification is only possible if a polyhydric alcohol or an epoxide was used as further component in process step 1a2), since only then n-nonyl ethers are obtained which still have free, esterifiable OH groups.

As the acid component for the esterification, it is possible to use all organic and inorganic acids known to the person skilled in the art, which are capable of reacting with OH functional groups and organic compounds. Particularly preferred according to the invention is the use of mono-, di- or polycarboxylic acids. Suitable monocarboxylic acids in this context are, for example, acetic acid, butyric acid, acrylic acid, methacrylic acid, oleic acid, oxalic acid, stearic acid, succinic acid, citric acid, fumaric acid, maleic acid, benzoic acid or citric acid, while as dicarboxylic acids, for example, oxalic acid, malonic acid, succinic acid, Glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, tartaric acid, malic acid, α-ketoglutaric acid, oxalacetic acid, orthophthalic acid, isophthalic acid or terephthalic acid can be used. An example of a suitable tricarboxylic acid is, for example, trimellitic acid. In addition to the organic acids mentioned above, it is also possible to use inorganic acids, such as, for example, sulfuric acid, phosphoric acid or boric acid, so that the corresponding sulphates, phosphates or bristles are obtained. Sulfonic acids, such as, for example, benzenesulfonic acid, n-nonylsulfonic acid, dodecylbenzenesulfonic acid, dodecylbenzenesulfonate, dodecylbenzenesulfonic acid, ammonium dodecylbenzenesulfonate, benzenesulfonic acid or dodecylbenzenesulfonic acid, can also be used as the acid. Also conceivable is the use of a mixture of at least two of the abovementioned acid components, in particular also the use of a mixture of an organic and of an inorganic acid.

Farther it is preferred that the acid component with the n-nonyl ether is implemented in such a proportion that the molar ratio of carboxylic acid groups: hydroxyl groups in a range of 1: 1.0 to 1: 5.0, more preferably in one Range from 1: 1.2 to 1: 2 and most preferably in one range from 1: 1.7 to 1: 1.9.

The Esterification is preferably carried out in the presence of an esterification catalyst. As esterification catalysts, acids, such as for example, sulfuric acid or p-toluenesulfonic acid, or Metals and their compounds are used. Are suitable For example, tin, titanium, zirconium, as finely divided metals or expediently in the form of their salts, oxides or soluble organic compounds are used. The Metal catalysts are in contrast to protic acids High-temperature catalysts, their full activity in usually reach only at temperatures above 180 ° C. However, they are preferred according to the invention because they have fewer byproducts compared to proton catalysis, such as for example, olefins. Particularly according to the invention preferred esterification catalysts are one or more divalent ones Tin compounds or tin compounds or elemental tin, the can react with the starting materials to divalent tin compounds. For example can be used as a catalyst tin, tin (II) chloride, stannous sulfate, stannous (II) alcoholates or tin (II) salts of organic acids, in particular of Mono- and dicarboxylic acids. Particularly preferred tin catalysts are tin (II) oxalate and tin (II) benzoate. The implementation The esterification reaction can be carried out by methods known to those skilled in the art respectively. It may be particularly advantageous that at to remove water formed from the reaction mixture from the reaction, this removal of the water preferably by distillation, optionally by distillation with excess used 1,2-propanediol takes place. Furthermore, it is preferred to the esterification reaction at a temperature in a range of 50 to 300 ° C, especially preferably in a range of 100 to 250 ° C and most preferably in a range of 150 to 200 ° C. Again, the optimal temperatures depend on the use alcohol (s), the progress of the reaction, the type of catalyst and the catalyst concentration off and can for each individual case through experiments easily determined.

It is particularly preferred according to the invention that the n-nonyl ether described above as an additive in drilling fluids or cleaning agents used for drilling equipment becomes.

The The invention therefore also relates to a method for cleaning the surfaces boreholes, in particular the walls of boreholes, of conveyor or casing pipes or walls the casing, as well as for cleaning drilling equipment or cuttings, the surfaces first with a detergent containing the above-described n-nonyl ether in contact brought and optionally the surfaces subsequently be rinsed with water.

• (α1) 0,1 bis 50 Gew.-%, besonders bevorzugt 0,5 bis 35 Gew.-%, ferner bevorzugt 1,0 bis 15 Gew.-% und am meisten bevorzugt 1,2 bis 10 Gew.-% des n-Nonylethers,
• (α2) 0 bis 50 Gew.-%, besonders bevorzugt 0,5 bis 35 Gew.-%, ferner bevorzugt 1,0 bis 15 Gew.-% und am meisten bevorzugt 1,2 bis 10 Gew.-% weitere, vom n-Nonylether verschiedene Additive, sowie
• (α3) 1 bis 99,9 Gew.-%, besonders bevorzugt 30 bis 99 Gew.-%, ferner bevorzugt 70 bis 98 Gew.-% und am meisten bevorzugt 80 bis 97,6 Gew.-% Wasser,

wobei die Summe der Komponenten (α1) bis (α3) 100 Gew.-% beträgt, eingesetzt wird.In this context, it is particularly preferred that the cleaning agent is used in the form of an aqueous solution, an aqueous dispersion or an oil-in-water emulsion, including

• (α1) 0.1 to 50 wt .-%, particularly preferably 0.5 to 35 wt .-%, further preferably 1.0 to 15 wt .-% and most preferably 1.2 to 10 wt .-% of n-nonyl ether,
• (α2) 0 to 50 wt .-%, particularly preferably 0.5 to 35 wt .-%, further preferably 1.0 to 15 wt .-% and most preferably 1.2 to 10 wt .-% further, from n-nonyl ether various additives, as well
• (α3) from 1 to 99.9% by weight, particularly preferably from 30 to 99% by weight, more preferably from 70 to 98% by weight and most preferably from 80 to 97.6% by weight of water,

wherein the sum of the components (α1) to (α3) is 100 wt .-% is used.

Especially the amount of component (α1) in the aqueous Composition may vary and will vary with the type and extent adapted to the pollution.

As n-nonylether various additives (α2) are in particular weighting agents, flu id-loss additives, viscosity-regulating additives, wetting agents or salts. The general principles for the composition of the respective treatment fluids apply here.

Also the concomitant use of organic polymer compounds natural and / or synthetic origin may prove advantageous. To These are in particular starch or chemically modified Starches, cellulose derivatives such as carboxymethylcellulose, Guargum, Synthangum or purely synthetic water-soluble and / or water-dispersible polymer compounds, in particular of the type of high molecular weight polyacrylamide compounds with or without anionic or cationic modification.

Under Drilling devices fall in particular drilling equipment, such as the derrick, the drill string, especially the drill string and the drill bit, cleaning equipment, solid waste disposal plant, In particular, vibrating screens or centrifuges, pumps, motors or gearbox, or the drilling platform or parts thereof. to Cleaning the drilling equipment will include the cleaning agent the n-nonyl ether on the surfaces of the objects sprayed or applied or the objects to be cleaned are immersed in the aqueous compositions. there The contaminants dissolve away from the surfaces. Subsequently, the surfaces are so with water put that in contact with the impurities be removed, for example by the surface with is sprayed a stream of water.

Farther can the cleaning agent containing the n-nonyl ether to use for cleaning cuttings, the so-called cuttings. These are required for drilling and must be used for offshore drilling deposited on the bottom of the lake in the vicinity of the drilling platform, which lead to a strong entry of mineral oil into the environment can. To an ecological load of the sea largely To avoid, the cuttings are cleaned before and from the leftovers the drilling fluid freed. The detergent containing the n-nonyl ether can be used for all cleaning processes known to the person skilled in the art, which occur in the field of soil drilling, both offshore drilling as well as drilling on land. This includes in particular the removal of paraffin deposits from borehole walls. Usually Boreholes are cleaned by adding a cleaning fluid is pumped through the well under pressure and through the detergent the deposits removed from the walls of the borehole become. Subsequently, the impurities with the Fluid transported from the well.

• (β1) das Bohren eines Bohrloches in die Erde mittels eines über ein Bohrgestänge angetriebenen Bohrkopfes,
• (β2) das Einführen eines Futterrohres in das Bohrloch, sowie
• (β3) das Einführen von Zement in zumindest einen Teilbereich des Zwischenraumes zwischen der Außenseite des Futterrohres und den Wandungen des Bohrloches,

wobei vor Durchführung des Verfahrensschrittes (β3) das Reinigungsmittel beinhaltend den n-Nonylether durch den Zwischenraum zwischen der Außenseite des Futterrohres und den Wandungen des Bohrloches geführt, vorzugsweise in diesem Zwischenraum zirkuliert wird. Dieses Zirkulieren kann beispielsweise dadurch erfolgen, dass das Reinigungsmittel durch das Futterrohr, vorzugsweise über das Bohrgestänge, nach unten gepumpt, am unteren Ende des Futterrohres, vorzugsweise am Bohrkopf bzw. am Bohrmeißel, austritt und dann durch den Zwischenraum zwischen der Außenseite des Futterrohres und den Wandungen des Bohrloches wieder nach oben steigt. Wird das Reinigungsmittel kontinuierlich durch das Futterrohr nach unten gepumpt, können auf diese Weise sowohl die Wandungen des Bohrloches als auch die Außenseite des Futterrohres gereinigt werden.According to a preferred embodiment of the method according to the invention described above, this includes the method steps

• (β1) drilling a wellbore into the earth by means of a drill bit driven by a drill string,
• (β2) introducing a casing into the well, as well
• (β3) introducing cement into at least a portion of the space between the outside of the casing and the walls of the wellbore,

wherein before carrying out the method step (β3), the cleaning agent containing the n-nonyl ether is passed through the intermediate space between the outside of the casing and the walls of the borehole, preferably circulated in this intermediate space. This circulation may be effected, for example, by the detergent pumping down through the casing, preferably down the drill pipe, at the bottom of the casing, preferably on the drill bit or bit, and then through the space between the outside of the casing and the casing Walls of the borehole rises again. If the cleaning agent is continuously pumped down through the casing, in this way both the walls of the wellbore and the outside of the casing can be cleaned.

According to one preferred embodiment of the invention Process for cleaning the surfaces of drilling equipment including the step of drilling a wellbore into the earth by means of a drill pipe driven drill head, wherein the cleaning agent including the n-nonyl ether at least partially through the drill head guided, preferably at least partially by this is circulated through, this passing or this circulate at least partially during the presence of the drill head in the borehole.

When Drilling equipment whose surface with the detergent In particular, drilling equipment, such as the derrick, the drill string, in particular the Drill pipe and drill bit, cleaning equipment, Plant for solids disposal, in particular vibrating screens or centrifuges, pumps, motors or gears, or the drilling platform or parts thereof.

• (β1) das Bohren eines Bohrloches in die Erde mittels eines über ein Bohrgestänge angetriebenen Bohrkopfes,
• (β2) das Einführen eines Futterrohres in das Bohrloch,
• (β3) das Einführen von Zement in zumindest einen Teilbereich des Zwischenraumes zwischen der Außenseite des Futterrohres und den Wandungen des Bohrloches,
• (β4) gegebenenfalls das Einführen eines Förderrohres in das Futterrohr,
• (β5) gegebenenfalls das Einführen einer Dichtungsflüssigkeit in den Zwischenraum zwischen der Außenseite des Förderrohres und den der Innenseite des Futterrohres,

wobei Oberflächen des Bohrloches, des Führungsrohres, des Bohrgestänges oder des Bohrkopfes mit dem Reinigungsmittel beinhaltend den n-Nonylether in Kontakt gebracht werden. Insbesondere kann dieses in Kontakt bringen gemäß den vorstehend beschriebenen, bevorzugten Ausführungsformen des erfindungsgemäßen Verfahrens zum Reinigen der Oberflächen von Bohrlöchern oder Bohreinrichtungen erfolgen. Es ist demnach bevorzugt, dass vor Durchführung des Verfahrensschrittes (β3) das Reinigungsmittel beinhaltend den n-Nonylether durch den Zwischenraum zwischen der Außenseite des Futterrohres und den Wandungen des Bohrloches hindurchgeführt, vorzugsweise durch diesen Zwischenraum zirkuliert wird.A contribution to the solution of the abovementioned objects is also made by a method for producing a borehole, including the method steps

• (β1) drilling a wellbore into the earth by means of a drill bit driven by a drill string,
• (β2) inserting a casing into the well,
• (β3) introducing cement into at least a portion of the space between the outside of the casing and the walls of the wellbore,
• (β4) optionally introducing a delivery tube into the casing,
• (β5) optionally introducing a sealing liquid into the space between the outside of the conveying tube and the inside of the casing,

wherein surfaces of the borehole, the guide tube, the drill string or the drill head are brought into contact with the cleaning agent containing the n-nonyl ether. In particular, this may be brought into contact according to the above-described, preferred embodiments of the inventive method for cleaning the surfaces of boreholes or drilling devices. It is therefore preferred that before carrying out the method step (β3), the cleaning agent containing the n-nonyl ether passed through the gap between the outside of the casing and the walls of the wellbore, preferably circulated through this gap.

As sealing liquid, which is introduced into the intermediate space between the outside of the conveying tube and the inside of the casing in method step (β5), all materials known to the person skilled in the art for this purpose can be used. As an example, at this point those sealing liquids are called, in the US 7,219,735 to be discribed.

• (β5) auch die Verfahrensschritte
• (β6) das Fördern von Öl oder Gas durch das Bohrloch, sowie
• (β7) das Reinigen oder Raffinieren des geförderten Öls oder Gases,

beinhaltet, wobei auch hier die Oberflächen des Bohrloches, des Förderrohres, des Bohrgestänges oder des Bohrkopfes mit dem Reinigungsmittel beinhaltend den n-Nonylether in Kontakt gebracht werden. Auch hier kann dieses in Kontakt bringen gemäß den vorstehend beschriebenen, bevorzugten Ausführungsformen des erfindungsgemäßen Verfahrens zum Reinigen der Oberflächen von Bohrlöchern oder Bohrgeräten erfolgen.A further contribution to the solution of the abovementioned objects is also provided by a process for the production of an oil or a gas which, in addition to the abovementioned process steps (β1) to (β3) and optionally (β4) and

• (β5) also the process steps
• (β6) conveying oil or gas through the well, as well
• (β7) purifying or refining the extracted oil or gas,

includes, wherein also the surfaces of the borehole, the production pipe, the drill pipe or the drill head with the cleaning agent containing the n-nonyl ether are brought into contact. Again, this can be brought into contact according to the above-described, preferred embodiments of the inventive method for cleaning the surfaces of boreholes or drilling rigs.

The Invention also relates to a method for the production of boreholes, in which a drilling fluid is pumped through a borehole, wherein as Bohrspülung a composition comprising the Initially described n-nonyl ether is used.

According to one particular embodiment of this method is This composition is a water-in-oil emulsion.

• I) 28,9 bis 99 Gew.-%, besonders bevorzugt 60 bis 90 Gew.-% und am meisten bevorzugt 70 bis 80 Gew.-%, jeweils bezogen auf das Gesamtgewicht der Zusammensetzung, einer mit Wasser nicht mischbaren, organischen Öl-Phase,
• II) 1 bis 48 Gew.-%, vorzugsweise, besonders bevorzugt 5 bis 40 Gew.-% und am meisten bevorzugt 10 bis 30 Gew.-%, jeweils bezogen auf das Gesamtgewicht der Zusammensetzung, Wasser oder wässrige Phase,
• III) 0,1 bis 20 Gew.-%, besonders bevorzugt 1 bis 15 Gew.-% und am meisten bevorzugt 5 bis 10 Gew.-%, jeweils bezogen auf das Gesamtgewicht der Zusammensetzung, des eingangs beschriebenen n-Nonylethers, sowie
• IV) 0 bis 70 Gew.-%, besonders bevorzugt 1 bis 5 Gew.-% und am meisten bevorzugt 1,5 bis 3 Gew.-%, jeweils bezogen auf das Gesamtgewicht der Zusammensetzung, mindestens eines weiteren Additivs,

enthält, wobei die Summe der Komponenten I) bis IV) 100 Gew.-% beträgt.In this connection it is particularly preferred that the composition

• I) from 28.9 to 99% by weight, more preferably from 60 to 90% by weight and most preferably from 70 to 80% by weight, based in each case on the total weight of the composition, of a water-immiscible organic oil Phase,
• II) from 1 to 48% by weight, preferably, particularly preferably from 5 to 40% by weight and most preferably from 10 to 30% by weight, based in each case on the total weight of the composition, of water or aqueous phase,
• III) 0.1 to 20 wt .-%, particularly preferably 1 to 15 wt .-% and most preferably 5 to 10 wt .-%, each based on the total weight of the composition of the n-nonyl ether described above, and
• IV) from 0 to 70% by weight, particularly preferably from 1 to 5% by weight and most preferably from 1.5 to 3% by weight, based in each case on the total weight of the composition, of at least one further additive,

contains, wherein the sum of the components I) to IV) is 100 wt .-%.

• a) Paraffine mit 5 bis 22 C-Atomen und/oder
• b) Paraffine mit 5 bis 22 C-Atomen und/oder
• c) internen Olefine mit 12 bis 30 C-Atomen im Molekül und/oder
• d) Carbonsäureestern der allgemeinen Formel R-COO-R, in der R für einen linearen oder verzweigten, gesättigten oder ungesättigten Alkylrest mit 15 bis 25 C-Atomen steht und R' einen gesättigten, linearen oder verzweigten Alkylrest mit 3 bis 22 C-Atomen bedeutet, und/oder
• e) Mineralöle, und/oder
• f) lineare alpha-Olefine (LAOs) mit 12 bis 30 C-Atomen, und/oder
• g) Carbonate.

In connection with the water-in-oil emulsion described above, it is preferred that the organic oil phase I) is wholly or partially selected from the group of

• a) paraffins having 5 to 22 C atoms and / or
• b) paraffins with 5 to 22 carbon atoms and / or
• c) internal olefins having 12 to 30 carbon atoms in the molecule and / or
• d) carboxylic acid esters of the general formula R-COO-R in which R is a linear or branched, saturated or unsaturated alkyl radical having 15 to 25 C atoms and R 'is a saturated, linear or branched alkyl radical having 3 to 22 C atoms means, and / or
• e) mineral oils, and / or
• f) linear alpha-olefins (LAOs) having 12 to 30 carbon atoms, and / or
• g) carbonates.

In this context, it is further preferred that this water-in-oil emulsion a Density of the liquid component in a range of 1.2 to 3.0 g / cm ³ and in particular in a range of 1.5 to 3.0 g / cm ³ . The oil phase of the systems according to the invention contains the components a) to e) alone or the components a), b), d) or e) together in admixture with ester c) and optionally in admixture with other suitable oil phases. There are also any mixtures of the oil phases a) to e) with each other possible.

Component a)

As component a) linear or branched paraffins having 5 to 22 carbon atoms are used according to the invention. Paraffins - more correctly referred to as alkanes - are known to be saturated hydrocarbons which follow the linear or branched representatives of the general empirical formula C _n H _{2n + 1} . The cyclic alkanes follow the general empirical formula C _n H _2n . Particularly preferred are the linear and branched paraffins, whereas cyclic paraffins are less preferred. Especially preferred is the use of branched paraffins. Furthermore, those paraffins are preferred which are liquid at room temperature, ie those having 5 to 16 carbon atoms per molecule. However, it may also be preferred to use paraffins with 17 to 22 C atoms, which have a waxy consistency. However, it is preferred to use mixtures of the different paraffins, and it is particularly preferred if these mixtures are still liquid at 21 ° C. Such mixtures may, for. B. from paraffins with 10 to 21 carbon atoms are formed. Paraffins are particularly preferred oil phases - alone or as a mixture component with other oil phases - in drilling fluids - preferably those of the invert type, in which the crosslinked glycerol or oligoglycerol esters according to the invention are used as thickeners.

Component b)

As component b) internal olefins (hereinafter abbreviated to IO) can be used according to the invention. In this case, IOs are likewise compounds known per se, which can be prepared by all methods known to the person skilled in the art. The EP 0 787 706 A1 describes z. Example, a method for the synthesis of IOs by isomerization of alpha-olefins to sulfonic or persulfonic acids. Characteristically, the IOs so obtained are linear and contain at least one olefinic double bond that is not in the alpha position of the alkyl chain. Preferably, according to the invention, such IO or IO mixtures are used which contain IO having 12 to 30 C atoms in the molecule, preferably having 14 to 24 C atoms and in particular having up to 20 C atoms in the molecule.

Component c)

Furthermore, esters of the general formula R-COO-R ', in which R is a linear or branched, saturated or unsaturated alkyl radical having 15 to 25 C atoms, and R' is a saturated, linear or branched alkyl radical having 6 to 22 C atoms Atoms means part of the oil phases according to the invention. Also such esters are known chemical compounds. Their principal use in drilling fluids is z. B. Subject of the EP 0 374 672 A1 or the EP 0 374 671 A1 , Particularly preferred is the use of such esters whose radical R is a saturated or unsaturated alkyl radical having 15 to 25 and R 'is a saturated alkyl radical having 3 to 10 carbon atoms. The saturated compounds are particularly preferred. It is preferred in the inventive teaching that in the oil phase in addition to the ester as described above a maximum of 15 wt .-% (based on the oil phase) of other esters with radicals R, which is more than 23 C for alkyl radicals Atoms are included.

Component d)

mineral oils are a collective name for those from mineral raw materials (Petroleum, brown and hard coal, wood or peat) won liquid distillation products consisting essentially of mixtures consist of saturated hydrocarbons. Preferably The mineral oils contain only small amounts of aromatic Hydrocarbons, preferably less than 3 wt .-%. Preferred are based on liquid oils at 21 ° C of petroleum. The mineral oils preferably have Boiling points from 180 to 300 ° C on.

Component e)

Linear alpha-olefins (LAO for short) are unbranched in 1-position ("alpha-C-atom") unsaturated hydrocarbons. They can be based on natural substances, but are also obtained synthetically, in particular on a large scale. Natural-based LAOs are obtained by dehydration of natural-based fatty alcohols as linear products with a straight-chain carbon number. Synthetically obtained LAOs, produced by the oligomerization of ethylene, often contain straight-chain carbon numbers in the chain, but processes for the production of nonradiomeric alpha-olefins are also known today. For the purposes of the definition according to the invention, owing to their volatility, as a rule at least 10, preferably at least 12 to 14 C atoms in the molecule are present. The upper limit of LAO flowable is in the range of C ₁₈ to C ₂₀ . However, this upper limit is not one for the usability of this class of substance within the scope of the invention restrictively. The upper limit of suitable LAO compounds for use in the teaching according to the invention thus lies well above the aforementioned limit of C ₁₈ to C ₂₀ and can reach, for example, C ₃₀ .

Component f)

For the purposes of the present application, carbonates are understood as meaning carbonic acid esters of fatty alcohols having 8 to 22 carbon atoms, preferably the diesters of carbonic acid. Such compounds and their use as an oil phase for drilling fluids are described in U.S. Patent Nos. 5,342,074; DE 40 18 228 A1 ,

• (i) Ester aus C_1-5-Monocarbonsäuren und 1- und/oder mehrfunktionellen Alkoholen, wobei Reste aus 1-wertigen Alkoholen wenigstens 6, bevorzugt wenigstens 8 C-Atome aufweisen und die mehrwertigen Alkohole bevorzugt 2 bis 6 C-Atome im Molekül besitzen,
• (ii) Mischungen sekundärer Ester, ausgewählt aus der Gruppe der Propylcarboxylat, Butylcarboxylat, Pentylcarboxylat, Hexylcarboxylat, Heptylcarboxylat, Octylcarboxylat, Nonylcarboxylate, Decylcarboxylat, Undecylcarboxylat, Dodecylcarboxylat, Tridecylcarboxylat, Tetradecylcarboxylat, Pentadecylcarboxylat, Hexadecylcarboxylat, Heptadecylcarboxylat, Octadecylcarboxylat, Nonadecylcarboxylat, Eicosylcarboxylat, Uneicocarboxylat, Doeicosylcarboxylat und Isomeren davon, wobei die sekundären Ester jeweils eine Carboxylat-Rest mit 1 bis 5 C-Atomen aufweisen, wasserunlösliche Ether einwertiger Alkohole mit 6 bis 24 C-Atomen,
• (iii) wasserunlösliche Alkohole mit 8 bis 36 C-Atomen
• (iv) poly-alpha-Olefine (PAO)
• (v) Mischungen der Komponente (i) bis (iv)

In addition to the components a) to f), other, water-insoluble constituents may be present in the oil phase I), provided that they are ecologically compatible. Further particularly suitable mixing constituents of the oil phase I) according to the invention are therefore in detail:

• (I) esters of C _1-5 monocarboxylic acids and 1- and / or polyfunctional alcohols, where radicals of monohydric alcohols have at least 6, preferably at least 8 C atoms and the polyhydric alcohols preferably 2 to 6 C atoms in the molecule have,
• (Ii) mixtures of secondary esters selected from the group consisting of propyl carboxylate, butyl carboxylate, Pentylcarboxylat, Hexylcarboxylat, Heptylcarboxylat, Octylcarboxylat, Nonylcarboxylate, Decylcarboxylat, Undecylcarboxylat, Dodecylcarboxylat, Tridecylcarboxylat, Tetradecylcarboxylat, Pentadecylcarboxylat, Hexadecylcarboxylat, Heptadecylcarboxylat, octadecyl, nonadecyl, eicosyl, Uneicocarboxylat, Doeicosylcarboxylate and isomers thereof, the secondary esters each having a carboxylate radical having 1 to 5 C atoms, water-insoluble ethers of monohydric alcohols having 6 to 24 C atoms,
• (iii) water-insoluble alcohols having 8 to 36 C atoms
• (iv) poly-alpha olefins (PAO)
• (v) Mixtures of component (i) to (iv)

The oil phase I) of the composition used as a drilling fluid in the form of a water-in-oil emulsion preferably have pour points below 0 ° C., preferably below -5 ° C. (measured by DIN ISO 3016: 1982-10 ) on. The Brookfield viscosity of the oil phase at 0 ° C is at most 50 mPas. The compositions used as drilling fluids, when formed as oil-based drilling mud of the W / O type, have a plastic viscosity (PV) in the range of 10 to 70 mPas and a yield point YP of 5 to 60 lb / 100 ft ² , each determined at 50 ° C, on. The kinematic viscosity of the oil phase measured according to Ubbelohde at 20 ° C should preferably be at most 12 mm ² / sec. The aqueous phase of the compositions according to the invention preferably has a pH in the range from 7.5 to 12, preferably from 7.5 to 11 and in particular from 8 to 10.

As the aqueous phase according to component II), the composition used as a drilling fluid preferably comprises aqueous salt solutions, preferably saturated salt solutions, it being possible to use as salts all alkali metal or alkaline earth metal halides known to the person skilled in the art. Examples of suitable salts are, in particular, KCl, NaCl, LiCl, KBr, NaBr, LiBr, CaCl ₂ , and MgCl ₂ , among which CaCl ₂ , NaCl and KCl or mixtures of these salts are particularly preferred.

When other additives which according to the component IV) in the composition used as Bohrspülung may be contained, in particular additives are selected from the group consisting of surfactants as Zumischkomponente for the crosslinked glycerol or oligoglycerol esters, weighting agents, fluid loss additives, pH modifiers, other viscosity modifying agents Additives, wetting agents, salts, biocides, inhibitors of unwanted water exchange between drilled Formations - eg. B water-swellable clays and / or salt layers - and the z. As water-based rinsing liquid, Netzmit stuffs to better deposit the emulsified oil phase on solid surfaces, z. B. to improve the lubricity, but also to improve the oleophilic closure of exposed rock formations, resp. Rock surfaces, corrosion inhibitors, alkali reserves and emulsifiers into consideration.

It here the general laws apply for the composition of the respective treatment fluids, for the below with the appropriate Bohrspülschlämme exemplary statements are made. The additives can be water-soluble, oil-soluble and / or water or oil dispersible.

As surfactants anionic, nonionic zwitterionic or cationic surfactants can be used. However, preferred are the nonionic and anionic surfactants. Typical examples of anionic surfactants are soaps, alkylbenzenesulfonates, alkanesulfonates, olefinsulfonates, alkyl ether sulfonates, glycerol ether sulfonates, methyl ester sulfonates, sulfo fatty acids, alkyl sulfates, fatty alcohol ether sulfates, glycerol ether sulfates, fatty acid ether sulfates, hydroxy mixed ether sulfates, monoglyceride (ether) sulfates, fatty acid amide (ether) sulfates, mono- and dialkyl sulfosuccinates, mono and dialkyl sulfosuccinamates, sulfotriglycerides, amide soaps, ether carboxylic acids and their salts. The latter are particularly preferred surfactant components within the meaning of the present technical teaching. Typical examples of Nonionic surfactants are fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, fatty acid polyglycol ethers, fatty acid amide polyglycol ethers, fatty amine polyglycol ethers, alkoxylated triglycerides, mixed ethers, optionally partially oxidized alk (en) yloligoglycosides or glucuronic acid derivatives, fatty acid N-alkylglucamides, polyol fatty acid esters, sugar esters, sorbitan esters, polysorbates and amine oxides. If the nonionic surfactants contain polyglycol ether chains, these may have a conventional, but preferably a narrow homolog distribution. The surfactants are an optional ingredient in the additives. They are preferably used in amounts of 0.01 to 2 wt .-%, in particular from 0.1 to 1.5 wt .-% and preferably from 0.2 to 0.5 wt .-%, in each case based on the total Water-in-oil emulsion, used.

When Emulsifiers are preferably nonionic emulsifiers in question, which in particular are assigned to one of the following material classes: (Oligo) alkoxylates - especially lower alkoxylates, wherein here corresponding ethoxylates and / or propoxylates particular Meaningful - of lipophilic radicals containing and basic molecules capable of alkoxylation are natural and / or synthetic origin. Alkoxylates of the type indicated are known as such - d. H. with terminal free hydroxyl group on the alkoxylate radical - nonionic However, emulsifiers, the corresponding compounds can also be end-capped, for example by esterification and / or etherification. Another important class of nonionic Emulsifiers for the purposes of the invention are partial esters and / or partial ethers of polyfunctional alcohols in particular 2 to 6 C atoms and 2 to 6 OH groups and / or their oligomers with lipophilic radicals containing acids and / or alcohols. In particular, compounds of this type are also suitable, which additionally in their molecular structure (oligo-) alkoxy radicals and in particular incorporated corresponding oligo-ethoxy radicals contain. The polyfunctional alcohols having 2 to 6 OH groups in the basic molecule or the derivative thereof Oligomers may in particular diols and / or triols or their oligomerization products being the glycol and the glycerol or their oligomers may be of particular importance. The area Partial ethers of polyfunctional alcohols are also known nonionic emulsifiers of the ethylene oxide / propylene oxide / butylene oxide block polymer type assigned. Another example of corresponding emulsifier components are alkyl (poly) glycosides of long-chain alcohols as well as those already Named fatty alcohols natural and / or synthetic Origin or alkylolamides, amine oxides and lecithins. The concomitant use of commercially available alkyl (poly) glycoside compounds today (APG compounds) as emulsifier components in the invention Sense can be particularly interesting because of others this is an emulsifier class of particularly pronounced ecocompatibility is. Without claim to completeness are from the here listed substance classes of suitable emulsifier components additionally named the following representatives: (oligo) alkoxylates of fatty alcohols, fatty acids, fatty amines, fatty amides, fatty acid and / or fatty alcohol esters and / or ethers, alkanolamides, alkylphenols and / or their reaction products with formaldehyde and other reaction products lipophilic radical-containing carrier molecules with lower alkoxides. As indicated, the respective reaction products also be at least partly closed end groups. Examples for partial esters and / or partial ethers multifunctional Alcohols are in particular the corresponding partial esters with fatty acids, for example of the type of glycerol mono- and / or diesters, Glycol monoesters, corresponding partial esters of oligomerized polyfunctional Alcohols, Sorbitanpartialester and the like and corresponding Compounds with ether groups.

Also the concomitant use of organic polymer compounds natural and / or synthetic origin as further additives can be considerable Importance in this regard. To name here are in particular Starch or chemically modified starches, cellulose derivatives such as carboxymethylcellulose, guar gum, synthangum or purely synthetic water-soluble and / or water-dispersible polymer compounds, in particular of the type of high molecular weight polyacrylamide compounds with or without anionic or cationic modification. thinner for viscosity regulation: the so-called thinners may be organic or inorganic, examples of Organic thinner are tannins and / or Qebracho extract. Further examples are lignite and lignite derivatives, in particular lignosulfonates.

As a preferred means against fluid loss (fluid loss additive) is in particular organophilic lignite, while preferred pH modifiers, for example, the EP 0 382 701 A1 can be removed. The in the EP 0 382 701 A1 described invention is based on the finding that in water-in-oil type ester-based drilling fluids additives should be used, which ensure that the rheological properties of the drilling fluid do not change even if increasing amounts of free carboxylic acids by partial ester hydrolysis be released. If possible, these free carboxylic acids should be converted into compounds which have stabilizing and emulsifying properties. For this purpose, the EP 0 382 701 A1 before, alkaline amines with high oleophilic and as low as possible To add water solubility, which are able to form salts with the free acids. Typical examples of such amine compounds are primary, secondary and / or tertiary amines, which are predominantly water-insoluble and which moreover can be at least partially alkoxylated and / or substituted by hydroxyl groups. Further examples include aminoamides and / or heterocycles containing nitrogen as the ring atom. Suitable examples are basic amines which have at least one long-chain hydrocarbon radical having 8 to 36 carbon atoms, preferably having 10 to 24 carbon atoms, wherein these hydrocarbon radicals may also be mono- or polyunsaturated.

The Amounts in which the above-described further additives the composition used as a drilling fluid in the case a water-in-oil emulsion may be added, as appropriate those quantities in which these compounds have become obsolete known in the art water-in-oil based drilling fluids be added.

In low weight compositions, component IV) is preferably a weighting agent, such as BaSO ₄ , in which case, in the case of a low added composition, component IV) is preferably used in an amount of up to 20% by weight. For more heavily weighted compositions, the component IV) is preferably used in an amount of 20 to 50 wt .-%, while in heavily weighted compositions 50 to 70 wt .-% of component IV) can be used.

Farther it is preferred according to the invention that the composition, if it is present as a water-in-oil emulsion, a nanoemulsion or a microemulsion, preferably water drops or Drop of an aqueous phase with a drop size less than 1000 microns, preferably one drop size in a range of 5 nm to 1000 μm, particularly preferred with a drop size in a range of 10 nm to 850 μm, more preferably one drop size in a range of 20 nm to 700 μm, more preferably with a drop size in a range of 50 nm to 500 microns included. The term "microemulsion" and "nanoemulsion" according to the invention characterize emulsion, which contain drops in the micrometer or nanometer range, There is some distinction between these two areas and thus also these two terms can give. According to one Part of the literature and drilling fluids Prior art, among microemulsions, are preferably such emulsions understood spontaneously with a combination of the emulsion components whereas the formation of nanoemulsions is usually the supply of energy, for example in the form of a Homogenizing, especially in the form of high-pressure homogenization, requires.

in the Case of a water-in-oil emulsion as a drilling fluid used composition can this by any one skilled in the art known method for producing such a water-in-oil emulsion getting produced. So it is particularly conceivable, first the basic emulsion of the organic oil phase as a continuous phase and then produce the water droplets emulsified therein the n-nonyl ether and optionally the further additives add. It is also conceivable, however, first the initially described Add n-nonyl ether of the organic oil phase and then from this oil phase and the water or the aqueous Solution to form the emulsion.

According to one another particular embodiment of the drilling fluid used composition is this one aqueous solution or an oil-in-water emulsion.

• I) 0 bis 48 Gew.-%, besonders bevorzugt 0,1 bis 20 Gew.-% und am meisten bevorzugt 1 bis 10 Gew.-%, jeweils bezogen auf das Gesamtgewicht der Zusammensetzung, einer mit Wasser nicht mischbaren organischen Öl-Phase,
• II) 29,9 bis 99,9 Gew.-%, besonders bevorzugt 60 bis 99 Gew.-% und am meisten bevorzugt 70 bis 95 Gew.-%, jeweils bezogen auf das Gesamtgewicht der Zusammensetzung, Wasser oder wässrige Phase,
• III) 0,1 bis 20 Gew.-%, besonders bevorzugt 1 bis 15 Gew.-% und am meisten bevorzugt 5 bis 10 Gew.-%, jeweils bezogen auf das Gesamtgewicht der Zusammensetzung, des eingangs beschriebenen n-Nonylethers,
• IV) 0 bis 70 Gew.-%, besonders bevorzugt 1 bis 5 Gew.-% und am meisten bevorzugt 1,5 bis 3 Gew.-%, jeweils bezogen auf das Gesamtgewicht der Zusammensetzung, mindestens eines weiteren Additivs,

wobei die Summe der Komponenten I) bis IV) 100 Gew.-% beträgt.In this connection it is particularly preferred that the composition

• I) 0 to 48 wt .-%, particularly preferably 0.1 to 20 wt .-% and most preferably 1 to 10 wt .-%, each based on the total weight of the composition, of a water-immiscible organic oil phase .
• II) from 29.9 to 99.9% by weight, particularly preferably from 60 to 99% by weight and most preferably from 70 to 95% by weight, based in each case on the total weight of the composition, of water or aqueous phase,
• III) 0.1 to 20 wt .-%, particularly preferably 1 to 15 wt .-% and most preferably 5 to 10 wt .-%, each based on the total weight of the composition of the n-nonyl ether described above,
• IV) from 0 to 70% by weight, particularly preferably from 1 to 5% by weight and most preferably from 1.5 to 3% by weight, based in each case on the total weight of the composition, of at least one further additive,

wherein the sum of components I) to IV) is 100% by weight.

When organic oil phase, aqueous phase and more Additives are those organic oil phases, aqueous Phases and other additives, which are already mentioned above in Related to the water-in-oil emulsion were called.

Also in the case of an oil-in-water emulsion as a composition used as a drilling fluid, it can be prepared by any method known to those skilled in the art for preparing such an oil-in-water emulsion. Thus, it is conceivable in particular first to prepare the base emulsion from water or the aqueous solution as the continuous phase and the droplets of the oil phase emulsified therein and then to add the n-nonyl ether described initially and optionally the further additives. However, it is also conceivable first to add the n-nonyl ether described at the outset to the organic oil phase and then to form the emulsion from this oil phase and the water or the aqueous solution.

• (α1) das Bereitstellen der erfindungsgemäßen Zusammensetzung, insbesondere der erfindungsgemäßen Zusammensetzung in Form einer Wasser-in-Öl-Emulsion, einer wässrigen Lösung oder einer Öl-in-Wasser-Emulsion;
• (α2) das Bohren eines Loches in die Erde;
• (α3) das Einleiten, vorzugsweise das Zirkulieren, der im Verfahrensschritt (α1) bereitgestellten Zusammensetzung zumindest teilweise in das bzw. in dem Bohrloch;

wobei das Einleiten, vorzugsweise das Zirkulieren vorzugsweise mindestens teilweise während des Bohrens in Verfahrensschritt (α2) erfolgt.According to a preferred embodiment of this method for producing boreholes, in which a drilling fluid is pumped through a borehole, this comprises the method steps:

• (α1) providing the composition according to the invention, in particular the composition according to the invention in the form of a water-in-oil emulsion, an aqueous solution or an oil-in-water emulsion;
• (α2) drilling a hole in the ground;
• (α3) introducing, preferably circulating, the composition provided in step (α1) at least partially into or in the wellbore;

wherein the introduction, preferably the circulation preferably takes place at least partially during the drilling in method step (α2).

The The composition of the invention thus acts as a drilling fluid when drilling holes in the Earth, preferably when drilling for oil or natural gas.

• (α1) das Bereitstellen der als Bohrspülung eingesetzen Zusammensetzung, insbesondere der als Bohrspülung eingesetzten Zusammensetzung in Form einer Wasser-in-Öl-Emulsion, einer wässrigen Lösung oder einer Öl-in-Wasser-Emulsion;
• (α2) das Bohren eines Loches in die Erde;
• (α3) das Einleiten, vorzugsweise das Zirkulieren der im Verfahrensschritt (α1) bereitgestellten Zusammensetzung zumindest teilweise in das bzw. in dem Bohrloch, wobei auch hier das Einleiten bzw. das Zirkulieren vorzugsweise mindestens teilweise während des Bohrens in Verfahrensschritt (α2) erfolgt;
• (α4) das Fördern von Öl oder Gas aus der Erde durch das im Verfahrensschritt (α2) gebohrte Loch;
• (α2) gegebenenfalls das Reinigen oder Raffinieren des im Verfahrensschritt (α3) geförderten Öls oder Gases.

A contribution to the solution of the objects mentioned at the outset is therefore also provided by a process for the production of an oil or a gas, comprising the process steps:

• (α1) providing the composition used as a drilling fluid, in particular the composition used as a drilling fluid in the form of a water-in-oil emulsion, an aqueous solution or an oil-in-water emulsion;
• (α2) drilling a hole in the ground;
• (α3) introducing, preferably circulating, the composition provided in step (α1) at least partially into or in the borehole, wherein also here the introduction or circulation preferably takes place at least partially during drilling in method step (α2);
• (α4) conveying oil or gas out of the earth through the hole drilled in step (α2);
• (α2) optionally purifying or refining the oil or gas delivered in step (α3).

a Contribute to the solution of the above-mentioned tasks also a cleaning agent and a drilling fluid, preferably a drilling fluid in the form of the water-in-oil emulsion described above or the above-described oil-in-water emulsion.

The Invention will now be closer by way of non-limiting examples explained.

EXAMPLE 1: Preparation of di-n-nonyl ether

31.6 g of pelargonic acid (0.2 mol, ^Emery® 1203) and 150 ml of methanol were placed in a glass flask and 3 g of concentrated sulfuric acid were added. The mixture was refluxed for 4 hours. Thereafter, 3.5 g of anhydrous sodium carbonate were added and the excess alcohol distilled off. The pelargonic acid methyl ester was distilled off in vacuo (p about 16 mbar) at 95-100 ° C.

29.2 g of the resulting Pelargonsäuremethylesters were with 6 wt .-% copper chromite catalyst added and in an autoclave at 230 ° C and a hydrogen pressure of 250 bar for 4 hours stirred for a long time. Thereafter, the catalyst was filtered off and the Filtrate distilled in vacuo. The boiling point was about 113 ° C at 26 mbar, the yield was 79%.

Of the approach described above for the preparation of n-nonanol was repeated several times.

577 g of the thus obtained n-nonanol were in a flask presented with water and with 0.1 g of trifluoromethanesulfonic acid added. The reaction mixture was refluxed (ca. 225 ° C) until 36 ml of water had separated. After cooling, the product is mixed with 100 ml of 5% sodium carbonate solution and washed 100 ml of water. For workup, the crude product dried and distilled in vacuo. It was di-n-nonyl ether in obtained in a yield of 503 g.

EXAMPLE 2: Preparation of nonyl diethylene glycol ether

433 g of n-nonyl alcohol, which was obtained as in Example 1 by reduction of pelargonic acid methyl ester, were mixed with 5 g of a 30 wt .-% solution of potassium hydroxide in methanol and heated to 100 ° C in an autoclave. At this temperature, the existing traces of methanol were evacuated and vented five times Nitrogen removed. After increasing the reaction temperature to 150 ° C, a total of 264 g of ethylene oxide were added in portions, so that the pressure in the reactor did not exceed 5 × 10 ⁵ Pa. After completion of the reaction was cooled to about 90 ° C and evacuated for the separation of remaining traces of ethylene oxide for about 15 minutes. A slightly yellow liquid was obtained.

EXAMPLE 3: Preparation of a drilling fluid

It became a conventional Kalkspülung from 7.6 g prehydrated bentonite, 1.15 g ferrochromolignosulfonate, 2.3 g slaked lime, 0.38 g starch and 0.76 g NaOH. This Kalkspülung were 5 wt .-% of the obtained in Example 2 Nonyldoethylene glycol ethers added.

QUOTES INCLUDE IN THE DESCRIPTION

This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.

Cited patent literature

• WO 2006/021328 A [0010]
• US Pat. No. 2,813,113 [0010]
• - DE 10070770 C [0010]
• US 6498261 [0010]
• GB 813842 A [0010]
• - DE 19511668 A [0018]
• DE 102004056786 A [0019]
• WO 97/035823 A [0019]
• - DE 4010606 A [0020]
• US 7219735 [0038]
• EP 0787706 A1 [0046]
• EP 0374672 A1 [0047]
• EP 0374671 A1 [0047]
• DE 4018228 A1 [0050]
• EP 0382701 A1 [0059, 0059, 0059]

Cited non-patent literature

• - "Ozonation of Alkenes in Alcohols as Solvents", dissertation by Eberhard Rischbieter, University of Carolo-Wilhelmina zu Braunschweig, 2000 [0010]
• Harold A., Wittcoff, Bryan G., Reuben, Jeffrey S. Plotkin in "Fats and Oils", Industrial Organic Chemicals (Second Edition) (2004), John Wiley & Sons, Inc., pages 411-434 [0010]
• - DIN ISO 3016: 1982-10 [0052]

Claims (23)

Use of an n-nonyl ether which is available is by reaction of an n-nonyl alcohol component with another Component, which with the n-nonyl alcohol component to form an n-nonyl ether is able to react as an additive in drilling borehole compositions. Use according to claim 1, wherein the n-nonyl ether as an additive in drilling fluids or cleaning agents for Drilling equipment is used. Use according to claim 1 or 2, wherein the further Component, which with the n-nonyl alcohol component to form an n-nonyl ether, an alcohol, an epoxide Halogen alkane or a mixture of at least two of them. Use according to claim 3, wherein the further component is an alcohol selected from the group consisting of C ₁ - to C ₃₀ -alkanols, C ₁ - to C ₃₀ -diols, C ₁ - to C ₃₀ -triols, polyalcohols, polyether alcohols and mixtures from at least two of these alcohols. Use according to one of the preceding claims, wherein the n-nonyl alcohol component to at least 80 wt .-%, based to the n-nonyl alcohol component, is obtained from pelargonic acid. Use according to claim 5, wherein the pelargonic acid is obtained from oleic acid. Use according to claim 6, wherein the pelargonic acid is produced petrochemically. Use according to one of the preceding claims, wherein the n-nonyl alcohol component contains less than 10% by weight, based on the n-nonyl alcohol component, of C ₈ and C ₁₀ alcohols. A method for cleaning the surfaces of Drilling holes, drilling equipment or cuttings, the Surfaces first with a detergent including an n-nonyl ether as in any of the claims 1 and 3 to 8 defined, brought into contact and optionally then rinse the surfaces with water become. The method of claim 9, including the method steps (Β1) drilling a borehole into the ground by means of a a drill pipe driven drill head, (Β2) the insertion of a casing into the well, as well (Β3) the introduction of cement into at least one subarea the space between the outside of the casing and the walls of the borehole, being before performing the process step (β3) containing the detergent an n-nonyl ether as in any of claims 1 and 3 defined to 8, by the space between the outside the casing and the walls of the borehole, is preferably circulated in this space. The method of claim 9, including the method steps (Β1) drilling a borehole into the ground by means of a a drill pipe driven drill head, the A cleaning agent comprising an n-nonyl ether, as in one of Claims 1 and 3 to 8 defined, at least partially is passed through the drill head, this Passing at least partially during the Presence of the drill head in the borehole takes place. A method for producing a borehole, including the process steps (β1) drilling a hole in the ground by means of a drill pipe driven drill head, (β2) insertion a casing into the borehole, (β3) insertion of cement in at least a portion of the space between the outside of the casing and the walls of the wellbore, (Β4) optionally introducing a delivery pipe into the casing, (β5) optionally introducing a sealing liquid in the space between the outside of the conveyor tube and the inside of the Casing, with surfaces of the borehole, the Guide tube, the drill string or the drill head with a detergent containing an n-nonyl ether, as in one of claims 1 and 3 to 8 defined, in contact to be brought. A method of producing an oil or a gas, comprising the steps of (β1) drilling a wellbore into the soil by means of a drill bit driven by a drill string, (β2) inserting a casing into the wellbore, (β3) introducing cement into at least a portion of the space between the outside of the casing and the walls of the wellbore, (β4) optionally introducing a conveying tube in the casing, (β5) optionally introducing a sealing liquid into the space between the outside of the conveying tube and the inside of the casing, (β6) conveying oil or gas through the well, and (β7) cleaning or refining the casing funded oil or gas, wherein surfaces of the wellbore, the guide tube, the drill pipe or the drill head with a cleaning agent comprising an n-nonyl ether as defined in any one of claims 1 and 3 to 8, or with a composition comprising an n-nonyl ether, as defined in any one of claims 1 to 7, are brought into contact. A method of making wellbores, in which a drilling fluid is pumped through a borehole, being a drilling fluid containing a composition an n-nonyl ether as in any of claims 1 and 3 to 8 is used. The method of claim 14, wherein the composition is a water-in-oil emulsion. The method of claim 15, wherein the composition I) From 28.9 to 99% by weight, based on the total weight of the composition, of a water-immiscible, organic oil phase, II) From 1 to 48% by weight, based on the total weight of the composition, Water or aqueous phase, III) 0.1 to 20% by weight, based on the total weight of the composition, that in claims 1 and 3 to 8 defined n-nonyl ether, IV) 0 to 70% by weight, based on the total weight of the composition, at least one further additive, contains, where the sum of the components I) to IV) is 100% by weight. The method of claim 15 or 16, wherein the water-in-oil emulsion a nanoemulsion or a microemulsion which is water droplets or drops of an aqueous phase with a drop size in a range of 5 nm to 1000 μm. The method of claim 14, wherein the composition an aqueous solution or an oil-in-water emulsion is. The method of claim 18, wherein the composition I) 0 to 48% by weight, based on the total weight of the composition, a water-immiscible, organic oil phase, II) From 29.9 to 99.9% by weight, based on the total weight of the composition, Water or aqueous phase, III) 0.1 to 20% by weight, based on the total weight of the composition, that in claims 1 and 3 to 8 defined n-nonyl ether, IV) 0 to 70% by weight, based on the total weight of the composition, at least one further additive, contains, where the sum of the components I) to IV) is 100% by weight. Method according to one of claims 16 to 19, wherein the at least one additive selected an additive from the group consisting of thickeners, clays, agents against fluid loss, pH modifiers, viscosity modifiers, agents for filtration control, emulsifiers, salts, wetting agents, Weighting agents and dispersants. Method according to one of claims 14 to 20, including the process steps: (α1) providing a composition according to any one of claims 15 to 20; (Α2) drilling a hole in the ground; (α3) initiating, preferably the circulation in step (α1) provided at least partially into or in the borehole. The method of claim 21, wherein the initiating, preferably circulating at least partially during of drilling in process step (α2) takes place. A process for producing an oil or a gas containing the process steps (Α1) providing a composition according to any one of the claims 15 to 20; (α2) drilling a hole in the ground; (Α3) the introduction, preferably the circulation in the process step (α1) provided at least partially in or in the borehole; (α4) conveying of oil or gas from the earth by the in the process step (α2) drilled hole; (α2) optionally the Purification or refining of the process step (α3) subsidized oil or gas.