EP2240550A1

EP2240550A1 - Cleaning agents based on organic amine sulfates for drilling devices

Info

Publication number: EP2240550A1
Application number: EP09708051A
Authority: EP
Inventors: Heinz Müller; Diana MÄKER
Original assignee: Emery Oleochemicals GmbH
Current assignee: Emery Oleochemicals GmbH
Priority date: 2008-02-08
Filing date: 2009-02-06
Publication date: 2010-10-20
Also published as: WO2009098309A1; DE102008008250A1

Abstract

The invention relates to the use of a compound of general formula R-O-SO3-R1R2R3NH+ in which R represents a saturated, unsaturated, branched or linear alkyl radical comprising 6 to 22 carbon atoms, and R1, R2, and R3, which can be identical or different, represent a hydrogen atom or a saturated, unsaturated, branched or linear hydroxyalkyl radical comprising 1 to 5 carbon atoms, for cleaning boreholes, drilling devices, or drill cuttings. The invention further relates to a method for cleaning surfaces of boreholes, drilling devices, or drill cuttings, a method for creating a borehole, and a method for producing an oil or gas.

Description

Boron-based cleaning agents based on organic amine sulphate

The present invention relates to the use of a compound of the general formula ROS (VR ¹ R ² R ³ NH ⁺ , a method for cleaning surfaces of boreholes, drilling equipment or cuttings, a method for producing a borehole and a method for producing an oil or a gas.

When drilling and extracting oil or natural gas deposits, purification steps have to be added in many places in order to ensure trouble-free operation of the drilling and production process. Thus, after the actual drilling, the borehole must be prepared for the extraction of oil or gas (complete). To stabilize the borehole, an outer tube, called a casing or casing, is introduced and cemented in. The cement is passed through the tube in an aqueous, liquid form, emerges at the bottom of the casing and hardens between the borehole wall and outer In order to ensure an optimal cementing process, it is necessary to clear the borehole wall and casings of adhering residues of drilling mud and finely divided, adhering solids, otherwise there is a danger that voids or channels will be created in the concrete layer which will increase the stability of the concrete In addition, residues of the drilling mud with the cement can form a gelatinous mass which prevents setting of the cement, which also leads to reduced stability of the cement mantle.

After the casing has been placed in the well, the actual production tubing, which has a smaller diameter than the casing, is installed. Between the outer wall of the conveyor tube and the inner wall of the casing still a sealing liquid is introduced. Before the introduction of the sealing liquid, the so-called packer-ßuid "', the annulus between Casing and conveying pipe cleaned, in particular, all finely divided solids that still adhere to the casing or conveyor pipe wall must be removed to ensure the performance of the sealing liquid.

The selection of the cleaning agent suitable for the above-described tasks also depends on the type of drilling fluid used. In principle, one can distinguish between water-based and oil-based rinses. Today, oil-based rinses are often used, either as so-called "true-oil-muds", ie rinses containing no or only minor amounts, usually below 50% by weight, based on the rinse, dispersed water, or so-called invert muds ", Which contain between 5 and 45 wt .-% of water as a dispersed phase, so form a W / O emulsion. In addition, water-based OAV emulsions are known which contain a heterogeneous, finely dispersed oil phase in a closed aqueous phase. Petroleum products, such as mineral oils or diesel oils, are usually used as the oil phase. Due to the ever stricter environmental requirements but also synthetic oil phases have been developed recently, containing, for example, esters of certain fatty acids. Drilling muds based on such ester oils are described by way of example in the publications EP-A-0 386 636, EP-A-0 374 671 and EP-A-0 374 672 and show markedly improved properties with respect to their biodegradability and toxicity compared to petroleum products.

The cleaning agents, like the cement during the cementing process, are pumped down in liquid form through the drill string, emerge at the bottom of the borehole and are flushed upwards in the annular space between the pipe and the borehole wall. In doing so, they dissolve residues of the drilling fluid and solid particles adhering to the surfaces and transport them out of the borehole. Such a method is described in detail, for example, in WO-A-94/29570. The agents are usually used in the form of aqueous or nonaqueous solutions or dispersions. However, they can also be added in concentrated form directly to the drilling mud. cleaning supplies For the above-described objects, for example, mixtures of citric acid, pyrophosphate and potassium salts, which are used in solid or dissolved form. These agents are suitable for true-oil as well as invert drilling fluids.

WO-A-95/17244 describes a composition for cleaning oil-contaminated surfaces having surfactants with HLB values of at least 8, in combination with an oil. Preferred surfactants mentioned are ethoxylated sorbitan fatty acid esters. Although agents based on ethoxylated sorbitan fatty acid esters have good detergency, but in terms of biodegradability and toxicity, such agents may not yet meet all the requirements required by increasingly stringent environmental legislation.

In WO-A-98/19043, specific soy polyol alkoxylates are disclosed as highly effective cleaning agents for drilling equipment, while WO-A-2006/007977 teaches the use of lithium salts of fatty alcohol sulfates for cleaning wells, drills or cuttings.

It is an object of the present invention to overcome, at least in part, the drawbacks associated with cleaning devices for boreholes, boring devices or cuttings that arise from the prior art.

In particular, the present invention has the object to provide a cleaning agent for cleaning boreholes, drilling equipment or cuttings, which is not only toxicologically safe, but also in comparison to the known from the prior art detergents by improved ecotoxicity with comparable application properties characterized in particular with comparable seawater solubility or detergency. A contribution to the solution of the abovementioned objects is afforded by the use of a compound of the general formula

RO-SO ₃ ^" R ¹ R ² R ³ NH ⁺

in the

R is a saturated, unsaturated, branched or linear alkyl radical having 6 to 22 carbon atoms, more preferably 8 to 16 carbon atoms, even more preferably 10 to 14 carbon atoms, and most preferably 12 carbon atoms, and

R ¹ , R ² and R ^{3 represent} a saturated, unsaturated, branched or linear hydroxyalkyl radical having 1 to 5 carbon atoms, more preferably 1 to 4 carbon atoms, even more preferably 1 to 3 carbon atoms and most preferably 2 carbon atoms, or for a are hydrogen, where the radicals R ^1, R ² and R ³ may be the same or different,

for cleaning boreholes, drilling equipment or cuttings.

It should be noted at this point that not the entire amount of the compound of the general formula RO-SO ₃ ^" R ¹ R ² R ³ NH ⁺ must be present in the form in which the alkyl sulfate is deprotonated and the hydroxyalkylamine is protonated (as in US Pat in the formula RO-SO ₃ ^" R ¹ R ² R ³ NH ⁺ indicated). Rather, depending on the pH of the composition in which the compound of the general formula RO-SO ₃ ^" R ¹ R ² R ³ NH ⁺ is present, the alkyl sulfate also at least partially protonated and the hydroxyalkylamine at least partially

- A - can be deprotonated (so that the compound can be at least partially described by the general formula RO-SO ₃ H • R ¹ R ² R ³ N)

The anions ROS (V (alkyl sulfates) are preferably the sulfation products of primary alcohols, preferably the sulfation products of fatty alcohols, which are obtainable by reacting fatty alcohols with concentrated sulfuric acid, gaseous sulfur trioxide, chlorosulfonic acid or sulfamic acid A high water-solubility, low hardness sensitivity and, if the chain length is sufficient, a high detergency Typical examples of alkyl sulfates which can be used in accordance with the invention are the sulfation products of caproic alcohol, caprylic alcohol, capric alcohol, 2-ethylhexyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol , Palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol and erucyl alcohol, and technical mixtures thereof obtained by high-pressure hydrogenation of technical methyl ester fraction nen or aldehydes can be obtained from the Roelen oxo synthesis. Particularly preferred are alkyl sulfates based on fatty alcohols having 8 to 16 carbon atoms, more preferably those based on fatty alcohols having 10 to 14 carbon atoms, with lauryl sulfate as the anion R-O-S (V is most preferred.

Furthermore, it may be in the compound of the general formula RO-SO ₃ ^"

R ¹ R ² R ³ NH ⁺ also be a mixture containing various alkyl sulfates. In this connection, however, it is particularly preferred that at least 50% by weight, more preferably at least 70% by weight, still more preferably at least 90% by weight, and most preferably at least

95 wt .-% of the anions RO-SO ₃ ^" consist of lauryl sulfate.

In connection with the cation R ¹ R ² R ³ NH ⁺ , it is particularly preferred according to the invention that at least one of the radicals R ¹ , R ² or R ^{3 is} -CH ₂ CH ₂ -OH-ReSt. In this context, it is further preferred that the cation R ¹ R ² R ³ NH ^{+ is} a cation selected from the group consisting of the ammonium salt of monoethanolamine, diethanolamine, triethanolamine or a mixture of at least two thereof, the ammonium salt of monoethanolamine is particularly preferred.

As in the case of the anion ROS (V, the compound of the general formula ROS (VR ¹ R ² R ³ NH ^{+ may} also be a mixture which contains various cations R ¹ R ² R ³ NH ⁺ however, it is particularly preferred that at least 50% by weight, more preferably at least 70% by weight, even more preferably at least 90% by weight and most preferably at least 95% by weight of the cations R ¹ R ² R ³ NH ⁺ consist of the ammonium salt of monoethanolamine.

Very particular preference according to the invention as a compound of the general formula RO-SO ₃ ^" R ¹ R ² R ³ NH ⁺ is a compound selected from the group consisting of monoethanolamine lauryl sulfate, diethanolamine lauryl sulfate, triethanolamine lauryl sulfate or a mixture of at least two of these sulfates, with monoethanolamine lauryl sulfate on most preferred.

The preparation of the compound having the general formula RO-SO ₃ ^"

R ¹ R ² R ³ NH ⁺ can be prepared, for example, by mixing the anion in the protonated form, for example lauric sulfuric acid, with the corresponding

R ¹ R ² R ³ N compound in the base form, for example with monoethanolamine,

Diethanolamine. Triethanolamine or a mixture of at least two of these bases. In the case of the use of monoethanolamine as a compound having the general formula ROS O ₃ ^"R ¹ R ² R ³ NH ^+, this compound can also commercially, for example under the trade name of Texaco pon ^® by the company Cognis GmbH, Germany, is related.

According to a particular embodiment of the inventive use of the compound having the general formula RO-SO ₃ ^" R ¹ R ² R ³ NH ⁺ can this in In particular, ethoxylated fatty alcohols and especially with 2 to 10 ethylene oxide units, more preferably with 2 to 8 ethylene oxide units, even more preferably with 2 to 6 ethylene oxide units and most preferably with 4 E - Ethylene oxide units ethoxylated fatty alcohols are preferred. Fatty alcohols are, in particular C ₆ - to C-fatty alcohols, still more preferably Cs to C ₁₂ - fatty alcohols are suitable, wherein Cs-fatty alcohols are most preferred. Suitable fatty alcohols are, for example, selected from the group consisting of caproic alcohol, caprylic alcohol, capric alcohol, 2-ethylhexyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, galdoleyl alcohol, behenyl alcohol and erucyl.

According to the invention particularly preferred alkoxylated fatty alcohols, which (in combination with the compound of the general formula ROS VR ¹ R ² R ³ NH ⁺ may be used, in particular with 4 ethylene oxide units, ethoxylated C 8 fatty alcohols such as, for example, under the trade designation De- hydol ^® 04 are available from Cognis.

In connection with the combined use of the compound of the general formula ROS (VR ¹ R ² R ³ NH ⁺ and the alkoxylated fatty alcohol, it is further preferred that the compound of the general formula RO-SO ₃ ^" R ¹ R ² R ³ NH ⁺ and the alkoxylated fatty alcohol is used in a relative weight ratio ranging from 5: 1 to 1: 5, more preferably from 4: 1 to 1: 4, and most preferably from 2: 1 to 1: 2, particularly in the case of 4 ethylene oxide units, ethoxylated Cs fatty alcohol as the alkoxylated fatty alcohol of the insert in a relative ratio compound of the general formula RO-SO ₃ ^"R ¹ R ² R ³ NH ^+: alkoxylated fatty alcohol is from 1.5: 1 to 1: 1.5, and in particular of 1: 1, whereby the compound of the general formula RO-SO ₃ ^" R ¹ R ² R ³ NH ⁺ and the alkoxylated fatty alcohol in the form of separate solutions or in a single solution in which both compounds are present, the use in a single solution being particularly preferred. In this solution, these two compounds are then present in the above-mentioned relative proportions.

According to another particular embodiment of the inventive use of the compound having the general formula ROS (VR ¹ R ² R ³ NH ⁺ can this in combination with a compound of general formula

R ^{4 is} -O- [CH ₂ CR ⁵ HO] "- R ⁶ -COOH,

be used in the

R ^{4 is} a saturated, unsaturated, branched or linear alkyl radical having 4 to 20 carbon atoms, particularly preferably having 6 to 12 carbon atoms and most preferably having 8 to 10 carbon atoms,

R ^{5 is} a methyl radical or a hydrogen atom, particularly preferably a hydrogen atom,

n is an integer in a range of 2 to 20, more preferably 3 to 16, and most preferably 4 to 6, and

R ^{6 is} an alkylene radical having 1 to 10 carbon atoms, more preferably having 1 to 4 carbon atoms, and most preferably a methylene radical

stand.

Conceivable as a compound of the general formula

R ⁴ -O- [CH ₂ CR ⁵ HO] "- R ⁶ -COOH in particular, a mixture in which at least two different compounds of the general formula R ⁴ -O- [CH ₂ CR ⁵ HO] "- R ⁶ -COOH may be contained, wherein these two different compounds may differ, for example, in their radical R ⁴ , in the number of ethylene oxide or propylene oxide units or in both ,

Particularly preferred according to the invention is the use of a compound of the general formula R ⁴ -O- [CH ₂ CR ⁵ HO] "- R ⁶ -COOH, in which

R ^{4 is} a saturated alkyl radical having 8 carbon atoms, R ^{5 is} a hydrogen atom, n is the number 5 and R ^{6 is} a methylene radical, - R ^{4 is} a saturated alkyl radical having 8 carbon atoms, R ^{5 is} a Hydrogen atom, n is the number 8 and R ^{6 is} a methylene radical, or

R ^{4 is} a saturated alkyl radical having 12 or 14 carbon atoms, R ^{5 is} a hydrogen atom, n is the number 10 and R ^{6 is} a methylene radical.

In this connection, particularly preferred are for example the products commercially available from Kao under the trade name Akypo ^® as Akypo ^® LF 1 (ether carboxylic acid-based octanol, ethoxylated with 5 moles of ethylene oxide), Akypo ^® LF 2 (ether carboxylic acid-based octanol ethoxylated with 8 moles of ethylene oxide), Akypo RLM 100 ^® (ether carboxylic acid based on C 12/14 alcohol ethoxylated with 10 moles ethylene oxide). A according to the invention suitable mixture in which at least two different compounds of the general formula R ⁴ -O- [CH ₂ CR ⁵ HO] "- R may be contained ⁶ -COOH, for example, by the company Kao under the trade name Akypo ^® LF 4 available product which is a mixture of a compound in which R ^{4 is} a heptyl radical, R ^{5 is} a hydrogen atom, n is the number 9 and R ^{6 is} a methylene radical, and a compound in which R ^{4 is} a hexyl radical, R ^{5 is} a hydrogen atom, n is the number 4 and R ^{6 is} a methylene radical. In connection with the combined use of the compound of general formula ROS (VR ¹ R ² R ³ NH ⁺ and the compound of general formula R ⁴ -O- [CH ₂ CR ⁵ HO] "- R ⁶ -COOH it is furthermore preferred that the compound of the general formula ROS (VR ¹ R ² R ³ NH ⁺ and the compound of the general formula R ⁴ -O- [CH ₂ CR ⁵ HO] "- R ⁶ -COOH in a relative weight ratio in a range of 5: 1 to 1: 5, more preferably from 4: 1 to 1: 4, and most preferably from 2: 1 to 1: 2 are used, wherein in particular in the case of an ethoxylated with 6 ethylene oxide units Cs-ether carboxylic acid as the compound general formula R ⁴ -O- [CH ₂ CR ⁵ HO] "- R ⁶ -COOH the use in a relative ratio of compound of the general formula RO-SO ₃ ^" R ¹ R ² R ³ NH ⁺ : compound of general formula R ⁴ -O- [CH ₂ CR ⁵ HO] "- R ⁶ -COOH of 1.5: 1 to 1: 1.5 and in particular of 1: 1. In this case, the compound of the general n formula RO-SO ₃ ^" R ¹ R ² R ³ NH ⁺ and the compound of the general formula R ⁴ -O- [CH ₂ CR ⁵ HO]" - R ⁶ -COOH in the form of separate solutions or in a single solution, in the two compounds are present, the use in a single solution is particularly preferred. In this solution, these two compounds are then present in the above-mentioned relative proportions.

Furthermore, it is preferred according to the invention for the compound of the general formula RO-SO ₃ ^" R ¹ R ² R ³ NH ^{+ to be present} in the form of an aqueous composition which is, for example, an aqueous solution, an aqueous dispersion or an oil-in-oil. Water emulsion can be, including

(αl) 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

Compound of the general formula RO-SO ₃ ^" R ¹ R ² R ³ NH ⁺ (cc2) 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 the compound of the general formula ROS (VR ¹ R ² R ³ NH ⁺ various additives, where as additives also the abovementioned alkoxylated fatty alcohol or the abovementioned compound of the general formula R ⁴ -O- [CH ₂ CR ⁵ HO] R ⁶ -COOH can be included as well

(cc3) 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 (αl) to (α3) is 100 wt .-% is used.

In particular, the amount of component (αl) in the aqueous composition can vary and is adapted to the nature and extent of the contamination.

When the compound of the general formula RO-SO ₃ ^"R ¹ R ² R ³ NH ^+, various additives (α2), come in addition to the already above-mentioned alcohol-xylierten fatty alcohols or in addition to the ready above-mentioned compound of the general formula R ⁴ -O - [CH ₂ CR ⁵ HO] "- R ⁶ -COOH, in particular weighting agents, fluid-loss additives, viscosity-regulating additives, wetting agents or salts, in which case the general rules for the composition of the respective treatment liquids apply.

The concomitant use of organic polymer compounds of natural and / or synthetic origin may prove advantageous. Particularly noteworthy here are 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.

Also useful as an additive are thinners for viscosity control, these thinners may be organic or inorganic nature and include, inter alia, tannins and / or Qebracho Extrak, lignite and lignite derivatives, in particular lignosulfonates include.

The compound of the general formula ROS (VR ¹ R ² R ³ NH ⁺ is used according to the invention for the cleaning of boreholes, in particular the walls of boreholes, conveyor or casing pipes or walls of the casing, as well as for cleaning drilling equipment or cuttings.

In particular drilling equipment, such as the derrick, the drill string, in particular the drill pipe and the drill bit, cleaning equipment, plant for solids disposal, in particular shakers or centrifuges, pumps, motors or gearboxes, or the drilling platform or parts thereof. To clean the drilling equipment, the compound of the general formula ROS (VR ¹ R ² R ³ NH ⁺ , preferably in the form of the aqueous composition described above, is sprayed or applied to the surfaces of the articles or the articles to be cleaned are immersed in the aqueous compositions. In the process, the contaminants are removed from the surfaces and the surfaces are brought into contact with water in such a way that the agents are removed together with the impurities, for example by spraying the surface with a stream of water.

Furthermore, the compound of the general formula RO-SO ₃ ^" R ¹ R ² R ³ NH ^{+ can be used} for cleaning cuttings, the so-called" cut " These occur during drilling and must be deposited in offshore drilling on the bottom of the lake in the vicinity of the drilling platform, which can lead to a strong input of mineral oil into the environment in order to avoid an environmental pollution of the sea, the cuttings upstream forth cleaned and freed of residues of the drilling mud. the compound of general formula ROS (VR ¹ R ² R ³ NH ⁺ can all known in the art cleaning processes which occur in geological drilling both off-shore Typically, wellbores are cleaned by pumping a cleaning fluid under pressure through the wellbore and removing the debris from the walls of the wellbore by the cleaning fluid Then the impurities are mixed with the liquid from the boh transported.

A contribution to achieving the abovementioned objects is also provided by a method for cleaning the surfaces of boreholes, drilling devices or drill cuttings, the surfaces initially comprising a cleaning fluid comprising the compound of the general formula RO-SO ₃ ^" R ¹ R ² R ³ NH ⁺ , preferably being an aqueous composition as described above, and optionally rinsing the surfaces with water.

According to a preferred embodiment of the inventive method for cleaning the surfaces of boreholes this includes the process steps

(ßl) drilling a borehole in the ground by means of a drill bit driven by a drill string,

(ß2) the insertion of a casing into the well, as well (ß3) the introduction of cement into at least a portion of the space between the outside of the casing and the walls of the wellbore,

wherein prior to carrying out the method step (β3), the cleaning liquid 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 can be effected, for example, by the cleaning fluid being pumped down through the casing, preferably down the drill pipe, at the bottom of the casing, preferably on the drill bit or drill bit, and then through the space between the outside of the casing and the walls of the borehole rises again. If the cleaning liquid 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 a preferred embodiment of the method according to the invention for cleaning the surfaces of drilling devices, the method comprises the step of drilling a borehole into the ground by means of a drill bit driven by a drill string, the cleaning liquid comprising the compound of the general formula ROS (VR ¹ R ² R ³ NH ⁺ at least partially passed through, preferably at least partially circulated through, the boring head, said passage being at least partially during the presence of the boring head in the borehole.

In particular, drills, such as the derrick, the drill string, in particular the drill string and the drill bit, cleaning systems, plant for solid disposal, in particular shaking, come as drilling devices whose surface can be cleaned with the cleaning fluid. sieves or centrifuges, pumps, motors or gears, or the drilling platform or parts thereof.

A contribution to the solution of the abovementioned objects is also made by a method for producing a borehole, including the method steps

(ß2) the insertion of a casing into the well,

(ß3) the introduction of cement into at least a portion of the space between the outside of the casing and the walls of the wellbore,

(ß4) optionally introducing a delivery pipe into the casing,

(ß5) optionally introducing a sealing liquid in the space between the outside of the conveying tube and the inside of the casing,

wherein surfaces of the wellbore, the guide tube, the drill string or the drill head are contacted with a cleaning liquid comprising the compound of the general formula ROS (VR ¹ R ² R ³ NH ⁺ , which is preferably the above-described aqueous composition 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 (.beta.3), the cleaning liquid containing the compound of the general Formula RO-SO ₃ ^" R ¹ R ² R ³ NH ⁺ through the space between the ßenseite of the casing and the walls of the wellbore, preferably through this space is circulated.

As sealing liquid, which is introduced in step (ß5) in the space between the outside of the conveying tube and the inside of the casing, all known to the expert for this purpose materials can be used. As an example, at this point those sealing liquids are mentioned, which are described in US 7,219,735.

A further contribution to the solution of the abovementioned objects is also provided by a process for producing 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

(ß6) the conveyance of oil or gas through the borehole, as well

(β7) purifying or refining the oil or gas being pumped,

Here, too, the surfaces of the borehole, of the conveyor pipe, of the drill string or of the drill head are provided with a cleaning liquid containing the compound of the general formula ROS (VR ¹ R ² R ³ NH ⁺ , which is preferably the above-described aqueous composition Again, 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 rigs.

The invention will now be explained in more detail by way of non-limiting examples.

EXAMPLES 1. Measurement of the cleaning effects

Tests were carried out with the detergents according to the invention. For this purpose, 8 g of a drilling fluid were applied with a brush to the inside of a (pre-weighed) measuring cup. Subsequently, 250 ml of the 1.5% by weight (based on the amount of active substance) aqueous cleaning solution was added to the beaker and stirred for 3 minutes in an IKA laboratory stirrer at 700 rpm.

The measuring cup is placed on a filter paper with the opening facing downwards for 2 minutes. Thereafter, the weight of the measuring cup is determined. The weight loss is a measure of the cleaning performance. If, theoretically, the measuring cup were to reach the weight before the measurement, this would be rated as 100% cleaning performance.

The drilling fluid had the following composition:

Ester oil C ₈ -C ₄ fatty acid 2-ethylhexyl ester 250 ml

Emulsifier (Amidoamine) 10 g Fluid loss additive (hydrophobized lignite) 10 g

Lime 12 g

CaCl ₂ × 2 H ₂ O 27 g

Weight (calcium carbonate) 100 g

BaSO ₄ 100 g Hymond Prima Clay 43 g

Water 84 g

The oil / water ratio was 75:25. The drilling mud was aged at 200 ^° F (93 ^° C) for 16 hours. The results of the test are shown in Table 1: The following cleaning solutions were used and the following cleaning effects were achieved:

Table 1

¹ ^ For surfactant mixtures (Examples 2 and 3) were 0.75 wt .-% of Monoethano laminlaurylsulfates and 0.75 wt .-% of the Cs-ether carboxylic acid having 6 ethylene oxide units and the Cs fatty alcohol having 4 ethylene oxide units in of the cleaning solution.

In a further test, the toxicity and the biodegradability of the inventive Hy droxyalkylamin- salts compared to the biodegradability of WO-A-2006/007977 described lithium salts was tested. The toxicity was measured on cells of the genus Arcatia tonsa (according to ISO 10253, 1988). The biodegradation was determined by an aerobic degradation test (Marine Bodies ISO / TC 147 / SC 5AVG 4 N 141). The results are shown in Table 2: Table 2

Claims

claims

1. Use of a compound of the general formula

RO-SO ₃ ^" R ¹ R ² R ³ NH ⁺

in the

R is a saturated, unsaturated, branched o- or linear alkyl radical having 6 to 22 carbon atoms and

R ¹ , R ² and R ^{3 represent} a saturated, unsaturated, branched or linear hydroxyalkyl radical having 1 to 5 carbon atoms or a hydrogen atom, where the radicals R ¹ , R ² and R ^{3 may be} identical or different,

for cleaning boreholes, drilling equipment or drill bits.

2. Use according to claim 1, wherein the radical R is a saturated, unsaturated, branched or linear alkyl radical having 8 to 16 carbon atoms.

3. Use according to claim 2, wherein the anion RO-SO ₃ ^"is lauric sulfate.

4. Use according to one of the preceding claims, wherein at least one of the radicals R ¹ , R ² or R ^{3 is} a -CH ₂ CH ₂ -OH-ReSt.

5. Use according to one of the preceding claims, wherein the cation R ¹ R ² R ³ NH ^{+ is} a cation selected from the group consisting of the ammonium salt of monoethanolamine, diethanolamine, triethanolamine or a mixture of at least two thereof.

6. Use according to one of the preceding claims, wherein the compound of the general formula

RO-SO ₃ ^" R ¹ R ² R ³ NH ⁺

Monoethanolaminlaurylsulfat is.

7. Use according to one of the preceding claims, wherein the compound of the general formula RO-SO ₃ ^" R ¹ R ² R ³ NH ^{+ is used} in combination with an alkoxylated fatty alcohol.

8. Use according to claim 7, wherein the alkoxylated fatty alcohol is an ethoxylated with 2 to 10 ethylene oxide units C ₆ - to cis-fatty alcohol.

The use according to any one of claims 7 or 8, wherein the compound has the general formula RO-SO ₃ ^" R ¹ R ² R ³ NH ⁺ and the alkoxylated fatty alcohol in a relative weight ratio ranging from 5: 1 to 1: 5 be used.

10. Use according to any one of claims 1 to 6, wherein the compound of the general formula RO-SO ₃ ^" R ¹ R ² R ³ NH ⁺ in combination with a compound of general formula

R ^{4 is} -O- [CH ₂ CR ⁵ HO] "- R ⁶ -COOH, in the

R ^{4 is} a saturated, unsaturated, branched or linear alkyl radical having 4 to 20 carbon atoms,

R ^{5 is} a methyl radical or a hydrogen atom, n is an integer in the range of 2 to 20, and

R ^{6 is} an alkylene radical having 1 to 10 carbon atoms

stands.

11. Use according to claim 10, wherein

R ^{4 is} a saturated alkyl radical having 6 to 10 carbon atoms,

R ^{5 represents} a hydrogen atom, n represents an integer in the range of 4 to 8, and

R ^{6 is} a methylene radical

stands.

12. The use according to any one of claims 9 or 10, wherein the compound of the general formula RO-SO ₃ ^" R ¹ R ² R ³ NH ⁺ and the compound of the general formula R ⁴ -O- [CH ₂ CR ⁵ HO]" R ⁶ -COOH in a relative weight ratio in a range of 5: 1 to 1: 5 are used.

13. The use according to any one of the preceding claims, wherein the compound of the general formula ROS (VR ¹ R ² R ³ NH ⁺ in the form of an aqueous composition comprising

(αl) from 0.1 to 50% by weight of the compound of the general formula RO-SO ₃ ^" R ¹ R ² R ³ NH ⁺ ,

(cc2) 0 to 50 wt .-% more, of the compound of the general

Formula RO-SO ₃ ^" R ¹ R ² R ³ NH ⁺ various additives, and (oc3) 1 to 99.9 wt .-% water, wherein the sum of the components (αl) to (α3) is 100 wt .-% , is used.

14. A method for cleaning the surfaces of boreholes, drilling devices or drill cuttings, the surfaces being initially filled with a cleaning fluid comprising the compound of the general formula RO-SO ₃ ^'' R ¹ R ² R ³ NH ⁺ , as in one of claims 1 to 6, or contacted with a composition as defined in claim 13, and optionally rinsing the surfaces with water subsequently.

15. The method of claim 14, including the method steps

(ßl) drilling a borehole in the ground by means of a over

Drill pipe driven drill head,

(ß2) the insertion of a casing into the borehole, and (ß3) the introduction of cement into at least a portion of the space between the outside of the casing and the walls of the borehole, wherein before performing the method step (ß3) the cleaning liquid comprising the compound of general formula RO-SO ₃ ^" R ¹ R ² R ³ NH ⁺ , as defined in any one of claims 1 to 6, or the composition as defined in claim 13, by the Space between the outside of the casing and the walls of the wellbore guided, preferably in this space is circulated.

16. The method of claim 14, including the method steps

(ßl) drilling a borehole in the ground by means of a over

A drill pipe driven drill head, wherein the cleaning fluid comprising the compound of the general formula ROS (VR ¹ R ² R ³ NH ⁺ , as defined in any of claims 1 to 6) or the composition as defined in claim 13, at least partially through the drill head this passage is at least partially made during the presence of the drill bit in the wellbore.

17. A method for producing a borehole, comprising the method steps (ßl) drilling a borehole in the ground by means of a via a

(Ss2) inserting a casing into the borehole, (ß3) introducing cement into at least a portion of the drill pipe

Space between the outside of the casing and the walls of the well,

(ß4) optionally introducing a delivery pipe into the casing, (ß5) optionally introducing a sealing liquid in the

Gap 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 with a cleaning fluid containing the compound of the general formula RO-SO ₃ ^" R ¹ R ² R ³ NH ⁺ , as in one according to claims 1 to 6, or are brought into contact with a composition as defined in claim 13.

18. A process for producing an oil or a gas, including the process steps

(ßl) drilling a borehole in the ground by means of a over

(B2) inserting a casing into the borehole, (ß3) introducing cement into at least a portion of the space between the outside of the casing and the walls of the wellbore,

(ß4) optionally introducing a delivery pipe into the casing,

(β6) conveying oil or gas through the wellbore, and (ß7) purifying or refining the extracted oil or gas, with surfaces of the wellbore, guide tube, drill string or drill head containing a cleaning fluid containing the

A compound of the general formula ROS (VR ¹ R ² R ³ NH ⁺ as defined in any one of claims 1 to 6 or brought into contact with a composition as defined in claim 13).