DE102009041983A1 - Alkoxylated trialkanolamine condensates and their use as emulsion breakers - Google Patents

Abstract

The invention relates to the use of alkoxylated trialkanolamine condensates, obtainable by alkaline-catalyzed condensation of trialkanolamines and subsequent alkoxylation with at least one C- to C-alkylene oxide, with a number average molecular weight of 500 to 500,000 g / mol, which comprise 2 to 250 trialkanolamine units, and whose average degree of alkoxylation is between 1 and 200 alkylene oxide units per free OH group, in amounts of 0.0001 to 5% by weight, based on the oil content of the emulsion to be split, for splitting water into oil emulsions.

Description

The present invention relates to alkoxylated trialkanolamine condensates, the use of alkoxylated trialkanolamine condensates for cleaving water-oil emulsions, especially in crude oil production, and a process for cleaving a water-in-oil emulsion by adding at least one alkoxylated trialkanolamine condensate to the emulsion.

Crude oil accumulates in its promotion as an emulsion with water. Before further processing of the crude oil these crude oil emulsions must be split into the oil and water content. For this one uses in general so-called crude oil or Erdölemulsionsspalter, or also briefly called "petroleum breaker". Petroleum breakers are surface-active polymeric compounds capable of effecting, within a short time, the required separation of the emulsion components.

As demulsifiers are mainly alkoxylated alkylphenol-formaldehyde resins, nonionic alkylene oxide block copolymers and crosslinked with Bisepoxiden variants used. Provide overviews "Something Old, Something New: A Discussion about Demulsifiers", TG Balson, pp. 226-238 in Proceedings in the Chemistry in the Oil Industry VIII Symposium, Nov. 3 - 5, 2003, Manchester, UK , such as "Crude Oil Emulsions: A State-Of-The-Art Review", S. Kokal, pp. 5-13, Society of Petroleum Engineers SPE 77497 ,

U.S. 4,032,514 discloses the use of alkylphenol-aldehyde resins to cleave petroleum emulsions. These resins are obtainable from the condensation of a para-alkylphenol with an aldehyde, mostly formaldehyde.

Such resins are often used in alkoxylated form, such as in DE-A-24 45 873 is disclosed. For this purpose, the free phenolic OH groups are reacted with an alkylene oxide.

In addition to the free phenolic OH groups and free OH groups of alcohols or NH groups of amines can be alkoxylated, such as in U.S. 5,401,439 is disclosed.

As further petroleum emulsion breakers are in U.S. 4,321,146 Alkylene oxide block copolymers and in U.S. 5,445,765 alkoxylated polyethyleneimines.

Alkoxylated dendritic polyesters (dendrimers) are biodegradable (OECD 306) petroleum emulsion breakers in DE-A-103 29 723 disclosed. Also according to OECD 306 biodegradable splitters are in DE-A-103 25 198 disclosed. These are alkoxylated, crosslinked polyglycerols.

The disclosed cleavers can be used as individual components, in mixtures with other emulsion breakers, or else as crosslinked products.

Polycondensates of alkanolamines, preferably triethanolamine polycondensates, are described as inverse demulsifiers (oil-in-water emulsions). The condensation can be carried out with basic catalysts, such as in U.S. 2 407 895 disclosed or with acidic catalysts such as in U.S. 4,505,839 or DE-A-40 03 243 revealed, done.

WO-2009/060060 discloses the use of alkoxylated condensates of trialkanolamines obtained by acid catalyzed condensation of trialkanolamines. However, acid catalyzed trialkanolamine condensates have the disadvantage that they reach a very high molecular weight and that the condensation reaction is poorly controllable.

The different properties (eg asphaltene, paraffin and salinity, chemical composition of natural emulsifiers) and water content of various crude oils make it essential to further develop the existing oil splitters. In particular, a low metering rate and broad applicability of the oil separator to be used in addition to the desired higher efficiency from an economic and environmental point of view in the foreground.

It was thus the task of developing new oil splitters, which are the equivalent or superior to the already known Erdölspaltern in effect, and can be used in even lower dosage.

It surprisingly turned out that alkoxylated trialkanolamine condensates obtained by alkaline condensation show an excellent action as petroleum breakers even at very low dosages.

The invention therefore relates to the use of alkoxylated trialkanolamine condensates, obtainable by alkaline-catalyzed condensation of trialkanolamines and subsequent alkoxylation with at least one C ₂ -C ₄ -alkylene oxide having a number-average molecular weight of 500 to 500,000 g / mol, containing 2 to 250 trialkanolamine units and whose average degree of alkoxylation is between 1 and 200 alkylene oxide units per free OH group, in amounts of 0.0001 to 5 wt .-%, based on the oil content of the emulsion to be cleaved, for the splitting of water in oil emulsions.

Another object of the invention is a process for the cleavage of a water-in-oil emulsion by the emulsion 0.0001 to 5 wt .-%, based on the weight of the emulsion, of at least one alkoxylated trialkanolamine condensate is added, which catalyzed by alkaline Condensation of trialkanolamines and subsequent alkoxylation with at least one C ₂ - to C ₄ -alkylene oxide is obtainable, and has a number-average molecular weight of 500 to 500,000 g / mol and 2 to 250 trialkanolamine units, and whose average degree of alkoxylation 1 to 200 alkoxy units per free OH Group is.

The invention further provides alkoxylated trialkanolamine condensates obtainable by alkaline-catalyzed condensation of trialkanolamines and subsequent alkoxylation with at least one C ₂ -C ₄ -alkylene oxide, such that the average degree of alkoxylation is 1 to 200 alkoxy units per free OH group, and 2 to 250 trialkanolamine units and have a number average molecular weight of 500 to 500,000 g / mol.

In a preferred embodiment, the molecular weight of the alkoxylated trialkanolamine condensates is from 1,000 to 350,000 g / mol.

The trialkanolamine condensate is prepared by alkaline-catalyzed condensation of trialkanolamines. There are trialkanolamines of the general formula N (CH ₂ CHR ¹ OH) (CH ₂ CHR ² OH) (CH ₂ CHR ³ OH) where R ¹ , R ² and R ^{3 are} independently H, methyl, ethyl or phenyl.

Examples of usable monomers for the polycondensation reaction are triethanolamine, triisopropanolamine, tris (2-hydroxybutyl) amine, diethanolisopropanolamine, diethanol-2-hydroxy-2-phenylethanamine, diisopropylethanolamine, and mixtures thereof.

The reaction temperature for the condensation reaction is generally between 150 and 300 ° C, preferably between 240 and 280 ° C. The reaction is usually carried out under atmospheric pressure. It can z. B. NaOH or KOH can be used as catalysts. The catalyst is used in amounts of 0.1 to 25 wt .-% based on the weight of the reaction mixture. The condensation generally takes 1-24 hours, preferably 3-16 hours.

worin R¹, R² und R³ unabhängig voneinander für H, Methyl, Ethyl oder Phenyl stehen, und R⁴, R⁵ und R⁶ unabhängig voneinander für OH oder eine Gruppe der Formel (2)

stehen, mit der Maßgabe, dass nicht alle Reste R⁴, R⁵ und R⁶ gleichzeitig für OH stehen.The trialkanolamine polycondensates thus obtained can be represented by the formula (1)

in which R ¹ , R ² and R ³ independently of one another are H, methyl, ethyl or phenyl, and R ⁴ , R ⁵ and R ⁶ independently of one another are OH or a group of the formula (2)

with the proviso that not all radicals R ⁴ , R ⁵ and R ^{6 are} simultaneously OH.

The resulting branched structures contain 2 to 250 of the trialkanolamine units. The degree of condensation increases with increasing reaction time, and is determined by determining the OH number.

The determination of the OH number is carried out according to Standard DIN 53240 of December 1971 , Preferably, the OH number is between 450-800 mgKOH / g of substance.

wobei R¹, R² und R³ unabhängig voneinander für H, Methyl, Ethyl oder Phenyl, und R⁴, R⁵ und R⁶ unabhängig voneinander für OH oder eine Gruppe der Formel (2) stehen.Due to the trifunctionality of the trialkanolamines used for the condensation, structural units are formed which can be represented by formula (3) (polycondensate chain end), formula (4) (linear polycondensate chain part) and formula (5) (branched polycondensate chain part). A trialkanolamine unit is understood here to mean the trivalent radical which results from formula (1) by the formal abstraction of the radicals R ⁴ , R ⁵ and R ⁶ .

wherein R ¹ , R ² and R ^{3 are} independently H, methyl, ethyl or phenyl, and R ⁴ , R ⁵ and R ^{6 are} independently OH or a group of formula (2).

The trialkanolamine polycondensates obtained from the alkali-catalyzed condensation are then alkoxylated with at least one C ₂ -C ₄ -alkylene oxide. The alkylene oxide is used in molar excess. The alkoxylation is carried out, as known in the art, by reacting the trialkanolamine polycondensates with an alkylene oxide under elevated pressure of generally 1.1 to 20 bar at temperatures of 50 to 200 ° C. The alkoxylation takes place on the free OH groups of the trialkanolamine polycondensates.

So much alkylene oxide is used that the average degree of alkoxylation is between 1 and 200 alkylene oxide units per free OH group. By average degree of alkoxylation is meant here the average number of alkoxy units attached to each free OH group. It is preferably from 5 to 150, in particular from 10 to 100.

The alkylene oxide is preferably ethylene oxide, propylene oxide or a mixture of ethylene oxide and propylene oxide. The alkoxy groups can be arranged in blocks or randomly.

worin
R¹, R² und R³ die oben angegebene Bedeutung haben, und R⁴, R⁵ und R⁶ unabhängig voneinander für eine Gruppe der Formel (7)

oder eine Gruppe der Formel (8) stehen -O-(B-O)_m-(A-O)_n-H (8) worin A und B für voneinander verschiedene C₂- bis C₄-Alkoxygruppen, bevorzugt Ethylen- oder Propylengruppen, und n und m für ganze Zahlen von 1 bis 100 stehen, mit der Maßgabe, dass nicht alle Reste R⁴, R⁵ und R⁶ gleichzeitig Reste der Formel (8) bedeuten.The alkoxylated trialkanolamine polycondensates prepared by the process described can be represented by formula (6).

wherein
R ¹ , R ² and R ^{3 have} the abovementioned meaning, and R ⁴ , R ⁵ and R ⁶ independently of one another represent a group of the formula (7)

or a group of formula (8) -O- (BO) _m - (AO) _n -H (8) wherein A and B are different C ₂ to C ₄ alkoxy groups, preferably ethylene or propylene groups, and n and m are integers from 1 to 100, with the proviso that not all of R ⁴ , R ⁵ and R ⁶ mean at the same time radicals of the formula (8).

Again, the number of trialkanolamine units is between 2 and 250.

The alkylene oxide units (AO) and (BO) may be either the same alkylene oxide units or different alkylene oxide units. In the latter case, the alkylene oxide units may be present randomly or, as in the case of a preferred embodiment, arranged in a block.

In a preferred embodiment, (AO) and (BO) represent one block of ethylene oxide units, or (AO) and (BO) one block of propylene oxide units.

In another preferred embodiment, (AO) is propylene oxide units and (BO) is ethylene oxide units, or (AO) is ethylene oxide units and (BO) is propylene oxide units. The ratio of the propylene oxide units to the ethylene oxide units in the alkoxylated trialkanolamine polycondensate is preferably between 40: 1 and 1: 5, preferably between 30: 1 and 1: 4, in particular between 20: 1 and 1: 2.

The alkoxylated trialkanolamine polycondensate obtained after condensation and alkoxylation has a molecular weight of from 500 to 500,000 units, especially from 1,000 to 350,000 units.

The alkoxylated trialkanolamine condensates in a preferred embodiment have a water number of 7-22. The water number is a unitless number and is calculated according to DIN EN 12836 certainly.

The water number describes the HLB value (hydrophilic-lipophilic balance) of surface-active substances and is a measure of the water-solubility of the alkoxylated trialkanolamine condensates. A high water content of more than 15 means a good water solubility, a low water content of less than 10 means a good oil solubility. The number of water depends on the ratio of the number of EO groups to PO- Groups off. Alkoxylated trialkanolamine condensates with high numbers of water split emulsions faster, but produce a separated water with a larger oil content. With small numbers of water, the cleavage is slower, but the oil content of the separated water is lower.

A preferred subject matter of the present invention is the use of the alkoxylated trialkanolamine polycondensates as splitters for oil / water emulsions in petroleum production.

For use as petroleum breakers, the alkoxylated trialkanolamine polycondensates are added to the water-in-oil emulsions, preferably in solution. As solvents for the alkoxylated trialkanolamine polycondensates, preference is given to paraffinic, aromatic or alcoholic solvents. The alkoxylated trialkanolamine polycondensates are used in amounts of 0.0001 to 5, preferably 0.0005 to 2, in particular 0.0008 to 1 and especially 0.001 to 0.1 wt .-% based on the oil content of the emulsion to be cleaved.

Examples

Alkaline-condensed trialkanolamines:

In a 500 ml three-necked flask with contact thermometer, stirrer and Wasserauskreiser 225 g trialkanolamine and 0.5 mol% NaOH 50% were mixed in water. While stirring, the reaction mixture was heated and the resulting reaction water distilled off continuously. The course of the reaction was monitored by means of OH number determination and the reaction was stopped when a given OH number had been reached.

Table 1 shows synthetic examples of inventive, alkaline condensed Trialkanolaminkondensate. Table 1: Alkaline condensed trialkanolamine condensates according to the invention example monomer T Time OH number n 1 TEA (100%) 250/270 2.2 708 2-3 2 TEA (100%) 250/270 2.3 515 8-9 3 TIPA (100%) 250/270 2.6 677 3-4 4 DEIPA (100%) 250/270 2.4 631 4-5 5 DEPEA (100%) 250/270 2.4 625 4-5 6 TEA: TIPA 1: 1 250/270 2.6 623 3-4 7 TEA: DEIPA 1: 1 250/270 2.4 588 5-6

An indication of temperature and time such as 250/270 and 2/3 means that 250 ° C were held for 2 hours, then 270 ° C for 3 hours.

Abbreviations:

• TEA

  = Triethanolamine

  TIPA

  = Triisopropanolamine

  DEIPA

  = Diethanolisopropanolamine

  DEPEA

  = Diethanol-2-phenylethanolamine

  T

  = Reaction temperature [° C]

  Time

  = Reaction time [hours]

  OH number

  = Hydroxyl number [mgKOH / g substance]

  n

  = average degree of condensation

For comparison purposes, two acid condensed triethanolamine polycondensates were prepared according to WO 2009060060 A1 Example 1a) and Example 3a), p. 12. Their properties are shown in Table 2. Table 2: Acid-condensed triethanolamine polycondensates (comparative examples) example monomer T Time OH number V3 TEA (100%) 227 3.5 733 V4 TEA (100%) 227 7 476

Alkoxylation of Trialkanolaminpolykondensate

ethoxylation

The trialkanol polycondensates or their oxpropylates obtained by the general polycondensation method were introduced into a 1 l glass autoclave and adjusted to a final alkali number of about 2.5 mg KOH / g substance with sodium methylate solution. The autoclave was rendered inert with nitrogen, heated to 135 ° C after pressure test and the pressure in the autoclave with nitrogen to about 0.8-1.0 bar. Thereafter, the desired amount of ethylene oxide was added at a maximum of 140 ° C, the pressure should not exceed 4.5 bar. After dosing, the reaction is continued at a maximum of 140 ° C. until the pressure remains constant.

propoxylation

The trialkanol polycondensates or their ethoxylates obtained by the general polycondensation method were introduced into a 1 l glass autoclave and adjusted to a final alkali number of about 1.5 mg KOH / g substance with sodium methylate solution. The autoclave was rendered inert with nitrogen, heated to 125 ° C after pressure test and the pressure in the autoclave with nitrogen to about 0.8-1.0 bar. Thereafter, the desired amount of propylene oxide was added at a maximum of 130 ° C, wherein the pressure should not exceed 3.5 bar. After dosing, the reaction is continued at a maximum of 130 ° C. until the pressure remains constant.

The following Tables 3 and 4 show synthesis examples, wherein the polycondensate in question was first propoxylated and then ethoxylated. Table 3: Propoxylated-ethoxylated polycondensates example Product from example PO per OH EO per OH water number 8th 1 20 0 10.3 9 1 20 2 12.0 10 1 20 4 13.6 11 1 20 6 16.0 12 1 20 8th 17.9 13 1 20 10 20.5 14 1 30 0 8.9 15 1 30 5 12.2 16 1 30 7 13.6 17 1 30 9 15.8 18 1 30 11 18.0 19 1 30 13 20.2 20 1 50 0 7.8 21 1 50 8th 11.9 22 1 50 10 13.8 23 1 50 13 15.8 24 1 50 16 19.1 25 1 50 18 20.5 26 4 20 4 12.8 27 4 20 6 15.2 28 4 20 8th 16.9 29 4 20 10 19.0 30 5 30 6 11.1 31 5 30 12 18.8 Table 4: Alkoxylates prepared from acid condensed trethanolamine polycondensates for comparative purposes example Product from example PO per OH EO per OH water number V5 V3 30 5 12.0 V6 V3 30 7 13.3 V7 V4 30 5 11.8 V8 V4 30 7 13.1

The following Tables 5 and 6 show synthesis examples, wherein the polycondensate in question was first ethoxylated and then propoxylated. Table 5: Ethoxylated-propoxylated polycondensates example Product from example EO per OH PO per OH water number OH number 32 1 4 0 254 33 1 6 0 184 34 1 8th 0 145 35 1 4 20 12.2 36 1 6 20 12.5 37 1 8th 20 13.2 38 1 4 30 10.1 39 1 6 30 10.6 40 1 8th 30 10.9 41 3 5 0 154 42 3 20 0 59 43 4 4 20 12.0 44 4 6 20 12.2 45 4 8th 20 12.9 46 5 4 15 13.1 47 5 6 15 13.8 48 5 8th 15 14.4 49 6 5 0 156 50 6 20 0 60

With only ethoxylated trialkanolamine condensates, no water number can be determined; instead, the OH number was determined. Table 6: Alkoxylates prepared for comparison from acid condensed trethanolamine polycondensates example Product from example EO per OH PO per OH water number V9 V3 4 20 11.9 V10 V3 6 20 12.3 V11 V3 8th 20 12.9

Determination of the splitting efficiency of petroleum emulsion separators

To determine the effectiveness of an emulsion breaker, the water separation from a crude oil emulsion per time as well as the appearance of the separated water and the phase boundary were determined optically. In each case, 100 ml of the crude oil emulsion were introduced into breaker glasses (conically tapered, screwable, graduated glass bottles), in each case a defined amount of the emulsion breaker was metered with a micropipette just below the surface of the oil emulsion, and the breaker was mixed into the emulsion by intensive shaking.

Thereafter, the breaker glasses were placed in a tempering bath (50 ° C.) and the water separation was monitored.

• a) bei ”Wasser” – der Eintrag ”+”, dass das abgetrennt Wasser klar ist – der Eintrag ”O”, dass das abgetrennte Wasser trüb ist – der Eintrag ”–”, dass das abgetrennte Wasser durch Verölung intransparent ist, und
• b) bei ”Phasengrenze” – der Eintrag ”+” eine scharfe Phasengrenze – der Eintrag ”O” eine leichte Muddebildung (d. h. keine ebene Phasengrenze) – der Eintrag ”–” eine starke Muddebildung (d. h. eine Meniskusbildung)

Spaltwirkung der beschriebenen Spalter Ursprung der Rohölemulsion: Hebertshausen, Deutschland Wassergehalt der Emulsion: 48% Demulgiertemperatur: 50°C Tabelle 7: Wirksamkeit der alkoxylierten Trialkanolaminpolykondensate als Emulsionsspalter im Vergleich zu einem Polymin-Oxpropylat, Dosierrate 250 ppm (Handelsprodukt, V1). Wasserabscheidung [ml] pro Zeit [min] durch Produkt aus Beispiel Zeit [min] Wasser Phasengrenze 5 10 20 30 45 60 120 8 0 0,5 17 40 44 46 46 + + 14 0 0,5 12 30 42 44 45 + + 20 0 0,5 9 20 40 44 45 + + V1 1 3 7 13 28 44 44 + + Tabelle 8: Wirksamkeit der alkoxylierten Trialkanolaminpolykondensate als Emulsionsspalter im Vergleich zu sauer kondensierten Triethanolaminpolykondensat-Alkoxylaten V5–V8 (Dosierrate 75 ppm) Wasserabscheidung [ml] pro Zeit [min] durch Produkt aus Beispiel Zeit [min] Wasser Phasengrenze 10 20 30 45 60 90 120 9 0 3 16 28 33 46 48 + 0 10 0 19 29 35 44 45 46 + 0 11 0 16 30 34 41 44 46 + + 12 0,5 2 12 34 36 42 44 + 0 13 0 0,5 2 11 25 32 34 0 + 15 0 18 30 34 35 42 44 + 0 16 5 24 30 34 34 42 43 + – 17 14 23 28 30 32 38 41 + 0 18 9 18 20 23 26 31 33 + 0 19 4 18 23 28 29 30 33 0 + 21 2 20 26 28 30 32 34 + 0 26 0 17 28 36 44 45 46 + + 27 0,5 16 31 33 40 43 45 + + 28 0,5 4 14 36 38 42 44 + 0 29 0 0,5 1 10 22 30 34 0 + 30 0 16 30 36 38 42 44 + 0 31 1 18 24 28 32 33 33 + 0 V5 0 5 16 22 25 29 34 0 – V6 1 12 19 26 29 33 34 0 – V7 0 6 14 21 26 30 33 0 – V8 2 16 25 28 31 33 36 0 – Tabelle 9: Wirksamkeit der alkoxylierten Trialkanolaminpolykondensate als Emulsionsspalter im Vergleich zu einem Oligoamin-gestarteten EO-PO-Block-Polymer, Dosierrate 75 ppm (Handelsprodukt, V2) und sauer kondensierten Triethanolaminpolykondensat-Alkoxylaten V9–V11 Wasserabscheidung [ml] pro Zeit [min] durch Produkt aus Beispiel Zeit [min] Wasser Phasengrenze 10 20 30 45 60 90 120 35 0 4 16 33 42 43 44 + 0 36 6 21 34 41 43 45 45 + 0 37 3 28 36 39 42 42 44 + + 38 6 22 33 40 42 43 44 + 0 39 2 20 35 40 42 44 44 + + 40 4 25 34 41 43 44 44 + + V2 0 14 35 38 40 44 44 + 0 V9 0 2 11 17 30 34 38 0 0 V10 2 16 22 31 34 38 40 0 0 V11 1 18 25 33 35 38 41 0 0 The fission efficiency is assessed by a skilled observer. It means

• (a) in the case of "water" - the entry "+" indicates that the separated water is clear - the entry "O" indicates that the separated water is cloudy - the entry "-" indicates that the separated water is non-transparent due to oiling, and
• b) in the case of "phase boundary" - the entry "+" a sharp phase boundary - the entry "O" a slight muddying (ie no flat phase boundary) - the entry "-" a strong muddying (ie a meniscus formation)

Cleavage action of the splitter described Origin of crude oil emulsion: Hebertshausen, Germany Water content of the emulsion: 48% Demulgiertemperatur: 50 ° C Table 7: Effectiveness of the alkoxylated trialkanolamine polycondensates as emulsion breakers compared to a polymine oxpropylate, dosage rate 250 ppm (commercial product, V1). Water separation [ml] per time [min] by product from example Time [min] water phase boundary 5 10 20 30 45 60 120 8th 0 0.5 17 40 44 46 46 + + 14 0 0.5 12 30 42 44 45 + + 20 0 0.5 9 20 40 44 45 + + V1 1 3 7 13 28 44 44 + + Table 8: Effectiveness of the alkoxylated trialkanolamine polycondensates as emulsion breakers in comparison with acid condensed triethanolamine polycondensate alkoxylates V5-V8 (dosing rate 75 ppm) Water separation [ml] per time [min] by product from example Time [min] water phase boundary 10 20 30 45 60 90 120 9 0 3 16 28 33 46 48 + 0 10 0 19 29 35 44 45 46 + 0 11 0 16 30 34 41 44 46 + + 12 0.5 2 12 34 36 42 44 + 0 13 0 0.5 2 11 25 32 34 0 + 15 0 18 30 34 35 42 44 + 0 16 5 24 30 34 34 42 43 + - 17 14 23 28 30 32 38 41 + 0 18 9 18 20 23 26 31 33 + 0 19 4 18 23 28 29 30 33 0 + 21 2 20 26 28 30 32 34 + 0 26 0 17 28 36 44 45 46 + + 27 0.5 16 31 33 40 43 45 + + 28 0.5 4 14 36 38 42 44 + 0 29 0 0.5 1 10 22 30 34 0 + 30 0 16 30 36 38 42 44 + 0 31 1 18 24 28 32 33 33 + 0 V5 0 5 16 22 25 29 34 0 - V6 1 12 19 26 29 33 34 0 - V7 0 6 14 21 26 30 33 0 - V8 2 16 25 28 31 33 36 0 - Table 9: Effectiveness of the alkoxylated trialkanolamine polycondensates as emulsion breakers in comparison with an oligoamine-initiated EO-PO block polymer, metering rate 75 ppm (commercial product, V2) and acid condensed triethanolamine polycondensate alkoxylates V9-V11 Water separation [ml] per time [min] by product from example Time [min] water the phase boundary 10 20 30 45 60 90 120 35 0 4 16 33 42 43 44 + 0 36 6 21 34 41 43 45 45 + 0 37 3 28 36 39 42 42 44 + + 38 6 22 33 40 42 43 44 + 0 39 2 20 35 40 42 44 44 + + 40 4 25 34 41 43 44 44 + + V2 0 14 35 38 40 44 44 + 0 V9 0 2 11 17 30 34 38 0 0 V10 2 16 22 31 34 38 40 0 0 V11 1 18 25 33 35 38 41 0 0

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• US 4032514 [0004]
• DE 2445873A [0005]
• US 5401439 [0006]
• US 4321146 [0007]
• US 5445765 [0007]
• DE 10329723 A [0008]
• DE 10325198 A [0008]
• US 2407895 [0010]
• US 4505839 [0010]
• DE 4003243 A [0010]
• WO 2009/060060 [0011]
• WO 2009060060 A1 [0042]

Cited non-patent literature

• "Something Old, Something New: A Discussion about Demulsifiers", TG Balson, pp. 226-238 in Proceedings in the Chemistry in the Oil Industry VIII Symposium, Nov. 3 - 5, 2003, Manchester, UK [0003]
• "Crude Oil Emulsions: A State-Of-The-Art Review", S. Kokal, pages 5-13, Society of Petroleum Engineers SPE 77497 [0003]
• Standard DIN 53240 of December 1971 [0024]
• DIN EN 12836 [0035]

Claims (11)

Use of alkoxylated trialkanolamine condensates obtainable by alkaline-catalyzed condensation of trialkanolamines and subsequent alkoxylation with at least one C ₂ -C ₄ -alkylene oxide having a number-average molecular weight of 500 to 500,000 g / mol, comprising 2 to 250 trialkanolamine units, and their average degree of alkoxylation between 1 and 200 alkylene oxide units per free OH group, in amounts of 0.0001 to 5 wt .-%, based on the oil content of the emulsion to be cleaved, for the cleavage of water in oil emulsions. Use according to claim 1, characterized in that the trialkanolamine polycondensate contains at least one of the structures of the formulas (3), (4) or (5) before the alkoxylation,

wherein R ¹ , R ² and R ^{3 are} independently H, methyl, ethyl or phenyl, and R ⁴ , R ⁵ and R ^{6 are} independently OH or a group of formula (2)

with the proviso that not all radicals R ⁴ , R ⁵ and R ^{6 are} simultaneously OH. Use according to claim 1 and / or 2, characterized in that the polycondensate after alkoxylation has a number average molecular weight of 1000 to 350,000 units. Use according to one or more of claims 1 to 3, characterized in that both alkylene oxide units (AO) and (BO) are ethylene oxide units. Use according to one or more of claims 1 to 3, characterized in that both alkylene oxide units (AO) and (BO) are propylene oxide units. Use according to one or more of claims 1 to 3, characterized in that (AO) are propylene oxide units and (BO) ethylene oxide units, or (AO) ethylene oxide units and (BO) propylene oxide units, wherein the ratio of the propylene oxide units to the ethylene oxide units in the alkoxylated trialkanolamine polycondensate is between 40: 1 and 1: 5. Use according to one or more of claims 1 to 6, characterized in that the alkoxylated trialkanolamine polycondensates are represented by formula (6)

in which R ¹ , R ² and R ³ independently of one another represent H, methyl, ethyl or phenyl, and R ⁴ , R ⁵ and R ⁶ independently of one another represent a group of the formula (7)

or a group of formula (8) -O- (BO) _m - (AO) _n -H (8) wherein A and B are ethylene and / or propylene groups and n and m are integers from 1 to 100, with the proviso that not all radicals R ⁴ , R ⁵ and R ^{6 are} simultaneously radicals of the formula (8). Use according to one or more of claims 1 to 7, wherein the alkoxylated trialkanolamine condensates have an OH number of 25-300 mgKOH / g substance. Use according to one or more of claims 1 to 8, wherein the alkoxylated trialkanolamine condensates have a water number of 7-22. Alkoxylated trialkanolamine condensates, obtainable by alkaline-catalyzed condensation of trialkanolamines and subsequent alkoxylation with at least one C ₂ - to C ₄ -alkylene oxide, so that the average degree of alkoxylation is 1 to 200 alkoxy units per free OH group, and 2 to 250 Trialkanolamineinheiten include and have number-average molecular weight of 500 to 500,000 g / mol. A process for cleaving a water-in-oil emulsion by adding to the emulsion from 0.0001 to 5% by weight, based on the weight of the emulsion, of at least one alkoxylated trialkanolamine condensate obtained by alkaline catalyzed condensation of trialkanolamines followed by alkoxylation at least one C ₂ - to C ₄ alkylene oxide is available, and has a number average molecular weight of 500 to 500,000 g / mol and 2 to 250 Trialkanolamineinheiten, and whose average degree of alkoxylation is 1 to 200 alkoxy units per free OH group.