DE102012005279A1 - Use of crosslinked and alkoxylated polyamidoamine exhibiting reactive groups that are alkoxylated with alkylene oxide, and specific average degree of alkoxylation, for splitting water-in-oil emulsions in crude oil extraction - Google Patents

Abstract

Use of crosslinked and alkoxylated polyamidoamine exhibiting reactive groups that are alkoxylated with at least one 2-4C alkylene oxide, and an average degree of alkoxylation of 1-200 alkylene oxide units per reactive group, for splitting water-in-oil emulsions, is claimed. The crosslinked and alkoxylated polyamidoamine is used in an amount of 0.00001-5 wt.%, based on the oil content of the emulsion to be demulsified. Independent claims are also included for: (1) the crosslinked and alkoxylated polyamidoamine exhibiting an average degree of alkoxylation of 3-100 alkylene oxide units per reactive group and a number average molecular weight of 500-200000 g/mole; and (2) splitting the water-in-oil emulsion, comprising adding at least one crosslinked and alkoxylated polyamidoamine (0.00001-5 wt.%, based on the weight of the emulsion) to the emulsion.

Description

The present invention relates to the use of alkoxylated, crosslinked polyamidoamines for the splitting of water-oil emulsions, in particular in crude oil production.

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 Erdölemulsionsspalter. Petroleum emulsion separators 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 and "Production Chemicals for the Oil and Gas Industry", Malcolm A. Kelland, pages 291-311 in Demulsifiers, CRC Press, Taylor & Francis Group ,

US 4032514 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-2445873 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 US 5401439 is disclosed.

As further petroleum emulsion breakers are in US 4321146 Alkylene oxide block copolymers and in US 5445765 alkoxylated polyethyleneimines.

Alkoxylated dendritic polyesters (dendrimers) are biodegradable (OECD 306) petroleum emulsion breakers in DE-A-10329723 disclosed. Also according to OECD 306 biodegradable splitters are in DE-A-10325198 and WO-2010/124773 disclosed. These are alkoxylated, crosslinked polyglycerols and alkoxylated (meth) acrylate copolymers.

Alkoxylated alkylamines are useful as efficient petroleum emulsion breakers in DE-A-102009042971 and DE-A-102009041983 disclosed.

The use of linearly alkoxylated polyamidoamines based on ethylenediamine and acrylic acid as Erdölemulsionsspalter are in CN 101418230 and DE-4221936 disclosed.

The disclosed breakers can be used as individual components or in mixtures with other emulsion breakers.

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 low dosage.

It turned out, surprisingly, that alkoxylated polyamidoamines after crosslinking, for example with multifunctional glycidyl ethers, have an excellent action as petroleum breakers even at very low dosages.

The invention therefore relates to the use of crosslinked polyamidoamines whose reactive groups are alkoxylated with at least one C ₂ -C ₄ -alkylene oxide, so that the average degree of alkoxylation is between 1 and 200 alkylene oxide units per reactive group, the average degree of alkoxylation here being the average Number of alkoxy units attached to each reactive group, for the splitting of water in oil emulsions, in amounts of 0.00001 to 5 wt .-%, based on the oil content of the emulsion to be cleaved.

Another object of the invention is a process for the cleavage of a water-in-oil emulsion by the emulsion 0.00001 to 5 wt .-%, based on the oil content of the emulsion, of at least one crosslinked polyamidoamine is added, the reactive groups with alkoxylated at least one C ₂ - to C ₄ alkylene oxide so that the average degree of alkoxylation is between 1 and 200 alkylene oxide units per reactive group, the mean degree of alkoxylation here being understood to mean the average number of alkoxy units attached to each reactive group.

The invention further provides crosslinked polyamidoamines whose reactive groups have been alkoxylated with at least one C ₂ -C ₄ -alkylene oxide, such that the average degree of alkoxylation is between 1 and 200 alkylene oxide units per reactive group, the average number of alkoxy units being below average degree of alkoxylation here which are attached to each reactive group.

The compounds of the invention are prepared from polyamidoamines as a precursor. The polyamidoamines used as precursor are accessible by Michael addition of a polyamine with acrylic ester and subsequent polycondensation. Polyamines of the general formula are preferably used H ₂ N - ((CR ¹ R ² ) _n - (CR ³ R ⁴ ) _m -NH) _p -H in which
R ¹ , R ² , R ³ , R ⁴ independently of one another are H or methyl
n is a number from 1 to 3
m for a number from 1 to 3
p is a number from 1 to 3
stand and acrylic acid esters of the general formula CH ₂ = CR ⁵ -COO-R ⁶ in which
R ^5, independently of one another H or methyl
R ^{6 is} independently H, methyl, ethyl, propyl or butyl
stand.

Polyamines and acrylic esters react in a Michael addition to give a polyamine ester (shown here for n, m = 1):

als x, so findet eine Reaktion wie folgt statt:

die beliebig oft wiederholbar ist, und zur Polykondensation führt.The compound thus obtained is capable of polycondensation with itself, wherein the terminal amino group with the carbonyl group forms an amide bond, and an alcohol R ⁶ -OH is eliminated. If one calls the divalent group

as x, a reaction takes place as follows:

which is repeated as often as desired, and leads to polycondensation.

Obtained therefrom are preferably polyamidoamines of the general formula H- (HN - ((CR ¹ R ²⁾ _n - (CR ³ R ⁴⁾ _m -NH) _p -CH ₂ -CHR ⁵ -CO) _q -OR ⁶ in which
R ¹ , R ² , R ³ , R ⁴ independently of one another are H or methyl
R ⁵ , independently of one another, denote H or methyl
R ^{6 is} independently H, methyl, ethyl, propyl or butyl
n is a number from 1 to 3
m for a number from 1 to 3
p is a number from 1 to 3
q for numbers from 1 to 200
stand.

The following general rules illustrate how the polyamidoamine precursors can be prepared

General Procedure 1: Reaction of bisethylenetriamine with methyl acrylate

In a 500 ml three-necked flask equipped with a contact thermometer, stirrer, reflux condenser and condenser, 1 mol of methyl acrylate were added to 1 mol of bisethylenetriamine starting at room temperature and then heated at 130.degree. C. for 3 hours. The resulting methanol was discarded.

General Procedure 2: Reaction of bisethylenetriamine with methyl methacrylate

In a 500 ml three-necked flask equipped with a contact thermometer, stirrer, reflux condenser and condenser 1 mol of methyl methacrylate were added to 1 mol of bisethylenetriamine starting at room temperature and then heated at 130 ° C for 3 hours. The resulting methanol was discarded.

In the aforementioned embodiments, the polyamidoamines may be present as linear and dendritic polycondensate having molecular weights in the ranges of 200 to 100,000 g / mol. In a preferred embodiment, the average molecular weight is 500 to 10,000 g / mol, particularly preferably 700 to 5,000 g / mol and very particularly preferably 900 to 3,500 g / mol.

All molecular weights in this application are to be understood as weight-average molecular weights Mw. They are to be determined by means of gel permeation chromatography against polyethylene glycol standard. The compounds of the invention are crosslinked. The crosslinking can take place both before and after the alkoxylation. It is thus possible to first crosslink and then to alkoxylate the not yet alkoxylated polyamidoamines which are suitable as precursors. It is also possible to crosslink the already alkoxylated polyamidoamines.

wobei
k für eine Zahl von 2 bis 8, vorzugsweise 3 bis 6 steht, und
R⁷ ein Rest ist, der durch die formale Abstraktion der OH-Gruppe aus einem Alkohol mit 2 bis 8 OH-Gruppen gebildet werden kann, wobei R⁷ zwischen 2 und 30 Kohlenstoffatome umfasst, deren Abfolge durch Sauerstoffatome unterbrochen sein kann.Preferably, the crosslinking takes place by reaction of the non-alkoxylated polyamidoamines or the alkoxylated polyamidoamines with a glycidyl ether of the formula

in which
k is a number from 2 to 8, preferably 3 to 6, and
R ^{7 is} a radical which can be formed by the formal abstraction of the OH group from an alcohol having 2 to 8 OH groups, wherein R ⁷ comprises between 2 and 30 carbon atoms, the sequence of which may be interrupted by oxygen atoms.

The following crosslinking agents are particularly preferred for the crosslinking reaction: Bisphenol A diglycidyl ether, butane-1,4-diol diglycidyl ether, hexane-1,6-diol diglycidyl ether, ethylene glycol diglycidyl ether, cyclohexanedimethanol diglycidyl ether, resorcinol diglycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether, Glycerinpropoxylattriglycidylether, polyglycerol polyglycidyl ether, p-Aminophenoltriglycidylether, polyethylene , Polypropylene glycol diglycidyl ether, pentaerythritol tetraglycidyl ether, sorbitol polyglycidyl ether, trimethylolpropane triglycidyl ether, castor oil triglycidyl ether, diaminobiphenyl tetraglycidyl ether, neopentyl glycol diglycidyl ether, but-2-ene-1,4-diol diglycidyl ether, perhydro-bisphenol A diglycidyl ether.

In a preferred embodiment, the crosslinking step before the alkoxylation with 0.1-1.0 mol, more preferably 0.2-0.8 mol of the crosslinking agent, based on 1 mol of polyamidoamine, performed. The crosslinked polyamidoamines obtained from this crosslinking step are then in this embodiment alkoxylated with one or more C ₂ -C ₄ alkoxides, preferably ethylene oxide (EO) or propylene oxide (PO), wherein the alkylene oxide units are random or, as in the case of a preferred Embodiment, arranged in blocks. In the case of the mixed alkoxylates arranged in block form, the molar ratio of PO to EO is preferably between 100: 1 and 1: 100, preferably between 60: 1 and 1:60, in particular between 30: 1 and 1:30.

In a preferred embodiment, the average degree of alkoxylation is from 2 to 150 alkylene oxide units, more preferably from 3 to 100 alkylene oxide units, and most preferably from 10 to 70 Alkylene oxide units per reactive group. By reactive group is meant functional groups having active H atoms. Active H atoms are H atoms, which can be replaced by alkoxy groups in an alkoxylation reaction. Reactive groups in this case are the free terminal amine or alcohol groups. Their numbers are calculated via the corresponding amine number (for example after DIN 53176 ) or OH number (for example after DIN 53240 ) certainly.

In a further preferred embodiment, the crosslinking step after the propoxylation and before the subsequent ethoxylation or after the ethoxylation and before the subsequent propoxylation of the polyamidoamines with 0.5-10 particularly preferably 0.8 to 8 especially 1-5 wt .-% crosslinker , based on the alkoxylate carried out. The ratio of PO to EO in this embodiment is preferably between 100: 1 and 1: 100, preferably between 60: 1 and 1:60, in particular between 30: 1 and 1:30.

In a further preferred embodiment, the crosslinking step after the alkoxylation of the polyamidoamines is carried out with 0.5-10, particularly preferably 0.8 to 8, especially 1-5,% by weight of crosslinking agent, based on the alkoxylate. The ratio of PO to EO is preferably between 100: 1 and 1: 100, preferably between 60: 1 and 1:60, in particular between 30: 1 and 1:30.

In all embodiments, it is preferred that the alkoxylation be carried out with a mixture of C ₂ to C ₄ alkylene oxides comprising propylene oxide. In a further preferred embodiment, alkoxylation is carried out with pure propylene oxide. In a further preferred embodiment, the alkoxylated polyamidoamines per reactive group contain on average at least one propylene oxide unit.

The alkoxylated polyamidoamines obtained after crosslinking and alkoxylation preferably have a molecular weight of from 500 to 500,000 units, in particular from 2,000 to 200,000 units, especially from 3,000 to 10,000 units.

The alkoxylated, crosslinked polyamidoamines in a preferred embodiment have a water number of 5-30. 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 surfactants and is a measure of the water solubility of the alkoxylated, crosslinked polyamidoamines. A high water content of more than 18 means a good water solubility, a low water content of less than 13 means a good oil solubility. The number of water depends on the ratio of the number of EO groups to PO groups. The high-alkoxylated, cross-linked polyamidoamines generally tend to break emulsions faster but produce a higher oil separated water. With small numbers of water, the cleavage is generally slower, but the oil content of the separated water is lower.

A preferred subject of the present invention is the use of the alkoxylated crosslinked polyamidoamines as breakers for oil / water emulsions in petroleum production.

For use as petroleum breakers, the alkoxylated, crosslinked polyamidoamines are added to the water in oil emulsions, preferably in solution. As solvents for the alkoxylated, crosslinked polyamidoamines, preference is given to paraffinic, aromatic or alcoholic solvents. The alkoxylated, crosslinked polyamidoamines are used in amounts of 0.00001 to 5, preferably 0.0002 to 2, in particular 0.0004 to 1 and especially 0.001 to 0.1 wt .-% based on the oil content of the emulsion to be cleaved.

Examples

The Michael addition and the subsequent polycondensation were carried out according to the following instructions:

General Procedure 1: Reaction of bisethylenetriamine with methyl acrylate

In a 500 ml three-necked flask equipped with a contact thermometer, stirrer, reflux condenser and condenser, 1 mol of methyl acrylate were added to 1 mol of bisethylenetriamine starting at room temperature and then heated at 130.degree. C. for 3 hours. The resulting methanol was discarded.

General Procedure 2: Reaction of bisethylenetriamine with methyl methacrylate

In a 500 ml three-necked flask equipped with a contact thermometer, stirrer, reflux condenser and condenser 1 mol of methyl methacrylate were added to 1 mol of bisethylenetriamine starting at room temperature and then heated at 130 ° C for 3 hours. The resulting methanol was discarded.

General rule for networking

General rule 3: Polyamidoamine crosslinking before alkoxylation

In a 500 ml three-necked flask equipped with a contact thermometer, stirrer and reflux condenser, 1 mol of polyamidoamine, 0.2-0.8 mol of crosslinker and alkaline catalyst (final alkali number 0.5-3.5 mg KOH / g) were mixed. With stirring, the reaction mixture was gradually heated to 120 ° C within three hours and then reacted at this temperature. The completeness of the reaction (usually 3-4 hours) is determined by determining the epoxide number.

General Procedure 4: Crosslinking of the alkoxylated polyamidoamine

In a 500 ml three-necked flask with contact thermometer, stirrer and reflux condenser, 1 mol of alkoxylated polyamidoamine, 1.0-5.0 wt .-% crosslinker and alkaline catalyst (Endalkalizahl 0.5 mg KOH / g) were mixed. With stirring, the reaction mixture was gradually heated to 120 ° C and then reacted at this temperature. The completeness of the reaction (usually 6-8 hours) is determined by determining the epoxide number.

General procedure for alkoxylations

Ethoxylation crosslinked polyamidoamine

The crosslinked polyamidoamines or their oxpropylates obtained according to the general crosslinking instructions 1 and 2 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 crosslinked polyamidoamine

The crosslinked polyamidoamines or their ethoxylates obtained according to the general crosslinking instructions 1 and 2 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.

Ethoxylation uncrosslinked polyamidoamine

The polyamidoamines or their oxpropylates were introduced into a 1 l glass autoclave and adjusted with Natriummethylatlösung a final alkali number of about 2.5 mg KOH / g substance. 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 uncrosslinked polyamidoamine

The polyamidoamines or their ethoxylates were introduced into a 1 l glass autoclave and adjusted with Natriummethylatlösung a final alkali number of about 1.5 mg KOH / g substance. 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. Table 1: Polyamidoamine (bisethylenetriamine / methyl acrylate) + butane-1,4-diol diglycidyl ether + PO + EO example Molar ratio of polyamidoamine to crosslinker mol PO per mole of amine mol of EO per mole of amine water number 1 1: 0.4 10 0 15.1 2 1: 0.4 20 0 11.8 3 1: 0.4 30 0 9.2 4 1: 0.4 42 0 7.0 5 1: 0.4 54 0 6.8 6 1: 0.4 10 5 18.6 7 1: 0.4 20 5 15.2 8th 1: 0.4 30 5 12.8 9 1: 0.4 42 5 10.7 10 1: 0.4 54 5 8.9 11 1: 0.4 10 10 20.3 12 1: 0.4 20 10 18.5 13 1: 0.4 30 10 14.7 14 1: 0.4 42 10 12.2 15 1: 0.4 54 10 10.1 16 1: 0.4 10 20 24.8 17 1: 0.4 20 20 22.9 18 1: 0.4 30 20 18.1 19 1: 0.4 42 20 14.2 20 1: 0.4 54 20 12.9 Table 2: Polyamidoamine (bis-ethylenediamine / methyl methacrylate) + butane-1,4-diol diglycidyl ether + PO + EO example Molar ratio of polyamidoamine to crosslinker mol PO per mole of amine mol of EO per mole of amine water number 21 1: 0.4 10 0 13.7 22 1: 0.4 20 0 10.6 23 1: 0.4 30 0 8.8 24 1: 0.4 42 0 7.1 25 1: 0.4 54 0 6.9 26 1: 0.4 10 15 21.4 27 1: 0.4 20 15 18.1 28 1: 0.4 30 15 15.0 29 1: 0.4 42 15 11.9 30 1: 0.4 54 15 9.4 Table 3: Polyamidoamine (bisethylenetriamine / methyl methacrylate) + bisphenol A diglycidyl ether + PO + EO example Molar ratio of polyamidoamine to crosslinker mol PO per mole of amine mol of EO per mole of amine water number 31 1: 0.25 20 0 9.8 32 1: 0.25 20 10 13.2 33 1: 0.25 30 20 16.1 34 1: 0.25 30 30 19.2 Table 4: Polyamidoamine (bis-ethylenediamine / methyl methacrylate) + PO + bisphenol A diglycidyl ether + EO example mol PO per mole of amine Wt .-% crosslinker mol of EO per mole of amine water number 35 10 2 10 14.1 36 20 2 10 12.8 37 30 2 10 10.9 38 10 5 20 19.03 39 20 5 20 16.9 40 30 5 20 13.2 Table 5: Polyamidoamine (bisethylenetriamine / methyl methacrylate) + PO + EO + bisphenol A diglycidyl ether example mol PO per mole of amine mol of EO per mole of amine Wt .-% crosslinker water number 41 50 0 2 - * 42 50 10 2 - * 43 50 20 2 - * 44 50 0 5 - * 45 50 10 5 - * 46 50 20 5 - * * At final cross-linking a determination of the water value could not be carried out

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 and the drainage of the oil was determined. 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 separator 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 and the water separation followed.

• – 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.

Spaltwirkung der beschriebenen Spalter Ursprung der Rohölemulsion: Hebertshausen, Deutschland Wassergehalt der Emulsion: 48 Demulgiertemperatur: 50°C After completion of emulsion splitting samples were taken from the oil from the upper part of the splitter glass (so-called Topöl). A 15 ml centrifuge tube (graduated) is treated with 5 ml of Shellsol ^® A 150 ND and 10 ml oil sample is filled, shaken, the vial by hand, to achieve a thorough mixing, and then centrifuged at 1500 rpm for 5 minutes. After centrifugation, 3 phases, a clear water phase, a brown emulsion phase and a black oil phase are observed in the centrifuge glass. The read volumes of the water or emulsion phase are multiplied by a factor of 10 and the values thus determined as%. Water and% emulsion specified. The remainder to 100% is the oil phase. A particularly good demulsification is when the sum of% water and% emulsion is as small as possible. In comparison of two equal sums of% water and% emulsion, it is preferred if the proportion of% water is as large as possible. In this way, the new splitters were assessed after water separation and drainage of the oil. The quality of the separated water was judged by a skilled observer. It means

• - the entry "+" that the separated water is clear
• - the entry "O" that the separated water is cloudy
• - the entry "-" indicates that the separated water is non-transparent due to oiling.

Cleavage action of the splitter described Origin of crude oil emulsion: Hebertshausen, Germany Water content of the emulsion: 48 Demulgiertemperatur: 50 ° C

Table 6 indicates the effectiveness of the alkoxylated, crosslinked polyamidoamines as emulsion breakers in comparison to Dissolvan 5022 and Dissolvan 3245. Shown are the water separation in ml after the specified time. Table 6: Fission efficiency example Product from example Water separation [ml] after a given time [min] %-Water %-Emulsion water 10 20 30 60 120 47 4 5 10 25 35 43 0.8 1.2 + 48 5 10 20 40 47 47 0.8 1.2 + 49 17 30 45 45 45 45 1.6 1.6 - 50 18 20 35 42 45 45 1.2 1.6 O 51 24 5 10 15 30 43 0.7 1.2 + 52 30 15 20 30 42 45 1.2 2.9 O 53 32 20 28 40 44 45 1.0 2.3 O 54 33 20 30 42 45 45 1.2 2.5 O 55 37 5 15 28 40 45 0.8 1.0 + 56 40 2 10 25 35 45 0.5 1.0 + 57 43 15 25 40 45 45 2.5 0.5 O ⁵⁸ Dissolvan ^® 5022 1 5 15 38 44 0.8 2.5 - 59 Dissolvan ^® 3245 22 36 42 45 48 0.5 1.5 O

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]
• WO 2010/124773 [0008]
• DE 102009042971 A [0009]
• DE 102009041983 A [0009]
• CN 101418230 [0010]
• DE 4221936 [0010]

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]
• "Production Chemicals for the Oil and Gas Industry", Malcolm A. Kelland, pages 291-311 in Demulsifiers, CRC Press, Taylor & Francis Group. [0003]
• DIN 53176 [0030]
• DIN 53240 [0030]
• DIN EN 12836 [0035]

Claims (18)

Use of crosslinked alkoxylated polyamidoamines whose reactive groups have been alkoxylated with at least one C ₂ -C ₄ -alkylene oxide and whose average degree of alkoxylation is between 1 and 200 alkylene oxide units per reactive group, in amounts of from 0.00001 to 5% by weight on the oil content of the emulsion to be split, for the splitting of water in oil emulsions. Use according to claim 1, wherein a polyamidoamine according to formula (1) is used, H (HN - ((CR ¹ R ² ) _n - (CR ³ R ⁴ ) _m -NH) _p -CH ₂ -CHR ⁵ -CO) _q -OR ⁶ where R ¹ , R ² , R ³ , R ⁴ independently of one another are H or methyl R ⁵ , independently of one another H or methyl R ⁶ are each independently H, methyl, ethyl, propyl or butyl n for a number from 1 to 3 m is a number from 1 to 3 p for a number from 1 to 3 q for numbers from 1 to 200. Use according to claim 1, wherein the crosslinking with multifunctional glycidyl ethers occurs prior to the alkoxylation and the molar ratio of multifunctional glycidyl ethers to polyamidoamine is 0.2-0.8. Use according to claim 1, wherein the crosslinking with multifunctional glycidyl ethers occurs in blockwise alkoxylation between the individual blocks. Use according to claim 1, wherein the crosslinking with multifunctional glycidyl ethers takes place after the alkoxylation. Use according to one or more of claims 4 and / or 5, wherein the multifunctional glycidyl ether with 1-5 wt .-%, based on the alkoxylated polyamidoamine, is used. Use according to one or more of claims 1-6, wherein the crosslinker is selected from bisphenol A diglycidyl ether, butane-1,4-dioldiglycidyl ether, hexane-1,6-dioldiglycidyl ether, ethylene glycol diglycidyl ether, cyclohexanedimethanol diglycidyl ether, resorcinol diglycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether, glycerol propoxylate triglycidyl ether , polyglycerol polyglycidyl ether, p-Aminophenoltriglycidylether, polyethylene glycol, polypropylene glycol diglycidyl ether, pentaerythritol tetraglycidyl ether, sorbitol polyglycidyl ether, trimethylolpropane triglycidyl ether, Castoröltriglycidylether, Diaminobiphenyltetraglycidylether, neopentyl glycol, but-2-en-1,4-diol diglycidyl ether, perhydro-bisphenol A diglycidyl ether. Use according to one or more of claims 1 to 7, wherein is alkoxylated with a mixture of C ₂ - to C ₄ alkylene oxides containing propylene oxide. Use according to one or more of claims 1 to 8, wherein per reactive group on average at least 1 propylene oxide group is present. Use according to one or more of claims 1 to 7, wherein is alkoxylated with pure propylene oxide. Use according to one or more of Claims 1 to 9, in which the alkylene oxides used are propylene oxide and ethylene oxide, the ratio of the propylene oxide units to the ethylene oxide units in the crosslinked alkoxylated polyamidoamine being between 30: 1 and 1:30. Use according to one or more of claims 1 to 11, wherein the average degree of alkoxylation per reactive group is between 3 and 100. Use according to one or more of claims 1 to 12, wherein the crosslinked alkoxylated polyamidoamines have a molecular weight of 500 to 200,000 units. Use according to one or more of claims 1 to 13, wherein the crosslinked alkoxylated polyamidoamines have a water number of 5 to 30. Crosslinked alkoxylated polyamidoamines whose reactive groups are alkoxylated with at least one C ₂ -C ₄ -alkylene oxide and whose average degree of alkoxylation is between 3 and 100 alkylene oxide units per reactive group and which have a number-average molecular weight of 500 to 200,000 g / mol. Alkoxylated, crosslinked polyamidoamines according to claim 15, wherein the polyamidoamine corresponds to formula (1) H (HN - ((CR ¹ R ² ) _n - (CR ³ R ⁴ ) _m -NH) _p -CH ₂ -CHR ⁵ -CO) _q -OR ⁶ where R ¹ , R ² , R ³ , R ⁴ independently of one another are H or methyl R ⁵ , independently of one another H or methyl R ⁶ are each independently H, methyl, ethyl, propyl or butyl n for a number from 1 to 3 m is a number from 1 to 3 p for a number from 1 to 3 q for numbers from 1 to 200. Alkoxylated, crosslinked polyamidoamines according to Claim 15 and / or 16, in which the crosslinker is selected from bisphenol A diglycidyl ether, butane-1,4-diol diglycidyl ether, hexane-1,6-diol diglycidyl ether, ethylene glycol diglycidyl ether, cyclohexane dimethanol diglycidyl ether, resorcinol diglycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether, Glycerinpropoxylattriglycidylether, polyglycerol polyglycidyl ether, p-Aminophenoltriglycidylether, polyethylene glycol, polypropylene glycol diglycidyl ether, pentaerythritol tetraglycidyl ether, sorbitol polyglycidyl ether, trimethylolpropane triglycidyl ether, Castoröltriglycidylether, Diaminobiphenyltetraglycidylether, neopentyl glycol, but-2-en-1,4-diol diglycidyl ether, perhydro-bisphenol A diglycidyl ether. A method of cleaving a water-in-oil emulsion by adding to the emulsion from 0.00001 to 5% by weight, based on the weight of the emulsion, of at least one crosslinked alkoxylated polyamidoamine having a number average molecular weight of from 500 to 200,000 g / mol, whose reactive groups are alkoxylated with at least one C ₂ - to C ₄ -alkylene oxide, so that the average degree of alkoxylation is 3 to 100 alkoxy units per reactive group.