EP0074592A2 - Bisamides, processes for their preparation and their use - Google Patents

Bisamides, processes for their preparation and their use Download PDF

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EP0074592A2
EP0074592A2 EP82108171A EP82108171A EP0074592A2 EP 0074592 A2 EP0074592 A2 EP 0074592A2 EP 82108171 A EP82108171 A EP 82108171A EP 82108171 A EP82108171 A EP 82108171A EP 0074592 A2 EP0074592 A2 EP 0074592A2
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formula
group
hydrogen
mol
bisamides
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French (fr)
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EP0074592A3 (en
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Werner Dr. Ritschel
Helmut Dr. Diery
Martin Dr. Hille
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Hoechst AG
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Hoechst AG
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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G33/00Dewatering or demulsification of hydrocarbon oils
    • C10G33/04Dewatering or demulsification of hydrocarbon oils with chemical means

Definitions

  • the task of a demulsifier is to break the emulsion at the lowest possible application concentration and, in this separation process, to achieve complete water separation without expenditure or with minimal additional heat, and to reduce the salt content to a minimum.
  • the quality criteria for delivered crude oil are the residual salt content and the water content.
  • the crude oils have different compositions depending on their provinces and the natural emulsion stabilizers in the oil have a complicated and differentiated chemical structure, so that splitters have to be developed for each one. Due to different funding and processing conditions, the demands placed on a demulsifier are even more diverse. By constantly opening up new and changing the production conditions of older oil fields, the development of optimal demulsifiers for the respective purpose remains an acute task.
  • the compounds of the above formula are prepared by firstly using a dimerized fatty acid of the formula II with a compound of formula III condensed to a compound of formula IV, this compound of the formula IV optionally reacted with ethylene oxide and / or propylene oxide or butylene oxide, the reaction product obtained with an acid of the formula V. esterified and then optionally neutralized or quaternized.
  • Preferred dimerized fatty acids are the products which are commercially available under the names (R) Fripol 1010, (R) pripol 1022 and Fatty Acid 7002. See also RW Johnson in "Fatty acids" These products can also contain parts of trimeric or higher condensed fatty acids. For example, Pr ip ol L022 20% contains trimeric shares and p r ip ol 1010 only about 3%.
  • the dimerized fatty acids are first condensed with two moles of a compound of formula III.
  • Such compounds are, for example, aminoethylethanolamine, diethanolamine., Propylene diamine, alkyl propylene diamine, ethylene diamine, diethylene triamine, triethylene tetramine, tetramethylene pentamine, pentaethylene hexamine, mixed ethylene / propylene polyamines such as 3- (2-aminoethyl) aminopropylamine, N, N'-bis- (3 ) ethylenediamine.
  • the condensation can take place without solvent in the melt of the reactants or in the presence of an inert solvent at the boiling point of the solvent.
  • the solvent used here is preferably toluene or xylene, which also serves to remove the water of reaction formed.
  • the bisamide of formula IV formed in this condensation can then be alkoxylated by known methods, preferably in the presence of a basic catalyst such as sodium methylate or sodium hydroxide.
  • a basic catalyst such as sodium methylate or sodium hydroxide.
  • Preferred alkylene oxides are ethylene oxide, but also mixtures of ethylene oxide with propylene oxide or butylene oxide.
  • oxyalkylation products or the bisamides of the formula IV are then esterified with one or more carboxylic acids of the formula V.
  • C a -C 22 fatty acids are preferably used as carboxylic acids.
  • the quantitative ratio between carboxylic acids and bisamides of the formula IV or its oxyalkylation products can be chosen so that one or more acyl groups are present in the ester.
  • the esterification can be carried out with pure carboxylic acids of the formula V or with mixtures of various such carboxylic acids. Analogous to the first stage, the reaction can also be carried out in the melt of the reactants are at temperatures of approx. 160 - 180 ° C or in an inert solvent as described above.
  • alkylating reagents such as e.g. Methyl chloride, benzyl chloride, dimethyl sulfate or trimethyl phosphate, preferably at temperatures of 60 - 70 ° C in a lower alcohol or in toluene.
  • the products obtained in this way are very suitable for demulsifying crude oil emulsions both in the quaternized and in the partially or non-quaternized or neutralized form.
  • These crude oil emulsion products are added in a concentration of 2 to 400, preferably 5 to 50 ppm, either in undiluted form or as solutions which are diluted in a ratio of up to 1: 200 with an organic solvent.
  • R means the alkyl skeleton of a dimerized fatty acid with 34 carbon atoms.
  • the bisamide IVd is heated in a distillation apparatus with 500 g (2 mol) of tallow fatty acid until 35 ml of H 2 O have been distilled off. Then 1030 g of isobutanol are added and 120 g (2 mol) of glacial acetic acid are added dropwise at 60.degree. The acetate is obtained as a 50% solution in isobutanol.
  • the compounds of the invention of raw b lemulsionen shown at the usual conditions in the oil fields and amounts used.
  • the demulsifiers were injected as 50% isobutanolic solutions with microdosing devices.
  • the emulsified water is separated in conical, calibrated, stopper-closable glasses and the amount of emulsion used is 100 em 3 each.
  • the amounts of emulsion water separated in certain times are given in%.
  • the absolute water content of the emulsions was determined according to Dean-Stark by means of preliminary tests.
  • the dosing quantity of the demulsifiers, the absolute water content of the emulsion, the separation temperature and the origin of the emulsion are listed in the individual tables.
  • the corrosion-inhibiting action of the compounds according to the invention is determined by the weight loss of test coupons with a surface area of 20 cm 2 in 20% sodium chloride solution over 6 hours at 60 ° C. A stream of carbon dioxide constantly bubbles through the stirred, saline solution. Table 4 shows the inhibitory activity in%.

Abstract

Bisamide der Formel <IMAGE> wobei R das Alkylgerüst einer dimerisierten Fettsäure mit 22 bis 42, vorzugsweise 34 C-Atomen, R1 Wasserstoff oder eine Gruppe der Formel -(CnH2n-X)a-Zv-R2 R2 Wasserstoff oder eine Gruppe -COR3, R3 C1-C22-, vorzugsweise C8-C22-Alkyl, X ein Sauerstoffatom oder eine Gruppe der Formel N-Bm, B Wasserstoff, Methyl, Ethyl, Benzyl oder eine Gruppe der Formel -Zv-R2, n eine Zahl von 2 bis 6, vorzugsweise 2 oder 3, a eine Zahl von 0 bis 5, v eine Zahl von 0 bis 100, vorzugsweise 0 bis 20, Z eine Gruppe der Formel -C2H4X (C3H6X)b oder CH2-CHYO oder CnH2n b eine Zahl von 0 bis 5, vorzugsweise 0, 1 oder 2, i eine Zahl von 0 bis 2(a+b)+2 und A ein Anion, m eine Zahl von 1 bis 2, Y Wasserstoff, Methyl oder Ethyl bedeutet, Verfahren zu deren Herstellung und deren Verwendung als Demulgatoren von Rohölemulsionen.Bisamides of the formula <IMAGE> where R is the alkyl skeleton of a dimerized fatty acid having 22 to 42, preferably 34 C atoms, R1 is hydrogen or a group of the formula - (CnH2n-X) a-Zv-R2 R2 is hydrogen or a group -COR3, R3 C1-C22-, preferably C8-C22-alkyl, X is an oxygen atom or a group of the formula N-Bm, B is hydrogen, methyl, ethyl, benzyl or a group of the formula -Zv-R2, n is a number from 2 to 6 , preferably 2 or 3, a a number from 0 to 5, v a number from 0 to 100, preferably 0 to 20, Z a group of the formula -C2H4X (C3H6X) b or CH2-CHYO or CnH2n b a number from 0 to 5, preferably 0, 1 or 2, i is a number from 0 to 2 (a + b) +2 and A is an anion, m is a number from 1 to 2, Y is hydrogen, methyl or ethyl, process for their preparation and their Use as demulsifiers of crude oil emulsions.

Description

Bei der Förderung von Rohölemulsionen erfolgt bekanntlich eine zunehmende Verwässerung der geförderten Rohöle. Dieses mitgeförderte Wasser bildet mit dem Rohöl eine Wasser-in- Öl-Emulsion, wobei in dem einemulgierten Wasser Salze wie Natriumchlorid, Calziumchlorid und Magnesiumchlorid gelöst sein können. Außerdem sind in den Rohölemulsionen häufig Kohlensäure und Schwefelwasserstoff enthalten. All diese Substanzen bewirken Korrosionsschäden in den Fördereinrichtungen und in der Raffinerie, so daß allein schon aus diesem Grund das salzhaltige Wasser aus der Rohölemulsion mit Hilfe von Demulgatoren abgetrennt werden muß.As is well known, when crude oil emulsions are extracted there is an increasing dilution of the extracted crude oils. This co-pumped water forms a water-in-oil emulsion with the crude oil, and salts such as sodium chloride, calcium chloride and magnesium chloride can be dissolved in the emulsified water. In addition, carbonic acid and hydrogen sulfide are often contained in the crude oil emulsions. All of these substances cause corrosion damage in the conveyor systems and in the refinery, so that for this reason alone, the salty water must be separated from the crude oil emulsion with the aid of demulsifiers.

Ein Demulgator hat die Aufgabe, bei einer möglichst geringen Anwendungskonzentration die Emulsion zu brechen und bei diesem Separationsprozeß möglichst ohne Aufwendung oder mit minimaler zusätzlicher Wärme eine vollständige Wasserabscheidung zu bewirken und den Salzgehalt auf ein Minimum zu reduzieren. Die Qualitätskriterien für geliefertes Rohöl sind der Restgehalt an Salz und der Wassergehalt.The task of a demulsifier is to break the emulsion at the lowest possible application concentration and, in this separation process, to achieve complete water separation without expenditure or with minimal additional heat, and to reduce the salt content to a minimum. The quality criteria for delivered crude oil are the residual salt content and the water content.

Die Rohöle sind je nach ihrer Provinienz unterschiedlich zusammengesetzt und die im Öl vorhandenen natürlichen Emulsionsstabilisatoren besitzen einen komplizierten und differenzierten chemischen Aufbau, so daß für jedes gezielt Spalter entwickelt werden müssen. Bedingt durch unterschiedliche Förderungs- und Aufbereitungsbedingungen werden die Anforderungen, die an einen Demulgator gestellt werden, noch vielfältiger. Durch das ständige Erschließen neuer und Änderung der Förderbedingungen älterer Ölfelder bleibt daher die Entwicklung optimaler Demulgatoren für den jeweiligen Zweck eine akute Aufgabe.The crude oils have different compositions depending on their provinces and the natural emulsion stabilizers in the oil have a complicated and differentiated chemical structure, so that splitters have to be developed for each one. Due to different funding and processing conditions, the demands placed on a demulsifier are even more diverse. By constantly opening up new and changing the production conditions of older oil fields, the development of optimal demulsifiers for the respective purpose remains an acute task.

Als nichtionische Demulgatoren für Erdölemulsionen sind bereits Umsetzungsprodukte von Alkylenoxid mit Alkylphenol-Aldehyd-Harzen bekannt (US-PS 2 499 368, 2 499 270, 2 560 333 und 2 574 543). Auch die Verwendung von Block-und Mischpolymerisaten aus Propylenoxid und Ethylenoxid für diesen Zweck ist bekannt (FR-PS 1 069 615 und DE-PS 1 018 179).Reaction products of alkylene oxide with alkylphenol-aldehyde resins are already known as nonionic demulsifiers for petroleum emulsions (US Pat. Nos. 2,499,368, 2,499,270, 2,560,333 and 2,574,543). The use of block and copolymers of propylene oxide and ethylene oxide for this purpose is also known (FR-PS 1 069 615 and DE-PS 1 018 179).

Es wurde nun gefunden, daß neue Bisamide neben ihrer ausgezeichneten Wirkung als Demulgatoren für Rohöl auch gute Effekte als Korrosionsinhibitoren zeigen.It has now been found that new bisamides, in addition to their excellent action as demulsifiers for crude oil, also have good effects as corrosion inhibitors.

Gegenstand der Erfindung sind neue Bisamide der Formel

Figure imgb0001

  • wobei R das Alkylgerüst einer dimerisierten Fettsäure mit 22 bis 42, vorzugsweise 34 C-Atomen,
  • R1 Wasserstoff oder eine Gruppe der Formel -(CnH2n-X)a-Zv-R2,
  • R2 Wasserstoff oder eine Gruppe -COR3,
  • R 3 C1-C22-, vorzugsweise C8-C22-Alkyl,
  • X ein Sauerstoffatom oder eine Gruppe der Formel N-Bm,
  • B Wasserstoff, Methyl, Ethyl, Benzyl oder eine Gruppe der Formel -Zv-R2,
  • n eine Zahl von 2 bis 6, vorzugsweise 2 oder 3,
  • a eine Zahl von 0 bis 5,
  • v eine Zahl von 0 bis 100, vorzugsweise 0 bis 20,
  • Z eine Gruppe der Formel
    -C2H4X ( C3H6X)b oder CH2-CHY-0 oder CnH2n
  • m 1 oder 2
  • Y Wasserstoff, Methyl, Ethyl,
  • b eine Zahl von 0 bis 5, vorzugsweise 0, 1 oder 2,
  • i eine Zahl von 0 bis 2 (a+b)+2 und
  • A ein Anion bedeutet, wie beispielsweise das Chlorid-, Bromid-, Methylsulfat-, Ethylsulfat- oder Dialkylphosphat-Ion.
The invention relates to new bisamides of the formula
Figure imgb0001
  • where R is the alkyl skeleton of a dimerized fatty acid with 22 to 42, preferably 34 C atoms,
  • R 1 is hydrogen or a group of the formula - (C n H 2n -X) a -Z v -R 2 ,
  • R 2 is hydrogen or a group -COR 3 ,
  • R 3 is C 1 -C 22 , preferably C 8 -C 22 alkyl,
  • X is an oxygen atom or a group of the formula NB m ,
  • B is hydrogen, methyl, ethyl, benzyl or a group of the formula -Z v -R 2 ,
  • n is a number from 2 to 6, preferably 2 or 3,
  • a is a number from 0 to 5,
  • v is a number from 0 to 100, preferably 0 to 20,
  • Z is a group of the formula
    -C 2 H 4 X (C 3 H 6 X) b or CH 2 -CHY-0 or C n H 2n
  • m 1 or 2
  • Y is hydrogen, methyl, ethyl,
  • b is a number from 0 to 5, preferably 0, 1 or 2,
  • i a number from 0 to 2 (a + b) +2 and
  • A represents an anion, such as the chloride, bromide, methyl sulfate, ethyl sulfate or dialkyl phosphate ion.

Die oben aufgeführten Symbole X, B, R1, R2, Z, n, a, v und b können innerhalb einer Verbindung jeweils gleiche oder voneinander verschiedene Bedeutungen annehmen.The symbols X, B, R 1 , R 2 , Z, n, a, v and b listed above can each have the same or different meanings within a compound.

Die Herstellung der Verbindungen der obigen Formel erfolgt, indem man zunächst eine dimerisierte Fettsäure der Formel II

Figure imgb0002
mit einer Verbindung der Formel III
Figure imgb0003
zu einer Verbindung der Formel IV kondensiert,
Figure imgb0004
diese Verbindung der Formel IV gegebenenfalls mit Ethylenoxid und/oder Propylenoxid bzw. Butylenoxid umsetzt, das erhaltene Reaktionsprodukt mit einer Säure der Formel V
Figure imgb0005
verestert und anschließend gegebenenfalls neutralisiert oder quaternisiert.The compounds of the above formula are prepared by firstly using a dimerized fatty acid of the formula II
Figure imgb0002
with a compound of formula III
Figure imgb0003
condensed to a compound of formula IV,
Figure imgb0004
this compound of the formula IV optionally reacted with ethylene oxide and / or propylene oxide or butylene oxide, the reaction product obtained with an acid of the formula V.
Figure imgb0005
esterified and then optionally neutralized or quaternized.

Als dimerisierte Fettsäure kommen vorzugsweise die Produkte in Frage, die unter den Bezeichnungen (R) Fripol 1010, (R) pri- pol 1022 und Fatty Acid 7002 im Handel erhältlich sind. Siehe auch R. W. Johnson in "Fatty acids" Diese Produkte können auch Anteile von trimeren oder höher kondensierten Fettsäuren enthalten. So enthält zum Beispiel Pripoll022 ca. 20 % trimere Anteile undpripol 1010 nur ca. 3 %. Die dimerisierten Fettsäuren werden zunächst kondensiert mit zwei Mol einer Verbindung der Formel III. Derartige Verbindungen sind beispielsweise Aminoethylethanolamin, Diethanolamin., Propylendiamin, Alkylpropylendiamin, Ethylendiamin, Diethylentriamin, Triethylentetramin, Tetramethylenpentamin, Pentaethylenhexamin, gemischte Ethylen/ Propylen-Polyamine wie 3-(2-Aminoethyl)aminopropylamin, N,N'-Bis-(3-aminopropyl)-ethylendiamin.Preferred dimerized fatty acids are the products which are commercially available under the names (R) Fripol 1010, (R) pripol 1022 and Fatty Acid 7002. See also RW Johnson in "Fatty acids" These products can also contain parts of trimeric or higher condensed fatty acids. For example, Pr ip ol L022 20% contains trimeric shares and p r ip ol 1010 only about 3%. The dimerized fatty acids are first condensed with two moles of a compound of formula III. Such compounds are, for example, aminoethylethanolamine, diethanolamine., Propylene diamine, alkyl propylene diamine, ethylene diamine, diethylene triamine, triethylene tetramine, tetramethylene pentamine, pentaethylene hexamine, mixed ethylene / propylene polyamines such as 3- (2-aminoethyl) aminopropylamine, N, N'-bis- (3 ) ethylenediamine.

Die Kondensation kann erfolgen ohne Lösemittel in der Schmelze der Reaktionspartner oder in Gegenwart eines inerten Lösemittels bei den Siedetemperaturen des Lösemittels. Als Lösemittel dient hier vorzugsweise Toluol oder Xylol, das gleichzeitig dazu dient, das gebildete Reaktionswasser zu entfernen.The condensation can take place without solvent in the melt of the reactants or in the presence of an inert solvent at the boiling point of the solvent. The solvent used here is preferably toluene or xylene, which also serves to remove the water of reaction formed.

Das bei dieser Kondensation entstandene Bisamid der Formel IV kann dann nach bekannten Methoden oxalkyliert werden, vorzugsweise in Gegenwart eines basischen Katalysators wie Natriummethylat oder Natriumhydroxid. Als Alkylenoxide kommen vorzugsweise Ethylenoxid in Frage aber auch Mischungen von Ethylenoxid mit Propylenoxid oder Butylenoxid.The bisamide of formula IV formed in this condensation can then be alkoxylated by known methods, preferably in the presence of a basic catalyst such as sodium methylate or sodium hydroxide. Preferred alkylene oxides are ethylene oxide, but also mixtures of ethylene oxide with propylene oxide or butylene oxide.

Diese Oxalkylierungsprodukte oder die Bisamide der Formel IV, werden dann mit einer oder mehreren Carbonsäuren der Formel V verestert. Als Carbonsäuren werden vorzugsweise Ca-C22-Fettsäuren verwendet. Das Mengenverhältnis zwischen Carbonsäuren und Bisamiden der Formel IV bzw. dessen Oxalkylierungsprodukten kann so gewählt werden, daß eine oder mehrere Acylgruppen in dem Ester vorhanden sind.These oxyalkylation products or the bisamides of the formula IV are then esterified with one or more carboxylic acids of the formula V. C a -C 22 fatty acids are preferably used as carboxylic acids. The quantitative ratio between carboxylic acids and bisamides of the formula IV or its oxyalkylation products can be chosen so that one or more acyl groups are present in the ester.

Die Veresterung kann erfolgen mit reinen Carbonsäuren der Formel V oder mit Mischungen verschiedener derartiger Carbonsäuren. Analog zu der ersten Stufe kann auch hier die Reaktion in der Schmelze der Reaktionspartner durchgeführt werden bei Temperaturen von ca. 160 - 180°C oder in einem inerten Lösungsmittel wie oben beschrieben.The esterification can be carried out with pure carboxylic acids of the formula V or with mixtures of various such carboxylic acids. Analogous to the first stage, the reaction can also be carried out in the melt of the reactants are at temperatures of approx. 160 - 180 ° C or in an inert solvent as described above.

Die so erhaltenen Ester können dann noch neutralisiert oder quäterniert werden, entweder durch einfache Addition von Säuren für den Fall B=H oder durch Umsetzung mit alkylierenden Reagenzien wie z.B. Methylchlorid, Benzylchlorid, Dimethylsulfat oder Trimethylphosphat, vorzugsweise bei Temperaturen von 60 - 70°C in einem niederen Alkohol oder in Toluol.The esters thus obtained can then be neutralized or quaternized, either by simple addition of acids for the case B = H or by reaction with alkylating reagents such as e.g. Methyl chloride, benzyl chloride, dimethyl sulfate or trimethyl phosphate, preferably at temperatures of 60 - 70 ° C in a lower alcohol or in toluene.

Die so erhaltenen Produkte eignen sich sowohl in der quaternisierten wie auch in der teil- oder nichtquaternisierten bzw. neutralisierten Form sehr gut zum Demulgieren von Rohölemulsionen. Man setzt diese Produkte der Rohölemulsion in Konzentration von 2 bis 400, vorzugsweise 5 bis 50 ppm zu entweder in unverdünnter Form oder als Lösungen, die im Verhältnis bis 1:200 mit einem organischen Lösungsmittel verdünnt werden.The products obtained in this way are very suitable for demulsifying crude oil emulsions both in the quaternized and in the partially or non-quaternized or neutralized form. These crude oil emulsion products are added in a concentration of 2 to 400, preferably 5 to 50 ppm, either in undiluted form or as solutions which are diluted in a ratio of up to 1: 200 with an organic solvent.

Die folgenden Beispiele sollen die Erfindung erläutern.The following examples are intended to illustrate the invention.

Allgemeine Arbeitsvorschrift zur Herstellung von Bisamiden der Formel IV:

  • In einer Destillationsapparatur werden 0.5 Mol einer dimeren Fettsäure mit einem Mol eines Amins ohne Lösungsmittel erhitzt, bis 18 ml H20 abdestilliert sind. Man erhält viskose, nach Erwärmen gießbare Produkte.
General working instructions for the production of bisamides of the formula IV:
  • In a distillation apparatus, 0.5 mol of a dimeric fatty acid is heated with one mol of an amine without a solvent until 18 ml of H 2 O have been distilled off. Viscous products which can be poured after heating are obtained.

Herstellung von IVa:Production of IVa:

Nach der allg. Arbeitsvorschrift aus 285 g (0.5 Mol) Pripol 1022 und 104 g (1 Mol) Aminoethylethanolamin.According to the general. Procedure of 285 g (0.5 mol) of P RIPOL 1022 and 104 g (1 mole) of aminoethylethanolamine.

Herstellung von IVb:Production of IVb:

Aus 285 g (0.5 Mol)pripol 1022 und 103 g (1 Mol) Diethylentriamin.From 285 g (0.5 mol) pripol 1022 and 103 g (1 mol) diethylenetriamine.

Herstellung von IVc:Production of IVc:

Aus 420 g (0.5 Mol) Fatty Acid 7002 und 60 g (1 Mol) Ethylendiamin.From 420 g (0.5 mol) of Fatty Acid 7002 and 60 g (1 mol) of ethylenediamine.

Herstellung von IVd:Production of IVd:

Aus 285 g (0.5 Mol) Pripol 1010 und 180 g (1 Mol) Tetraethylenpentamin.From 285 g (0.5 mol) Pripol 1010 and 180 g (1 mol) tetraethylene pentamine.

Beispiel 1:Example 1:

An das nach der allg. Arbeitsvorschrift hergestellte Bisamid IVa werden nach bekannter Methode 660 g (15 Mol) Ethylenoxid addiert. Dann werden 250 g (1 Mol) Stearinsäure zugegeben und in einer Destillationsapparatur erhitzt, bis 18 g H20 abdestilliert sind. Man fügt 1300 g Isobutanol zu und setzt in einem Autoklaven mit Methylchlorid um, bis keine weitere Aufnahme mehr erfolgt. Man erhält eine 50 $ige Lösung in Isobutanol der Verbindung der Formel

Figure imgb0006
660 g (15 mol) of ethylene oxide are added to the bisamide IVa produced according to the general working instructions by a known method. Then 250 g (1 mol) of stearic acid are added and the mixture is heated in a distillation apparatus until 18 g of H 2 O have been distilled off. 1300 g of isobutanol are added and the mixture is reacted with methyl chloride in an autoclave until no further absorption takes place. A 50 $ solution in isobutanol of the compound of the formula is obtained
Figure imgb0006

V1 + V2 = 30; R bedeutet hier und im folgenden das Alkylgerüst einer dimerisierten Fettsäure mit 34 C-Atomen.V 1 + V 2 = 30; Here and below, R means the alkyl skeleton of a dimerized fatty acid with 34 carbon atoms.

Beispiel 2:Example 2:

Das Bisamid IVb wird in einer Destillationsapparatur mit 120 g (0.5 Mol) Talgfettsäure erhitzt, bis 8 ml H20 abdestilliert sind. Dann werden in einem Autoklaven nach bekannter Weise 280 g (5 Mol) Propylenoxid addiert, anschließend fügt man 250 g (1 Mol) Stearinsäure zu und destilliert 18 g H20 ab. Nach Zugabe von 990 g Isobutanol erhält man eine braune, gießbare Flüssigkeit mit einem Substanzgehalt von 50 %, darunter als Hauptkomponente die Verbindung der Formel

Figure imgb0007
R3 = Talgfettalkyl, V1 + V2 +2V3 = 10The bisamide IVb is heated in a distillation apparatus with 120 g (0.5 mol) of tallow fatty acid until 8 ml of H 2 O have been distilled off. Then 280 g (5 mol) of propylene oxide are added in an autoclave in a known manner, then 250 g (1 mol) of stearic acid are added and 18 g of H 2 O are distilled off. After adding 990 g of isobutanol, a brown, pourable liquid with a substance content of 50% is obtained, including the compound of the formula as the main component
Figure imgb0007
R 3 = tallow fatty alkyl, V 1 + V 2 + 2V 3 = 10

Beispiel 3:Example 3:

An das Bisamin IVc werden nach üblicher Methode 220 g (0.5 Mol) Ethylenoxid und 280 g (5 Mol) Propylenoxid addiert. Dann mwird mit 250 g (1 Mol) Talgfettsäure wie in Beispiel 1 verestert. Man gibt anschließend 1400 g Isobutanol zu, tropft bei 65°C 250 g (2 Mol) Dimethylsulfat und 80 g 50 %ige NaOH zu und rührt noch 2 Stunden bei dieser Temperatur nach. Man erhält eine 50 %ige Lösung der Wirksubstanz der Formel

Figure imgb0008
X = H + CH3, v1 + v2 = 20,
R3 = Talgfettalkyl.220 g (0.5 mol) of ethylene oxide and 280 g (5 mol) of propylene oxide are added to the bisamine IVc by the customary method. Then is esterified with 250 g (1 mol) of tallow fatty acid as in Example 1. 1400 g of isobutanol are then added, 250 g (2 mol) of dimethyl sulfate and 80 g of 50% NaOH are added dropwise at 65 ° C. and the mixture is stirred for a further 2 hours at this temperature. A 50% solution of the active substance of the formula is obtained
Figure imgb0008
X = H + CH 3 , v 1 + v 2 = 20,
R 3 = tallow fatty alkyl.

Beispiel 4:Example 4:

Das Bisamid IVd wird in einer Destillationsapparatur mit 500 g (2 Mol) Talgfettsäure erhitzt, bis 35 ml H20 abdestilliert sind. Dann gibt man 1030 g Isobutanol zu und tropft bei 60°C 120 g (2 Mol) Eisessig zu. Man erhält das Acetat als 50 %ige Lösung in Isobutanol.The bisamide IVd is heated in a distillation apparatus with 500 g (2 mol) of tallow fatty acid until 35 ml of H 2 O have been distilled off. Then 1030 g of isobutanol are added and 120 g (2 mol) of glacial acetic acid are added dropwise at 60.degree. The acetate is obtained as a 50% solution in isobutanol.

Beispiel 5:Example 5:

In einer Destillationsapparatur werden 285 g (0.5 Mol) Pripol 1022 mit 105 g (1 Mol) Diethanolamin erhitzt, bis 18 ml H20 abdestilliert sind. Dann gibt man 240 g (1 Mol) Talgfettsäure zu und destilliert weitere 18 ml H20 ab. Nach Zugabe von 590 g Isobutanol erhält man eine 50 %ige Lösung der Wirksubstanz der Formel

Figure imgb0009
R 3 = Talgfettalkyl.In a distillation apparatus, 285 g (0.5 mol) of Pripol 1022 are heated with 105 g (1 mol) of diethanolamine until 18 ml of H 2 O have been distilled off. Then 240 g (1 mol) of tallow fatty acid are added and a further 18 ml of H 2 O are distilled off. After adding 590 g of isobutanol, a 50% solution of the active substance of the formula is obtained
Figure imgb0009
R 3 = tallow fatty alkyl.

Im folgenden wird die demulgierende Wirkung der erfindungsgemäßen Verbindungen an Rohblemulsionen bei den in den Ölfeldern üblichen Bedingungen und Einsatzmengen gezeigt. Die Demulgatoren wurden dabei als 50 %ige isobutanolische Lösungen mit Mikrodosiereinrichtungen injiziert. Die Abscheidung des emulgierten Wassers erfolgt in konischen, kalibrierten, mit Stopfen verschließbaren Gläsern und die Emulsionseinsatzmenge beträgt jeweils 100 em3. In den Versuchstabellen werden die in bestimmten Zeiten abgeschiedenen Mengen Emulsionswasser in % angegeben. Durch Vorversuche wurde der absolute Wassergehalt der Emulsionen jeweils nach Dean-Stark bestimmt. Die Dosiermenge der Demulgatoren, der absolute Wassergehalt der Emulsion, die Separiertemperatur und der Emulsionsursprung sind in den einzelnen Tabellen aufgeführt.

Figure imgb0010
Figure imgb0011
Figure imgb0012
In the following the demulsifying action, the compounds of the invention of raw b lemulsionen shown at the usual conditions in the oil fields and amounts used. The demulsifiers were injected as 50% isobutanolic solutions with microdosing devices. The emulsified water is separated in conical, calibrated, stopper-closable glasses and the amount of emulsion used is 100 em 3 each. In the test tables, the amounts of emulsion water separated in certain times are given in%. The absolute water content of the emulsions was determined according to Dean-Stark by means of preliminary tests. The dosing quantity of the demulsifiers, the absolute water content of the emulsion, the separation temperature and the origin of the emulsion are listed in the individual tables.
Figure imgb0010
Figure imgb0011
Figure imgb0012

Inhibierung der KorrosionInhibition of corrosion

Die korrosionsinhibierende Wirkung der erfindungsgemäßen Verbindungen wird durch den Gewichtsverlust von Test-Coupons mit 20 cm2 Oberfläche in 20 %iger Natriumchloridlösung über 6 Stunden bei 60°C ermittelt. Durch die gerührte, saline Lösung perlt ständig ein Strom von Kohlendioxid. Die Tabelle 4 gibt die Inhibierwirkung in % an.

Figure imgb0013
The corrosion-inhibiting action of the compounds according to the invention is determined by the weight loss of test coupons with a surface area of 20 cm 2 in 20% sodium chloride solution over 6 hours at 60 ° C. A stream of carbon dioxide constantly bubbles through the stirred, saline solution. Table 4 shows the inhibitory activity in%.
Figure imgb0013

Claims (3)

1. Bisamide der Formel
Figure imgb0014
wobei R das Alkylgerüst einer dimerisierten Fettsäure mit 22 bis 42, vorzugsweise 34 C-Atomen, R1 Wasserstoff oder eine Gruppe der Formel -(CnH2n-X)a-Zv-R2 R2 Wasserstoff oder eine Gruppe -COR3, R 3 C1-C22-, vorzugsweise C8-C22-Alkyl, X ein Sauerstoffatom oder eine Gruppe der Formel N-Bm, B Wasserstoff, Methyl, Ethyl, Benzyl oder eine Gruppe der Formel -Zv-R2, n eine Zahl von 2 bis 6, vorzugsweise 2 oder 3, a eine Zahl von 0 bis 5, v eine Zahl von 0 bis 100, vorzugsweise 0 bis 20, Z eine Gruppe der Formel -C2H4X (C3H6X)b oder CH2-CHYO oder CnH2n b eine Zahl von 0 bis 5, vorzugsweise 0, 1 oder 2, i eine Zahl von 0 bis 2(a+b)+2 und A ein Anion, m 1 oder 2, Y Wasserstoff, Methyl oder Ethyl bedeutet.
1. Bisamides of the formula
Figure imgb0014
where R is the alkyl skeleton of a dimerized fatty acid with 22 to 42, preferably 34 C atoms, R 1 is hydrogen or a group of the formula - (C n H 2n -X) a -Z v -R 2 R 2 is hydrogen or a group -COR 3 , R 3 is C 1 -C 22 , preferably C 8 -C 22 alkyl, X is an oxygen atom or a group of the formula NB m , B is hydrogen, methyl, ethyl, benzyl or a group of the formula -Z v -R 2 , n is a number from 2 to 6, preferably 2 or 3, a is a number from 0 to 5, v is a number from 0 to 100, preferably 0 to 20, Z is a group of the formula -C 2 H 4 X (C 3 H 6 X) b or CH 2 -CHYO or C n H 2n b is a number from 0 to 5, preferably 0, 1 or 2, i a number from 0 to 2 (a + b) +2 and A an anion, m 1 or 2, Y represents hydrogen, methyl or ethyl.
2. Verfahren zur Herstellung der Bisamide nach Anspruch 1, dadurch gekennzeichnet, daß man
zunächst eine dimerisierte Fettsäure der Formel II
Figure imgb0015
mit einer Verbindung der Formel III
Figure imgb0016
zu einer Verbindung der Formel IV kondensiert,
Figure imgb0017
diese Verbindung der Formel IV gegebenenfalls mit Ethylenoxid und/oder Propylenoxid bzw. Butylenoxid umsetzt, das erhaltene Reaktionsprodukt mit einer Säure der Formel V
Figure imgb0018
verestert und anschließend gegebenenfalls neutraliesiert oder quaternisiert.
2. A process for the preparation of the bisamides according to claim 1, characterized in that
first a dimerized fatty acid of formula II
Figure imgb0015
with a compound of formula III
Figure imgb0016
condensed to a compound of formula IV,
Figure imgb0017
this compound of the formula IV optionally reacted with ethylene oxide and / or propylene oxide or butylene oxide, the reaction product obtained with an acid of the formula V.
Figure imgb0018
esterified and then optionally neutralized or quaternized.
3. Verwendung der Bisamide nach Anspruch 1 als Demulgatoren für Rohölemulsionen.3. Use of the bisamides according to claim 1 as demulsifiers for crude oil emulsions.
EP82108171A 1981-09-10 1982-09-04 Bisamides, processes for their preparation and their use Withdrawn EP0074592A3 (en)

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DE19813135832 DE3135832A1 (en) 1981-09-10 1981-09-10 BISAMID, METHOD FOR THE PRODUCTION AND USE THEREOF

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