EP0572881A1 - Process for the separation of water in oil emulsions - Google Patents
Process for the separation of water in oil emulsions Download PDFInfo
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- EP0572881A1 EP0572881A1 EP93108316A EP93108316A EP0572881A1 EP 0572881 A1 EP0572881 A1 EP 0572881A1 EP 93108316 A EP93108316 A EP 93108316A EP 93108316 A EP93108316 A EP 93108316A EP 0572881 A1 EP0572881 A1 EP 0572881A1
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- fatty amine
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- dicarboxylic acid
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- 0 *N(*)C1*C1 Chemical compound *N(*)C1*C1 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING 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
- C10G33/00—Dewatering or demulsification of hydrocarbon oils
- C10G33/04—Dewatering or demulsification of hydrocarbon oils with chemical means
Definitions
- the invention relates to a method for separating petroleum emulsions of the water-in-oil type using ester products.
- oil is diluted when oil is extracted.
- the water that is conveyed forms a water-in-oil emulsion with the oil.
- Salts such as sodium chloride, calcium chloride and / or magnesium chloride can be dissolved in the emulsified water.
- the emulsion water must be separated before the oil is transported to the refinery. In the refinery, before the distillation, the salt content is further reduced by renewed emulsion formation with fresh water and demulsification. A too high salt content in the crude oil could lead to malfunctions and corrosion in the refinery.
- a petroleum splitter also called a demulsifier or emulsion splitter, has the task of breaking the emulsion in as low a concentration as possible and, in this separation process, as far as possible without water or with minimal additional expenditure of heat and to achieve complete water separation and to reduce the salt content to a minimum.
- the quality criteria for delivered crude oil are the residual salt and the water content.
- the crude oils have different compositions depending on their provenance.
- the natural emulsion stabilizers have a complex, differentiated chemical Construction.
- selective splitters have to be developed.
- the different requirements for a petroleum splitter become even more diverse due to different production and processing conditions. Due to the constant opening up of new oil fields and the change in the production conditions of older oil fields, the development of optimal demulsifiers remains an acute problem, and a large number of different types of demulsifiers and demulsifier mixtures are required.
- esterification products are described as petroleum splitters in US Pat. No. 4,734,523 and in European Patent Application 0 333 135 A2 (Derwent unit, Accession Number 89-271925 / 38).
- the splitters in the US patent are reaction products of an oxyalkylated primary fatty amine and a diol compound with a dicarboxylic acid and those of the European patent application are reaction products of an oxyalkylated primary fatty amine and an adduct of a diol compound and a glycidyl ether with a dicarboxylic acid. With these demulsifiers a good and quick separation of water and salt is achieved.
- esterification products from an oxyalkylated primary fatty amine (as the sole component which supplies OH groups) and a dicarboxylic acid are also very effective petroleum splitters and that this is particularly the case when the esterification product consists of an oxyalkylated primary fatty amine and a dicarboxylic acid the group of dimeric (dimerized) fatty acids.
- the process according to the invention for separating petroleum emulsions of the water-in-oil type is accordingly characterized in that the emulsions are treated with an effective amount of an esterification product from an oxyalkylated primary fatty amine of the formula 1 below wherein R1 is an alkyl radical or alkenyl radical having 6 to 23 carbon atoms, R2 is H or CH3 and within the chain of the polyoxalkylene radical, arranged in blocks or randomly, can also take on both meanings, and a and b are numbers from a total of 2 to 30 , with the proviso that neither a nor b is zero, and 0.5 to 1.5 moles per mole of oxyalkylated primary fatty amine, preferably 0.5 to 1.1 moles per mole of oxyalkylated primary fatty amine, of a dicarboxylic acid, preferably one from the group of dimeric fatty acids.
- R1 is an alkyl radical or alkenyl radical having 6 to 23 carbon atom
- ester products would also be suitable as demulsifiers for any emulsion or even water-in-oil petroleum emulsions, and the preferred esterification products according to the invention (that is, those of an oxyalkylated primary fatty amine and a dimeric fatty acid as Dicarboxylic acid components) are not even mentioned in the two documents, they should rather be regarded as new.
- R 1 is a Is an alkyl radical with 8 to 18 carbon atoms or an alkenyl radical with 8 to 18 carbon atoms (it preferably contains 1 to 3 double bonds)
- R 2 is H and a and b (identical or different, whole or fractional) numbers from a total of 2 to 15, taking into account the stipulation given above.
- the oxyalkylation of primary fatty amines is well known and can be carried out by one of the methods for the oxyalkylation of compounds bearing acidic (active) H atoms.
- the oxyalkylated fatty amines can contain units of ethylene oxide or propylene oxide or units of ethylene oxide and propylene oxide which are present in random or block form in accordance with the meanings of R 2, preference being given to the ethoxylated primary fatty amines, ie those containing only ethylene oxide units.
- the fatty amines used for the oxyalkylation can, according to the meanings of R 1, be individual primary fatty amines or mixtures thereof.
- fatty amines whose hydrocarbon chain contains one or more double bonds, such as the residues of oleic, linoleic or linolenic acid.
- the preferred primary fatty amines are the technically available products such as stearylamine, coconut fatty amine or tallow fatty amine (in these technical products there are alkyl residues with essentially 8 to 18 carbon atoms).
- Preferred dicarboxylic acids are those of formula 2 below (these are simple dicarboxylic acids) HOOC-R3-COOH wherein R3 is an alkylene radical of the formula - (CH2) z -, in which z is an integer from 1 to 10, preferably 4 to 8, and wherein the alkylene radical with 1 or 2 OH groups or with 1 or 2 C1 to C18 -Alkyl or C3 to C18 alkenyl may be substituted, or is a vinylene radical or a p-phenylene radical, and those of formula 3 below (these are dicarboxylic acids from the group of dimerized unsaturated C18 fatty acids) HOOC-R4-COOH in which R4 is a divalent hydrocarbon radical with 34 C atoms (R4 thus represents the radical containing 34 C atoms which is formed during the dimerization of an unsaturated fatty acid with 18 C atoms to a dicarboxylic acid with a total of 36 C atoms).
- malonic acid succinic acid, glutaric acid, adipic acid, pimelic acid and so on may be mentioned in the homologous series, furthermore tartronic acid, malic acid and tartaric acid as well as fumaric acid and maleic acid and finally terephthalic acid.
- Particularly preferred simple dicarboxylic acids are those of the homologous series from adipic acid to sebacic acid, furthermore maleic acid, fumaric acid, dodecylsuccinic acid and dodecenylsuccinic acid. It goes without saying that instead of these dicarboxylic acids it is also possible to use their anhydrides, halides or esters of lower alkanols.
- Dimeric fatty acids are usually produced by addition polymerization (dimerization) of mono- or polyunsaturated fatty acids.
- the number of carbon atoms and the structure of the dicarboxylic acids obtained essentially depend on the starting fatty acids and on the reaction conditions during the dimerization.
- Various types and structures of dimeric fatty acids are commercially available.
- dimeric fatty acids preferred those which are produced by dimerization of unsaturated C18 fatty acids, for example oleic acid, linoleic acid, linolenic acid or tallow fatty acid (dimerization is known to mean the union of two identical molecules to form a new molecule, the dimer, by addition reaction).
- the dimerization of C18 fatty acids is usually carried out at a temperature of 150 to 250 ° C, preferably 180 to 230 ° C, with or without a dimerization catalyst.
- the dicarboxylic acid obtained (this is the dimeric fatty acid) corresponds to the formula 3 given, where R4 is the divalent link formed in the dimerization of the C18 fatty acid, which carries the two -COOH groups and has 34 carbon atoms.
- R4 is preferably an acyclic (aliphatic) or a mono- or bicyclic (cycloaliphatic) radical with 34 C atoms.
- the acyclic radical is usually a branched (substituted) and mono- to trisaturated alkyl radical with 34 carbon atoms.
- the cycloaliphatic radical generally also has 1 to 3 double bonds.
- the preferred dimeric fatty acids described are generally a mixture of two or more dicarboxylic acids of the formula 3 with structurally different R4 radicals.
- the dicarboxylic acid mixture often has a more or less large content of trimeric fatty acids which have arisen during the dimerization and have not been removed during the working up of the product by distillation.
- dimeric fatty acids which are formed in the dimerization of the C1, fatty acids mentioned are given in terms of formula, the hydrocarbon radical bearing the two -COOH groups being an acyclic, monocyclic or bicyclic radical:
- the dicarboxylic acids described ie the simple dicarboxylic acids and the dimeric fatty acids, the latter are preferred; they are generally technical products which are commercially available under the name "dimerized fatty acids” or "dimer fatty acids” and, as already mentioned above, can contain a more or less high proportion of trimerized fatty acids.
- the polycondensation esterification can be carried out using a higher-boiling inert solvent such as toluene, xylene or technical aromatic cuts or without solvent in the melt and under cover with a protective gas, preference being given to carrying out in solvents is.
- the reflux temperature of the reaction mixture is expediently chosen as the reaction temperature and the water of reaction formed is removed azeotropically.
- the water of reaction is distilled off directly from the reaction mixture.
- the reaction temperature is 100 to 220 ° C, preferably 130 to 200 ° C.
- an alkaline or acidic catalyst is used, as is expedient in esterification reactions, acidic catalysis with, for example, hydrohalic acid, phosphoric acid, sulfuric acid, sulfonic acid or haloacetic acid as the catalyst being preferred.
- acidic catalysis with, for example, hydrohalic acid, phosphoric acid, sulfuric acid, sulfonic acid or haloacetic acid as the catalyst being preferred.
- the course and the end of the reaction can be checked using the water of reaction formed or by determining the acid number. It is preferred to conduct the reaction to about 90 to 100% conversion, that is, until essentially no more water of reaction is formed.
- the procedure is preferably such that the two reaction components in the stated molar ratio, furthermore a solvent and acidic esterification catalyst are placed in a reaction vessel and this mixture is stirred at 100 to 220 ° C., preferably 130, while passing through an inert gas to 200 ° C, heated and held at this temperature with continuous discharge of the water formed (azeotropic distillation) until the reaction is complete.
- the esterification product obtained which generally has an acid number of ⁇ 10, preferably 2 to 8, can be purified from the catalyst used by washing with water and is the petroleum splitter according to the invention.
- the reaction time is in the range from 5 to 20 h.
- These esterification products are yellow to brown colored, more or less viscous liquids. They have a special chemical, especially when a dimerized fatty acid is used Structure on. Since their preparation is preferably carried out in the presence of solvents, they are generally in the form of a concentrated solution (active substance content preferably 60 to 80% by weight).
- the ester products (polyester) proposed according to the invention are notable for a high demulsifying effect.
- complete water separation and a reduction in salinity are achieved after a short separation time.
- raw oils that are specific to the consumption are obtained after a short separation time at the usual processing temperatures. They also have the effect that the separated water is practically free of oil, so that a complete oil separation from the separated water and thus good water quality is achieved.
- oil splitters a sharp separation between the oil and water phases is also achieved, which is another great advantage.
- the amount of demulsifier used according to the invention can vary within wide limits. It depends in particular on the type of petroleum and the processing temperature.
- the effective amount is generally 5 to 100 g per ton, preferably 10 to 50 g per ton.
- the splitters described are preferably used in solution for the purpose of better dosage and distributability.
- Water or organic liquids are suitable as solvents, for example alcohols such as methanol, isopropanol and / or butanol, aromatic hydrocarbons such as toluene and / or xylene or commercially available mixtures of higher aromatics.
- the two reaction components are therefore used in a molar ratio of 1: 1.
- 205 g of xylene are added as solvent, which is 25% by weight, based on the total weight of the two reaction components.
- the mixture is heated and kept at a temperature of 130 to 140 ° C for 2 hours, the reaction components reacting with esterification and the water of reaction distilled off azeotropically.
- the mixture is kept at a temperature of 160 to 170 ° C. for a further 10 hours.
- the course and the end of the esterification reaction are followed by determining the acid number.
- the esterification product obtained with a degree of conversion of 98% is a liquid with a viscosity of 1.1 Pa s.
Abstract
Description
Die Erfindung betrifft ein Verfahren zum Trennen von Erdölemulsionen vom Wasser-in-Öl-Typ unter Verwendung von Esterprodukten.The invention relates to a method for separating petroleum emulsions of the water-in-oil type using ester products.
Bei der Förderung von Erdöl tritt bekanntlich eine Verwässerung des Öls ein. Das mitgeförderte Wasser bildet mit dem Öl eine Wasser-in-Öl-Emulsion. In dem emulgierten Wasser können Salze wie Natriumchlorid, Calciumchlorid und/oder Magnesiumchlorid gelöst sein. Das Emulsionswasser muß vor dem Transport des geförderten Öls zur Raffinerie abgetrennt werden. In der Raffinerie wird vor der Destillation der Salzgehalt durch eine erneute Emulsionsbildung mit Süßwasser und Demulgierung weiter abgesenkt. Ein zu hoher Salzgehalt im Rohöl könnte zu Störungen und Korrosion in der Raffinerie führen. Ein Erdölspalter, auch Demulgator oder Emulsionsspalter genannt, hat die Aufgabe, in möglichst geringer Konzentration die Emulsion zu brechen und bei diesem Separationsprozeß möglichst ohne oder mit minimaler zusätzlicher Aufwendung von Wärme eine vollständige Wasserabscheidung zu bewirken und den Salzgehalt auf ein Minimum zu reduzieren. Die Qualitätskriterien für geliefertes Rohöl sind das Restsalz und der Wassergehalt.As is well known, oil is diluted when oil is extracted. The water that is conveyed forms a water-in-oil emulsion with the oil. Salts such as sodium chloride, calcium chloride and / or magnesium chloride can be dissolved in the emulsified water. The emulsion water must be separated before the oil is transported to the refinery. In the refinery, before the distillation, the salt content is further reduced by renewed emulsion formation with fresh water and demulsification. A too high salt content in the crude oil could lead to malfunctions and corrosion in the refinery. A petroleum splitter, also called a demulsifier or emulsion splitter, has the task of breaking the emulsion in as low a concentration as possible and, in this separation process, as far as possible without water or with minimal additional expenditure of heat and to achieve complete water separation and to reduce the salt content to a minimum. The quality criteria for delivered crude oil are the residual salt and the water content.
Die Rohöle sind je nach ihrer Provenienz unterschiedlich zusammengesetzt. Die natürlichen Emulsionsstabilisatoren besitzen einen komplizierten, differenzierten chemischen Aufbau. Zur Überwindung ihrer Wirkung müssen selektive Spalter entwickelt werden. Durch verschiedene Förder- und Aufbereitungsbedingungen werden die Anforderungen, die an einen Erdölspalter gestellt werden, noch vielfältiger. Durch das ständige Erschließen neuer Erdölfelder und die Änderung der Förderbedingungen älterer Erdölfelder bleibt die Entwicklung optimaler Demulgatoren ein akutes Problem, und es werden eine große Anzahl verschiedenartig aufgebauter Demulgatoren und Demulgatormischungen benötigt.The crude oils have different compositions depending on their provenance. The natural emulsion stabilizers have a complex, differentiated chemical Construction. To overcome their effects, selective splitters have to be developed. The different requirements for a petroleum splitter become even more diverse due to different production and processing conditions. Due to the constant opening up of new oil fields and the change in the production conditions of older oil fields, the development of optimal demulsifiers remains an acute problem, and a large number of different types of demulsifiers and demulsifier mixtures are required.
In der US-Patentschrift 4,734,523 und in der europäischen Patentanmeldung 0 333 135 A2 (Derwent-Referat, Accession Number 89-271925/38) werden bestimmte Veresterungsprodukte als Erdölspalter beschrieben. Die Spalter der US-Patentschrift sind Umsetzungsprodukte aus einem oxalkylierten primären Fettamin und einer Diolverbindung mit einer Dicarbonsäure und jene der europäischen Patentanmeldung sind Umsetzungsprodukte aus einem oxalkylierten primären Fettamin und einem Addukt aus einer Diolverbindung und einem Glycidylether mit einer Dicarbonsäure. Mit diesen Demulgatoren wird eine gute und schnelle Abscheidung von Wasser und Salz erreicht.Certain esterification products are described as petroleum splitters in US Pat. No. 4,734,523 and in European Patent Application 0 333 135 A2 (Derwent unit, Accession Number 89-271925 / 38). The splitters in the US patent are reaction products of an oxyalkylated primary fatty amine and a diol compound with a dicarboxylic acid and those of the European patent application are reaction products of an oxyalkylated primary fatty amine and an adduct of a diol compound and a glycidyl ether with a dicarboxylic acid. With these demulsifiers a good and quick separation of water and salt is achieved.
Es wurde nun gefunden, daß auch Veresterungsprodukte aus einem oxalkylierten primären Fettamin (als alleinige OH-Gruppen lieferende Komponente) und einer Dicarbonsäure sehr effektive Erdölspalter sind und daß dies besonders dann der Fall ist, wenn das Veresterungsprodukt aus einem oxalkylierten primären Fettamin und einer Dicarbonsäure aus der Gruppe der dimeren (dimerisierten) Fettsäuren hergestellt worden ist.It has now been found that esterification products from an oxyalkylated primary fatty amine (as the sole component which supplies OH groups) and a dicarboxylic acid are also very effective petroleum splitters and that this is particularly the case when the esterification product consists of an oxyalkylated primary fatty amine and a dicarboxylic acid the group of dimeric (dimerized) fatty acids.
Das erfindungsgemäße Verfahren zum Trennen von Erdölemulsionen vom Wasser-in-Öl-Typ ist demnach dadurch gekennzeichnet, daß man den Emulsionen eine wirksame Menge von einem Veresterungsprodukt aus einem oxalkylierten primären Fettamin der nachstehenden Formel 1
worin R¹ ein Alkylrest oder Alkenylrest mit 6 bis 23 C-Atomen ist, R² H oder CH₃ ist und innerhalb der Kette des Polyoxalkylenrestes, in Blöcken oder statistisch angeordnet, auch beide Bedeutungen annehmen kann, und a und b Zahlen von insgesamt 2 bis 30 sind, mit der Maßgabe, daß weder a noch b Null ist,
und 0,5 bis 1,5 mol pro mol oxalkyliertes primäres Fettamin, vorzugsweise 0,5 bis 1,1 mol pro mol oxalkyliertes primäres Fettamin, von einer Dicarbonsäure, vorzugsweise einer solchen aus der Gruppe der dimeren Fettsäuren, zusetzt.The process according to the invention for separating petroleum emulsions of the water-in-oil type is accordingly characterized in that the emulsions are treated with an effective amount of an esterification product from an oxyalkylated primary fatty amine of the formula 1 below
wherein R¹ is an alkyl radical or alkenyl radical having 6 to 23 carbon atoms, R² is H or CH₃ and within the chain of the polyoxalkylene radical, arranged in blocks or randomly, can also take on both meanings, and a and b are numbers from a total of 2 to 30 , with the proviso that neither a nor b is zero,
and 0.5 to 1.5 moles per mole of oxyalkylated primary fatty amine, preferably 0.5 to 1.1 moles per mole of oxyalkylated primary fatty amine, of a dicarboxylic acid, preferably one from the group of dimeric fatty acids.
In der europäischen Patentanmeldung 0 035 263 A2 (Derwent-Referat, Accession Number 68257D/38) und in der deutschen Offenlegungsschrift 30 32 216 A1 (Derwent-Referat, Accession Number 28817E/15) sind Veresterungsprodukte aus einem oxalkylierten primären Fettamin und einer einfachen Dicarbonsäure beschrieben, sie werden aber als Textilweichmacher oder Haarbehandlungsmittel empfohlen. Ein Hinweis, daß solche Esterprodukte auch als Demulgatoren für irgendeine Emulsion oder gar für Erdölemulsionen vom Typ Wasser-in-Öl geeignet wären, wird nicht gegeben, und die gemäß Erfindung bevorzugten Veresterungsprodukte (das sind jene aus einem oxalkylierten primären Fettamin und einer dimeren Fettsäure als Dicarbonsäurekomponente) werden in den beiden Dokumenten nicht einmal erwähnt, sie dürften vielmehr als neu anzusehen sein.In European patent application 0 035 263 A2 (Derwent unit, Accession Number 68257D / 38) and in German Offenlegungsschrift 30 32 216 A1 (Derwent unit, Accession Number 28817E / 15) there are esterification products of an oxyalkylated primary fatty amine and a simple dicarboxylic acid described, but they are recommended as fabric softeners or hair treatment agents. There is no indication that such ester products would also be suitable as demulsifiers for any emulsion or even water-in-oil petroleum emulsions, and the preferred esterification products according to the invention (that is, those of an oxyalkylated primary fatty amine and a dimeric fatty acid as Dicarboxylic acid components) are not even mentioned in the two documents, they should rather be regarded as new.
Was die genannten oxalkylierten primären Fettamine der Formel 1 betrifft, sind solche bevorzugt, wobei R¹ ein Alkylrest mit 8 bis 18 C-Atomen ist oder ein Alkenylrest mit 8 bis 18 C-Atomen (er enthält vorzugsweise 1 bis 3 Doppelbindungen), R² H ist und a und b (gleich oder verschieden, ganze oder gebrochene) Zahlen von insgesamt 2 bis 15 sind, unter Berücksichtigung der oben angegebenen Maßgabe.As for the above-mentioned oxyalkylated primary fatty amines of formula 1, preference is given to those in which R 1 is a Is an alkyl radical with 8 to 18 carbon atoms or an alkenyl radical with 8 to 18 carbon atoms (it preferably contains 1 to 3 double bonds), R 2 is H and a and b (identical or different, whole or fractional) numbers from a total of 2 to 15, taking into account the stipulation given above.
Die Oxalkylierung von primären Fettaminen ist wohlbekannt und kann nach einer der Methoden zur Oxalkylierung von acide (aktive) H-Atome tragenden Verbindungen durchgeführt werden. Die oxalkylierten Fettamine können gemäß den Bedeutungen von R² Einheiten des Ethylenoxids oder Propylenoxids oder statistisch oder blockweise vorliegende Einheiten des Ethylenoxids und Propylenoxids enthalten, wobei die ethoxylierten, das heißt nur Ethylenoxid-Einheiten enthaltenden primären Fettamine bevorzugt sind. Bei den zur Oxalkylierung eingesetzten Fettaminen kann es sich gemäß den Bedeutungen von R¹ um einzelne primäre Fettamine oder um Gemische davon handeln. Es kann sich auch um solche Fettamine handeln, deren Kohlenwasserstoffkette eine oder mehrere Doppelbindungen enthält, wie die Reste der Öl-, Linol- oder Linolensäure. Die bevorzugten primären Fettamine sind die technisch verfügbaren Produkte wie Stearylamin, Cocosfettamin oder Talgfettamin (in diesen technischen Produkten liegen Alkylreste mit im wesentlichen 8 bis 18 C-Atomen vor).The oxyalkylation of primary fatty amines is well known and can be carried out by one of the methods for the oxyalkylation of compounds bearing acidic (active) H atoms. The oxyalkylated fatty amines can contain units of ethylene oxide or propylene oxide or units of ethylene oxide and propylene oxide which are present in random or block form in accordance with the meanings of R 2, preference being given to the ethoxylated primary fatty amines, ie those containing only ethylene oxide units. The fatty amines used for the oxyalkylation can, according to the meanings of R 1, be individual primary fatty amines or mixtures thereof. It can also be those fatty amines whose hydrocarbon chain contains one or more double bonds, such as the residues of oleic, linoleic or linolenic acid. The preferred primary fatty amines are the technically available products such as stearylamine, coconut fatty amine or tallow fatty amine (in these technical products there are alkyl residues with essentially 8 to 18 carbon atoms).
Bevorzugte Dicarbonsäuren sind solche der nachstehenden Formel 2 (das sind einfache Dicarbonsäuren)
HOOC-R³-COOH
worin R³ ein Alkylenrest der Formel -(CH₂)z- ist, in der z eine ganze Zahl von 1 bis 10, vorzugsweise 4 bis 8, bedeutet und wobei der Alkylenrest mit 1 oder 2 OH-Gruppen oder mit 1 oder 2 C₁ bis C₁₈-Alkyl oder C₃ bis C₁₈-Alkenyl substituiert sein kann, oder ein Vinylenrest oder ein p-Phenylenrest ist,
und solche der nachstehenden Formel 3 (das sind Dicarbonsäuren aus der Gruppe der dimerisierten ungesättigten C₁₈-Fettsäuren)
HOOC-R⁴-COOH
worin R⁴ ein zweiwertiger Kohlenwasserstoffrest mit 34 C-Atomen ist (R⁴ stellt also den 34 C-Atome enthaltenden Rest dar, der bei der Dimerisation einer ungesättigten Fettsäure mit 18 C-Atomen zu einer Dicarbonsäure mit insgesamt 36 C-Atomen entsteht).Preferred dicarboxylic acids are those of formula 2 below (these are simple dicarboxylic acids)
HOOC-R³-COOH
wherein R³ is an alkylene radical of the formula - (CH₂) z -, in which z is an integer from 1 to 10, preferably 4 to 8, and wherein the alkylene radical with 1 or 2 OH groups or with 1 or 2 C₁ to C₁₈ -Alkyl or C₃ to C₁₈ alkenyl may be substituted, or is a vinylene radical or a p-phenylene radical,
and those of formula 3 below (these are dicarboxylic acids from the group of dimerized unsaturated C₁₈ fatty acids)
HOOC-R⁴-COOH
in which R⁴ is a divalent hydrocarbon radical with 34 C atoms (R⁴ thus represents the radical containing 34 C atoms which is formed during the dimerization of an unsaturated fatty acid with 18 C atoms to a dicarboxylic acid with a total of 36 C atoms).
Was die bevorzugten einfachen Dicarbonsäuren betrifft, seien im einzelnen genannt Malonsäure, Bernsteinsäure, Glutarsäure, Adipinsäure, Pimelinsäure und so weiter in der homologen Reihe, ferner Tartronsäure, Äpfelsäure und Weinsäure sowie die Fumarsäure und Maleinsäure und schließlich die Terephthalsäure. Besonders bevorzugte einfache Dicarbonsäuren sind jene der homologen Reihe von Adipinsäure bis Sebacinsäure, ferner Maleinsäure, Fumarsäure, Dodecylbernsteinsäure und Dodecenylbernsteinsäure. Es versteht sich von selbst, daß anstelle dieser Dicarbonsäuren auch deren Anhydride, Halogenide oder Ester von niedrigen Alkanolen eingesetzt werden können.As for the preferred simple dicarboxylic acids, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid and so on may be mentioned in the homologous series, furthermore tartronic acid, malic acid and tartaric acid as well as fumaric acid and maleic acid and finally terephthalic acid. Particularly preferred simple dicarboxylic acids are those of the homologous series from adipic acid to sebacic acid, furthermore maleic acid, fumaric acid, dodecylsuccinic acid and dodecenylsuccinic acid. It goes without saying that instead of these dicarboxylic acids it is also possible to use their anhydrides, halides or esters of lower alkanols.
Dimere Fettsäuren werden in der Regel durch Additionspolymerisation (Dimerisation) von einfach oder mehrfach ungesättigten Fettsäuren hergestellt. Die Anzahl der C-Atome und die Struktur der erhaltenen Dicarbonsäuren hängt im wesentlichen von den Ausgangsfettsäuren und von den Reaktionsbedingungen bei der Dimerisation ab. Dimere Fettsäuren verschiedenster Art und Struktur sind im Handel erhältlich. Im Rahmen der vorliegenden Erfindung sind als dimere Fettsäuren solche bevorzugt, die durch Dimerisation von ungesättigten C18-Fettsäuren hergestellt werden, zum Beispiel von Ölsäure, Linolsäure, Linolensäure oder Talgfettsäure (unter Dimerisation versteht man bekanntlich die Vereinigung von zwei identischen Molekülen zu einem neuen Molekül, dem Dimeren, durch Additionsreaktion). Die Dimerisation von C₁₈-Fettsäuren wird in der Regel bei einer Temperatur von 150 bis 250 °C, vorzugsweise 180 bis 230 °C, mit oder ohne Dimerisierungskatalysator durchgeführt. Die erhaltene Dicarbonsäure (das ist die dimere Fettsäure) entspricht der angegebenen Formel 3, wobei R⁴ das bei der Dimerisation der C₁₈-Fettsäure gebildete zweiwertige Verbindungsglied ist, das die beiden -COOH-Gruppen trägt und 34 C-Atome aufweist. R⁴ ist vorzugsweise ein acyclischer (aliphatischer) oder ein mono- oder bicyclischer (cycloaliphatischer) Rest mit 34 C-Atomen. Der acyclische Rest ist in der Regel ein verzweigter (substituierter) und ein- bis dreifach ungesättigter Alkylrest mit 34 C-Atomen. Der cycloaliphatische Rest hat im allgemeinen ebenfalls 1 bis 3 Doppelbindungen. Die beschriebenen bevorzugten dimeren Fettsäuren sind im allgemeinen ein Gemisch von zwei oder mehreren Dicarbonsäuren der Formel 3 mit strukturell verschiedenen R⁴-Resten. Das Dicarbonsäuregemisch hat häufig einen mehr oder weniger großen Gehalt von trimeren Fettsäuren, die bei der Dimerisation entstanden sind und bei der destillativen Aufarbeitung des Produktes nicht entfernt worden sind. Im folgenden seien einige dimere Fettsäuren, die bei der Dimerisation der genannten C₁₈-Fettsäuren entstehen, formelmäßig angegeben, wobei der die beiden -COOH-Gruppen tragende Kohlenwasserstoffrest ein acyclischer, monocyclischer oder bicyclischer Rest ist:
Von den beschriebenen Dicarbonsäuren, das sind die einfachen Dicarbonsäuren und die dimeren Fettsäuren, sind die letzteren bevorzugt; es handelt sich in der Regel um technische Produkte, die im Handel unter der Bezeichnung "dimerisierte Fettsäuren" oder "Dimerfettsäuren" erhältlich sind und, wie oben bereits erwähnt, einen mehr oder weniger hohen Anteil an trimerisierten Fettsäuren enthalten können.Dimeric fatty acids are usually produced by addition polymerization (dimerization) of mono- or polyunsaturated fatty acids. The number of carbon atoms and the structure of the dicarboxylic acids obtained essentially depend on the starting fatty acids and on the reaction conditions during the dimerization. Various types and structures of dimeric fatty acids are commercially available. In the context of the present invention are as dimeric fatty acids preferred those which are produced by dimerization of unsaturated C18 fatty acids, for example oleic acid, linoleic acid, linolenic acid or tallow fatty acid (dimerization is known to mean the union of two identical molecules to form a new molecule, the dimer, by addition reaction). The dimerization of C₁₈ fatty acids is usually carried out at a temperature of 150 to 250 ° C, preferably 180 to 230 ° C, with or without a dimerization catalyst. The dicarboxylic acid obtained (this is the dimeric fatty acid) corresponds to the formula 3 given, where R⁴ is the divalent link formed in the dimerization of the C₁₈ fatty acid, which carries the two -COOH groups and has 34 carbon atoms. R⁴ is preferably an acyclic (aliphatic) or a mono- or bicyclic (cycloaliphatic) radical with 34 C atoms. The acyclic radical is usually a branched (substituted) and mono- to trisaturated alkyl radical with 34 carbon atoms. The cycloaliphatic radical generally also has 1 to 3 double bonds. The preferred dimeric fatty acids described are generally a mixture of two or more dicarboxylic acids of the formula 3 with structurally different R⁴ radicals. The dicarboxylic acid mixture often has a more or less large content of trimeric fatty acids which have arisen during the dimerization and have not been removed during the working up of the product by distillation. In the following, some dimeric fatty acids which are formed in the dimerization of the C₁, fatty acids mentioned are given in terms of formula, the hydrocarbon radical bearing the two -COOH groups being an acyclic, monocyclic or bicyclic radical:
Of the dicarboxylic acids described, ie the simple dicarboxylic acids and the dimeric fatty acids, the latter are preferred; they are generally technical products which are commercially available under the name "dimerized fatty acids" or "dimer fatty acids" and, as already mentioned above, can contain a more or less high proportion of trimerized fatty acids.
Die Veresterung der beiden Reaktionskomponenten, oxalkyliertes primäres Fettamin und Dicarbonsäure, erfolgt im Verhältnis von 1 mol Fettamin zu 0,5 bis 1,5 mol Dicarbonsäure, vorzugsweise 0,5 bis 1,1 mol Dicarbonsäure. Die unter Polykondensation verlaufende Veresterung kann unter Verwendung eines höhersiedenden inerten Lösungsmittels wie Toluol, Xylol oder technische Aromatenschnitte oder ohne Lösungsmittel in der Schmelze und unter Abdeckung mit einem Schutzgas durchgeführt werden, wobei die Durchführung in Lösungsmitteln bevorzugt ist. Bei Veresterung mit einem Lösungsmittel wählt man als Reaktionstemperatur zweckmäßigerweise die Rückflußtemperatur des Reaktionsgemisches und entfernt das gebildete Reaktionswasser azeotrop. Bei Veresterung in Substanz wird das Reaktionswasser direkt aus der Reaktionsmischung abdestilliert. Die Reaktionstemperatur liegt bei 100 bis 220 °C, vorzugsweise 130 bis 200 °C. Zur Beschleunigung der Reaktion verwendet man, wie es bei Veresterungsreaktionen zweckmäßig ist, einen alkalischen oder sauren Katalysator, wobei die saure Katalyse mit zum Beispiel einer Halogenwasserstoffsäure, Phosphorsäure, Schwefelsäure, Sulfonsäure oder Halogenessigsäure als Katalysator bevorzugt ist. Der Verlauf und das Ende der Reaktion kann mit Hilfe des entstehenden Reaktionswassers oder durch die Bestimmung der säurezahl kontrolliert werden. Es ist bevorzugt, die Reaktion bis auf einen etwa 90 bis 100%igen Umsatz zu führen, das heißt, bis im wesentlichen kein Reaktionswasser mehr gebildet wird. Zur Herstellung des erfindungsgemäßen Erdölspalters wird man also vorzugsweise so vorgehen, daß man die beiden Reaktionskomponenten im angegeben Molverhältnis, ferner ein Lösungsmittel und sauren Veresterungskatalysator in einem Reaktionsgefäß vorlegt und diese Mischung unter Rühren und Durchleiten eines inerten Gases auf 100 bis 220 °C, vorzugsweise 130 bis 200 °C, erhitzt und bei dieser Temperatur unter kontinuierlicher Austragung des entstehenden Wassers hält (azeotrope Destillation), bis die Umsetzung beendet ist. Das erhaltene Veresterungsprodukt, das im allgemeinen eine Säurezahl von < 10, vorzugsweise 2 bis 8, hat, kann durch Waschen mit Wasser vom eingesetzten Katalysator gereinigt werden und stellt den erfindungsgemäßen Erdölspalter dar. Die Reaktionszeit liegt im Bereich von 5 bis 20 h. Diese Veresterungsprodukte sind gelb bis braun gefärbte, mehr oder weniger viskose Flüssigkeiten. Sie weisen, vor allem im Falle des Einsatzes einer dimerisierten Fettsäure, eine spezielle chemische Struktur auf. Da ihre Herstellung bevorzugt in Gegenwart von Lösungsmitteln durchgeführt wird, liegen sie in der Regel in Form einer konzentrierten Lösung vor (Wirkstoffgehalt vorzugsweise bei 60 bis 80 Gew.-%).The esterification of the two reaction components, oxyalkylated primary fatty amine and dicarboxylic acid, takes place in the ratio of 1 mol fatty amine to 0.5 to 1.5 mol dicarboxylic acid, preferably 0.5 to 1.1 mol dicarboxylic acid. The polycondensation esterification can be carried out using a higher-boiling inert solvent such as toluene, xylene or technical aromatic cuts or without solvent in the melt and under cover with a protective gas, preference being given to carrying out in solvents is. When esterifying with a solvent, the reflux temperature of the reaction mixture is expediently chosen as the reaction temperature and the water of reaction formed is removed azeotropically. In the case of esterification in bulk, the water of reaction is distilled off directly from the reaction mixture. The reaction temperature is 100 to 220 ° C, preferably 130 to 200 ° C. To accelerate the reaction, an alkaline or acidic catalyst is used, as is expedient in esterification reactions, acidic catalysis with, for example, hydrohalic acid, phosphoric acid, sulfuric acid, sulfonic acid or haloacetic acid as the catalyst being preferred. The course and the end of the reaction can be checked using the water of reaction formed or by determining the acid number. It is preferred to conduct the reaction to about 90 to 100% conversion, that is, until essentially no more water of reaction is formed. To produce the petroleum splitter according to the invention, the procedure is preferably such that the two reaction components in the stated molar ratio, furthermore a solvent and acidic esterification catalyst are placed in a reaction vessel and this mixture is stirred at 100 to 220 ° C., preferably 130, while passing through an inert gas to 200 ° C, heated and held at this temperature with continuous discharge of the water formed (azeotropic distillation) until the reaction is complete. The esterification product obtained, which generally has an acid number of <10, preferably 2 to 8, can be purified from the catalyst used by washing with water and is the petroleum splitter according to the invention. The reaction time is in the range from 5 to 20 h. These esterification products are yellow to brown colored, more or less viscous liquids. They have a special chemical, especially when a dimerized fatty acid is used Structure on. Since their preparation is preferably carried out in the presence of solvents, they are generally in the form of a concentrated solution (active substance content preferably 60 to 80% by weight).
Die erfindungsgemäß vorgeschlagenen Esterprodukte (Polyester) zeichnen sich durch eine hohe Demulgierwirkung aus. Bei den üblichen Erdölaufbereitungstemperaturen wird schon nach kurzer Separationszeit eine vollständige Wasserabscheidung und Reduzierung des Salzgehaltes erreicht. Mit diesen Erdölspaltern werden also bei den üblichen Aufbereitungstemperaturen nach kurzer Separationszeit abnahmespezifische Roherdöle erhalten. Sie bewirken darüber hinaus, daß das abgetrennte Wasser praktisch frei von Öl ist, daß also auch eine vollständige Ölabscheidung aus dem abgetrennten Wasser und damit eine gute Wasserqualität erreicht wird. Mit diesen Erdölspaltern wird ferner eine scharfe Trennung zwischen der Öl- und Wasserphase erreicht, was einen weiteren großen Vorteil darstellt. Die Einsatzmenge an erfindungsgemäßem Demulgator kann in weiten Grenzen variieren. Sie hängt insbesondere von der Art des Erdöls und der Aufbereitungstemperatur ab. Die wirksame Menge beträgt im allgemeinen 5 bis 100 g pro Tonne, vorzugsweise 10 bis 50 g pro Tonne. Die beschriebenen Spalter werden zum Zwecke der besseren Dosierung und Verteilbarkeit vorzugsweise in Lösung eingesetzt. Als Lösungsmittel sind Wasser oder organische Flüssigkeiten geeignet, zum Beispiel Alkohole wie Methanol, Isopropanol und/oder Butanol, aromatische Kohlenwasserstoffe wie Toluol und/oder Xylol oder handelsübliche Mischungen aus höheren Aromaten.The ester products (polyester) proposed according to the invention are notable for a high demulsifying effect. At the usual petroleum treatment temperatures, complete water separation and a reduction in salinity are achieved after a short separation time. With these petroleum splitters, raw oils that are specific to the consumption are obtained after a short separation time at the usual processing temperatures. They also have the effect that the separated water is practically free of oil, so that a complete oil separation from the separated water and thus good water quality is achieved. With these oil splitters, a sharp separation between the oil and water phases is also achieved, which is another great advantage. The amount of demulsifier used according to the invention can vary within wide limits. It depends in particular on the type of petroleum and the processing temperature. The effective amount is generally 5 to 100 g per ton, preferably 10 to 50 g per ton. The splitters described are preferably used in solution for the purpose of better dosage and distributability. Water or organic liquids are suitable as solvents, for example alcohols such as methanol, isopropanol and / or butanol, aromatic hydrocarbons such as toluene and / or xylene or commercially available mixtures of higher aromatics.
Die Erfindung wird nun an Beispielen noch näher erläutert.The invention will now be explained in more detail using examples.
In einem Reaktionsgefäß, das mit Rührer, Wasserabscheider, Rückflußkühler und Thermometer ausgestattet ist, werden 690 g (1,0 mol) von einem Talgfettamin, reagiert mit 10 mol Ethylenoxid, vorgelegt, das ist ein Fettamin der Formel I mit R¹ = C₁₄H₂₉ (5 %), C₁₆H₃₃ (30 %) und C₁₈H₃₇ (65 %), R² = H und 
- (1) Talgfettamin mit 15 mol Ethylenoxid
- (2) Dodecenylbernsteinsäureanhydrid
Molverhältnis von (1) : (2) = 1 : 0,5
Durchführung wie in Beispiel 1
Umsetzungsgrad 99 %, Viskosität 0,35 Pa s
- (1) tallow fatty amine with 15 moles of ethylene oxide
- (2) Dodecenyl succinic anhydride
Molar ratio of (1): (2) = 1: 0.5
Carried out as in Example 1
Degree of conversion 99%, viscosity 0.35 Pa s
- (1) Oleylamin mit 5 mol Ethylenoxid
- (2) Dimerfettsäure
(Gehalt an dimerisierter Fettsäure: 98 Gew.-%)
Molverhältnis von (1) : (2) = 1 : 0,7
Durchführung wie in Beispiel 1
Umsetzungsgrad 95 %, Viskosität 2,1 Pa s
- (1) Oleylamine with 5 moles of ethylene oxide
- (2) Dimer fatty acid
(Content of dimerized fatty acid: 98% by weight)
Molar ratio of (1): (2) = 1: 0.7
Carried out as in Example 1
Degree of conversion 95%, viscosity 2.1 Pa s
- (1) Talgfettamin mit 10 mol Ethylenoxid
- (2) Technische Dimerfettsäure
(Gehalt an dimerisierter Fettsäure: 83 Gew.-%, Gehalt an trimerisierter Fettsäure: 17 Gew.-%)
Molverhältnis von (1) : (2) = 1 : 1,5
Durchführung wie in Beispiel 1
Umsetzungsgrad 97 %, Viskosität 3,4 Pa s
- (1) tallow fatty amine with 10 moles of ethylene oxide
- (2) Technical dimer fatty acid
(Content of dimerized fatty acid: 83% by weight, content of trimerized fatty acid: 17% by weight)
Molar ratio of (1): (2) = 1: 1.5
Carried out as in Example 1
Degree of conversion 97%, viscosity 3.4 Pa s
- (1) Cocosfettamin mit 6 mol Propylenoxid und 20 mol Ethylenoxid, blockweise angeordnet
- (2) Maleinsäureanhydrid
Äquivalentverhältnis von (1) : (2) = 1 : 1
Durchführung wie in Beispiel 1
Umsetzungsgrad 98 %, Viskosität 0,9 Pa s
- (1) Coconut fatty amine with 6 mol propylene oxide and 20 mol ethylene oxide, arranged in blocks
- (2) Maleic anhydride
Equivalent ratio of (1): (2) = 1: 1
Carried out as in Example 1
Degree of conversion 98%, viscosity 0.9 Pa s
Die Esterprodukte der Beispiele 1 bis 5 wurden zum Trennen von zwei verschiedenen Erdölemulsionen vom Typ Wasser-in-Öl eingesetzt. Die Ergebnisse sind in den nachstehenden Tabellen 1 und 2 zusammengefaßt und beweisen die hohe Wirksamkeit der beschriebenen Spalter.
Claims (8)
und 0,5 bis 1,5 mol pro mol oxalkyliertes primäres Fettamin von einer Dicarbonsäure zusetzt.Process for separating water-in-oil type petroleum emulsions, characterized in that the emulsions are treated with an effective amount of an esterification product of an oxyalkylated primary fatty amine of formula 1 below
and adding 0.5 to 1.5 moles per mole of oxyalkylated primary fatty amine from a dicarboxylic acid.
HOOC-R³-COOH
worin R³ ein Alkylenrest der Formel -(CH₂)z- ist, in der z eine ganze Zahl von 1 bis 10 bedeutet und wobei der Alkylenrest mit 1 oder 2 OH-Gruppen oder mit 1 oder 2 C₁ bis C₁₈-Alkyl oder C₃ bis C₁₈-Alkenyl substituiert sein kann, oder ein Vinylenrest oder ein p-Phenylenrest ist,
oder von einer Dicarbonsäure aus der Gruppe der dimeren Fettsäuren zugesetzt wird.The method of claim 1, wherein an esterification product of the oxyalkylated primary fatty amine and 0.5 to 1.5 moles per mole of fatty amine of a dicarboxylic acid of formula 2 below
HOOC-R³-COOH
wherein R³ is an alkylene radical of the formula - (CH₂) z -, in which z is an integer from 1 to 10 and where the alkylene radical can be substituted with 1 or 2 OH groups or with 1 or 2 C₁ to C₁₈ alkyl or C₃ to C₁₈ alkenyl, or is a vinylene radical or a p-phenylene radical,
or is added by a dicarboxylic acid from the group of dimeric fatty acids.
HOOC-R³-COOH
worin R³ ein Alkylenrest der Formel -(CH₂)z- ist, in der z eine ganze Zahl von 1 bis 10 bedeutet und wobei der Alkylenrest mit 1 oder 2 OH-Gruppen oder mit 1 oder 2 C₁ bis C₁₈-Alkyl oder
C₃ bis C₁₈-Alkenyl substituiert sein kann, oder ein Vinylenrest oder ein p-Phenylenrest ist,
oder von einer Dicarbonsäure aus der Gruppe der dimeren Fettsäuren der nachstehenden Formel 3
HOOC-R⁴-COOH
worin R⁴ ein zweiwertiger Kohlenwasserstoffrest mit 34 C-Atomen ist,
zugesetzt wird.A process according to claim 1, wherein an esterification product of an oxyalkylated primary fatty amine of formula 1, wherein R¹ is an alkyl radical with 8 to 18 C atoms or an alkenyl radical with 8 to 18 C atoms, R² is H and a and b are numbers total 2 to 15, and 0.5 to 1.5 mol per mol of fatty amine of a dicarboxylic acid of the following formula 2
HOOC-R³-COOH
wherein R³ is an alkylene radical of the formula - (CH₂) z -, in which z is an integer from 1 to 10 and wherein the alkylene radical with 1 or 2 OH groups or with 1 or 2 C₁ to C₁₈ alkyl or
C₃ to C₁₈ alkenyl may be substituted, or is a vinylene radical or a p-phenylene radical,
or from a dicarboxylic acid from the group of the dimeric fatty acids of the formula 3 below
HOOC-R⁴-COOH
where R⁴ is a divalent hydrocarbon radical with 34 C atoms,
is added.
HOOC-R⁴-COOH
worin R⁴ ein zweiwertiger Kohlenwasserstoffrest mit 34 C-Atomen ist,
zugesetzt wird.A process according to claim 1, wherein an esterification product of an oxyalkylated primary fatty amine of formula 1, wherein R¹ is an alkyl radical with 8 to 18 C atoms or an alkenyl radical with 8 to 18 C atoms, R² is H and a and b are numbers from 2 to 15 in total, and 0.5 to 1.5 mol per mol of fatty amine from a dicarboxylic acid of the formula HOOC- (CH₂) z -COOH, where z is an integer from 4 to 8, or from a dicarboxylic acid from the group of dimeric fatty acids of formula 3 below
HOOC-R⁴-COOH
where R⁴ is a divalent hydrocarbon radical with 34 C atoms,
is added.
HOOC-R⁴-COOH
worin R⁴ ein zweiwertiger Kohlenwasserstoffrest mit 34 C-Atomen ist,
zugesetzt wird.The method of claim 1, wherein an esterification product of the oxyalkylated primary fatty amine and 0.5 to 1.5 moles per mole of fatty amine of a dicarboxylic acid from the group of dimeric fatty acids of formula 3 below
HOOC-R⁴-COOH
where R⁴ is a divalent hydrocarbon radical with 34 C atoms,
is added.
HOOC-R⁴-COOH
worin R⁴ ein zweiwertiger Kohlenwasserstoffrest mit 34 C-Atomen ist,
zugesetzt wird.A process according to claim 1, wherein an esterification product of an oxyalkylated primary fatty amine of formula 1, wherein R¹ is an alkyl radical with 8 to 18 C atoms or an alkenyl radical with 8 to 18 C atoms, R² is H and a and b are numbers total 2 to 15, and 0.5 to 1.5 mol per mol of fatty amine from a dicarboxylic acid from the group of the dimeric fatty acids of the formula 3 below
HOOC-R⁴-COOH
where R⁴ is a divalent hydrocarbon radical with 34 C atoms,
is added.
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| DE4217985A DE4217985A1 (en) | 1992-05-30 | 1992-05-30 | Process for separating water-in-oil type petroleum emulsions |
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| US (1) | US5385674A (en) |
| EP (1) | EP0572881B1 (en) |
| JP (1) | JP3499900B2 (en) |
| AT (1) | ATE157116T1 (en) |
| BR (1) | BR9302096A (en) |
| DE (2) | DE4217985A1 (en) |
| DK (1) | DK0572881T3 (en) |
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| WO2012028542A1 (en) | 2010-08-30 | 2012-03-08 | Akzo Nobel Chemicals International B.V. | Use of polyester polyamine and polyester polyquaternary ammonium compounds as corrosion inhibitors |
| WO2013092440A1 (en) | 2011-12-19 | 2013-06-27 | Akzo Nobel Chemicals International B.V. | Compositions comprising polyester polyamine and polyester polyquaternary ammonium corrosion inhibitors and chelating agents |
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| DE19524127A1 (en) * | 1995-07-03 | 1997-01-09 | Huels Chemische Werke Ag | Amphiphilic compounds with several hydrophilic and hydrophobic groups based on alkoxylated amines and / or amides and di-, oligo- or polycarboxylic acids |
| US5817155A (en) * | 1996-08-08 | 1998-10-06 | Shiseido Co., Ltd. | Emulsion for hair treatment |
| US7611725B2 (en) | 2002-01-31 | 2009-11-03 | Croda, Inc. | Additives and products including oligoesters |
| DE102005028500A1 (en) * | 2005-06-17 | 2006-12-28 | Basf Ag | Aminocarboxylic acid esters with EO / PO / BuO block polymers and their use as emulsion breakers |
| US8697615B2 (en) * | 2010-12-14 | 2014-04-15 | Nalco Company | Polyepihalohydrin reverse emulsion breakers |
| BR112013015812B1 (en) | 2010-12-28 | 2020-03-24 | Akzo Nobel Chemicals International B.V. | USE OF A PRODUCT OBTAINABLE BY THE REACTION OF A FATTY ACID OR ACID MIXTURE, PRODUCT OBTAINABLE BY THE REACTION OF A FATTY ACID OR ACID MIXTURE, METHOD FOR THE PRODUCTION OF A PRODUCT AND METHOD FOR PROTECTING A METALLIC SURFACE AGAINST METALLIC SURFACE |
| RU2652712C1 (en) * | 2017-08-28 | 2018-04-28 | Общество С Ограниченной Ответственностью "Ника-Петротэк" | Demulsifying composition and a method of its use |
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| DE3007930A1 (en) * | 1980-03-01 | 1981-09-24 | Henkel KGaA, 4000 Düsseldorf | NEW POLYESTER COMPOUNDS, A METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS A TEXTILE SOFTENER |
| DE3032216A1 (en) * | 1980-08-27 | 1982-04-08 | Henkel KGaA, 4000 Düsseldorf | Hair shampoo and cosmetic compsn. - contg. polyester prepd. by condensing di:carboxylic acid and alkoxylated tert. amine and opt. neutralising with acid |
| DE3526601A1 (en) * | 1985-07-25 | 1987-01-29 | Hoechst Ag | OXALKYLATED POLYESTERAMINE, METHOD FOR THE PRODUCTION AND USE THEREOF |
| DE3927638A1 (en) * | 1989-08-22 | 1991-02-28 | Hoechst Ag | AMINE-FREE ESTERIFIED GLYCIDYL ETHER ADDITION PRODUCTS AND THEIR USE |
-
1992
- 1992-05-30 DE DE4217985A patent/DE4217985A1/en not_active Withdrawn
-
1993
- 1993-05-22 AT AT93108316T patent/ATE157116T1/en not_active IP Right Cessation
- 1993-05-22 DK DK93108316.6T patent/DK0572881T3/en active
- 1993-05-22 DE DE59307148T patent/DE59307148D1/en not_active Expired - Fee Related
- 1993-05-22 EP EP93108316A patent/EP0572881B1/en not_active Expired - Lifetime
- 1993-05-27 US US08/068,630 patent/US5385674A/en not_active Expired - Lifetime
- 1993-05-27 EG EG33493A patent/EG20364A/en active
- 1993-05-28 NO NO931718A patent/NO304797B1/en unknown
- 1993-05-28 RU RU93005217A patent/RU2105788C1/en active
- 1993-05-28 JP JP12755093A patent/JP3499900B2/en not_active Expired - Fee Related
- 1993-05-28 MY MYPI93001019A patent/MY107782A/en unknown
- 1993-05-28 MX MX9303169A patent/MX9303169A/en unknown
- 1993-05-28 BR BR9302096A patent/BR9302096A/en not_active IP Right Cessation
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0267517A2 (en) * | 1986-11-13 | 1988-05-18 | Hoechst Aktiengesellschaft | Branched polyoxyalkylene polyesters, process for their preparation and their use |
| EP0269887A2 (en) * | 1986-11-13 | 1988-06-08 | Hoechst Aktiengesellschaft | Branched quaternary polyoxyalkylene polyesters, process for their preparation and their use |
| EP0333135A2 (en) * | 1988-03-18 | 1989-09-20 | Hoechst Aktiengesellschaft | Esterified Glycidylether-addition products and their use |
| WO1991011242A1 (en) * | 1990-01-29 | 1991-08-08 | Henkel Kommanditgesellschaft Auf Aktien | Process for separating oil-water emulsions |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011000895A1 (en) | 2009-07-03 | 2011-01-06 | Akzo Nobel Chemicals International B.V. | Polymeric corrosion inhibitors |
| US8372336B2 (en) | 2009-07-03 | 2013-02-12 | Akzo Nobel Chemicals International B.V. | Polymeric corrosion inhibitors |
| WO2012028542A1 (en) | 2010-08-30 | 2012-03-08 | Akzo Nobel Chemicals International B.V. | Use of polyester polyamine and polyester polyquaternary ammonium compounds as corrosion inhibitors |
| US8940227B2 (en) | 2010-08-30 | 2015-01-27 | Akzo Nobel Chemical International B.V. | Use of polyester polyamine and polyester polyquaternary ammonium compounds as corrosion inhibitors |
| WO2013092440A1 (en) | 2011-12-19 | 2013-06-27 | Akzo Nobel Chemicals International B.V. | Compositions comprising polyester polyamine and polyester polyquaternary ammonium corrosion inhibitors and chelating agents |
| WO2023011800A1 (en) | 2021-08-05 | 2023-02-09 | Clariant International Ltd | Use of complex polyester amines and polyester quaternary ammonium compounds as corrosion inhibitors |
| US11845892B2 (en) | 2021-08-05 | 2023-12-19 | Clariant International Ltd | Use of complex polyesteramines and polyester polyquaternary ammonium compounds as corrosion inhibitors |
Also Published As
| Publication number | Publication date |
|---|---|
| MY107782A (en) | 1996-06-15 |
| ATE157116T1 (en) | 1997-09-15 |
| JPH06128558A (en) | 1994-05-10 |
| NO931975D0 (en) | 1993-05-28 |
| EG20364A (en) | 1999-01-31 |
| JP3499900B2 (en) | 2004-02-23 |
| DE59307148D1 (en) | 1997-09-25 |
| NO304797B1 (en) | 1999-02-15 |
| DE4217985A1 (en) | 1993-12-02 |
| US5385674A (en) | 1995-01-31 |
| MX9303169A (en) | 1993-12-01 |
| RU2105788C1 (en) | 1998-02-27 |
| BR9302096A (en) | 1993-12-07 |
| EP0572881B1 (en) | 1997-08-20 |
| NO931975L (en) | 1993-12-01 |
| DK0572881T3 (en) | 1998-03-23 |
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