EP0541018B1 - Oil demulsifier - Google Patents

Oil demulsifier Download PDF

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Publication number
EP0541018B1
EP0541018B1 EP92118674A EP92118674A EP0541018B1 EP 0541018 B1 EP0541018 B1 EP 0541018B1 EP 92118674 A EP92118674 A EP 92118674A EP 92118674 A EP92118674 A EP 92118674A EP 0541018 B1 EP0541018 B1 EP 0541018B1
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Prior art keywords
water
emulsion
oil
petroleum
moles
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German (de)
French (fr)
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EP0541018A3 (en
EP0541018A2 (en
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Guenther Elfers
Wilfried Dr. Sager
Hans-Henning Dr. Vogel
Knut Dr. Oppenlaender
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BASF SE
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BASF SE
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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 petroleum emulsion splitters based on alkoxylated polyethyleneimines and processes for demulsifying petroleum emulsions, in which the petroleum emulsion splitters according to the invention are used.
  • Oil and water emulsions are produced in large quantities during the extraction and processing of crude oil, with the continuous outer phase depending on the proportions of water to oil, the natural emulsifier system contained in the oil and the history of the origin of the emulsion.
  • the majority of the crude oil is produced as a water-in-oil emulsion and has to be split by adding chemical demulsifiers.
  • block polymers of ethylene and / or propylene oxide as splitters for water-in-oil emulsions.
  • German published application 15 45 250 e.g. a dewatering process is known in which various alkylene oxide polymers and compounds derived therefrom with hydrophilic end groups are added to the water-in-oil emulsions, but these are not yet fully effective enough and often only at full temperatures. However, after use, they leave too much residual water, residual salt or residual emulsion, and above all they are only sufficiently effective with a few special types of oil.
  • the water-in-oil emulsions are often heated with high energy consumption in order to then achieve the low water, salt and possibly residual emulsions required for further processing with a chemical or electro-chemical process.
  • water-in-oil emulsions can also be split at the temperatures at which they are conveyed, ie between 10 ° C. and 40 ° C., with the addition of suitable splitters without heating.
  • DE-OS 22 27 546 teaches that rapid dewatering of crude oils can be achieved by the addition of demulsifying substances based on derivatives of polyalkylene oxides.
  • the process is characterized in that at least one polyalkylene polyamine with at least two recurring alkyleneimine units in the molecule is added to the crude oils at least one polyalkylene polyamine completely 10 to 300 times oxalkylated on the nitrogen atoms.
  • the salt water separated in this way still contains certain amounts of residual oil, with oil-in-water emulsions preferably forming.
  • the amount of emulsified crude oil in the oil-in-water emulsions can be up to 5%.
  • demulsifiers so-called deoilers, which are mostly cationic polymers, such as those e.g. be described in DE-34 04 538. Typical products are also described in U.S. Patents 4,333,947 and 3,893,615.
  • DE 24 35 714 A1 teaches to completely quaternize polyalkylene polyamines, as are known from DE-OS 22 27 546. This additional process step is however complex and should therefore also be avoided for cost reasons.
  • the present invention was therefore based on the object of providing petroleum emulsion splitters which not only bring about good splitting of water-in-oil emulsions, but also lead to the water which is split off containing as little residual oil as possible and which are as simple to produce as possible .
  • petroleum emulsion splitters based on alkoxylated polyethyleneimines which are characterized in that they are alkoxylated by a polyethyleneimine having a molecular weight (weight average M w ) of 2,500 to 35,000 with 5 to 40 moles of propylene oxide and 5 to 40 moles of ethylene oxide can be obtained per ethyleneimine unit in the polyethyleneimine.
  • crude oil emulsion splitters are known, which are produced by alkoxylation, especially with ethylene and propylene oxide, of polyalkylene polyamines, but the quantitative ratios of alkylene oxide to polyalkylene polyamine given there include a very wide range (10 to 300 times alkoxylation of each Nitrogen atom) and according to the examples, polyethyleneimines with a MW of 2,100 to 86,000, reacted with 70 to 95 moles of propylene oxide and 20 to 28 moles of ethylene oxide, are used.
  • Emulsion splitters are preferred, for their preparation polyethyleneimines with a molecular weight M w of 5,000 to 25,000 are used and which are obtained by alkoxylation of the polyethyleneimines with 5 to 30 moles of propylene oxide and 5 to 20 moles of ethylene oxide, in each case based on an ethyleneimine unit in the polyethyleneimine .
  • the emulsion splitters according to the invention also have the advantage that they contain no metal salts, in particular corrosion-promoting chlorides.
  • the invention also relates to a process for the demulsification of petroleum emulsions, in which the emulsion at temperatures of 10 ° C to 130 ° C, preferably at 50 ° C to 80 ° C, with the petroleum emulsion splitter according to the invention or with solutions containing the petroleum emulsion splitter included, treated.
  • the emulsion splitters are produced in a manner known per se in a one- or multi-stage, preferably two-stage, procedure.
  • an alkaline catalyst such as sodium methylate, potassium tert-butoxide, potassium hydroxide, sodium hydroxide, basic ion exchanger etc. added, followed by further oxalkylation with the required amounts of alkylene oxide at about 125 ° C to 135 ° C.
  • the reaction can be carried out, for example, by pressing on the entire amount of alkylene oxide in the presence of water-containing or -free alkaline catalyst and allowing it to react at temperatures between 125 ° C. and 135 ° C.
  • a higher proportion of by-products, such as pure polyalkylene glycol ethers, can occur here, but this has no significant influence on the desired properties of the products.
  • the ratio of propylene oxide to ethylene oxide can be varied in the ranges given above.
  • Starting products for the preparation of the compounds to be added according to the invention are generally known polyethyleneimines, prepared in a conventional manner from ethyleneimine.
  • the specified molecular weights were determined by light scattering.
  • the emulsion splitters according to the invention can also be used together with other emulsion splitters, e.g. with the alkoxylated alkylphenol formaldehyde resins known from DE-OS 27 19 978.
  • the splitters are preferred because of their associated better meterability than solutions with 20 to 90% by weight splitters.
  • Mixtures of organic solvents e.g. methanol
  • organic solvents e.g. Toluene, xylenes, tetrahydrofuran, dioxane, C1-C13 alcohols, glycols and light petroleum fractions of the boiling point mentioned.
  • solutions these are expediently adjusted to an active substance content (splitter content) of 40 to 60% by weight or 70 to 90% by weight.
  • splitter content active substance content
  • the solutions are preferred to crude oils added to the probes (in the field).
  • the cleavage then already runs at the temperature of the freshly pumped water-in-oil emulsion at such a rate that the emulsion can be broken on the way to the processing plant. There it is separated in a possibly heated separator and possibly with the help of an electric field without difficulty into pure oil and salt water.
  • the splitters are expediently added to the crude oil emulsions in amounts (active ingredient) of 0.1 to 200 ppm, preferably 5 to 50 ppm, based on the weight of the emulsion to be split, at temperatures between 10 ° C. and 130 ° C., preferably 50 ° C to 80 ° C added.
  • the rapid breakers to be used according to the invention can be used for water-in-oil emulsions with about 0.1 to 99% by weight salt water content. Crude oil emulsions of various origins come into consideration as oils that can be drained quickly in this way.
  • the splitter A produced according to the synthesis example is added in an amount of 25 ppm to three different crude oil emulsions from West Africa at 40 ° C. with stirring, and the samples are then left to stand. The separated amounts of water were measured after certain time intervals.
  • oil emulsions having a splitter B which had been prepared by alkoxylation of polyethyleneimine with a molecular weight of about 21,000 (M w) with 36 moles of ethylene oxide and 86 moles of propylene oxide per ethyleneimine were placed in the manner indicated above.
  • Table I The results are shown in Table I.
  • Table I Splitter deposited H2O in ml after 10min 20 min 30 min 45min 1h 2h 3h Crude oil emulsion I A 4th 15 40 43 45 45 47 B 8th 15 25th 40 43 47 47 Crude oil emulsion II A 2nd 5 25th 35 38 38 39 B 1 3rd 5 10th 15 20th 22 Crude oil emulsion III A 40 40 40 40 40 40 B 0 2nd 2nd 2nd 2nd 2nd 2nd 2nd 2nd
  • the test emulsions tested were the crude oil emulsions specified in Example 2.1, which were treated with the demulsifier at ambient temperature. The results are shown in Table II.
  • Table II Splitter Crude oil emulsion Assessment number A I. 2nd B I. 8th A II 3rd B II 6 A III 1 B III 9 It can be seen from the test results that, on the one hand, the petroleum emulsion splitter according to the invention behaves advantageously with regard to its splitting properties (Table I) compared to a comparison substance which differs from the splitter according to the invention essentially by a significantly higher degree of propoxylation. On the other hand, the splitter according to the invention achieves very good separation of the residual oil from the separated water (Table II).

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Polyethers (AREA)
  • Liquid Carbonaceous Fuels (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
  • Colloid Chemistry (AREA)

Description

Die Erfindung betrifft Erdölemulsionsspalter auf der Basis von alkoxylierten Polyethyleniminen und Verfahren zum Demulgieren von Erdöl-Emulsionen, bei denen die erfindungsgemäßen Erdölemulsionsspalter eingesetzt werden.The invention relates to petroleum emulsion splitters based on alkoxylated polyethyleneimines and processes for demulsifying petroleum emulsions, in which the petroleum emulsion splitters according to the invention are used.

Bei der Förderung und Weiterverarbeitung von Rohöl fallen in großen Mengen Öl-Wasser-Emulsionen an, wobei die kontinuierliche äußere Phase von den Mengenverhältnissen Wasser zu Öl, dem natürlichen, im Öl enthaltenen Emulgatorsystem und der Entstehungsgeschichte der Emulsion abhängt. Bei der Förderung fällt der größte Teil des Rohöls als Wasser-in-Öl-Emulsion an und muß durch Zugabe chemischer Demulgatoren gespalten werden.Oil and water emulsions are produced in large quantities during the extraction and processing of crude oil, with the continuous outer phase depending on the proportions of water to oil, the natural emulsifier system contained in the oil and the history of the origin of the emulsion. The majority of the crude oil is produced as a water-in-oil emulsion and has to be split by adding chemical demulsifiers.

Es ist bekannt, Blockpolymerisate aus Äthylen- und/oder Propylenoxid als Spalter für Wasser-in-Öl-Emulsionen einzusetzen. Aus der deutschen Offenlegungsschrift 15 45 250 ist z.B. ein Entwässerungsverfahren bekannt, bei dem verschiedene Alkylenoxidpolymerisate und davon abgeleitete Verbindungen mit hydrophilen Endgruppen den Wasser-in-Öl-Emulsionen zugesetzt werden, die aber noch nicht schnell genug und häufig nur bei erhöhten Temperaturen ihre volle Wirksamkeit entfalten. Sie hinterlassen jedoch nach ihrer Anwendung einen noch zu großen Gehalt an Restwasser, Restsalz oder Restemulsion, und vor allem sind sie nur bei wenigen speziellen Ölsorten genügend wirksam.It is known to use block polymers of ethylene and / or propylene oxide as splitters for water-in-oil emulsions. From German published application 15 45 250, e.g. a dewatering process is known in which various alkylene oxide polymers and compounds derived therefrom with hydrophilic end groups are added to the water-in-oil emulsions, but these are not yet fully effective enough and often only at full temperatures. However, after use, they leave too much residual water, residual salt or residual emulsion, and above all they are only sufficiently effective with a few special types of oil.

Die Wasser-in-Öl-Emulsionen werden, je nach Viskosität, häufig unter hohem Energieaufwand erwärmt, um dann mit einer chemischen oder elektrisch-chemischen Arbeitsweise die zur Weiterverarbeitung erforderlichen niedrigen Gehalte an Wasser, Salz und eventuell Restemulsionen zu erzielen.Depending on the viscosity, the water-in-oil emulsions are often heated with high energy consumption in order to then achieve the low water, salt and possibly residual emulsions required for further processing with a chemical or electro-chemical process.

Es ist jedoch wünschenswert, daß die Wasser-in-Öl-Emulsionen auch bei den Temperaturen, bei denen sie gefördert werden, d.h. zwischen 10°C und 40°C, unter Zusatz von geeigneten Spaltern ohne Aufheizen gespalten werden können.However, it is desirable that the water-in-oil emulsions can also be split at the temperatures at which they are conveyed, ie between 10 ° C. and 40 ° C., with the addition of suitable splitters without heating.

Einen Universalspalter für alle Rohölsorten zu finden, ist aufgrund des verschiedenen Aufbaus der Rohöle nicht möglich, wie die bisherigen Erfahrungen zeigen.Finding a universal splitter for all types of crude oil is not possible due to the different structure of the crude oils, as previous experience has shown.

Immerhin ist es aber wünschenswert, für größere Mengen an verwandten Ölsorten einheitliche Spalter zu entwickeln, da sonst auf diesem Gebiet eine zu große Anzahl von Produkten erforderlich wäre.After all, it is desirable to develop uniform splitters for larger quantities of related types of oil, since otherwise too many products would be required in this area.

Die DE-OS 22 27 546 lehrt, daß eine Schnellentwässerung von Rohölen durch den Zusatz von demulgierend wirkenden Stoffen auf der Grundlage von Derivaten von Polyalkylenoxiden erreicht werden kann. Das Verfahren ist dadurch gekennzeichnet, daß man den Rohölen mindestens ein an den Stickstoffatomen vollständig jeweils 10- bis 300fach oxalkyliertes Polyalkylenpolyamin mit mindestens zwei wiederkehrenden Alkylenimin-Einheiten im Molekül zusetzt.DE-OS 22 27 546 teaches that rapid dewatering of crude oils can be achieved by the addition of demulsifying substances based on derivatives of polyalkylene oxides. The process is characterized in that at least one polyalkylene polyamine with at least two recurring alkyleneimine units in the molecule is added to the crude oils at least one polyalkylene polyamine completely 10 to 300 times oxalkylated on the nitrogen atoms.

Das auf diese Weise abgetrennte Salzwasser enthält noch gewisse Mengen Restöl, wobei sich bevorzugt Öl-in-Wasser-Emulsionen bilden. Die Menge an emulgiertem Rohöl in den Öl-in-Wasser-Emulsionen kann bis zu 5 % betragen. Zur Abtrennung dieses Restölgehaltes werden spezielle Demulgatoren, sogenannte Deoiler, verwendet, wobei es sich meist um kationische Polymere handelt, wie sie z.B. in DE-34 04 538 beschrieben werden. Typische Produkte werden ebenfalls in den US-Patentschriften 4 333 947 und 3 893 615 beschrieben.The salt water separated in this way still contains certain amounts of residual oil, with oil-in-water emulsions preferably forming. The amount of emulsified crude oil in the oil-in-water emulsions can be up to 5%. To remove this residual oil content, special demulsifiers, so-called deoilers, are used, which are mostly cationic polymers, such as those e.g. be described in DE-34 04 538. Typical products are also described in U.S. Patents 4,333,947 and 3,893,615.

Die Abtrennung von Restölmengen ist für die Ölfeldwasserklärung und -aufbereitung aus ökologischen und technischen Gründen notwendig, da beispielsweise bei der Verwendung des Wassers zur Sekundärförderung durch Wasserfluten Restölmengen im Wasser den Einpreßdruck erhöhen würden.The separation of residual oil quantities is necessary for oilfield water purification and treatment for ecological and technical reasons, since, for example, if the water is used for secondary production through flooding, residual oil quantities in the water would increase the injection pressure.

Es ist wünschenswert, daß bei der Emulsionsspaltung von Wasser-in-Öl-Emulsionen Mittel eingesetzt werden, die gleichzeitig einen ausgeprägten Deoilereffekt aufweisen, d.h. die in einem Schritt zu einem weitgehend Öl-freien abgetrennten Restwasser führen.It is desirable that in the emulsion splitting of water-in-oil emulsions agents are used which at the same time have a pronounced deoiler effect, i.e. which lead to a largely oil-free separated residual water in one step.

Zu diesem Zweck lehrt die DE 24 35 714 Al, Polyalkylenpolyamine, wie sie aus der DE-OS 22 27 546 bekannt sind, vollständig zu quaternieren. Dieser zusätzliche Verfahrensschritt ist jedoch aufwendig und sollte daher auch aus Kostengründen vermieden werden.For this purpose, DE 24 35 714 A1 teaches to completely quaternize polyalkylene polyamines, as are known from DE-OS 22 27 546. This additional process step is however complex and should therefore also be avoided for cost reasons.

Der vorliegenden Erfindung lag daher die Aufgabe zugrunde, Erdölemulsionsspalter zur Verfügung zu stellen, die nicht nur eine gute Aufspaltung von Wasser-in-Öl-Emulsionen bewirken, sondern auch dazu führen, daß das abgespaltene Wasser möglichst wenig Restöl enthält und die möglichst einfach herzustellen sind.The present invention was therefore based on the object of providing petroleum emulsion splitters which not only bring about good splitting of water-in-oil emulsions, but also lead to the water which is split off containing as little residual oil as possible and which are as simple to produce as possible .

Diese Aufgabe wird gelöst durch Erdölemulsionsspalter auf der Basis von alkoxylierten Polyethyleniminen, die dadurch gekennzeichnet sind, daß sie durch Alkoxylierung eines Polyethylenimins mit einem Molekulargewicht (Gewichtsmittel Mw) von 2 500 bis 35 000 mit 5 bis 40 Molen Propylenoxid und 5 bis 40 Molen Ethylenoxid pro Ethylenimineinheit im Polyethylenimin erhalten werden.This object is achieved by petroleum emulsion splitters based on alkoxylated polyethyleneimines, which are characterized in that they are alkoxylated by a polyethyleneimine having a molecular weight (weight average M w ) of 2,500 to 35,000 with 5 to 40 moles of propylene oxide and 5 to 40 moles of ethylene oxide can be obtained per ethyleneimine unit in the polyethyleneimine.

Aus der DE-OS 22 27 546 sind zwar Rohölemulsionsspalter bekannt, die durch Alkoxylierung, vor allem mit Ethylen- und Propylenoxid, von Polyalkylenpolyaminen hergestellt werden, die dort angegebenen Mengenverhältnisse Alkylenoxid zu Polyalkylenpolyamin umfassen jedoch einen sehr weiten Bereich (10- bis 300fache Alkoxylierung jedes Stickstoffatoms) und gemäß den Beispielen werden Polyethylenimine mit einem MG von 2 100 bis 86 000, umgesetzt mit 70 bis 95 Molen Propylenoxid und 20 bis 28 Molen Ethylenoxid, eingesetzt.From DE-OS 22 27 546, crude oil emulsion splitters are known, which are produced by alkoxylation, especially with ethylene and propylene oxide, of polyalkylene polyamines, but the quantitative ratios of alkylene oxide to polyalkylene polyamine given there include a very wide range (10 to 300 times alkoxylation of each Nitrogen atom) and according to the examples, polyethyleneimines with a MW of 2,100 to 86,000, reacted with 70 to 95 moles of propylene oxide and 20 to 28 moles of ethylene oxide, are used.

Es war daher überraschend, daß Polyethylenimine mit einem bestimmten Molekulargewicht und einem geringen Alkoxylierungsgrad, insbesondere Propoxylierungsgrad, ohne daß eine Quaternierung erforderlich ist, nicht nur als gute Wasserin-Öl-Demulgatoren wirken, sondern darüber hinaus auch einen ausgezeichneten Deoilereffekt aufweisen.It was therefore surprising that polyethyleneimines with a certain molecular weight and a low degree of alkoxylation, especially a degree of propoxylation, without the need for quaternization, not only act as good water-in-oil demulsifiers, but also have an excellent deoiler effect.

Bevorzugt sind Emulsionsspalter, zu deren Herstellung Polyethylenimine mit einem Molekulargewicht Mw von 5 000 bis 25 000 eingesetzt werden und die durch Alkoxylierung der Polyethylenimine mit 5 bis 30 Molen Propylenoxid sowie 5 bis 20 Molen Ethylenoxid, jeweils bezogen auf eine Ethylenimineinheit im Polyethylenimin, erhalten werden.Emulsion splitters are preferred, for their preparation polyethyleneimines with a molecular weight M w of 5,000 to 25,000 are used and which are obtained by alkoxylation of the polyethyleneimines with 5 to 30 moles of propylene oxide and 5 to 20 moles of ethylene oxide, in each case based on an ethyleneimine unit in the polyethyleneimine .

Die erfindungsgemäßen Emulsionsspalter haben auch den Vorteil, daß sie keine Metallsalze, insbesondere korrosionsfördernde Chloride enthalten.The emulsion splitters according to the invention also have the advantage that they contain no metal salts, in particular corrosion-promoting chlorides.

Die Erfindung betrifft auch ein Verfahren zur Demulgierung von Erdöl-Emulsionen, bei dem man die Emulsion bei Temperaturen von 10°C bis 130°C, bevorzugt bei 50°C bis 80°C, mit dem erfindungsgemäßen Erdölemulsionsspalter oder mit Lösungen, die den Erdölemulsionsspalter enthalten, behandelt.The invention also relates to a process for the demulsification of petroleum emulsions, in which the emulsion at temperatures of 10 ° C to 130 ° C, preferably at 50 ° C to 80 ° C, with the petroleum emulsion splitter according to the invention or with solutions containing the petroleum emulsion splitter included, treated.

Die Herstellung der Emulsionsspalter erfolgt in an sich bekannter Weise in ein- oder mehrstufiger, bevorzugt zweistufiger Arbeitsweise.The emulsion splitters are produced in a manner known per se in a one- or multi-stage, preferably two-stage, procedure.

Man geht beispielsweise bei zweistufiger Fahrweise so vor, daß man in der ersten Stufe auf das Polyethylenimin in Gegenwart von 1 bis 50 Gew.-% Wasser in einem mit Rührer versehenen Druckgefäß bei ca. 80°C bis 100°C so viel Alkylenoxid einwirken läßt, daß unter Absättigung sämtlicher Wasserstoffatome bindender Valenzen der Stickstoffatome das entsprechende Aminoalkanol entsteht.For example, in a two-stage procedure, the amount of alkylene oxide allowed to act in the first stage on the polyethyleneimine in the presence of 1 to 50% by weight of water in a pressure vessel provided with a stirrer at about 80 ° C. to 100 ° C. that the corresponding aminoalkanol is formed with saturation of all hydrogen atoms binding valences of the nitrogen atoms.

In zweiter Stufe werden nach Entfernung des Wassers, gegebenenfalls unter vermindertem Druck, ca. 0,5 bis 2 Gewichtsprozent - bezogen auf wasserfreien Aminoalkohol der ersten Stufe - eines alkalischen Katalysators, wie Natriummethylat, Kalium-tert.-Butylat, Kalium-, Natriumhydroxid, basische Ionenaustauscher u.a. zugefügt, woran sich die weitere Oxalkylierung mit den erforderlichen Mengen Alkylenoxid bei ca. 125°C bis 135°C anschließt.In the second stage, after removal of the water, optionally under reduced pressure, about 0.5 to 2 percent by weight, based on anhydrous amino alcohol of the first stage, of an alkaline catalyst, such as sodium methylate, potassium tert-butoxide, potassium hydroxide, sodium hydroxide, basic ion exchanger etc. added, followed by further oxalkylation with the required amounts of alkylene oxide at about 125 ° C to 135 ° C.

In einstufiger Fahrweise läßt sich die Umsetzung beispielsweise in der Weise durchführen, indem man in Gegenwart von wasserhaltigen oder -freien alkalischem Katalysator obiger Definition die gesamte Menge des Alkylenoxids aufpreßt und bei Temperaturen zwischen 125°C und 135°C durchreagieren läßt. Hier kann ein höherer Anteil an Nebenprodukten, wie reinen Polyalkylenglykolethern, auftreten, was aber keinen wesentlichen Einfluß auf die gewünschten Eigenschaften der Produkte hat.In a one-step procedure, the reaction can be carried out, for example, by pressing on the entire amount of alkylene oxide in the presence of water-containing or -free alkaline catalyst and allowing it to react at temperatures between 125 ° C. and 135 ° C. A higher proportion of by-products, such as pure polyalkylene glycol ethers, can occur here, but this has no significant influence on the desired properties of the products.

Bei der Herstellung der erfindungsgemäßen Spalter wird z.B. in erster Stufe 1,2-Propylenoxid zur Bildung des entsprechenden Propanolamins, anschließend weiteres Propylenoxid und schließlich Ethylenoxid aufgepreßt. Man kann aber auch umgekehrt verfahren, d.h. zuerst Ethylenoxid und anschließend Propylenoxid aufpressen. Beide Varianten sind ein- oder zweistufig realisierbar.In the manufacture of the splitters according to the invention e.g. in the first stage 1,2-propylene oxide to form the corresponding propanolamine, then further propylene oxide and finally ethylene oxide. But you can also do the opposite, i.e. first press ethylene oxide and then propylene oxide. Both variants can be implemented in one or two stages.

Wenn man nach dem Schema einer Mischpolymerisation arbeitet, kann man Mischungen aus Propylenoxid und Ethylenoxid verwenden.If you work according to the scheme of a mixed polymerization, you can use mixtures of propylene oxide and ethylene oxide.

Das Verhältnis von Propylenoxid zu Ethylenoxid kann dabei in den oben angegebenen Bereichen variiert werden.The ratio of propylene oxide to ethylene oxide can be varied in the ranges given above.

Zu dem vorstehend beschriebenen Alkoxylierungsschritt wird ausdrücklich auf die DE-OS 22 27 546 und die darin offenbarte Lehre Bezug genommen.For the alkoxylation step described above, reference is expressly made to DE-OS 22 27 546 and the teaching disclosed therein.

Ausgangsprodukte für die Herstellung der erfindungsgemäß zuzusetzenden Verbindungen sind allgemein bekannte Polyethylenimine, hergestellt in üblicher Weise aus Ethylenimin. Die angegebenen Molekulargewichte wurden durch Lichtstreuung bestimmt.Starting products for the preparation of the compounds to be added according to the invention are generally known polyethyleneimines, prepared in a conventional manner from ethyleneimine. The specified molecular weights were determined by light scattering.

Die erfindungsgemäßen Emulsionsspalter können auch mit anderen Emulsionsspaltern zusammen eingesetzt werden, z.B. mit den aus der DE-OS 27 19 978 bekannten alkoxylierten Alkylphenolformaldehydharzen.The emulsion splitters according to the invention can also be used together with other emulsion splitters, e.g. with the alkoxylated alkylphenol formaldehyde resins known from DE-OS 27 19 978.

Die Spalter werden bevorzugt wegen ihrer damit verbundenen besseren Dosierbarkeit als Lösungen mit 20 bis 90 Gew.% Spalter eingesetzt. Als Lösungsmittel können Mischungen von organischen Lösungsmitteln (z.B. Methanol) mit Wasser oder organische Lösungsmittel allein mit Siedegrenzen zwischen 50°C und 200°C dienen, z.B. Toluol, Xylole, Tetrahydrofuran, Dioxan, C₁-C₁₃-Alkohole, Glykole und Leichtbenzinfraktionen der genannten Siedegrenze.The splitters are preferred because of their associated better meterability than solutions with 20 to 90% by weight splitters. Mixtures of organic solvents (e.g. methanol) with water or organic solvents alone with boiling points between 50 ° C and 200 ° C, e.g. Toluene, xylenes, tetrahydrofuran, dioxane, C₁-C₁₃ alcohols, glycols and light petroleum fractions of the boiling point mentioned.

Im Falle der bevorzugten Verwendung von Lösungen werden diese zweckmäßig auf einen Wirksubstanzgehalt (Gehalt an Spalter) von 40 bis 60 Gew.% oder 70 bis 90 Gew.% eingestellt. Bei der Spaltung werden die Lösungen den Rohölen bevorzugt an den Sonden (im Feld) zugegeben. Die Spaltung verläuft dann bereits bei der Temperatur der frisch geförderten Wasser-in-Öl-Emulsion in einer solchen Geschwindigkeit, daß die Emulsion bereits auf dem Weg zu der Aufbereitungsanlage gebrochen werden kann. Sie wird dort in einem gegebenenfalls beheizten Abscheider und eventuell unter Zuhilfsnahme eines elektrischen Feldes ohne Schwierigkeiten in Reinöl und Salzwasser getrennt.In the case of the preferred use of solutions, these are expediently adjusted to an active substance content (splitter content) of 40 to 60% by weight or 70 to 90% by weight. When splitting, the solutions are preferred to crude oils added to the probes (in the field). The cleavage then already runs at the temperature of the freshly pumped water-in-oil emulsion at such a rate that the emulsion can be broken on the way to the processing plant. There it is separated in a possibly heated separator and possibly with the help of an electric field without difficulty into pure oil and salt water.

Die Spalter werden den Rohöl-Emulsionen zweckmäßig in Mengen (Wirkstoff) von 0,1 bis 200 ppm, bevorzugt 5 bis 50 ppm, bezogen auf das Gewicht der zu spaltenden Emulsion, bei Temperaturen zwischen 10°C und 130°C, bevorzugt 50°C bis 80°C, zugesetzt.The splitters are expediently added to the crude oil emulsions in amounts (active ingredient) of 0.1 to 200 ppm, preferably 5 to 50 ppm, based on the weight of the emulsion to be split, at temperatures between 10 ° C. and 130 ° C., preferably 50 ° C to 80 ° C added.

Die erfindungsgemäß anzuwendenden Schnellspalter können für Wasser-in-Öl-Emulsionen mit etwa 0,1 bis 99 Gew.% Salzwassergehalt verwendet werden. Als Öle, die auf diese Weise schnell entwässert werden können, kommen Rohölemulsionen der verschiedensten Provenienzen in Betracht.The rapid breakers to be used according to the invention can be used for water-in-oil emulsions with about 0.1 to 99% by weight salt water content. Crude oil emulsions of various origins come into consideration as oils that can be drained quickly in this way.

BeispieleExamples 1. Herstellung des Emulsionsspalters A (Synthesebeispiel)1. Preparation of the emulsion splitter A (synthesis example) 1. Stufe: In einem Rührautoklaven wurden1st stage: In a stirred autoclave

0,63 kg0.63 kg
Polyethylenimin (entspricht 6,0 Mol, bezogen auf monomeres Ethylenimin) (Polymin G 500, Wirkstoffgehalt: 41 % in Wasser, Molekulargewicht 16 000-19 000, nach Lichtstreuung) unter Stickstoff vorgelegt.Polyethyleneimine (corresponds to 6.0 moles, based on monomeric ethyleneimine) (Polymin G 500, active ingredient content: 41% in water, molecular weight 16,000-19,000, after light scattering) under nitrogen.
0,35 kg0.35 kg
Propylenoxid (6,0 Mol, bezogen auf monomeres Ethylenimin) wurden bei 90°C bis 95°C aufgepreßt. Man rührte bis zur Druckkonstanz, kühlte auf 80°C ab und entfernte das Wasser im Vakuum. Man erhielt 608 g (quant.) eines hochviskosen, bräunlichen Öls.Propylene oxide (6.0 mol, based on monomeric ethyleneimine) were injected at 90 ° C to 95 ° C. The mixture was stirred to constant pressure, cooled to 80 ° C. and the water was removed in vacuo. 608 g (quant.) Of a highly viscous, brownish oil were obtained.
2. Stufe: In einem Rührautoklaven wurden das Produkt aus Stufe 1 (608 g) und2nd stage: The product from stage 1 (608 g) and

10,0 g10.0 g
(1 Gew.-%, bezogen auf Einsatzstoffe der Stufe 1 Kalium-tert.-Butylat vorgelegt. Der Reaktor wurde mehrmals mit Stickstoff gespült, dann heizte man auf 125°C auf und preßte(1% by weight, based on feedstocks from stage 1, of potassium tert-butoxide. The reactor was flushed several times with nitrogen, then the mixture was heated to 125 ° C. and pressed
8,37 kg8.37 kg
(190 Mol) Ethylenoxid und(190 mol) ethylene oxide and
8,70 kg8.70 kg
(150 Mol) Propylenoxid bei 130°C auf. Nach Abkühlen auf 80°C erhielt man(150 mol) propylene oxide at 130 ° C. After cooling to 80 ° C was obtained
17,7 kg17.7 kg
an Produkt.of product.
2. Anwendungsbeispiele2. Examples of use 2.1 Wirksamkeit als Spalter in Wasser-in-Öl-Emulsionen2.1 Efficacy as a splitter in water-in-oil emulsions

Der gemäß Synthesebeispiel hergestellte Spalter A wird in einer Menge von 25 ppm unter Rühren drei verschiedenen Rohölemulsionen aus Westafrika bei 40°C zugegeben und anschließend werden die Proben stehengelassen. Die abgeschiedenen Wassermengen wurden nach bestimmten Zeitabständen gemessen.The splitter A produced according to the synthesis example is added in an amount of 25 ppm to three different crude oil emulsions from West Africa at 40 ° C. with stirring, and the samples are then left to stand. The separated amounts of water were measured after certain time intervals.

Zum Vergleich wurden die Erdölemulsionen mit einem Spalter B, der durch Alkoxylierung eines Polyethylenimins mit dem Molekulargewicht von ca. 21 000 (Mw) mit 36 Molen Ethylenoxid und 86 Molen Propylenoxid pro Ethylenimineinheit hergestellt worden war, in der oben angegebenen Weise versetzt.For comparison, the oil emulsions having a splitter B, which had been prepared by alkoxylation of polyethyleneimine with a molecular weight of about 21,000 (M w) with 36 moles of ethylene oxide and 86 moles of propylene oxide per ethyleneimine were placed in the manner indicated above.

Die Ergebnisse sind aus Tabelle I ersichtlich. Tabelle I Spalter abgeschiedenes H₂O in ml nach 10min 20min 30min 45min 1h 2h 3h Rohölemulsion I A 4 15 40 43 45 45 47 B 8 15 25 40 43 47 47 Rohölemulsion II A 2 5 25 35 38 38 39 B 1 3 5 10 15 20 22 Rohölemulsion III A 40 40 40 40 40 40 40 B 0 2 2 2 2 2 2 The results are shown in Table I. Table I Splitter deposited H₂O in ml after 10min 20 min 30 min 45min 1h 2h 3h Crude oil emulsion I A 4th 15 40 43 45 45 47 B 8th 15 25th 40 43 47 47 Crude oil emulsion II A 2nd 5 25th 35 38 38 39 B 1 3rd 5 10th 15 20th 22 Crude oil emulsion III A 40 40 40 40 40 40 40 B 0 2nd 2nd 2nd 2nd 2nd 2nd

2.2 Wirksamkeit als Deoiler in Öl-in-Wasser-Emulsionen2.2 Efficacy as a deoiler in oil-in-water emulsions

100 ml der zu testenden Erdöl-Emulsion wurde in 177,44 ml große, graduierte, klar durchsichtige Testflaschen mit rechteckigem Querschnitt gefüllt. Zu den Emulsionen in den Testflaschen wurden 25 Gew.-ppm des Demulgators zugegeben. Die die zu testenden Proben enthaltenden Testflaschen wurden 100 mal geschüttelt und dann auf Wasserklarheit entsprechend den nachstehend angegebenen Beurteilungskriterien beurteilt.100 ml of the petroleum emulsion to be tested was filled into 177.44 ml, graduated, clearly transparent test bottles with a rectangular cross section. 25 ppm by weight of the demulsifier was added to the emulsions in the test bottles. The test bottles containing the samples to be tested were shaken 100 times and then evaluated for water clarity according to the evaluation criteria given below.

Beurteilungskriterien:Assessment criteria:

1010th
Unbehandelt: keine Änderung im Aussehen der EmulsionUntreated: no change in the appearance of the emulsion
99
geringfügige Farbveränderung der Emulsionslight change in color of the emulsion
88th
Emulsion zeigt deutliche FarbänderungEmulsion shows clear color change
77
Wasser schwach gelbWater faint yellow
66
weißes Wasser - man kann Zahlen oder Buchstaben am Boden der Flasche sehenwhite water - you can see numbers or letters on the bottom of the bottle
55
weißes Wasser - man kann Zahlen oder Buchstaben an der Längsseite der Flasche sehen beim Blick durch die Flasche parallel zur schmalen Seitewhite water - you can see numbers or letters on the long side of the bottle when looking through the bottle parallel to the narrow side
44th
weißes Wasser - man kann Zahlen an der Längsseite der Flasche lesen beim Blick durch die Flasche parallel zur schmalen Seitewhite water - you can read numbers on the long side of the bottle when looking through the bottle parallel to the narrow side
33rd
weißes Wasser - man kann Zahlen an der schmalen Seite der Flasche sehen beim Blick durch die Flasche parallel zur Längsseite der Flaschewhite water - you can see numbers on the narrow side of the bottle when looking through the bottle parallel to the long side of the bottle
22nd
weißes Wasser - man kann Zahlen an der schmalen Seite der Flasche lesen beim Blick durch die Flasche parallel zur Längsseite der Flaschewhite water - you can read numbers on the narrow side of the bottle when looking through the bottle parallel to the long side of the bottle
11
sehr sauberes Wasser - man kann Zahlen an der schmalen Seite der Flasche beim Blick durch die Flasche parallel zur Längsseite der Flasche sehr gut lesenvery clean water - you can read numbers on the narrow side of the bottle when looking through the bottle parallel to the long side of the bottle

Die geprüften Testemulsionen waren die in Beispiel 2.1 angegebenen Rohölemulsionen, die bei Umgebungstemperatur mit dem Demulgator behandelt wurden. Die Ergebnisse sind in Tabelle II wiedergegeben. Tabelle II Spalter Rohölemulsion Beurteilungsziffer A I 2 B I 8 A II 3 B II 6 A III 1 B III 9 Aus den Versuchsergebnissen ist ersichtlich, daß sich der erfindungsgemäße Erdölemulsionsspalter zum einen bezüglich seiner Spalteigenschaften (Tabelle I) vorteilhaft verhält gegenüber einer Vergleichssubstanz, die sich im wesentlichen durch einen deutlich höheren Propoxylierungsgrad von dem erfindungsgemäßen Spalter unterscheidet. Zum anderen wird mit dem erfindungsgemäßen Spalter insbesondere eine sehr gute Abtrennung des Restöls aus dem abgeschiedenen Wasser erreicht (Tabelle II).The test emulsions tested were the crude oil emulsions specified in Example 2.1, which were treated with the demulsifier at ambient temperature. The results are shown in Table II. Table II Splitter Crude oil emulsion Assessment number A I. 2nd B I. 8th A II 3rd B II 6 A III 1 B III 9 It can be seen from the test results that, on the one hand, the petroleum emulsion splitter according to the invention behaves advantageously with regard to its splitting properties (Table I) compared to a comparison substance which differs from the splitter according to the invention essentially by a significantly higher degree of propoxylation. On the other hand, the splitter according to the invention achieves very good separation of the residual oil from the separated water (Table II).

Damit wird deutlich, daß durch das Zusammenwirken der speziellen, die erfindungsgemäßen Erdölemulsionsspalter charakterisierenden Parameter (d.h. Molekulargewicht des eingesetzten Polyethylenimins, Propoxylierungs- und Ethoxylierungsgrad) ein Spalter erhalten wird, der gegenüber den bekannten Spaltern erhebliche Vorteile aufweist.This makes it clear that the interaction of the special parameters characterizing the petroleum emulsion breakers according to the invention (i.e. molecular weight of the polyethyleneimine used, degree of propoxylation and ethoxylation) gives a breaker which has considerable advantages over the known breakers.

Claims (6)

  1. A petroleum emulsion breaker based on alkoxylated polyethyleneimines, which is obtained by alkoxylation of polyethyleneimines with a molecular weight Mw of 250035,000 with 5-40 moles of propylene oxide and 5-40 moles of ethylene oxide per ethyleneimine unit in the polyethyleneimine.
  2. A petroleum emulsion breaker as claimed in claim 1, wherein the polyethyleneimine has a molecular weight Mw of 5000-25,000.
  3. A petroleum emulsion breaker as claimed in claim 1, which is obtained by alkoxylation of polyethyleneimine with 5-30 moles of propylene oxide and 520 moles of ethylene oxide per ethyleneimine unit in the polyethyleneimine.
  4. A petroleum emulsion breaker as claimed in claim 1, which contains as second active component an alkoxylated alkylphenol/formaldehyde resin.
  5. A concentrated solution of a petroleum emulsion breaker, which is composed of 20-90% by weight of petroleum emulsion breaker as claimed in claim 1 and 10-80% by weight of an organic solvent, which may contain H₂O.
  6. A method for the demulsification of petroleum emulsions, which comprises treating the emulsion at from 10°C to 130°C, preferably 50°C to 80°C, with a solution of the emulsion breaker as claimed in claim 1.
EP92118674A 1991-11-07 1992-10-31 Oil demulsifier Expired - Lifetime EP0541018B1 (en)

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DE4136661A DE4136661A1 (en) 1991-11-07 1991-11-07 PETROLEUM EMULSION SPLITTER
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CA2082287A1 (en) 1993-05-08
EP0541018A3 (en) 1993-09-08
EP0541018A2 (en) 1993-05-12
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