EP1458951A1 - Use of sulphonated alkyl phenol formaldehydes in the stabilization of ashphaltenes in crude oil - Google Patents

Use of sulphonated alkyl phenol formaldehydes in the stabilization of ashphaltenes in crude oil

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Publication number
EP1458951A1
EP1458951A1 EP02798329A EP02798329A EP1458951A1 EP 1458951 A1 EP1458951 A1 EP 1458951A1 EP 02798329 A EP02798329 A EP 02798329A EP 02798329 A EP02798329 A EP 02798329A EP 1458951 A1 EP1458951 A1 EP 1458951A1
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Prior art keywords
asphaltenes
crude oil
compounds
ppm
formulas
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EP02798329A
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German (de)
French (fr)
Inventor
Ansgar Behler
Wolfgang Breuer
Matthias Hof
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Cognis IP Management GmbH
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Cognis Deutschland GmbH and Co KG
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/52—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning
    • C09K8/524—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning organic depositions, e.g. paraffins or asphaltenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
    • C08G61/10—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aromatic carbon atoms, e.g. polyphenylenes

Definitions

  • the present invention relates to certain sulfonated alkylphenol formaldehydes and their use for stabilizing asphaltenes in crude oil, and to a method for preventing the precipitation of asphaltenes in crude oils.
  • Crude oil is a complex mixture of different paraffinic and aromatic hydrocarbons, whereby the individual components have very different chemical and physical properties. In the distillation of crude oil, therefore, both highly volatile, low-viscosity components and waxy, highly viscous fractions are obtained. This last group includes petroleum resins and predominantly asphaltenes, which are colloidally disperse in the oil phase.
  • the asphaltenes consist of a mixture of different, saturated, unsaturated and aromatic hydrocarbons, especially naphthalene derivatives. There are also heterocyclic hydrocarbons, some of which also contain complexed metal ions. Asphaltenes are also rich in sulfur, nitrogen and oxygen compounds. Due to the complex composition, asphaltenes are generally characterized by their solubility.
  • the heptane or pentane-insoluble but toluene-soluble petroleum fraction is referred to as asphaltenes, the "dissolving" of the asphaltenes being a complex process for which a complete theoretical description has not yet existed (cf. EYSheu, OC Mullins, Asphaltenes - Fundamentals and Applications, Plenum Press, New York, 1995, Chapter I and Chapter III).
  • the micelles have different sizes depending on the temperature and composition of the oil phase. For example, it is known that lighter aromatic hydrocarbons in crude oil stabilize the asphaltene micelles. Under the conditions of oil production or production, however, the asphaltenes often precipitate, which leads to the formation of highly viscous, waxy to solid residues on the surface of the production facilities and the petroleum-containing formation surrounding the borehole leads. The asphalt residues clog the pores of the formation, which leads to a noticeable reduction in production rates and, in the worst case, can make production completely impossible. Asphalt residues on the surfaces of the production plants, for example the conveyor pipe or the walls of the casing of pipelines or separators, can also significantly hinder the production.
  • the object of the present invention was therefore to provide effective alternatives to the stabilizers known in the prior art for asphaltenes in crude oils, even with very different crude oil qualities. It has been found that certain sulfonated alkylphenol formaldehydes accomplish the above object.
  • the present application relates to the use of products obtainable by sulfonating compounds of the formulas (I) or (II) R
  • n is a number from 2 to 12 and R is a C3-C 2 alkyl, C6-C12-A17I or hydroxyaryl or C7-Ci2-aralkyl radical, as a stabilizer for asphaltenes in crude oil.
  • Ph in the formulas (I) and (II) denotes a phenol radical.
  • the sulfonation products used according to the invention are obtained by sulfonating compounds of the general formulas (I) and / or (II) which are known per se. These starting products are known for example from DE 197 09 797 A1. Reference is made here to the formulas (I) and (II) in claim 1 of DE 197 09 797 A1 and to the disclosure on page 2, lines 40 to 44 and the disclosure of page 3 of this document. The disclosure of these passages is expressly made to disclose the present application. The formulas (I) and (II) in DE 197 09 797 are identical to those of the present application. Such compounds are resins which are available, for example, under the name Dowfax DM 645 (Dow Chemicals).
  • the starting materials of the formulas (I) and (II) are sulfonated in a manner known per se using gaseous SO3. However, the sulfonation products are not neutralized according to the invention but are present as free acids.
  • the sulfonation of the starting materials is preferably carried out in a falling film reactor by means of a continuous process.
  • the gaseous sulfur trioxide is generated in situ by pyrolysis of pure sulfur.
  • the polyalkylformaldehyde resin used is preferably reacted in an equimolar ratio with sulfur trioxide.
  • the reaction itself advantageously takes place in a temperature range of 75-80 ° C.
  • the end product is preferably not neutralized.
  • the products according to the invention are obtained as aqueous solutions which can be formulated or used directly as asphaltene dispersants without further steps.
  • the sulfonated according to the invention Products surprisingly show significantly better properties than asphaltene inhibitors or asphaltene stabilizers than the compounds known from the prior art or their mixtures according to the teaching of DE 197 09 797 A1.
  • Crude oils are understood to be the unrefined petroleum that comes directly from the earth. These are complex mixtures of predominantly hydrocarbons with densities in the range from 0.65 to 1.02 g / cm 3 and calorific values from 38 to 46 MJ / kg.
  • the boiling points of the most important crude oil components are in the temperature range from 50 to 350 ° C (see Römpp Chemielexikon, Volume 2, 1997, pages 1210 to 1213).
  • the sulfated alkylphenol formaldehydes according to the invention i.e. their addition to the crude oils effectively prevents the precipitation of asphaltenes or the formation of residues.
  • Another object of the present invention relates to a method for preventing the precipitation of asphaltenes from crude oils, characterized in that sulfated alkylphenol formaldehydes are added to the crude oils as stabilizers in amounts of 100 to 2500 ppm as described above.
  • the present technical teaching also includes the use of the sulfonated -Akylpherrolformaldehyden-in the form of dilute solutions in aromatic solvents, preferably toluene.
  • dilute solutions preferably contain the polyesteramides in amounts of 2 to 50% by weight, in particular in amounts of 2 to 20 and particularly preferably 2 to 15% by weight.
  • Such formulations can also contain other additives, such as corrosion inhibitors or defoamers. Examples
  • the sulfonation of the starting materials was carried out in a falling film reactor by means of a continuous process.
  • the gaseous sulfur trioxide was generated by pyrolysis of pure sulfur in situ.
  • the polyalkyl formaldehyde resin used was reacted in an equimolar ratio with sulfur trioxide.
  • the reaction was carried out in a temperature range of 75-80 ° C.
  • the end product was not neutralized.
  • the active substance content was determined by Epton titration, the molar mass and the acid number as key figures.
  • the test is based on the fact that asphaltenes are soluble in aromatic but not aliphatic hydrocarbons.
  • dispersants can be tested by dissolving the oil or extracted asphaltenes in an aromatic solvent and then adding a non-aromatic solvent to produce a precipitate. Since asphaltenes are dark in color, the extent of the precipitation can be determined by UV spectroscopic measurement of the supernatant.
  • the following table shows the results of the precipitation tests at three concentrations of different formulations A to H according to the invention.
  • the absorption values of the experimental formulations were divided by the corresponding value of the positive sample (pure toluene) (information in the tables as relative absorption). The closer the values are to 1.0, the better the effect of the dispersant formulation. The values are shown in the following table.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

Disclosed is the use of sulphonated alkyl phenol formaldehydes as stabilizers for asphaltenes in crude oil.

Description

"Verwendung von sulfierten Alkylphenolformaldehyden zur Stabilisierung von Asphaltenen in Rohöl""Use of sulfonated alkylphenol formaldehydes to stabilize asphaltenes in crude oil"
Die vorliegende Erfindung betrifft bestimmte sulfierten Alkylphenolformaldehyden und deren Verwendung zur Stabilisierung von Asphaltenen in Rohöl sowie ein Verfahren zur Verhinderung der Ausfällung von Asphaltenen in Rohölen.The present invention relates to certain sulfonated alkylphenol formaldehydes and their use for stabilizing asphaltenes in crude oil, and to a method for preventing the precipitation of asphaltenes in crude oils.
Rohöl stellt eine komplexe Mischung verschiedener paraffinischer und aromatischer Kohlenwasserstoffe dar, wobei die einzelnen Bestandteile sehr unterschiedliche chemische und physikalische Eigenschaften aufweisen. Bei der Destillation von Rohöl erhält man daher sowohl sehr leichtflüchtige, niedrigviskose Bestandteile als auch wachsartige, hochviskose Fraktionen. Zu dieser letzten Gruppe gehören Erdölharze und zum überwiegenden Anteil Asphaltene, die in der Ölphase kolloid-dispers vorliegen.Crude oil is a complex mixture of different paraffinic and aromatic hydrocarbons, whereby the individual components have very different chemical and physical properties. In the distillation of crude oil, therefore, both highly volatile, low-viscosity components and waxy, highly viscous fractions are obtained. This last group includes petroleum resins and predominantly asphaltenes, which are colloidally disperse in the oil phase.
Die Asphaltene bestehen aus einer Mischung verschiedener, gesättigter, ungesättigter und aromatischer Kohlenwasserstoffe, insbesondere von Naphthalinderivaten. Daneben findet man auch heterocyclische Kohlenwasserstoffe, die zum Teil auch komplexierte Metallionen enthalten. Weiterhin sind Asphaltene reich an Schwefel-, Stickstoff- und Sauerstoffverbindungen. Aufgrund der komplexen Zusammensetzung werden Asphaltene im allgemeinen über ihre Löslichkeit charakterisiert. So bezeichnet man die in Heptan oder Pentan unlösliche aber in Toluol lösliche Erdölfraktion als Asphaltene, wobei das „Lösen" der Asphaltene einen komplexen Vorgang darstellt, für den bislang noch keine vollständige theoretische Beschreibung existiert (vgl. E.Y.Sheu, O.C. Mullins, Asphaltenes - Fundamentals and Applications, Plenum Press, New York, 1995, Chapter I und Chapter III).The asphaltenes consist of a mixture of different, saturated, unsaturated and aromatic hydrocarbons, especially naphthalene derivatives. There are also heterocyclic hydrocarbons, some of which also contain complexed metal ions. Asphaltenes are also rich in sulfur, nitrogen and oxygen compounds. Due to the complex composition, asphaltenes are generally characterized by their solubility. The heptane or pentane-insoluble but toluene-soluble petroleum fraction is referred to as asphaltenes, the "dissolving" of the asphaltenes being a complex process for which a complete theoretical description has not yet existed (cf. EYSheu, OC Mullins, Asphaltenes - Fundamentals and Applications, Plenum Press, New York, 1995, Chapter I and Chapter III).
Asphaltene liegen in der Ölphase des Rohöls als Micellkolloide vor, wobei die einzelnen Micellen jeweils aus mehreren unterschiedlichen Molekülen bestehen. Die Micellen weisen je nach Temperatur und Zusammensetzung der Ölphase unterschiedliche Größen auf. So ist z.B. bekannt, daß leichtere aromatische Kohlenwasserstoffe im Rohöl die Asphalten-Micellen stabilisieren. Bei den Bedingungen der Erdölproduktion bzw. -förderung kommt es aber häufig zu einer Ausfällung der Asphaltene, was zur Bildung von hochviskosen, wachsartig bis festen Rückständen auf der Oberfläche der Produktionsanlagen und der das Bohrloch umgebenden erdölhaltigen Formation führt. Die Asphaltenrückstände verstopfen die Poren der Formation, was zu einer spürbaren Verringerung der Förderraten führt und im schlimmsten Fall eine Förderung vollständig unmöglich machen kann. Auch Asphaltenrückstände auf den Oberflächen der Produktionsanlagen, beispielsweise dem Förderrohr oder den Wänden des Casings von Pipelines oder Separatoren können die Förderung erheblich behindern.Asphaltenes exist in the oil phase of the crude oil as micelle colloids, whereby the individual micelles each consist of several different molecules. The micelles have different sizes depending on the temperature and composition of the oil phase. For example, it is known that lighter aromatic hydrocarbons in crude oil stabilize the asphaltene micelles. Under the conditions of oil production or production, however, the asphaltenes often precipitate, which leads to the formation of highly viscous, waxy to solid residues on the surface of the production facilities and the petroleum-containing formation surrounding the borehole leads. The asphalt residues clog the pores of the formation, which leads to a noticeable reduction in production rates and, in the worst case, can make production completely impossible. Asphalt residues on the surfaces of the production plants, for example the conveyor pipe or the walls of the casing of pipelines or separators, can also significantly hinder the production.
Es sind daher verschiedene Methoden bekannt, Asphaltene im Rohöl dispergiert zu halten bzw. deren Ausfällung zu verhindern. Die DE 197 09 797 beschreibt dazu synergistisch wirkende Mischungen von Alkylphenolformaldehydharzen und bestimmten oxalkylierten Aminen als Asphalten-Dispergatoren. Aus der US 4,414,035 ist bekannt, daß Alkylarylsulfonsäurederivate, beispielsweise Dodecylbenzolsulfonsäure, geeignet ist, Asphaltenen in Rohölen zu dispergieren.Various methods are therefore known for keeping asphaltenes dispersed in the crude oil or for preventing their precipitation. DE 197 09 797 describes synergistic mixtures of alkylphenol formaldehyde resins and certain oxalkylated amines as asphaltene dispersants. From US 4,414,035 it is known that alkylarylsulfonic acid derivatives, for example dodecylbenzenesulfonic acid, are suitable for dispersing asphaltenes in crude oils.
In der Praxis zeigt sich aber häufig, daß die bekannten Hilfsmittel zur Asphalten-Stabilisierung je nach Art und Herkunft des Rohöls sehr unterschiedliche Wirksamkeiten aufweisen. Dies ist insbesondere auf die komplexe und sehr variable Struktur der Asphaltenen zurückzuführen. Daher werden weiterhin neue Mittel zur Asphaltenstabilisierung gesucht. Außerdem sind die im Stand der Technik bekannten Hilfsmittel häufig entweder toxisch und/oder ökologisch bedenklich. Sowohl aus Gründen der Umweltverträglichkeit von Arbeitsmitteln als auch aus Gründen des Arbeitsschutzes wird daher versucht, die Verwendung derartiger Substanzen zu vermeiden.In practice, however, it is often found that the known auxiliaries for asphaltene stabilization have very different efficacies depending on the type and origin of the crude oil. This is due in particular to the complex and very variable structure of the asphaltenes. Therefore, new means of asphalt stabilization are still being sought. In addition, the aids known in the prior art are often either toxic and / or ecologically questionable. Attempts are therefore made to avoid the use of such substances both for reasons of environmental compatibility of work equipment and for reasons of occupational safety.
Die Aufgabe der vorliegenden Erfindung war es daher auch bei sehr unterschiedlichen Rohölqualitäten wirksame Alternativen zu den im Stand der Technik bekannten Stabilisatoren für Asphaltene in Rohölen bereitzustellen. Es wurde gefunden, daß bestimmte sulfierten Alkylphenolformaldehyde die obige Aufgabe lösen.The object of the present invention was therefore to provide effective alternatives to the stabilizers known in the prior art for asphaltenes in crude oils, even with very different crude oil qualities. It has been found that certain sulfonated alkylphenol formaldehydes accomplish the above object.
Gegenstand der vorliegenden Anmeldung ist in einer ersten Ausführungsform die Verwendung von Produkten, erhältlich durch Sulfierung von Verbindungen der Formeln (I) oder (II) RIn a first embodiment, the present application relates to the use of products obtainable by sulfonating compounds of the formulas (I) or (II) R
I R-Ph-[-Ph-]n-Ph-R (I)I R-Ph - [- Ph-] n-Ph-R (I)
RR
I -[Ph-CH2-]n- (II)I - [Ph-CH 2 -] n- (II)
in denen n eine Zahl von 2 bis 12 bedeutet und R für einen C3-C2 Alkyl-, C6-C12-A17I- oder Hydroxyaryl bzw. C7-Ci2-Aralkylrest steht, als Stabilisator für Asphaltene in Rohöl. Weiterhin bedeutet Ph in den Formeln (I) und (II) einen Phenol-Rest.in which n is a number from 2 to 12 and R is a C3-C 2 alkyl, C6-C12-A17I or hydroxyaryl or C7-Ci2-aralkyl radical, as a stabilizer for asphaltenes in crude oil. Furthermore, Ph in the formulas (I) and (II) denotes a phenol radical.
Die erfindungsgemäß eingesetzten Sulfierprodukte werden durch Sulfierung von an sich bekannten Verbindungen der allgemeinen Formeln (I) und/oder (II) erhalten. Diese Ausgangsprodukte sind beispielweise aus der DE 197 09 797 A1 bekannt. Bezug genommen wird hierbei auf die Formeln (I) und (II) im Anspruch 1 der DE 197 09 797 A1 sowie auf die Offenbarung auf Seite 2, Zeilen 40 bis 44 sowie die Offenbarung der Seite 3 dieser Schrift. Die Offenbarung dieser Textstellen wird ausdrücklich auch zur Offenbarung der vorliegenden Anmeldung gemacht. Die Formeln (I) und (II) in der DE 197 09 797 sind identisch mit denen der vorliegende Anmeldung. Derartige Verbindungen stellen Harze dar, die beispielsweise unter der Bezeichnung Dowfax DM 645 (Dow Chemicals) erhältlich sind.The sulfonation products used according to the invention are obtained by sulfonating compounds of the general formulas (I) and / or (II) which are known per se. These starting products are known for example from DE 197 09 797 A1. Reference is made here to the formulas (I) and (II) in claim 1 of DE 197 09 797 A1 and to the disclosure on page 2, lines 40 to 44 and the disclosure of page 3 of this document. The disclosure of these passages is expressly made to disclose the present application. The formulas (I) and (II) in DE 197 09 797 are identical to those of the present application. Such compounds are resins which are available, for example, under the name Dowfax DM 645 (Dow Chemicals).
Die Sulfierung der Edukte der Formeln (I) und (II) erfolgt in an sich bekannter Weise mit gasförmigem SO3. Die Sulfierungsprodukte werden allerdings erfindungsgemäß nicht neutralisiert sondern liegen als freie Säuren vor. Die Sulfierung der Edukte wird vorzugsweise in einem Fallfilmreaktor mittels eines kontinuierlichen Verfahrens durchgeführt. Das gasförmige Schwefeltrioxid wird dabei durch Pyrolyse von reinem Schwefel in situ erzeugt. Das eingesetzte Polyalkylformaldehyd-Harz wird vorzugsweise im äquimolaren Verhältnis mit Schwefeltrioxid zur Reaktion gebracht. Die Reaktion selbst findet dann vorteilhafterweise in einem Temperaturbereich von 75-80°C statt. Das Endprodukt wird vorzugsweise nicht neutralisiert. Die erfindungsgemäßen Produkte fallen als wässerige Lösungen an, die ohne weitere Schritte direkt als Asphalten- Dispergatoren formuliert bzw. eingesetzt werden können. Die erfindungsgemäßen sulfierten Produkte zeigen dabei überraschenderweise deutlich bessere Eigenschaften als Asphalteninhibitoren bzw. Asphaltenstabilisatoren, als die aus dem Stand der Technik bekannten Verbindungen bzw. deren Abmischungen gemäß der Lehre der DE 197 09 797 A1. Unter Rohölen wird das unmittelbar aus der Erde kommende, nicht raffinierte Erdöl verstanden. Es handelt sich hierbei um komplexe Mischungen von überwiegend Kohlenwasserstoffen mit Dichten im Bereich von 0,65 bis 1 ,02 g/cm3 und Brennwerten von 38 bis 46 MJ/kg. Die Siedepunkte der wichtigsten Rohölbestandteile liegen im Temperaturbereich von 50 bis 350 °C (vergl. Römpp Chemielexikon, Band 2, 1997, Seiten 1210 bis 1213).The starting materials of the formulas (I) and (II) are sulfonated in a manner known per se using gaseous SO3. However, the sulfonation products are not neutralized according to the invention but are present as free acids. The sulfonation of the starting materials is preferably carried out in a falling film reactor by means of a continuous process. The gaseous sulfur trioxide is generated in situ by pyrolysis of pure sulfur. The polyalkylformaldehyde resin used is preferably reacted in an equimolar ratio with sulfur trioxide. The reaction itself then advantageously takes place in a temperature range of 75-80 ° C. The end product is preferably not neutralized. The products according to the invention are obtained as aqueous solutions which can be formulated or used directly as asphaltene dispersants without further steps. The sulfonated according to the invention Products surprisingly show significantly better properties than asphaltene inhibitors or asphaltene stabilizers than the compounds known from the prior art or their mixtures according to the teaching of DE 197 09 797 A1. Crude oils are understood to be the unrefined petroleum that comes directly from the earth. These are complex mixtures of predominantly hydrocarbons with densities in the range from 0.65 to 1.02 g / cm 3 and calorific values from 38 to 46 MJ / kg. The boiling points of the most important crude oil components are in the temperature range from 50 to 350 ° C (see Römpp Chemielexikon, Volume 2, 1997, pages 1210 to 1213).
Durch erfindungsgemäße Verwendung der sulfierten Alkylphenolformaldehyden d.h. deren Zusatz zu den Rohölen, wird das Ausfallen von Asphaltenen bzw. die Bildung von Rückständen wirkungsvoll verhindert. Um das Ausfallen von Asphaltenen zu verhindern, ist es vorteilhaft diese dem Rohöl in Mengen von 50 bis 2500 ppm, vorzugsweise von 100 bis 1000 ppm und insbesondere in Mengen von 150 bis 500 ppm (Aktivsubstanz) zuzusetzen.By using the sulfated alkylphenol formaldehydes according to the invention i.e. their addition to the crude oils effectively prevents the precipitation of asphaltenes or the formation of residues. In order to prevent the asphaltenes from precipitating, it is advantageous to add them to the crude oil in amounts of 50 to 2500 ppm, preferably from 100 to 1000 ppm and in particular in amounts of 150 to 500 ppm (active substance).
Ein weiterer Gegenstand der vorliegenden Erfindung betrifft ein Verfahren zur Verhinderung des Ausfallens von Asphaltenen aus Rohölen, dadurch gekennzeichnet, daß man den Rohölen sulfierten Alkylphenolformaldehyde gemäß der obigen Beschreibung als Stabilisatoren in Mengen von 100 bis 2500 ppm zusetzt.Another object of the present invention relates to a method for preventing the precipitation of asphaltenes from crude oils, characterized in that sulfated alkylphenol formaldehydes are added to the crude oils as stabilizers in amounts of 100 to 2500 ppm as described above.
Die vorliegende technische Lehre schließt auch die Verwendung der sulfierten -A kylpherrolformaldehyden-in-Form-von-verdünnten-Lösungen-in-aromatischen-Lösungsmitteln, vorzugsweise Toluol ein. Diese verdünnten Lösungen enthalten die Polyesteramide vorzugsweise in Mengen von 2 bis 50 Gew.-%, insbesondere in Mengen von 2 bis 20 und besonders bevorzugt 2 bis 15 Gew.-%. Derartige Formulierungen können noch weitere Additive, wie Korrosionsinhibitoren oder Entschäumer enthalten. B e i s p i e l eThe present technical teaching also includes the use of the sulfonated -Akylpherrolformaldehyden-in the form of dilute solutions in aromatic solvents, preferably toluene. These dilute solutions preferably contain the polyesteramides in amounts of 2 to 50% by weight, in particular in amounts of 2 to 20 and particularly preferably 2 to 15% by weight. Such formulations can also contain other additives, such as corrosion inhibitors or defoamers. Examples
Herstellung der Sulfierungsprodukte:Production of the sulfonation products:
Die Sulfierung der Edukte wurde in einem Fallfilmreaktor mittels eines kontinuierlichen Verfahrens durchgeführt. Das gasförmige Schwefeltrioxid wurde durch Pyrolyse von reinem Schwefel in situ erzeugt. Das verwendete Polyalkylformaldehyd-Harz wurde im äquimolaren Verhältnis mit Schwefeltrioxid zur Reaktion gebracht. Die Reaktion wurde in einem Temperaturbereich von 75- 80°C durchgeführt. Das Endprodukt wurde nicht neutralisiert. Als Kennzahlen wurden der Aktivsubstanzgehalt durch Epton-Titration, die Molmasse und Säurezahl bestimmt.The sulfonation of the starting materials was carried out in a falling film reactor by means of a continuous process. The gaseous sulfur trioxide was generated by pyrolysis of pure sulfur in situ. The polyalkyl formaldehyde resin used was reacted in an equimolar ratio with sulfur trioxide. The reaction was carried out in a temperature range of 75-80 ° C. The end product was not neutralized. The active substance content was determined by Epton titration, the molar mass and the acid number as key figures.
Typische Werte für ein Harz basierend auf Dowfax DM 650 sind im folgenden exemplarisch aufgeführt :Typical values for a resin based on Dowfax DM 650 are listed below as examples:
Test der dispergierenden Eigenschaften:Test of the dispersing properties:
Der Test basiert auf der Tatsache, daß Asphaltene in aromatischen, aber nicht in aliphatischen Kohlenwasserstoffen löslich sind. Somit können Dispergatoren getestet werden, indem man das Öl oder extrahierte Asphaltene in einem aromatischen Lösemittel löst und dann ein nichtaromatisches Lösungsmittel zusetzt, um einen Niederschlag zu erzeugen. Da Asphaltene von dunkler Farbe sind, kann das Ausmaß des Niederschlages durch eine UV-spektroskopische Messung der überstehenden Flüssigkeit bestimmt werden.The test is based on the fact that asphaltenes are soluble in aromatic but not aliphatic hydrocarbons. Thus, dispersants can be tested by dissolving the oil or extracted asphaltenes in an aromatic solvent and then adding a non-aromatic solvent to produce a precipitate. Since asphaltenes are dark in color, the extent of the precipitation can be determined by UV spectroscopic measurement of the supernatant.
Vorschrift Dispergiertest a) Eine 20-%ige Lösung von isolierten Asphaltenen in Toluol wird hergestellt;Regulation dispersion test a) A 20% solution of isolated asphaltenes in toluene is prepared;
b) 9,5 ml Heptan als Fällungsmittel für die Asphaltene, 0,5 ml toluolische Asphalten -Lösung und die entsprechenden Menge Dispergator-Lösung für die gewünschte Konzentration werden in einem 10 ml fassendem, graduiertem Glasrörchen vermischt und gut geschüttelt; c) als Negativprobe wird ein Röhrchen ohne Dispergator-Lösung angesetzt, als Positivprobe wird statt Heptan auch Toluol als Lösemittel verwendet; als zusätzlicher Vergleich wurden zwei Verkaufprodukte (Anticor DSA 800 und 711) in die Tests miteinbezogen;b) 9.5 ml of heptane as a precipitant for the asphaltenes, 0.5 ml of toluene asphaltene solution and the corresponding amount of dispersant solution for the desired concentration are mixed in a 10 ml graduated glass tube and shaken well; c) a tube without a dispersant solution is used as the negative sample; toluene is used as the solvent instead of heptane as the positive sample; as an additional comparison, two sales products (Anticor DSA 800 and 711) were included in the tests;
d) die Röhrchen werden über einen Zeitraum von 3 Stunden beobachtet und die Ausfallzeit der Asphaltene protokolliert; das Sediment sammelt sich dabei am Boden der Röhrchen;d) the tubes are observed over a period of 3 hours and the downtime of the asphaltenes is recorded; the sediment collects on the bottom of the tubes;
g) die Beurteilung der Sedimentmenge und des Aussehens der Lösung wird im Vergleich zu den der Positiv- und der Negativprobe durchgeführt. Zur Beurteilung der Niederschlagsmenge nimmt man eine Skala von 1-3 zur Hilfe, wobei 3 die größte Menge bedeutet.g) the assessment of the amount of sediment and the appearance of the solution is carried out in comparison with that of the positive and negative samples. A scale of 1-3 is used to assess the amount of precipitation, with 3 being the largest amount.
In der folgenden Tabelle sind die Ergebnisse der Fällungstests bei drei Konzentrationen verschiedener erfindungsgemäße Formulierungen A bis H aufgeführt.The following table shows the results of the precipitation tests at three concentrations of different formulations A to H according to the invention.
Tabelle 1 : Asphaltentest verschiedener Formulierungen Table 1: Asphalt test of various formulations
T= Ausfallzeit NS= Niederschlagsmenge (3 = Maximum)T = downtime NS = amount of precipitation (3 = maximum)
Um die Ergebnisse der spektroskopischen Untersuchung vergleichen zu können, wurden die Absorptionswerte der experimentellen Formulierungen durch den entsprechenden Wert der Positivprobe (reines Toluol) dividiert (Angabe in den Tabellen als relative Absorption). Je näher die Werte an 1 ,0 liegen, desto besser war die Wirkung der Dispergator-Formulierung. Die Werte sind in der folgenden Tabelle aufgeführt.In order to be able to compare the results of the spectroscopic examination, the absorption values of the experimental formulations were divided by the corresponding value of the positive sample (pure toluene) (information in the tables as relative absorption). The closer the values are to 1.0, the better the effect of the dispersant formulation. The values are shown in the following table.
Tabelle 2 : Relative Absorptionswerte der Asphalten-Lösungen Table 2: Relative absorption values of the asphaltene solutions

Claims

P a t e n t a n s p r ü c h e Patent claims
1. Verwendung von Produkten, erhältlich durch Sulfierung von Verbindungen der Formeln (I) oder (H)1. Use of products obtainable by sulfonating compounds of the formulas (I) or (H)
RR
II
R-Ph-[-Ph-]n-Ph-R (I)R-Ph - [- Ph-] n -Ph-R (I)
RR
I -[Ph-CH2-]n- (II)I - [Ph-CH 2 -] n- (II)
in denen Ph für einen Phenolrest steht, n eine Zahl von 2 bis 12 bedeutet und R für einen C3- C24 Alkyl-, C6-Ci2-Aryl- oder Hydroxyaryl- bzw. C7-Ci2-Aralkylrest steht, als Stabilisator für Asphaltene in Rohöl.in which Ph represents a phenol radical, n represents a number from 2 to 12 and R represents a C3-C24 alkyl, C6-Ci2-aryl or hydroxyaryl or C7-Ci2-aralkyl radical, as a stabilizer for asphaltenes in crude oil ,
2. Verwendung nach Anspruch 1 , dadurch gekennzeichnet, daß die Verbindungen sulfierten der Formel (I) und/oder (II) den Rohölen in Mengen von 50 bis 2500 ppm, vorzugsweise von 100 bis 1000 ppm und insbesondere von 150 bis 500 ppm zugesetzt werden.2. Use according to claim 1, characterized in that the sulfonated compounds of the formula (I) and / or (II) are added to the crude oils in amounts of 50 to 2500 ppm, preferably from 100 to 1000 ppm and in particular from 150 to 500 ppm ,
3. Verfahren zur Verhinderung des Ausfallens von Asphaltenen aus Rohölen, dadurch gekennzeichnet, daß man den Rohölen sulfierte Verbindungen gemäß Anspruch 1 als Stabilisatoren in Mengen von 100 bis 2500 ppm zusetzt.3. A method for preventing the precipitation of asphaltenes from crude oils, characterized in that sulfated compounds according to claim 1 are added to the crude oils as stabilizers in amounts of 100 to 2500 ppm.
4. Sulfierte Alkylphenolformaldehydharze, dadurch gekennzeichnet, daß sie durch Sulfierung von Verbindungen der Formeln (I) und/oder (II) gemäß Anspruch 1 erhalten werden.4. Sulfated alkylphenol formaldehyde resins, characterized in that they are obtained by sulfonating compounds of the formulas (I) and / or (II) according to claim 1.
5. Verfahren zur Herstellung von sulfiertem Alkylphenolformaldehydharzen, wobei man Verbindungen der Formeln (I) und/oder (II) gemäß Anspruch 1 , in einem Fallfilmreaktor in äquimolarem Verhältnis mit gasförmigem SO3 bei Temperaturen von 75 bis 80 °C zur Reaktion bringt, dadurch gekennzeichnet, daß die Reaktionsprodukte nicht neutralisiert werden. 5. A process for the preparation of sulfonated alkylphenol formaldehyde resins, wherein compounds of the formulas (I) and / or (II) according to claim 1, in a falling film reactor in an equimolar ratio with gaseous SO3 at temperatures of 75 to 80 ° C for reaction, characterized that the reaction products are not neutralized.
EP02798329A 2001-12-21 2002-12-12 Use of sulphonated alkyl phenol formaldehydes in the stabilization of ashphaltenes in crude oil Withdrawn EP1458951A1 (en)

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DE10163244 2001-12-21
DE10163244A DE10163244A1 (en) 2001-12-21 2001-12-21 Use of sulfonated alkylphenol formaldehydes to stabilize asphaltenes in crude oil
PCT/EP2002/014127 WO2003054348A1 (en) 2001-12-21 2002-12-12 Use of sulphonated alkyl phenol formaldehydes in the stabilization of ashphaltenes in crude oil

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CN102584641B (en) * 2011-12-14 2013-12-04 中国日用化学工业研究院 Process for preparing alkylphenol formaldehyde oligomer sulfonate
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US9523054B2 (en) * 2013-08-21 2016-12-20 Baker Hughes Incorporated Asphaltene stabilization in petroleum feedstocks by blending with biological source oil and/or chemical additive
WO2017095637A1 (en) * 2015-11-30 2017-06-08 Bp Corporation North America Inc. Screening methods for asphaltene stabilizers
US10907473B2 (en) 2017-11-14 2021-02-02 Chevron U.S.A., Inc. Low volume in-line filtration methods for analyzing hydrocarbon-containing fluid to evaluate asphaltene content and behavior during production operations
WO2024073492A1 (en) 2022-09-28 2024-04-04 Championx Llc Extended release asphaltene inhibitor composition

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