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EP0932746A2 - Use of alkanesulphonic acids as asphaltene dispersants - Google Patents

Use of alkanesulphonic acids as asphaltene dispersants

Info

Publication number
EP0932746A2
EP0932746A2 EP97912134A EP97912134A EP0932746A2 EP 0932746 A2 EP0932746 A2 EP 0932746A2 EP 97912134 A EP97912134 A EP 97912134A EP 97912134 A EP97912134 A EP 97912134A EP 0932746 A2 EP0932746 A2 EP 0932746A2
Authority
EP
European Patent Office
Prior art keywords
crude oils
asphaltenes
dispersants
carbon atoms
products derived
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP97912134A
Other languages
German (de)
French (fr)
Inventor
Dennis Miller
Axel Vollmer
Michael Feustel
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Clariant Produkte Deutschland GmbH
Original Assignee
Clariant GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Clariant GmbH filed Critical Clariant GmbH
Publication of EP0932746A2 publication Critical patent/EP0932746A2/en
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • C10G75/00—Inhibiting corrosion or fouling in apparatus for treatment or conversion of hydrocarbon oils, in general
    • C10G75/04—Inhibiting corrosion or fouling in apparatus for treatment or conversion of hydrocarbon oils, in general by addition of antifouling agents
    • 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

Definitions

  • Asphaltenes are components of crude oils. They contain a variety of
  • asphaltenes are described as the oil fraction that is soluble in benzene but not in n-pentane.
  • Asphaltenes are usually present in the crude oil as a colloidal dispersion. This is stabilized by oil resins.
  • Asphaltenes can fail during the production, refining, transport and storage of crude oil and products derived from it, such as heavy fuel oil or marine oil. Common causes of this failure are a drop in temperature or a change in the composition (eg evaporation of volatile components). Asphaltenes can also fail when flowing through porous media. Flooding with C0 2 during the production process can cause asphaltenes to flocculate or fail.
  • Some oils contain hydrocarbon waxes that fail at low temperatures. Interactions between the precipitation of wax and asphaltenes can increase the total amount of precipitated substance or its rate of formation.
  • Asphaltenes cause problems in the production and processing of crude oils. Asphaltenes are reflected in valves, pipes and conveyors. On hot surfaces, such as heat exchangers, the carbonization of these precipitates can make their removal very difficult. Precipitation reduces the efficiency of
  • Heavy oils which are often used to power ships, contain considerable amounts of asphaltenes.
  • the failure of asphaltenes can lead to poor combustion as well as difficulties in handling and storing the fuel. Burning disorders due to the precipitation of asphaltenes are also observed in power plants operated with heavy oils.
  • Bitumen, heavy oils and residues are sometimes diluted with solvents to reduce the viscosity for transportation. If asphaltenes fail in the process, handling problems arise.
  • the precipitation of asphaltenes can be prevented or reduced by small amounts of dispersants. These substances show one or more of the following effects:
  • asphaltenes have already precipitated, they can be removed using solvents.
  • a dispersant can improve the effectiveness of these solvents.
  • CA 2 029 465 and CA 2 075 749 describe alkylphenol formaldehyde resins in combination with hydrophilic-lipophilic vinyl polymers.
  • the asphaltene-dispersing properties of dodecylbenzenesulfonic acid have been described in US 4,414,035, also by D.-L Chang and HS Fogler (SPE paper No. 25185, 1993) and by MN Bouts et al. (J. pet. Technol. 47, 782-7, 1995).
  • Oxalkylated amines are described in US 5,421,993.
  • the previously known dispersants can only partially solve the problems caused by the precipitation of asphaltenes. Since oils vary in their composition, individual dispersants can only work effectively in a limited range. Sometimes even small changes in the oil composition have a great effect on the dispersing properties for asphaltenes. Therefore, the known dispersants are unsatisfactory in some cases and additional types are required.
  • the object was therefore to provide new asphaltene dispersants which do not have the disadvantages described of the previously known dispersants.
  • Chain lengths of C 8 -C 2 2. preferably C ⁇ -C ⁇ , can be used to avoid failure or precipitation of asphaltenes in crude oils and products derived therefrom.
  • the invention thus relates to crude oils and products derived therefrom, containing secondary alkanesulfonic acids as asphaltene dispersants, in which a chain length of 8 to 22 carbon atoms is present.
  • Products derived from crude oils are, for example, heavy heating oil, marine oil or bitumen.
  • the dispersants of the invention are used in an amount of 1 to 10,000, preferably 2 to 2,000, ppm.
  • the alkanesulfonic acid is preferably formulated as a solution or microemulsion with hydrocarbons, which may contain water and / or an aliphatic alcohol.
  • the dispersant contains 20-80% by weight, preferably 30-60% by weight, of alkanesulfonic acid, furthermore 20-80% by weight, preferably 20-70% by weight, of a hydrocarbon or a mixture of one Hydrocarbon and a C 2 -C 8 alcohol, and 0-30 wt .-% water.
  • Effective asphaltene dispersants can also be obtained by combining alkanesulfonic acids with other substances, in particular a) alkylphenol formaldehyde resins, b) oxyalkylated amines, c) wax dispersants.
  • Dispersants based on a combination of substances can be less sensitive to changes in oil compositions; this improves reliability.
  • the dispersion, the precipitation of asphaltenes depends on the nature of the hydrocarbon medium. Asphaltenes are soluble in aromatic but not in aliphatic hydrocarbons. Thus, dispersants can be tested by dissolving the oil or extracted asphaltenes in an aromatic solvent and then adding an aliphatic hydrocarbon to produce a precipitate. Since asphaltenes are dark in color, the amount of precipitation can be determined by a colorimetric measurement of the supernatant. The darker the supernatant, the more asphaltenes remain dispersed, ie the better the dispersant. This test is described in Canadian patent 20 29 465. In our version of the test, the precipitation medium is selected so that the asphaltenes fail for the most part, but not completely. Regulation dispersion test
  • toluene / dispersant mixture 25: 1 in a 10 ml graduated glass tube and shake well. This corresponds to a dispersant concentration of 2000 ppm. If necessary, the amount of dispersant can be varied. Pure toluene is used for the blank samples; c) 0.1 ml of the filtered oil solution is then added to the glass tube and also shaken well; d) leave the whole thing for 2 hours without vibrations.
  • the precipitated asphaltenes should be able to collect on the bottom of the tube; e) after this time the volume of the sediment is estimated on the basis of the graduation, the appearance of the entire sample is recorded and then 1 ml of the remaining phase is carefully taken up with a pipette;
  • the extracted amount is dissolved in 5 ml of toluene and photometrized at 600 nm.
  • A 100 (D - D 0 ) / D 0 ,
  • a max corresponds to complete dispersion of the asphaltenes. It can be estimated by carrying out a test without a disperser, using toluene instead of heptane - this keeps the asphaltenes completely dispersed.
  • the volume of the sediment provides further information about the effectiveness of the dispersant. The smaller the amount of sediment, the better the substance is dispersed.
  • the secondary alkanesulfonic acids had an average chain length of 15.5 carbon atoms.
  • the table shows the results of the dispersion test at various concentrations.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)

Abstract

The invention concerns the use of secondary alkanesulphonic acids as asphaltene dispersants in crude oils and products derived therefrom, the chain being between 8 and 22 carbon atoms long.

Description

Beschreibungdescription
Verwendung von Alkansulfonsäuren als Asphalten-DispergatorenUse of alkanesulfonic acids as asphaltene dispersants
Asphaltene sind Bestandteile von Rohölen. Sie enthalten eine Vielzahl vonAsphaltenes are components of crude oils. They contain a variety of
Strukturen, besonders hochmolekulare kondensierte aromatische Komponenten mit Heteroatomen. Angesichts der Komplexität ihrer Chemie werden Asphaltene als die Ölfraktion beschrieben, die in Benzol, aber nicht in n-Pentan löslich ist.Structures, especially high molecular weight condensed aromatic components with heteroatoms. Given the complexity of their chemistry, asphaltenes are described as the oil fraction that is soluble in benzene but not in n-pentane.
Im Rohöl liegen Asphaltene normalerweise als kolloidale Dispersion vor. Diese wird durch Ölharze stabilisiert.Asphaltenes are usually present in the crude oil as a colloidal dispersion. This is stabilized by oil resins.
Asphaltene können während der Produktion, der Raffination, des Transports und der Lagerung von Rohöl und davon abgeleiteten Produkten, wie z.B. schweres Heizöl oder Schiffsöl, ausfallen. Gemeinsame Ursachen für dieses Ausfallen sind ein Absinken der Temperatur oder ein Wechsel in der Zusammensetzung (z.B. Verdampfung von leicht flüchtigen Bestandteilen). Asphaltene können auch beim Fließen durch poröse Medien ausfallen. Fluten mit C02 während des Förderprozesses kann Asphaltene zum Flokkulieren oder zum Ausfallen bringen.Asphaltenes can fail during the production, refining, transport and storage of crude oil and products derived from it, such as heavy fuel oil or marine oil. Common causes of this failure are a drop in temperature or a change in the composition (eg evaporation of volatile components). Asphaltenes can also fail when flowing through porous media. Flooding with C0 2 during the production process can cause asphaltenes to flocculate or fail.
Manche Öle enthalten Kohlenwasserstoffwachse, die bei niedrigen Temperaturen ausfallen. Wechselwirkungen zwischen dem Ausfallen von Wachs und Asphaltenen können die Gesamtmenge an ausgefallener Substanz oder deren Bildungsgeschwindigkeit erhöhen.Some oils contain hydrocarbon waxes that fail at low temperatures. Interactions between the precipitation of wax and asphaltenes can increase the total amount of precipitated substance or its rate of formation.
Ausgefallene Asphaltene verursachen Probleme bei der Produktion und bei der Verarbeitung von Rohölen. Asphaltene schlagen sich nieder in Ventilen, Rohren und Fördereinrichtungen. An heißen Oberflächen, wie beispielsweise Wärmetauschern, kann die Carbonisierung dieser Niederschläge ihre Entfernung sehr schwierig machen. Die Niederschläge reduzieren den Wirkungsgrad vonFailed asphaltenes cause problems in the production and processing of crude oils. Asphaltenes are reflected in valves, pipes and conveyors. On hot surfaces, such as heat exchangers, the carbonization of these precipitates can make their removal very difficult. Precipitation reduces the efficiency of
Anlagen und können im schlimmsten Fall zu einer kompletten Blockierung und zu einem Produktionsstop führen, was hohe Kosten verursacht.Attachments and in the worst case can lead to a complete blockage and a production stop, which causes high costs.
Schweröle, die oft zum Antrieb von Schiffen verwendet werden, enthalten beträchtliche Mengen an Asphaltenen. Das Ausfallen von Asphaltenen kann sowohl zu schlechter Verbrennung als auch zu Schwierigkeiten bei der Handhabung und bei der Lagerung des Treibstoffes führen. Auch bei mit schweren Ölen betriebenen Kraftwerken werden Verbrennungsstörungen durch Ausfällung von Asphaltenen beobachtet.Heavy oils, which are often used to power ships, contain considerable amounts of asphaltenes. The failure of asphaltenes can lead to poor combustion as well as difficulties in handling and storing the fuel. Burning disorders due to the precipitation of asphaltenes are also observed in power plants operated with heavy oils.
Bitumen, Schweröle und Rückstände werden manchmal mit Lösemittel verdünnt, um die Viskosität für den Transport zu reduzieren. Wenn dabei Asphaltene ausfallen, so ergeben sich damit Probleme bei der Handhabung.Bitumen, heavy oils and residues are sometimes diluted with solvents to reduce the viscosity for transportation. If asphaltenes fail in the process, handling problems arise.
Das Ausfallen von Asphaltenen kann durch kleine Mengen an Dispergatoren verhindert oder verringert werden. Diese Substanzen zeigen einen oder mehrere der folgenden Effekte:The precipitation of asphaltenes can be prevented or reduced by small amounts of dispersants. These substances show one or more of the following effects:
a) Die Menge an Niederschlag wird reduziert; b) der Niederschlag bildet sich langsamer; c) der Niederschlag ist feiner verteilt; und d) die Neigung des Niederschlages, sich auf Oberflächen abzulagern, wird reduziert.a) The amount of precipitation is reduced; b) the precipitation is slower; c) the precipitation is more finely divided; and d) the tendency of the precipitate to deposit on surfaces is reduced.
Wenn sich bereits Niederschläge an Asphaltenen gebildet haben, können sie durch den Gebrauch von Lösemitteln entfernt werden. Die Zugabe eines Dispergators kann die Wirksamkeit dieser Lösemittel verbessern.If asphaltenes have already precipitated, they can be removed using solvents. The addition of a dispersant can improve the effectiveness of these solvents.
Eine Vielzahl von Asphalten-Dispergatoren sind bereits bekannt. CA 2 029 465 und CA 2 075 749 beschreiben Alkylphenolformaldehydharze in Kombination mit hydrophilen-lipophilen Vinylpolymeren. Die Asphalten- dispergierenden Eigenschaften von Dodecylbenzolsulfonsäure wurden beschrieben in US 4 414 035, außerdem durch D.-L Chang und H.S. Fogler (SPE paper No. 25185, 1993) und durch M.N. Bouts et al. (J. pet. Technol. 47, 782-7, 1995). Oxalkylierte Amine werden beschrieben in US 5 421 993.A large number of asphaltene dispersants are already known. CA 2 029 465 and CA 2 075 749 describe alkylphenol formaldehyde resins in combination with hydrophilic-lipophilic vinyl polymers. The asphaltene-dispersing properties of dodecylbenzenesulfonic acid have been described in US 4,414,035, also by D.-L Chang and HS Fogler (SPE paper No. 25185, 1993) and by MN Bouts et al. (J. pet. Technol. 47, 782-7, 1995). Oxalkylated amines are described in US 5,421,993.
Die bisher bekannten Dispergatoren können die durch das Ausfallen von Asphaltenen verursachten Probleme nur teilweise lösen. Da Öle in ihrer Zusammensetzung variieren, können einzelne Dispergatoren nur in einem beschränkten Bereich wirksam arbeiten. Manchmal haben sogar kleine Änderungen in der ölzusammensetzung einen großen Effekt auf die Dispergiereigenschaften für Asphaltene. Deshalb sind in einigen Fällen die bekannten Dispergatoren nicht zufriedenstellend und zusätzliche Typen sind erforderlich.The previously known dispersants can only partially solve the problems caused by the precipitation of asphaltenes. Since oils vary in their composition, individual dispersants can only work effectively in a limited range. Sometimes even small changes in the oil composition have a great effect on the dispersing properties for asphaltenes. Therefore, the known dispersants are unsatisfactory in some cases and additional types are required.
Es bestand somit die Aufgabe, neue Asphalten-Dispergatoren zur Verfügung zu stellen, die die beschriebenen Nachteile der bisher bekannten Dispergatoren nicht aufweisen.The object was therefore to provide new asphaltene dispersants which do not have the disadvantages described of the previously known dispersants.
Überraschenderweise wurde gefunden, daß sekundäre Alkansulfonsäuren mitSurprisingly, it was found that secondary alkanesulfonic acids with
Kettenlängen von C8-C22. vorzugsweise C^-C^, verwendet werden können, um Ausfall oder Niederschläge von Asphaltenen in Rohölen und davon abgeleiteten Produkten zu vermeiden.Chain lengths of C 8 -C 2 2. preferably C ^ -C ^, can be used to avoid failure or precipitation of asphaltenes in crude oils and products derived therefrom.
Gegenstand der Erfindung sind somit Rohöle und davon abgeleitete Produkte, enthaltend als Asphalten-Dispergator sekundäre Alkansulfonsäuren, bei denen eine Kettenlänge von 8 bis 22 C-Atomen vorliegt.The invention thus relates to crude oils and products derived therefrom, containing secondary alkanesulfonic acids as asphaltene dispersants, in which a chain length of 8 to 22 carbon atoms is present.
Von Rohölen abgeleitete Produkte sind beispielsweise schweres Heizöl, Schiffsöl oder Bitumen.Products derived from crude oils are, for example, heavy heating oil, marine oil or bitumen.
Die erfindungsgemäßen Dispergatoren werden in einer Menge von 1 bis 10.000, vorzugsweise von 2 bis 2.000 ppm eingesetzt.The dispersants of the invention are used in an amount of 1 to 10,000, preferably 2 to 2,000, ppm.
Die Alkansulfonsäure wird vorzugsweise formuliert als Lösung oder Mikroemulsion mit Kohlenwasserstoffen, die gegebenenfalls Wasser und/oder einen aliphatischen Alkohol enthält. Im allgemeinen enthält der Dispergator 20-80 Gew.-%, vorzugsweise 30-60 Gew.- %, an Alkansulfonsäure, ferner 20-80 Gew.-%, vorzugsweise 20-70 Gew.-%, eines Kohlenwasserstoffes oder einer Mischung aus einem Kohlenwasserstoff und einem C2-C8-Alkohol, sowie 0-30 Gew.-% Wasser.The alkanesulfonic acid is preferably formulated as a solution or microemulsion with hydrocarbons, which may contain water and / or an aliphatic alcohol. In general, the dispersant contains 20-80% by weight, preferably 30-60% by weight, of alkanesulfonic acid, furthermore 20-80% by weight, preferably 20-70% by weight, of a hydrocarbon or a mixture of one Hydrocarbon and a C 2 -C 8 alcohol, and 0-30 wt .-% water.
Wirksame Asphalten-Dispergatoren kann man ebenfalls erhalten, indem man Alkansulfonsäuren kombiniert mit anderen Substanzen, im besonderen a) Alkylphenolformaldehydharze, b) oxalkylierte Amine, c) Wachsdispergatoren.Effective asphaltene dispersants can also be obtained by combining alkanesulfonic acids with other substances, in particular a) alkylphenol formaldehyde resins, b) oxyalkylated amines, c) wax dispersants.
Dispergatoren, die auf einer Kombination von Subtanzen basieren, können weniger empfindlich reagieren auf veränderte ölzusammensetzungen; dies verbessert die Zuverlässigkeit.Dispersants based on a combination of substances can be less sensitive to changes in oil compositions; this improves reliability.
Beispiele:Examples:
Die folgenden Beispiele sollen die Erfindung näher erläutern.The following examples are intended to explain the invention in more detail.
Prinzip des DispergiertestesPrinciple of the dispersion test
Die Dispergierung, das Ausfallen von Asphaltenen hängt von der Natur des Kohlenwasserstoffmediums ab. Asphaltene sind in aromatischen, aber nicht in aliphatischen Kohlenwasserstoffen löslich. Somit können Dispergatoren getestet werden, indem man das Öl oder extrahierte Asphaltene in einem aromatischen Lösemittel löst und indem man dann einen aliphatischen Kohlenwasserstoff zugibt, um einen Niederschlag zu erzeugen. Da Asphaltene von dunkler Farbe sind, kann das Ausmaß des Niederschlages durch eine kolorimetrische Messung der überstehenden Flüssigkeit bestimmt werden. Je dunkler die überstehende Flüssigkeit ist, desto mehr Asphaltene bleiben dispergiert, d.h. umso besser ist der Dispergator. Dieser Test wird beschrieben im Canadischen Patent 20 29 465. In unserer Version des Tests wird das Fällungsmedium ausgewählt, so daß die Asphaltene zum größten Teil, aber nicht komplett ausfallen. Vorschrift DispergiertestThe dispersion, the precipitation of asphaltenes depends on the nature of the hydrocarbon medium. Asphaltenes are soluble in aromatic but not in aliphatic hydrocarbons. Thus, dispersants can be tested by dissolving the oil or extracted asphaltenes in an aromatic solvent and then adding an aliphatic hydrocarbon to produce a precipitate. Since asphaltenes are dark in color, the amount of precipitation can be determined by a colorimetric measurement of the supernatant. The darker the supernatant, the more asphaltenes remain dispersed, ie the better the dispersant. This test is described in Canadian patent 20 29 465. In our version of the test, the precipitation medium is selected so that the asphaltenes fail for the most part, but not completely. Regulation dispersion test
a) Eine 25 %ige Öl-Lösung in Toluol wird gefiltert, um Verunreinigungen zu beseitigen; b) 9,5 ml Heptan als Fällungsmittel für Asphaltene und 0,5 mla) A 25% oil solution in toluene is filtered to remove contaminants; b) 9.5 ml of heptane as a precipitant for asphaltenes and 0.5 ml
Toluol/Dispergator-Mischung (25:1 ) in ein gut 10 ml fassendes graduiertes Glasröhrchen vorlegen und gut schütteln. Dies entspricht einer Dispergatorkonzentration von 2000 ppm. Bei Bedarf kann die Menge Dispergator variiert werden. Für die Nullproben wird reines Toluol verwendet; c) in das Glasröhrchen wird dann 0,1 ml von der gefilterten Öl-Lösung dazugegeben und ebenfalls gut geschüttelt; d) das Ganze 2 Stunden ohne Erschütterungen stehenlassen. Die ausgefällten Asphaltene sollen sich am Boden des Röhrchens sammeln können; e) nach Ablauf dieser Zeit wird das Volumen des Sediments an Hand der Graduierung abgeschätzt, das Aussehen der gesamten Probe protokolliert und dann wird von der überständigen Phase 1 ml vorsichtig mit einer Pipette aufgenommen;Place the toluene / dispersant mixture (25: 1) in a 10 ml graduated glass tube and shake well. This corresponds to a dispersant concentration of 2000 ppm. If necessary, the amount of dispersant can be varied. Pure toluene is used for the blank samples; c) 0.1 ml of the filtered oil solution is then added to the glass tube and also shaken well; d) leave the whole thing for 2 hours without vibrations. The precipitated asphaltenes should be able to collect on the bottom of the tube; e) after this time the volume of the sediment is estimated on the basis of the graduation, the appearance of the entire sample is recorded and then 1 ml of the remaining phase is carefully taken up with a pipette;
f) die abgesaugte Menge wird in 5 ml Toluol gelöst und bei 600 nm photometriert.f) the extracted amount is dissolved in 5 ml of toluene and photometrized at 600 nm.
Bewertung des DispergiertestsEvaluation of the dispersion test
Als relatives Maß für die Dispergierwirkung wird folgender Ausdruck genommenThe following expression is taken as a relative measure of the dispersing action
A = 100 (D - D0)/D0 ,A = 100 (D - D 0 ) / D 0 ,
wobei D und D0 optische Dichte von Meßlösung und Blindprobe sind. Der maximal erreichbare Wert von A, Amax, entspricht vollständiger Dispergierung der Asphaltene. Sie kann abgeschätzt werden, indem ein Versuch ohne Dispergator, mit Toluol anstatt Heptan, durchgeführt wird - dadurch bleiben die Asphaltene vollständig dispergiert. Das Volumen des Sediments liefert eine weitere Information über die Wirksamkeit des Dispergators. Je kleiner die Menge an Sediment ist, desto besser ist die Substanz dispergiert.where D and D 0 are the optical density of the measurement solution and blank. The maximum achievable value of A, A max corresponds to complete dispersion of the asphaltenes. It can be estimated by carrying out a test without a disperser, using toluene instead of heptane - this keeps the asphaltenes completely dispersed. The volume of the sediment provides further information about the effectiveness of the dispersant. The smaller the amount of sediment, the better the substance is dispersed.
ErgebnisseResults
Die Untersuchungen wurden ausgeführt mit einem Schweröl, das beträchtliche Mengen an Asphaltenen enthielt. Die sekundären Alkansulfonsäuren hatten eine durchschnittliche Kettenlänge von 15,5 Kohlenstoffatomen. Die Tabelle zeigt die Ergebnisse des Dispergiertests bei verschiedenen Konzentrationen.The investigations were carried out with a heavy oil that contained considerable amounts of asphaltenes. The secondary alkanesulfonic acids had an average chain length of 15.5 carbon atoms. The table shows the results of the dispersion test at various concentrations.
Unter diesen Bedingungen würde das Maximum von A, das einer vollständigen Dispergierung des Asphaltens entspricht, bei etwa 500 liegen. Under these conditions the maximum of A, which corresponds to complete dispersion of the asphaltene, would be about 500.

Claims

Patentansprüche: Claims:
1. Rohöle und davon abgeleitete Produkte, enthaltend als Asphalten- Dispergator sekundäre Alkansulfonsäuren, bei denen eine Kettenlänge von 8 bis 22 C-Atomen vorliegt.1. Crude oils and products derived therefrom, containing as an asphaltene dispersant, secondary alkanesulfonic acids in which a chain length of 8 to 22 carbon atoms is present.
2. Rohöle gemäß Anspruch 1 , dadurch gekennzeichnet, daß die Alkansulfonsäuren eine Kettenlänge von 11 bis 18 C-Atomen aufweisen.2. Crude oils according to claim 1, characterized in that the alkanesulfonic acids have a chain length of 11 to 18 carbon atoms.
3. Rohöle gemäß Anspruch 1 , dadurch gekennzeichnet, daß die3. Crude oils according to claim 1, characterized in that the
Alkansulfonsäure als Lösung oder Mikroemulsion mit Kohlenwasserstoffen vorliegt.Alkanesulfonic acid is present as a solution or microemulsion with hydrocarbons.
4. Rohöle gemäß Anspruch 3, dadurch gekennzeichnet, daß die Kohlenwasserstoffe Wasser und/oder einen aliphatischen Alkohol enthalten.4. Crude oils according to claim 3, characterized in that the hydrocarbons contain water and / or an aliphatic alcohol.
5. Rohöle gemäß Anspruch 3 und 4, dadurch gekennzeichnet, daß der Asphalten-Dispergator 20-80 Gew.-%, vorzugsweise 30-60 Gew.-% an Alkansulfonsäure, 20-80 Gew.-%, vorzugsweise 20-70 Gew.-%, eines Kohlenwasserstoffes oder einer Mischung aus einem Kohlenwasserstoff und einem C2-C8-Alkohol, sowie 0-30 Gew.-% Wasser enthält.5. Crude oils according to claim 3 and 4, characterized in that the asphaltene dispersant 20-80 wt .-%, preferably 30-60 wt .-% of alkanesulfonic acid, 20-80 wt .-%, preferably 20-70 wt. -%, a hydrocarbon or a mixture of a hydrocarbon and a C 2 -C 8 alcohol, and contains 0-30 wt .-% water.
6. Rohöle gemäß mindestens einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß der Asphaltendispergator zusammen mit Alkylphenolformaldehydharzen, oxalkylierten Aminen, Wachsdispergatoren oder beliebigen Mischungen daraus eingesetzt wird.6. Crude oils according to at least one of claims 1 to 5, characterized in that the asphaltene dispersant is used together with alkylphenol formaldehyde resins, oxalkylated amines, wax dispersants or any mixtures thereof.
7. Verwendung von sekundären Alkansulfonsäuren mit einer Kettenlänge von 8 bis 22 C-Atomen als Asphalten-Dispergatoren in Rohölen und davon abgeleiteten Produkten gemäß mindestens einem der Ansprüche 1 bis 6. 7. Use of secondary alkanesulfonic acids with a chain length of 8 to 22 carbon atoms as asphaltene dispersants in crude oils and products derived therefrom according to at least one of claims 1 to 6.
8. Verfahren zum Dispergieren von Asphaltenen in Rohölen und davon abgeleiteten Produkten gemäß Anspruch 1 , dadurch gekennzeichnet, daß sekundäre Alkansulfonsäuren mit einer Kettenlänge von 8 bis 22 C-Atomen in einer Menge von 1 bis 10.000, vorzugsweise von 2 bis 2.000 ppm, dem Rohöl oder den davon abgleiteten Produkten zugegeben werden.8. A process for dispersing asphaltenes in crude oils and products derived therefrom according to claim 1, characterized in that secondary alkanesulfonic acids with a chain length of 8 to 22 carbon atoms in an amount of 1 to 10,000, preferably from 2 to 2,000 ppm, the crude oil or added to the products derived from it.
9. Verfahren gemäß Anspruch 8, dadurch gekennzeichnet, daß zusätzlich Alkylphenolformaldehydharze, oxalkylierte Amine, Wachsdispergatoren oder beliebige Mischungen daraus zugegeben werden. 9. The method according to claim 8, characterized in that in addition alkylphenol formaldehyde resins, oxalkylated amines, wax dispersants or any mixtures thereof are added.
EP97912134A 1996-10-15 1997-10-08 Use of alkanesulphonic acids as asphaltene dispersants Withdrawn EP0932746A2 (en)

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DE19642493A DE19642493A1 (en) 1996-10-15 1996-10-15 Use of alkanesulfonic acids as asphaltene dispersants
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PCT/EP1997/005513 WO1998016718A2 (en) 1996-10-15 1997-10-08 Use of alkanesulphonic acids as asphaltene dispersants

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US5925233A (en) 1999-07-20
WO1998016718A2 (en) 1998-04-23
BR9712323A (en) 1999-08-31
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JP2001502389A (en) 2001-02-20
CO4870786A1 (en) 1999-12-27
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