EP1913369A1 - Method for detecting a fuel additive component - Google Patents

Method for detecting a fuel additive component

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Publication number
EP1913369A1
EP1913369A1 EP06792588A EP06792588A EP1913369A1 EP 1913369 A1 EP1913369 A1 EP 1913369A1 EP 06792588 A EP06792588 A EP 06792588A EP 06792588 A EP06792588 A EP 06792588A EP 1913369 A1 EP1913369 A1 EP 1913369A1
Authority
EP
European Patent Office
Prior art keywords
fuel additive
fuel
additive component
indicator
analyte
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.)
Ceased
Application number
EP06792588A
Other languages
German (de)
French (fr)
Inventor
Jörn KARL
Armin Bader
Benjamin Kaufman
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.)
BASF SE
Original Assignee
BASF SE
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 BASF SE filed Critical BASF SE
Publication of EP1913369A1 publication Critical patent/EP1913369A1/en
Ceased legal-status Critical Current

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Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/26—Oils; Viscous liquids; Paints; Inks
    • G01N33/28—Oils, i.e. hydrocarbon liquids
    • G01N33/2835—Specific substances contained in the oils or fuels
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
    • G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
    • G01N21/78—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/22—Fuels; Explosives
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
    • G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
    • G01N21/78—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
    • G01N21/80—Indicating pH value
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T436/00—Chemistry: analytical and immunological testing
    • Y10T436/14—Heterocyclic carbon compound [i.e., O, S, N, Se, Te, as only ring hetero atom]
    • Y10T436/142222—Hetero-O [e.g., ascorbic acid, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T436/00—Chemistry: analytical and immunological testing
    • Y10T436/14—Heterocyclic carbon compound [i.e., O, S, N, Se, Te, as only ring hetero atom]
    • Y10T436/145555—Hetero-N

Definitions

  • the present invention relates to a method for the qualitative or quantitative detection of a fuel additive component, in particular in diesel fuel or gasoline. Furthermore, the subject of the present invention is the use of this method for the qualitative or quantitative detection of a fuel additive component in diesel fuel or gasoline.
  • Petrol consists of a hydrocarbon mixture, which may contain, for example, additives of oxygen-containing organic components and additives to improve the properties.
  • additives which are used in unleaded gasoline are e.g. Antioxidants, corrosion inhibitors, metal deactivators and detergents.
  • the additives are used inter alia to prevent corrosion, deposits in the inlet system, sludge formation and valve sticking in an internal combustion engine.
  • the additive concentrations are usually in gasoline in the range below 0.1 wt .-%.
  • the additives are usually already metered by the fuel manufacturer in the form of additive packages and added to the petrol when filling the tank trucks in the refinery.
  • diesel fuel Even with diesel fuel, the addition of additives for quality improvement has largely prevailed.
  • the diesel fuel is usually added additive packages with a total concentration below 0.1 wt .-%.
  • the most common additives for diesel fuel are flow improvers, lubricity improvers, ignition improvers, detergents, corrosion inhibitors and antifoams.
  • a method has been found for the qualitative or quantitative detection of a fuel additive component, which is part of an analyte containing fuel and / or other fuel additive components, which is characterized in that the analyte is brought into contact with an indicator and by the Interaction between fuel additive component and indicator determined change in the color properties of the indicator determined in the analyte.
  • the method according to the invention can be used qualitatively and quantitatively, i. It can hereby be proven whether a certain fuel additive component is present and in what quantity it is present.
  • the proof can be carried out in particular in the fuel itself, but also in the underlying additive packages.
  • the analyte, ie, the determination sample is thus the fuel or fuel additive package, which may be diluted with suitable inert solvents, if necessary, to carry out the determination.
  • all indicators are considered as indicators which change their color properties upon contact with and interaction with the fuel additive component, be they in the range of visible light or in the range of fluorescence or chemiluminescence behavior.
  • an acid-base indicator (also referred to as a pH indicator or neutralization indicator) is used.
  • the acids or bases on which these indicators are based show a color change which usually occurs in the visible range during their protolysis or deproteinization.
  • Typical examples of acid-base indicators are cresol red, metanil yellow, thymol blue, m-cresol purple, tropaeolin OO, 2,6-dinitrophenol, benzyl orange, 2,4-dinitrophenol, benzopurpurine 4 B, dimethyl yellow, Congo Red, Bromophenol blue, bromochlorophenol blue, methyl orange, ⁇ -naphthyl red, bromocresol green, 2,5-dinitrophenol, mixed indicator 5, methyl red, ethyl red, chlorophenol red, carminic acid, alizarin red S, 2-nitrophenol, litmus, bromocresol purple, bromophenol red, 4-nitrophenol, alizarin, Bromothymol blue, bromoxylenol blue,
  • bromocresol green As a particularly preferred acid-base indicator, bromocresol green, ⁇ -naphthyl red, 2,5-dinitrophenol, mixed indicator 5 or methyl red is used.
  • the acid-base indicator exploits basic functionalities in the fuel additive component to produce the color change.
  • adsorption indicators e.g. Fluorescein or eosin
  • fluorescence indicators e.g. Flucescein, eosin, benzoflavin, phloxine, chromotropic acid, methylumbelliferone, benzquinoline, morin, naphthols, naphthionic acid, quinine, coumarin or acridine
  • chemiluminescent indicators e.g. Lucigenin
  • redox indicators e.g. Neutral red, safranine or methylene blue
  • metal indicators metal indicators
  • a specific color change occurs when the indicator and the analyte come together, for example in the case of bromocresol green from yellow (acidic range below pH 3.8) to blue (alkaline range above pH 5, 4).
  • the occurrence of the color change is the evidence of the presence of the desired fuel additive component.
  • a blank test with an analyte to which a test quantity of the fuel additive component to be detected has been added and / or an analyte containing unadditized fuel is recommended.
  • the intensity of the coloration is determined after the change in the color properties in the analyte, ie after the color change has taken place.
  • the photometric determination is suitable in a preferred embodiment, usually using commercially available photometers.
  • the measurement is usually carried out by adding a certain amount of analyte to a set amount of the indicator, mixing (for example by shaking) and irradiating the sample in a sample vessel (cuvette) with light of a specific wavelength.
  • the measured absorbance correlated to a blank or to a calibration curve made with different amounts of the fuel additive component to be determined gives the amount of fuel additive component in the analyte.
  • the photometric determination of the extinction at a wavelength of 620 nm is recommended, for example.
  • the analyte used is diesel fuel or gasoline which, in addition to the fuel additive component to be detected, optionally contains further fuel additive components, ie the determination is carried out directly on the diesel or gasoline fuel supplied by the refineries and commercially available ,
  • petrol for operating internal combustion engines (gasoline engines) in motor vehicles are usually petroleum raffinates, which generally have a boiling range of 70 to 18O 0 C. They usually represent C5-C12 hydrocarbon mixtures of alkanes, alkenes, cycloalkanes, cycloalkenes and aromatics in varying composition. Petrol is preferably used unleaded.
  • the method according to the invention for detecting a fuel additive component can in principle also be carried out in kerosene as analyte.
  • Kerosene as a higher-boiling gasoline grade (boiling range about 180 to 27O 0 C) is used in particular in the aircraft sector.
  • diesel fuels whose major components are longer chain paraffins
  • those obtainable by coal gasification or gas liquefaction [GTL] fuels are also suitable.
  • mixtures of the abovementioned diesel fuels with regenerative fuels such as biodiesel or bioethanol.
  • regenerative fuels such as biodiesel or bioethanol.
  • Diesel fuels may also contain water, for example in an amount of up to 20% by weight, for example in the form of diesel-water microemulsions or as so-called "white diesel".
  • the process of the present invention is used to detect a polar detergent-additive component typically used as an additive in most types of fuel, particularly diesel fuel and gasoline, as well as in the underlying additive compositions (especially additive packages) for diesel or diesel fuel Petrol is located.
  • a polar detergent-additive component typically used as an additive in most types of fuel, particularly diesel fuel and gasoline, as well as in the underlying additive compositions (especially additive packages) for diesel or diesel fuel Petrol is located.
  • overall suitable polar detergent additives with in particular basic functionalities or polar functional groups, which interact with the indicators mostly in the sense of an acid-base interaction, are described below.
  • the above additive compositions and fuels may additionally contain various other fuel additive components such as demulsifiers, carrier oils, solvents and diluents, corrosion inhibitors, antioxidants, metal deactivators, antistatic agents, color markers, flow improvers, lubricity improvers, ignition improvers and antifoam agents.
  • Suitable other fuel additive components are also set forth below.
  • Detergent additives are commonly referred to as gasoline and diesel fuel scale inhibitors.
  • the detergent additives are amphiphilic substances having at least one hydrophobic hydrocarbon radical having a number average molecular weight (Mn) of from 85 to 20,000 and at least one polar moiety selected from:
  • the hydrophobic hydrocarbon radical in the above detergent additives which provides the sufficient solubility in the fuel, has a number average molecular weight (Mn) of 85 to 20,000, especially from 113 to 10,000, especially from 300 to 5000.
  • Mn number average molecular weight
  • polypropene or conventional (ie, with predominantly central double bonds) polybutene or polyisobutene with Mn 300 to 5000.
  • amines such as e.g.
  • Ammonia monoamines or polyamines, such as dimethylaminopropylamine, ethylenediamine, diethylenetriamine, triethylenetetramine or tetraethylenepentamine.
  • Corresponding additives based on poly (iso) butene are in particular in EP-B 244 616, corresponding additives based on polypropene are described in particular in WO 94/24231.
  • monoamino groups (a) containing additives are the polyisobutene epoxides by reaction with amines and subsequent dehydration and reduction of the amino alcohols obtainable compounds, as described in particular in DE-A 196 20 262.
  • Carboxyl groups or their alkali metal or alkaline earth metal salts (d) containing additives are preferably copolymers of C2-C4o-olefins with maleic anhydride having a total molecular weight of 500 to 20,000, the carboxyl groups wholly or partially to the alkali metal or alkaline earth metal salts and a remainder of the Carboxyl groups are reacted with alcohols or amines.
  • additives are known in particular from EP-A 307 815.
  • Such additives are primarily used to prevent valve seat wear and, as described in WO 87/01126, can be advantageously used in combination with conventional fuel detergents such as poly (iso) butenamines or polyetheramines.
  • Sulfonic acid groups or their alkali metal or alkaline earth metal salts (e) containing additives are preferably alkali metal or alkaline earth metal salts of a Sulfobern- steinklaklalesters, as described in particular in EP-A 639 632.
  • Such additives are mainly used to prevent valve seat wear and can be used to advantage in combination with conventional fuel detergents such as poly (iso) buteneamines or polyetheramines.
  • Polyoxy-C 2 -C 4 -alkylene groups (f) containing additives are preferably polyether or polyetheramines, which by reaction of C 2 -C 6 o-alkanols, C 6 -C 30 -alkanediols, mono- or di-C 2 -C 3 o-alkylamines, Ci-C 3 o-alkylcyclohexanols or Ci-C 30 - alkylphenols with 1 to 30 moles of ethylene oxide and / or propylene oxide and / or butylene oxide per hydroxyl group or amino group and, in the case of polyetheramines, by subsequent reductive amination with ammonia, monoamines or polyamines are available.
  • Such products are disclosed in particular in EP-A 310 875,
  • EP-A 356 725, EP-A 700 985 and US-A 4,877,416 In the case of polyesters, such products also fulfill carrier oil properties. Typical examples thereof are tridecanol or isotridecanol butoxylates, isononylphenol butoxylates and also polyisobutenol butoxylates and propoxylates and the corresponding reaction products with ammonia.
  • Carboxyl ester groups (g) containing additives are preferably esters of mono-, di- or tricarboxylic acids with long-chain alkanols or polyols, especially those having a minimum viscosity of 2 mm 2 / s at 100 0 C, as described in particular in DE-A 38 38 918 are.
  • Aliphatic or aromatic acids can be used as the mono-, di- or tricarboxylic acids, especially suitable as ester alcohols or polyols are long-chain representatives with, for example, 6 to 24 C atoms.
  • esters are adipates, phthalates, isophthalates, terephthalates and trimellitates of iso-octanol, iso-nonanol, iso-decanol and of isotridecanol. Such products also meet carrier oil properties.
  • derivatives with aliphatic polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine or tetraethylenepentamine.
  • the groups having hydroxyl and / or amino and / or amido and / or imido groups are, for example, carboxylic acid groups, acid anhydrides, acid amides of diamines or polyamines which, in addition to the amide function, still have free amine groups, succinic acid derivatives with an acid - And an amide function, carboxylic imides with monoamines, carboxylic imides with di- or polyamines, which still have free amine groups in addition to the imide function, and diimides, which are formed by the reaction of di- or polyamines with two succinic acid derivatives.
  • Such fuel additives are described in particular in US Pat. No. 4,849,572.
  • Mannich reaction of substituted phenols with aldehydes and mono- or polyamines generated groupings (i) containing additives are preferably reaction products of polyisobutene-substituted phenols with formaldehyde and mono- or polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine or dimethylaminopropylamine.
  • Such "polyisobutene-Mannich bases" are described in particular in EP-A-831 141.
  • Detergent additives from group (h) are particularly preferred in the process according to the invention. These are, in particular, polyisobutenyl-substituted succinimides, especially the imides with aliphatic polyamines. Such polyisobutenyl-substituted succinimides are primarily used as a polar fuel additive component with detergent action in diesel fuel.
  • Demulsifiers are substances which cause the separation of an emulsion. These may be both ionogenic and non-ionic substances which are effective at the phase boundary. Accordingly, basically all surface-active substances are suitable as demulsifiers. Particularly suitable demulsifiers are selected from anion-active compounds such as the alkali or alkaline earth salts of alkyl-substituted phenol and naphthalenesulfonates and the alkali or alkaline earth salts of fatty acids, as well as neutral compounds such as alcohol alkoxylates, e.g. Alcohol ethoxylates, phenol alkoxylates, e.g.
  • tert-butylphenol ethoxylate or tert-pentylphenol ethoxylate fatty acids, alkylphenols, condensation products of ethylene oxide (EO) and propylene oxide (PO), e.g. also in the form of EO / PO block copolymers, polyethyleneimines or else polysiloxanes.
  • EO ethylene oxide
  • PO propylene oxide
  • the additive composition and the fuel can also be combined with other conventional components and additives.
  • carrier oils without pronounced detergent action to name, and these come in particular when used in petrol fuel to fruition. Occasionally, however, they are also used in middle distillates.
  • Carrier oils are usually used in combination with detergent additives and exercise with these a solvent or washing function.
  • Carrier oils are typically high boiling, viscous, thermostable liquids which coat a hot metal surface and thereby prevent the formation or deposition of contaminants on the metal surface.
  • Suitable mineral carrier oils are fractions obtained in petroleum processing, such as bright stock or base oils with viscosities such as from class SN 500-2000; but also aromatic hydrocarbons, paraffinic hydrocarbons and alkoxyalkanols. Useful is also a technique known as "hydrocrack oil” and obtained in the refining of mineral oil fraction (vacuum distillate cut having a boiling range of about 360-500 0 C, available natural out catalytic high pressure table hydrogenated and isomerized and also deparaffinized mineral oil). Also suitable are mixtures of the abovementioned mineral carrier oils.
  • Examples of synthetic carrier oils which can be used according to the invention are selected from polyolefins (polyalphaolefins or polyethylenemolefins), (poly) esters, (poly) acrylates, polyethers, aliphatic polyetheramines, alkylphenol-initiated polyethers, alkylphenol-initiated polyetheramines and carboxylic acid esters of long-chain alkanols.
  • suitable polyethers or polyetheramines are preferably compounds containing polyoxy-C 2 -C 4 -alkylene groups, which are prepared by reacting C 2 -C 6 -alkanols, C 6 -C 50 -alkanediols, mono- or di-C 2 -C 30 -alkylamines, C 1 -C 30 -alkyl - Cyclohexanolen or Ci-C3o-Alkylphenolen with 1 to 30 mol of ethylene oxide and / or propylene oxide and / or butylene oxide per hydroxyl group or amino group and, in the case of polyether amines, by subsequent reductive amination with ammonia, mono amines or polyamines are available.
  • Such products are described in particular in EP-A 310 875, EP-A 356 725, EP-A 700 985 and US-A 4,877,416.
  • polyetheramines poly-C 2 -C 6 -alkylene oxide amines or functional derivatives thereof can be used. Typical examples of these are tridecanol or Isotridecanolbutoxylate, Isononylphenolbutoxylate and Polyisobutenolbutoxylate and propoxylates and the corresponding reaction products with ammonia.
  • carboxylic acid esters of long-chain alkanols are in particular esters of mono-, di- or tricarboxylic acids with long-chain alkanols or polyols, as described in particular in DE-A 38 38 918.
  • mono-, di- or tricarboxylic acids it is possible to use aliphatic or aromatic acids, especially suitable ester alcohols or polyols are long-chain representatives having, for example, 6 to 24 carbon atoms.
  • suitable representatives of the esters are adipates, phthalates, isophthalates, terephthalates and trimellitates of isooctanol, isononanol, isodecanol and isotridecanol, such as e.g. Di (n- or iso-tridecyl) phthalate.
  • suitable synthetic carrier oils are alcohol-started polyethers having about 5 to 35, such as about 5 to 30, C 3 -C 6 alkylene oxide units, for example selected from propylene oxide, n-butylene oxide and i-butylene oxide units, or mixtures from that.
  • suitable starter alcohols are long-chain alkanols or long-chain alkyl-substituted phenols, where the long-chain alkyl radical is in particular a straight-chain or branched C 6 -C 18 -alkyl radical.
  • Preferred examples are tridecanol and nonylphenol.
  • Further common additives are the cold properties of the fuel-improving additives, e.g. Nucleators, flow improvers, paraffin dispersants and mixtures thereof, e.g. Ethylene-vinyl acetate copolymers; Corrosion inhibitors, for example based on film-forming ammonium salts of organic carboxylic acids or of heterocyclic aromatics in the case of non-ferrous metal corrosion protection; dehazers; Anti-foaming agent, e.g.
  • siloxane compounds cetane number improvers (ignitability improvers); combustion improvers; Antioxidants or stabilizers, for example based on amines such as p-phenylenediamine, dicyclohexylamine or derivatives thereof or of phenols such as 2,4-di-tert-butylphenol or 3,5-di-tert-butyl-4-hydroxyphenylpropionic acid; Antistatic agents; Metallocenes such as ferrocene; Methylcyclopentadienyl manganese tricarbonyl; Lubricity improver, e.g.
  • fatty acids alkenyl succinic esters, bis (hydroxyalkyl) fatty amines, hydroxyacetamides or castor oil; as well as dyes (markers).
  • amines are added to lower the pH of the fuel.
  • Suitable diluents and solvents are, for example, aromatic and aliphatic hydrocarbons, for example Cs-Cio-alkanes, such as pentane, hexane, heptane, octane, nonane, decane, their constitution isomers and mixtures; Petroleum ethers, aromatics such as benzene, toluene, xylene and solvent naphtha; Alkanols of 3 to 8 carbon atoms, e.g. Propanol, isopropanol, n-butanol, sec-butanol, isobutanol and the like, in combination with hydrocarbon solvents; and alkoxyalkanoethylene.
  • aromatic and aliphatic hydrocarbons for example Cs-Cio-alkanes, such as pentane, hexane, heptane, octane, nonane, decane, their constitution isomers and mixtures
  • Suitable diluents are, for example, fractions obtained in petroleum processing, such as kerosene, naphtha or bright stock.
  • middle distillates especially in diesel fuels and heating oils preferred diluent used are naphtha, kerosene, diesel fuels, aromatic hydrocarbons such as Solvent Naphtha heavy, Solvesso ® or Shellsol ®, as well as mixtures of these solvents and diluents.
  • detergent additives e.g. those with the polar groupings (a) to (i), in the fuel, in particular in diesel fuel or gasoline, are used, they are the fuel usually in an amount of 10 to 5000 ppm by weight, especially 50 to 1000 parts by weight. ppm, added.
  • demulsifiers When demulsifiers are used, they are usually added to the fuel in an amount of 0.1 to 100 ppm by weight, especially 0.2 to 10 ppm by weight.
  • the subject of the present invention is the use of the described method for the qualitative or quantitative detection of a fuel additive component in a diesel fuel or gasoline containing the fuel additive component and optionally further fuel additive components as analytes lyte.
  • the method according to the invention is a simple detection method for a fuel additive component, in particular a basic detergent additive, in a fuel additive package or in the fuel itself and can also be carried out "on site", ie in the refinery or at the filling station, with simple measuring instruments
  • the detection method is largely independent of the origin of the respective fuel grade, ie the composition of the respective fuel has no influence on the interaction between the fuel additive component and the indicator caused change in the color properties of the indicator in the analyte.
  • Samples of commercially available unadditized diesel fuel from various refineries and refinery cuts were each mixed with the same amounts of a detergent additive based on the imide of polyisobutenylsuccinic anhydride (number average molecular weight of the polyisobutenyl radical: about 1000) and tetraethylene pentamine, which is in the form of a conventional Diesel performance package was added, additized in practical quantities. From the extinction values determined with the different dosing rates of the detergent additive in the individual diesel fuel samples (analytes) in a commercially available photometer, a corresponding calibration curve for the range from 0 to 170 ppm by weight of detergent additive (based on active substance) was prepared.
  • 1.0 ml of an ethanolic bromocresol green solution (13 mg bromocresol green in 100 ml ethanol, red-orange solution) was added to 10 ml of additized diesel fuel.
  • the measurements were carried out after a color change in the analyte from yellow to blue, which was initiated and completed by vigorously shaking the sample with the indicator solution in a volumetric flask, in a 1 ml cuvette at a wavelength of 620 nm.

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Abstract

Method for qualitatively or quantitatively detecting a fuel additive component which is part of an analyte comprising fuel and/or further fuel additive components by contacting the analyte with an indicator and determining the change in the colour properties of the indicator in the analyte caused by the interaction between fuel additive component and indicator.

Description

Verfahren zum Nachweis einer Kraftstoffadditiv-KomponenteMethod for detecting a fuel additive component
Beschreibungdescription
Die vorliegende Erfindung betrifft ein Verfahren zum qualitativen oder quantitativen Nachweis einer Kraftstoffadditiv-Komponente, insbesondere in Dieselkraftstoff oder Ottokraftstoff. Weiterhin ist Gegenstand der vorliegenden Erfindung die Verwendung dieses Verfahrens zum qualitativen oder quantitativen Nachweis einer Kraftstoffadditiv- Komponente in Dieselkraftstoff oder Ottokraftstoff.The present invention relates to a method for the qualitative or quantitative detection of a fuel additive component, in particular in diesel fuel or gasoline. Furthermore, the subject of the present invention is the use of this method for the qualitative or quantitative detection of a fuel additive component in diesel fuel or gasoline.
Ottokraftstoff besteht aus einem Kohlenwasserstoff-Gemisch, welches beispielsweise Zusätze von sauerstoffhaltigen organischen Komponenten sowie Additive zur Verbesserung der Eigenschaften enthalten kann. Derartige Zusatzstoffe (Additive), die in unverbleitem Ottokraftstoff verwendet werden, sind z.B. Antioxidantien, Korrosionsinhibi- toren, Metalldeaktivatoren und Detergentien. Der Einsatz der Additive erfolgt unter anderem, um Korrosion, Ablagerungen im Einlasssystem, Schlammbildung und Ventil- verklebungen in einer Brennkraftmaschine zu vermeiden. Die Additivkonzentrationen liegen üblicherweise in Ottokraftstoff im Bereich unter 0,1 Gew.-%. Die Additive werden meist bereits vom Kraftstoffhersteller in Form von Additivpaketen dosiert und beim Be- füllen der Tankwagen in der Raffinerie dem Ottokraftstoff beigemischt.Petrol consists of a hydrocarbon mixture, which may contain, for example, additives of oxygen-containing organic components and additives to improve the properties. Such additives which are used in unleaded gasoline are e.g. Antioxidants, corrosion inhibitors, metal deactivators and detergents. The additives are used inter alia to prevent corrosion, deposits in the inlet system, sludge formation and valve sticking in an internal combustion engine. The additive concentrations are usually in gasoline in the range below 0.1 wt .-%. The additives are usually already metered by the fuel manufacturer in the form of additive packages and added to the petrol when filling the tank trucks in the refinery.
Auch bei Dieselkraftstoff hat sich die Zugabe von Additiven zur Qualitätsverbesserung weitgehend durchgesetzt. Dabei werden dem Dieselkraftstoff meist Additivpakete mit einer Gesamtkonzentration unter 0,1 Gew.-% zugesetzt. Die gebräuchlichsten Additive für Dieselkraftstoff sind Fließverbesserer, Schmierfähigkeitsverbesserer, Zündverbesserer, Detergentien, Korrosionsinhibitoren und Antischaummittel.Even with diesel fuel, the addition of additives for quality improvement has largely prevailed. The diesel fuel is usually added additive packages with a total concentration below 0.1 wt .-%. The most common additives for diesel fuel are flow improvers, lubricity improvers, ignition improvers, detergents, corrosion inhibitors and antifoams.
Der analytische Nachweis von Kraftstoffadditiv-Komponenten in den Additivpaketen und insbesondere im Kraftstoff selbst war bisher problematisch. Aufgrund der geringen Dosiermenge der Pakete im Kraftstoff (typischerweise 150 bis 600 mg/kg) beträgt die Konzentration der einzelnen Additiv-Komponenten nur wenige ppm. Ferner erschwert der Kraftstoff als komplexe Matrix chemischer Verbindungen die Analytik. Bislang wird im Stand der Technik als zuverlässiger Nachweis für Kraftstoffadditiv-Komponenten nur das massenspektroskopische Analysenverfahren der Anmelderin gemäß der DE-A 10246 210 (1) beschrieben. Dieses Verfahren ist jedoch durchführungstechnisch und apparativ aufwendig.The analytical detection of fuel additive components in the additive packages and in particular in the fuel itself has been problematic. Due to the low dosage of the packages in the fuel (typically 150 to 600 mg / kg), the concentration of the individual additive components is only a few ppm. Furthermore, the fuel, as a complex matrix of chemical compounds, makes the analysis more difficult. To date, only the mass spectroscopic analysis method of the Applicant according to DE-A 10246 210 (1) is described in the prior art as a reliable proof of fuel additive components. However, this method is implementation technology and equipment expensive.
Aufgabe der vorliegenden Erfindung war es daher, ein einfacher durchzuführendes Nachweisverfahren für eine Kraftstoffadditiv-Komponente bereitzustellen, welches in- besondere auch „vor Ort", d.h. in der Raffinerie oder an der Tankstelle, durchgeführt werden kann. Überraschenderweise wurde nun gefunden, dass die insbesondere photometrisch leicht bestimmbare Änderung der Farbeigenschaften eines Indikators, welcher mit der Kraftstoffadditiv-Komponente in einem Analyten in Kontakt gebracht wird und hiermit wechselwirkt, hierfür die geeignete Methode darstellt.It was therefore an object of the present invention to provide a simple detection method for a fuel additive component, which can also be carried out "on site", ie in the refinery or at the filling station. Surprisingly, it has now been found that the change in the color properties of an indicator which can be easily determined in particular photometrically and which is brought into contact with the fuel additive component in an analyte and interacts with it, represents the suitable method for this purpose.
Demgemäß wurde ein Verfahren zum qualitativen oder quantitativen Nachweis einer Kraftstoffadditiv-Komponente, die Bestandteil eines Kraftstoff und/oder weitere Kraftstoffadditiv-Komponenten enthaltenden Analyten ist, gefunden, welches dadurch gekennzeichnet ist, dass man den Analyten mit einem Indikator in Kontakt bringt und die durch die Wechselwirkung zwischen Kraftstoffadditiv-Komponente und Indikator hervorgerufene Änderung der Farbeigenschaften des Indikators im Analyten bestimmt.Accordingly, a method has been found for the qualitative or quantitative detection of a fuel additive component, which is part of an analyte containing fuel and / or other fuel additive components, which is characterized in that the analyte is brought into contact with an indicator and by the Interaction between fuel additive component and indicator determined change in the color properties of the indicator determined in the analyte.
Das erfindungsgemäße Verfahren lässt sich qualitativ und quantitativ anwenden, d.h. es kann hiermit nachgewiesen werden, ob eine bestimmte Kraftstoffadditiv-Kompo- nente vorliegt und in welcher Menge sie vorliegt. Der Nachweis kann insbesondere im Kraftstoff selbst, aber auch in den zugrundeliegenden Additivpaketen durchgeführt werden. Der Analyt, also die Bestimmungsprobe, ist somit der Kraftstoff oder das Kraftstoffadditivpaket, welches erforderlichenfalls mit geeigneten inerten Lösungsmitteln zur Durchführung der Bestimmung verdünnt werden kann.The method according to the invention can be used qualitatively and quantitatively, i. It can hereby be proven whether a certain fuel additive component is present and in what quantity it is present. The proof can be carried out in particular in the fuel itself, but also in the underlying additive packages. The analyte, ie, the determination sample, is thus the fuel or fuel additive package, which may be diluted with suitable inert solvents, if necessary, to carry out the determination.
Als Indikatoren kommen im Prinzip alle Indikatoren in Betracht, die bei Inkontaktbrin- gung und Wechselwirkung mit der Kraftstoffadditiv-Komponente ihre Farbeigenschaften ändern, seien diese im Bereich des sichtbaren Lichtes oder im Bereich des Fluoreszenz- oder Chemilumineszenzverhaltens anzusiedeln.In principle, all indicators are considered as indicators which change their color properties upon contact with and interaction with the fuel additive component, be they in the range of visible light or in the range of fluorescence or chemiluminescence behavior.
In einer bevorzugten Ausführungsform setzt man einen Säure-Base-Indikator (auch als pH-Indikator oder Neutralisationsindikator bezeichnet) ein. Die diesen Indikatoren zugrundeliegenden Säuren oder Basen zeigen einen üblicherweise im sichtbaren Bereich auftretenden Farbumschlag bei ihrer Protolyse bzw. Deprotolyse. Typische Bei- spiele für Säure-Base-Indikatoren sind Kresolrot, Metanilgelb, Thymolblau, m-Kresol- purpur, Tropaeolin OO, 2,6-Dinitrophenol, Benzylorange, 2,4-Dinitrophenol, Benzopur- purin 4 B, Dimethylgelb, Kongorot, Bromphenolblau, Bromchlorphenolblau, Methylorange, α-Naphthylrot, Bromkresolgrün, 2,5-Dinitrophenol, Mischindikator 5, Methylrot, Ethylrot, Chlorphenolrot, Carminsäure, Alizarinrot S, 2-Nitrophenol, Lackmus, Brom- kresolpurpur, Bromphenolrot, 4-Nitrophenol, Alizarin, Bromthymolblau, Bromxylenol- blau, Brasilen, Nitrazingelb, Hämatoxylin, Phenolrot, 3-Nitrophenol, Neutralrot, Kresolrot, m-Kresolpurpur, Brilliantgelb, Orange I, α-Naphtholphthalein, Thymolblau, p-Xy- lenolblau, o-Kresolphthalein, Phenolphthalein, α-Naphtholbenzein,Thymolphthalein, Wasserblau, Alizaringelb 2 G, Alizaringelb R, Nilblau A, α-Naphtholviolett, Nitramin, Tropaeolin 0002, Tropaeolin O, Epsilonblau und Säurefuchsin. Der Farbumschlag bei Säure-Base-Indikatoren kann - was auch für andere Indikatoren gilt - einfarbig oder zweifarbig sein. Er sollte scharf und zu erkennen sein. Wenn dies nicht der Fall ist, mischt man geeignete einzelne Indikatoren zu Mischindikatoren.In a preferred embodiment, an acid-base indicator (also referred to as a pH indicator or neutralization indicator) is used. The acids or bases on which these indicators are based show a color change which usually occurs in the visible range during their protolysis or deproteinization. Typical examples of acid-base indicators are cresol red, metanil yellow, thymol blue, m-cresol purple, tropaeolin OO, 2,6-dinitrophenol, benzyl orange, 2,4-dinitrophenol, benzopurpurine 4 B, dimethyl yellow, Congo Red, Bromophenol blue, bromochlorophenol blue, methyl orange, α-naphthyl red, bromocresol green, 2,5-dinitrophenol, mixed indicator 5, methyl red, ethyl red, chlorophenol red, carminic acid, alizarin red S, 2-nitrophenol, litmus, bromocresol purple, bromophenol red, 4-nitrophenol, alizarin, Bromothymol blue, bromoxylenol blue, brasil, nitrazene yellow, hematoxylin, phenol red, 3-nitrophenol, neutral red, cresol red, m-cresol purple, brilliant yellow, orange I, α-naphtholphthalein, thymol blue, p-xylenol blue, o-cresolphthalein, phenolphthalein, α Naphtholbenzein, thymolphthalein, water blue, alizarin yellow 2G, alizarin yellow R, blue Nile A, α-naphthol violet, nitramine, Tropaeolin 0002, Tropaeolin O, epsilon blue, and acid fuchsin. The color change in acid-base indicators can - as is true for other indicators - be monochrome or bicoloured. He should be sharp and recognizable. If this is not the case, mix suitable individual indicators into mixed indicators.
Als besonders bevorzugten Säure-Base-Indikator setzt man Bromkresolgrün, α-Naph- thylrot, 2,5-Dinitrophenol, Mischindikator 5 oder Methylrot ein.As a particularly preferred acid-base indicator, bromocresol green, α-naphthyl red, 2,5-dinitrophenol, mixed indicator 5 or methyl red is used.
Der Säure-Base-Indikator nutzt insbesondere basische Funktionalitäten in der Kraftstoffadditiv-Komponente aus, um den Farbumschlag zu erzeugen.In particular, the acid-base indicator exploits basic functionalities in the fuel additive component to produce the color change.
Weitere für das erfindungsgemäße Verfahren prinzipiell einsetzbare Indikatoren sind Adsorptionsindikatoren, z.B. Fluorescein oder Eosin, Fluoreszenzindikatoren, z.B. FIu- orescein, Eosin, Benzoflavin, Phloxin, Chromotropsäure, Methylumbelliferon, Benzchi- nolin, Morin, Naphthole, Naphthionsäure, Chinin, Cumarin oder Acridin, Chemilumines- zenzindikatoren, z.B. Lucigenin, Redoxindikatoren, z.B. Neutralrot, Safranin oder Methylenblau, und Metallindikatoren (Metallochrom-Indikatoren).Further indicators which can be used in principle for the method according to the invention are adsorption indicators, e.g. Fluorescein or eosin, fluorescence indicators, e.g. Flucescein, eosin, benzoflavin, phloxine, chromotropic acid, methylumbelliferone, benzquinoline, morin, naphthols, naphthionic acid, quinine, coumarin or acridine, chemiluminescent indicators, e.g. Lucigenin, redox indicators, e.g. Neutral red, safranine or methylene blue, and metal indicators (metallo-hole indicators).
Für einen qualitativen Nachweis einer Kraftstoffadditiv-Komponente wird beobachtet, ob ein spezifischer Farbumschlag bei Zusammenbringen von Indikator und Analyt auf- tritt, beispielsweise im Falle von Bromkresolgrün von gelb (saurer Bereich unterhalb pH 3,8) nach blau (alkalischer Bereich oberhalb pH 5,4). Das Auftreten des Farbumschlages ist der Nachweis für das Vorliegen der gesuchten Kraftstoffadditiv-Komponente. Zur Sicherstellung, dass der Farbumschlag nicht durch andere Einflüsse ausgelöst worden ist, empfiehlt sich ein Blindversuch mit einem Analyten, dem eine Test- menge der nachzuweisenden Kraftstoffadditiv-Komponente zugesetzt wurde, und/oder einem Analyten, der unadditivierten Kraftstoff enthält.For a qualitative detection of a fuel additive component, it is observed whether a specific color change occurs when the indicator and the analyte come together, for example in the case of bromocresol green from yellow (acidic range below pH 3.8) to blue (alkaline range above pH 5, 4). The occurrence of the color change is the evidence of the presence of the desired fuel additive component. To ensure that the color change has not been triggered by other factors, a blank test with an analyte to which a test quantity of the fuel additive component to be detected has been added and / or an analyte containing unadditized fuel is recommended.
Für einen quantitativen Nachweis einer Kraftstoffadditiv-Komponente wird die Intensität der Färbung nach erfolgter Änderung der Farbeigenschaften im Analyten, also nach erfolgtem Farbumschlag, bestimmt. Hierzu eignet sich in einer bevorzugten Ausführungsform die photometrische Bestimmung, normalerweise unter Verwendung von handelsüblichen Photometern. Die Messung wird in der Regel so durchgeführt, dass man eine bestimmte Analyten-Menge mit einer festgesetzten Menge des Indikators versetzt, durchmischt (beispielsweise durch Schütteln) und die Probe in einem Pro- bengefäß (Küvette) mit Licht einer bestimmten Wellenlänge durchstrahlt. Die gemessene Extinktion in Korrelation zu einer Blindprobe oder zu einer mit unterschiedlichen Mengen der zu bestimmenden Kraftstoffadditiv-Komponente erstellten Eichkurve ergibt die Menge an Kraftstoffadditiv-Komponente im Analyten. Arbeitet man mit Bromkresolgrün als Säure-Base-Indikator, empfiehlt sich beispielsweise die photometrische Be- Stimmung der Extinktion bei einer Wellenlänge von 620 nm. In einer bevorzugten Ausführungsform setzt man als Analyten Dieselkraftstoff oder Ottokraftstoff ein, welcher neben der nachzuweisenden Kraftstoffadditiv-Komponente gegebenenfalls weitere Kraftstoffadditiv-Komponenten enthält, d.h. man führt die Bestimmung unmittelbar an dem von den Raffinerien gelieferten und im Handel erhältli- chen Diesel- oder Ottokraftstoff durch.For a quantitative proof of a fuel additive component, the intensity of the coloration is determined after the change in the color properties in the analyte, ie after the color change has taken place. For this purpose, the photometric determination is suitable in a preferred embodiment, usually using commercially available photometers. The measurement is usually carried out by adding a certain amount of analyte to a set amount of the indicator, mixing (for example by shaking) and irradiating the sample in a sample vessel (cuvette) with light of a specific wavelength. The measured absorbance correlated to a blank or to a calibration curve made with different amounts of the fuel additive component to be determined gives the amount of fuel additive component in the analyte. If one works with bromocresol green as the acid-base indicator, the photometric determination of the extinction at a wavelength of 620 nm is recommended, for example. In a preferred embodiment, the analyte used is diesel fuel or gasoline which, in addition to the fuel additive component to be detected, optionally contains further fuel additive components, ie the determination is carried out directly on the diesel or gasoline fuel supplied by the refineries and commercially available ,
Bei Ottokraftstoff zum Betreiben von Verbrennungsmotoren (Ottomotoren) in Kraftfahrzeugen handelt es sich üblicherweise um Erdölraffinate, die in der Regel einen Siedebereich von 70 bis 18O0C aufweisen. Sie stellen üblicherweise C5-Ci2-Kohlenwasser- stoff-Gemische aus Alkanen, Alkenen, Cycloalkanen, Cycloalkenen und Aromaten in wechselnder Zusammensetzung dar. Ottokraftstoff wird vorzugsweise unverbleit eingesetzt.In petrol for operating internal combustion engines (gasoline engines) in motor vehicles are usually petroleum raffinates, which generally have a boiling range of 70 to 18O 0 C. They usually represent C5-C12 hydrocarbon mixtures of alkanes, alkenes, cycloalkanes, cycloalkenes and aromatics in varying composition. Petrol is preferably used unleaded.
Das erfindungsgemäße Verfahren zum Nachweis einer Kraftstoffadditiv-Komponente lässt sich prinzipiell auch in Kerosin als Analyten durchführen. Kerosin als höher siedende Benzin-Qualität (Siedebereich etwa 180 bis 27O0C) wird insbesondere im Flugzeugsektor verwendet.The method according to the invention for detecting a fuel additive component can in principle also be carried out in kerosene as analyte. Kerosene as a higher-boiling gasoline grade (boiling range about 180 to 27O 0 C) is used in particular in the aircraft sector.
Bei Dieselkraftstoff (Mitteldestillat-Kraftstoff) handelt es sich üblicherweise um Erdölraf- finate, die in der Regel einen Siedebereich von 100 bis 4000C haben. Dies sind meist Destillate mit einem 95%-Punkt bis zu 36O0C oder auch darüber hinaus. Dies können aber auch sogenannte "Ultra low sulfur diese!" oder "City diese!" sein, gekennzeichnet durch einen 95%-Punkt von beispielsweise maximal 3450C und einem Schwefelgehalt von maximal 0,005 Gew.-% oder durch einen 95%-Punkt von beispielsweise 2850C und einem Schwefelgehalt von maximal 0,001 Gew.-%. Neben den durch Raffination erhältlichen Dieselkraftstoffen, deren Hauptbestandteile längerkettige Paraffine darstellen, sind solche, die durch Kohlevergasung oder Gasverflüssigung ["gas to liquid" (GTL) Kraftstoffe] erhältlich sind, geeignet. Geeignet sind auch Mischungen der vorstehend genannten Dieselkraftstoffe mit regenerativen Kraftstoffen wie Biodiesel oder Bioethanol. Von besonderem Interesse sind gegenwärtig Dieselkraftstoffe mit niedrigem Schwefelgehalt, das heißt mit einem Schwefelgehalt von weniger als 0,05 Gew.-%, vorzugsweise von weniger als 0,02 Gew.-%, insbesondere von weniger als 0,005 Gew.-% und speziell von weniger als 0,001 Gew.-% Schwefel. Dieselkraftstoffe können auch Wasser, z.B. in einer Menge bis zu 20 Gew.-%, enthalten, bei- spielsweise in Form von Diesel-Wasser-Mikroemulsionen oder als sogenannter "White Diesel".For diesel (middle distillate fuel), there are typically Erdölraf- finate that have a boiling range of 100 to 400 0 C in the rule. These are mostly distillates with a 95% point up to 36O 0 C or even beyond. But this can also be called "ultra low sulfur this!" or "City this!" be characterized by a 95% point of, for example, a maximum of 345 0 C and a maximum sulfur content of 0.005 wt .-% or by a 95% point of, for example 285 0 C and a maximum sulfur content of 0.001 wt .-%. In addition to refining diesel fuels whose major components are longer chain paraffins, those obtainable by coal gasification or gas liquefaction [GTL] fuels are also suitable. Also suitable are mixtures of the abovementioned diesel fuels with regenerative fuels such as biodiesel or bioethanol. Of particular interest currently are low sulfur diesel fuels, that is having a sulfur content of less than 0.05% by weight, preferably less than 0.02% by weight, more preferably less than 0.005% by weight, and especially of less than 0.001% by weight of sulfur. Diesel fuels may also contain water, for example in an amount of up to 20% by weight, for example in the form of diesel-water microemulsions or as so-called "white diesel".
In einer bevorzugten Ausführungsform wendet man das erfindungsgemäße Verfahren zum Nachweis einer polaren Kraftstoffadditiv-Komponente mit Detergenswirkung an, die sich üblicherweise als Additiv in den meisten Kraftstoffsorten, inbesondere in Dieselkraftstoff und in Ottokraftstoff, sowie in den zugrundeliegenden Additivzusammensetzungen (Additivpaketen) für insbesondere Diesel- oder Ottokraftstoff befindet. Ge- eignete polare Detergensadditive mit insbesondere basischen Funktionalitäten oder polaren funktionellen Gruppen, die zumeist im Sinne einer Säure-Base-Wechsel- wirkung mit den Indikatoren wechselwirken, sind nachfolgend ausgeführt.In a preferred embodiment, the process of the present invention is used to detect a polar detergent-additive component typically used as an additive in most types of fuel, particularly diesel fuel and gasoline, as well as in the underlying additive compositions (especially additive packages) for diesel or diesel fuel Petrol is located. overall suitable polar detergent additives with in particular basic functionalities or polar functional groups, which interact with the indicators mostly in the sense of an acid-base interaction, are described below.
Die genannten Additivzusammensetzungen und Kraftstoffe können zusätzlich davon verschiedene weitere Kraftstoffadditiv-Komponenten wie Demulgatoren, Trägeröle, Lösungs- und Verdünnungsmittel, Korrosionsinhibitoren, Antioxidantien, Metalldeakti- vatoren, Antistatika, Farbmarker, Fließverbesserer, Schmierfähigkeitsverbesserer, Zündverbesserer und Antischaummittel enthalten. Geeignete weitere Kraftstoffadditiv- Komponenten sind ebenfalls nachfolgend ausgeführt.The above additive compositions and fuels may additionally contain various other fuel additive components such as demulsifiers, carrier oils, solvents and diluents, corrosion inhibitors, antioxidants, metal deactivators, antistatic agents, color markers, flow improvers, lubricity improvers, ignition improvers and antifoam agents. Suitable other fuel additive components are also set forth below.
A) DetergensadditiveA) detergent additives
Als Detergensadditive (Detergentien) werden üblicherweise Ablagerungsinhibitoren für Ottokraftstoff und Dieselkraftstoff bezeichnet. Vorzugsweise handelt es sich bei den Detergensadditiven um amphiphile Substanzen, die mindestens einen hydrophoben Kohlenwasserstoffrest mit einem zahlengemittelten Molekulargewicht (Mn) von 85 bis 20 000 und mindestens eine polare Gruppierung besitzen, die ausgewählt ist unter:Detergent additives are commonly referred to as gasoline and diesel fuel scale inhibitors. Preferably, the detergent additives are amphiphilic substances having at least one hydrophobic hydrocarbon radical having a number average molecular weight (Mn) of from 85 to 20,000 and at least one polar moiety selected from:
(a) Mono- oder Polyaminogruppen mit bis zu 6 Stickstoffatomen, wobei mindestens ein Stickstoffatom basische Eigenschaften hat;(a) mono- or polyamino groups having up to 6 nitrogen atoms, at least one nitrogen atom having basic properties;
(b) Nitrogruppen, ggf. in Kombination mit Hydroxylgruppen;(b) nitro groups, optionally in combination with hydroxyl groups;
(c) Hydroxylgruppen in Kombination mit Mono- oder Polyaminogruppen, wobei mindestens ein Stickstoffatom basische Eigenschaften hat;(c) hydroxyl groups in combination with mono- or polyamino groups, wherein at least one nitrogen atom has basic properties;
(d) Carboxylgruppen oder deren Alkalimetall- oder Erdalkalimetallsalzen;(d) carboxyl groups or their alkali metal or alkaline earth metal salts;
(e) Sulfonsäuregruppen oder deren Alkalimetall- oder Erdalkalimetallsalzen;(e) sulfonic acid groups or their alkali metal or alkaline earth metal salts;
(f) Polyoxy-C2- bis C4-alkylengruppierungen, die durch Hydroxylgruppen, Mono- oder Polyaminogruppen, wobei mindestens ein Stickstoffatom basische Eigenschaften hat, oder durch Carbamatgruppen terminiert sind;(f) polyoxy-C 2 to C 4 alkylene moieties terminated by hydroxyl groups, mono- or polyamino groups, wherein at least one nitrogen atom has basic properties, or terminated by carbamate groups;
(g) Carbonsäureestergruppen;(g) carboxylic acid ester groups;
(h) aus Bernsteinsäureanhydrid abgeleiteten Gruppierungen mit Hydroxy- und/oder(h) from succinic anhydride derived groups with hydroxy and / or
Amino- und/oder Am ido- und/oder Imidogruppen; und/oderAmino and / or amido and / or imido groups; and or
(i) durch Mannich-Umsetzung von substituierten Phenolen mit Aldehyden und Mono- oder Polyaminen erzeugten Gruppierungen; Der hydrophobe Kohlenwasserstoffrest in den obigen Detergensadditiven, welcher für die ausreichende Löslichkeit im Kraftstoff sorgt, hat ein zahlengemitteltes Molekulargewicht (Mn) von 85 bis 20000, insbesondere von 113 bis 10000, vor allem von 300 bis 5000. Als typischer hydrophober Kohlenwasserstoffrest, insbesondere in Verbindung mit den polaren Gruppierungen (a), (c), (h) und (i), kommen der Polypropenyl-, Polybu- tenyl- und Polyisobutenylrest mit jeweils Mn = 300 bis 5000, insbesondere 500 bis 2500, vor allem 700 bis 2300, in Betracht.(i) moieties generated by Mannich reaction of substituted phenols with aldehydes and mono- or polyamines; The hydrophobic hydrocarbon radical in the above detergent additives, which provides the sufficient solubility in the fuel, has a number average molecular weight (Mn) of 85 to 20,000, especially from 113 to 10,000, especially from 300 to 5000. As a typical hydrophobic hydrocarbon radical, especially in combination with the polar groups (a), (c), (h) and (i), the polypropenyl, polybutenyl and polyisobutenyl radicals have in each case Mn = 300 to 5000, in particular 500 to 2500, especially 700 to 2300, into consideration.
Als Beispiele für obige Gruppen von Detergensadditiven seien die folgenden genannt:As examples of the above groups of detergent additives, the following are mentioned:
Mono- oder Polyaminogruppen (a) enthaltende Additive sind vorzugsweise Polyalken- mono- oder Polyalkenpolyamine auf Basis von Polypropen oder konventionellem (d.h. mit überwiegend mittenständigen Doppelbindungen) Polybuten oder Polyisobuten mit Mn = 300 bis 5000. Geht man bei der Herstellung der Additive von Polybuten oder Po- lyisobuten mit überwiegend mittenständigen Doppelbindungen (meist in der ß-und γ- Position) aus, bietet sich der Herstellweg durch Chlorierung und anschließende Ami- nierung oder durch Oxidation der Doppelbindung mit Luft oder Ozon zur Carbonyl- oder Carboxylverbindung und anschließende Aminierung unter reduktiven (hydrierenden) Bedingungen an. Zur Aminierung können hier Amine, wie z.B. Ammoniak, Mono- amine oder Polyamine, wie Dimethylaminopropylamin, Ethylendiamin, Diethylentriamin, Triethylentetramin oder Tetraethylenpentamin, eingesetzt werden. Entsprechende Additive auf Basis von Poly(iso)buten sind insbesondere in der EP-B 244 616, entsprechende Additive auf Basis von Polypropen sind insbesondere in der WO 94/24231 beschrieben.Mono- or polyamino groups (a) containing additives are preferably polyalkene mono- or Polyalkenpolyamine based on polypropene or conventional (ie, with predominantly central double bonds) polybutene or polyisobutene with Mn = 300 to 5000. Is one in the preparation of the additives of polybutene or Polyisobutene with predominantly intermediate double bonds (usually in the β and γ position), the preparation route by chlorination and subsequent amination or by oxidation of the double bond with air or ozone to carbonyl or carboxyl compound and subsequent amination under reductive offers (hydrogenating) conditions. For amination, amines such as e.g. Ammonia, monoamines or polyamines, such as dimethylaminopropylamine, ethylenediamine, diethylenetriamine, triethylenetetramine or tetraethylenepentamine. Corresponding additives based on poly (iso) butene are in particular in EP-B 244 616, corresponding additives based on polypropene are described in particular in WO 94/24231.
Weitere bevorzugte Monoaminogruppen (a) enthaltende Additive sind die Hydrierungsprodukte der Umsetzungsprodukte aus Polyisobutenen mit einem mittleren Polymerisationsgrad P = 5 bis 100 mit Stickoxiden oder Gemischen aus Stickoxiden und Sauerstoff, wie sie insbesondere in WO 97/03946 beschrieben sind.Further preferred monoamino groups (a) containing additives are the hydrogenation products of the reaction products of polyisobutenes having an average degree of polymerization P = 5 to 100 with nitrogen oxides or mixtures of nitrogen oxides and oxygen, as described in particular in WO 97/03946.
Weitere bevorzugte Monoaminogruppen (a) enthaltende Additive sind die aus Polyiso- butenepoxiden durch Umsetzung mit Aminen und nachfolgender Dehydratisierung und Reduktion der Aminoalkohole erhältlichen Verbindungen, wie sie insbesondere in DE-A 196 20 262 beschrieben sind.Further preferred monoamino groups (a) containing additives are the polyisobutene epoxides by reaction with amines and subsequent dehydration and reduction of the amino alcohols obtainable compounds, as described in particular in DE-A 196 20 262.
Nitrogruppen (b), ggf. in Kombination mit Hydroxylgruppen, enthaltende Additive sind vorzugsweise Umsetzungsprodukte aus Polyisobutenen des mittleren Polymerisationsgrades P = 5 bis 100 oder 10 bis 100 mit Stickoxiden oder Gemischen aus Stickoxiden und Sauerstoff, wie sie insbesondere in WO 96/03367 und WO 96/03479 be- schrieben sind. Diese Umsetzungsprodukte stellen in der Regel Mischungen aus reinen Nitropolyisobutenen (z.B. α,ß-Dinitropolyisobuten) und gemischten Hydroxynitropolyisobutenen (z.B. α-Nitro-ß-hydroxypolyisobuten) dar. Hydroxylgruppen in Kombination mit Mono- oder Polyaminogruppen (c) enthaltende Additive sind insbesondere Umsetzungsprodukte von Polyisobutenepoxiden, erhältlich aus vorzugsweise überwiegend endständige Doppelbindungen aufweisendem Polyiso- buten mit Mn = 300 bis 5000, mit Ammoniak, Mono- oder Polyaminen, wie sie insbe- sondere in EP-A 476 485 beschrieben sind.Nitro groups (b), optionally in combination with hydroxyl groups, containing additives are preferably reaction products of polyisobutenes of average degree of polymerization P = 5 to 100 or 10 to 100 with nitrogen oxides or mixtures of nitrogen oxides and oxygen, as described in particular in WO 96/03367 and WO 96/03479 are described. These reaction products generally represent mixtures of pure nitropolyisobutenes (eg α, β-dinitropolyisobutene) and mixed hydroxynitropolyisobutenes (eg α-nitro-β-hydroxypolyisobutene). Hydroxyl groups in combination with mono- or polyamino groups (c) containing additives are in particular reaction products of polyisobutene epoxides obtainable from preferably predominantly terminal double bonds having polyisobutene having Mn = 300 to 5000, with ammonia, mono- or polyamines, as in particular EP-A 476 485 are described.
Carboxylgruppen oder deren Alkalimetall- oder Erdalkalimetallsalze (d) enthaltende Additive sind vorzugsweise Copolymere von C2-C4o-Olefinen mit Maleinsäureanhydrid mit einer Gesamt-Molmasse von 500 bis 20 000, deren Carboxylgruppen ganz oder teilweise zu den Alkalimetall- oder Erdalkalimetallsalzen und ein verbleibender Rest der Carboxylgruppen mit Alkoholen oder Aminen umgesetzt sind. Solche Additive sind insbesondere aus der EP-A 307 815 bekannt. Derartige Additive dienen hauptsächlich zur Verhinderung von Ventilsitzverschleiß und können, wie in der WO 87/01126 beschrieben, mit Vorteil in Kombination mit üblichen Kraftstoffdetergenzien wie PoIy- (iso)butenaminen oder Polyetheraminen eingesetzt werden.Carboxyl groups or their alkali metal or alkaline earth metal salts (d) containing additives are preferably copolymers of C2-C4o-olefins with maleic anhydride having a total molecular weight of 500 to 20,000, the carboxyl groups wholly or partially to the alkali metal or alkaline earth metal salts and a remainder of the Carboxyl groups are reacted with alcohols or amines. Such additives are known in particular from EP-A 307 815. Such additives are primarily used to prevent valve seat wear and, as described in WO 87/01126, can be advantageously used in combination with conventional fuel detergents such as poly (iso) butenamines or polyetheramines.
Sulfonsäuregruppen oder deren Alkalimetall- oder Erdalkalimetallsalze (e) enthaltende Additive sind vorzugsweise Alkalimetall- oder Erdalkalimetallsalze eines Sulfobern- steinsäurealkylesters, wie er insbesondere in der EP-A 639 632 beschrieben ist. Derar- tige Additive dienen hauptsächlich zur Verhinderung von Ventilsitzverschleiß und können mit Vorteil in Kombination mit üblichen Kraftstoffdetergenzien wie Poly(iso)buten- aminen oder Polyetheraminen eingesetzt werden.Sulfonic acid groups or their alkali metal or alkaline earth metal salts (e) containing additives are preferably alkali metal or alkaline earth metal salts of a Sulfobern- steinsäurealkylesters, as described in particular in EP-A 639 632. Such additives are mainly used to prevent valve seat wear and can be used to advantage in combination with conventional fuel detergents such as poly (iso) buteneamines or polyetheramines.
Polyoxy-C2-C4-alkylengruppierungen (f) enthaltende Additive sind vorzugsweise PoIy- ether oder Polyetheramine, welche durch Umsetzung von C2-C6o-Alkanolen, C6-C30-Al- kandiolen, Mono- oder Di-C2-C3o-alkylaminen, Ci-C3o-Alkylcyclohexanolen oder Ci-C30- Alkylphenolen mit 1 bis 30 mol Ethylenoxid und/oder Propylenoxid und/oder Butylen- oxid pro Hydroxylgruppe oder Aminogruppe und, im Falle der Polyetheramine, durch anschließende reduktive Aminierung mit Ammoniak, Monoaminen oder Polyaminen erhältlich sind. Derartige Produkte werden insbesondere in EP-A 310 875,Polyoxy-C 2 -C 4 -alkylene groups (f) containing additives are preferably polyether or polyetheramines, which by reaction of C 2 -C 6 o-alkanols, C 6 -C 30 -alkanediols, mono- or di-C 2 -C 3 o-alkylamines, Ci-C 3 o-alkylcyclohexanols or Ci-C 30 - alkylphenols with 1 to 30 moles of ethylene oxide and / or propylene oxide and / or butylene oxide per hydroxyl group or amino group and, in the case of polyetheramines, by subsequent reductive amination with ammonia, monoamines or polyamines are available. Such products are disclosed in particular in EP-A 310 875,
EP-A 356 725, EP-A 700 985 und US-A 4 877 416 beschrieben. Im Falle von Polye- thern erfüllen solche Produkte auch Trägeröleigenschaften. Typische Beispiele hierfür sind Tridecanol- oder Isotridecanolbutoxylate, Isononylphenolbutoxylate sowie Polyiso- butenolbutoxylate und -propoxylate sowie die entsprechenden Umsetzungsprodukte mit Ammoniak.EP-A 356 725, EP-A 700 985 and US-A 4,877,416. In the case of polyesters, such products also fulfill carrier oil properties. Typical examples thereof are tridecanol or isotridecanol butoxylates, isononylphenol butoxylates and also polyisobutenol butoxylates and propoxylates and the corresponding reaction products with ammonia.
Carbonsäureestergruppen (g) enthaltende Additive sind vorzugsweise Ester aus Mono-, Di- oder Tricarbonsäuren mit langkettigen Alkanolen oder Polyolen, insbesondere solche mit einer Mindestviskosität von 2 mm2/s bei 1000C, wie sie insbesondere in DE-A 38 38 918 beschrieben sind. Als Mono-, Di- oder Tricarbonsäuren können alipha- tische oder aromatische Säuren eingesetzt werden, als Esteralkohole bzw.- polyole eignen sich vor allem langkettige Vertreter mit beispielsweise 6 bis 24 C-Atomen. Typi- sehe Vertreter der Ester sind Adipate, Phthalate, iso-Phthalate, Terephthalate und Tri- mellitate des iso-Octanols, iso-Nonanols, iso-Decanols und des iso-Tridecanols. Derartige Produkte erfüllen auch Trägeröleigenschaften.Carboxyl ester groups (g) containing additives are preferably esters of mono-, di- or tricarboxylic acids with long-chain alkanols or polyols, especially those having a minimum viscosity of 2 mm 2 / s at 100 0 C, as described in particular in DE-A 38 38 918 are. Aliphatic or aromatic acids can be used as the mono-, di- or tricarboxylic acids, especially suitable as ester alcohols or polyols are long-chain representatives with, for example, 6 to 24 C atoms. typical Representatives of the esters are adipates, phthalates, isophthalates, terephthalates and trimellitates of iso-octanol, iso-nonanol, iso-decanol and of isotridecanol. Such products also meet carrier oil properties.
Aus Bernsteinsäureanhydrid abgeleitete Gruppierungen mit Hydroxy- und/oder Amino- und/oder Amido- und/oder Imidogruppen (h) enthaltende Additive sind vorzugsweise entsprechende Derivate von Polyisobutenylbemsteinsäureanhydrid, welche durch Umsetzung von konventionellem oder hochreaktivem Polyisobuten mit Mn = 300 bis 5000 mit Maleinsäureanhydrid auf thermischem Weg oder über das chlorierte Polyisobuten erhältlich sind. Von besonderem Interesse sind hierbei Derivate mit aliphatischen PoIy- aminen wie Ethylendiamin, Diethylentriamin, Triethylentetramin oder Tetraethylenpen- tamin. Bei den Gruppierungen mit Hydroxy- und/oder Amino- und/oder Am ido- und/oder Imidogruppen handelt es sich beispielsweise um Carbonsäuregruppen, Säureannide, Säureamide von Di- oder Polyaminen, die neben der Amidfunktion noch freie Amingruppen aufweisen, Bernsteinsäurederivate mit einer Säure- und einer Amidfunktion, Carbonsäureimide mit Monoaminen, Carbonsäureimide mit Di- oder Polyaminen, die neben der Imidfunktion noch freie Amingruppen aufweisen, und Diimide, die durch die Umsetzung von Di- oder Polyaminen mit zwei Bernsteinsäurederivaten gebildet werden. Derartige Kraftstoffadditive sind insbesondere in US-A 4 849 572 beschrieben.Succinic anhydride-derived groupings containing hydroxyl and / or amino and / or amido and / or imido groups (h) are preferably corresponding derivatives of polyisobutenyl succinic anhydride obtained by reacting conventional or highly reactive polyisobutene having Mn = 300 to 5000 with maleic anhydride thermal route or via the chlorinated polyisobutene are available. Of particular interest here are derivatives with aliphatic polyamines, such as ethylenediamine, diethylenetriamine, triethylenetetramine or tetraethylenepentamine. The groups having hydroxyl and / or amino and / or amido and / or imido groups are, for example, carboxylic acid groups, acid anhydrides, acid amides of diamines or polyamines which, in addition to the amide function, still have free amine groups, succinic acid derivatives with an acid - And an amide function, carboxylic imides with monoamines, carboxylic imides with di- or polyamines, which still have free amine groups in addition to the imide function, and diimides, which are formed by the reaction of di- or polyamines with two succinic acid derivatives. Such fuel additives are described in particular in US Pat. No. 4,849,572.
Durch Mannich-Umsetzung von substituierten Phenolen mit Aldehyden und Mono- oder Polyaminen erzeugte Gruppierungen (i) enthaltende Additive sind vorzugsweise Umsetzungsprodukte von Polyisobuten-substituierten Phenolen mit Formaldehyd und Mono- oder Polyaminen wie Ethylendiamin, Diethylentriamin, Triethylentetramin, Tetra- ethylenpentamin oder Dimethylaminopropylamin. Die polyisobutenylsubstituierten Phenole können aus konventionellem oder hochreaktivem Polyisobuten mit Mn = 300 bis 5000 stammen. Derartige "Polyisobuten-Mannichbasen" sind insbesondere in der EP-A-831 141 beschrieben.By Mannich reaction of substituted phenols with aldehydes and mono- or polyamines generated groupings (i) containing additives are preferably reaction products of polyisobutene-substituted phenols with formaldehyde and mono- or polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine or dimethylaminopropylamine. The polyisobutenyl-substituted phenols may be derived from conventional or highly reactive polyisobutene having Mn = 300 to 5,000. Such "polyisobutene-Mannich bases" are described in particular in EP-A-831 141.
Zur genaueren Definition der einzelnen aufgeführten Kraftstoffadditive wird hier auf die Offenbarungen der obengenannten Schriften des Standes der Technik ausdrücklich Bezug genommen.For a more detailed definition of the individual listed fuel additives is hereby made to the disclosures of the above-mentioned documents of the prior art express reference.
Besonders bevorzugt werden beim erfindungsgemäßen Verfahren Detergensadditive aus der Gruppe (h). Hierbei handelt es sich insbesondere um Polyisobutenyl-substi- tuierte Bernsteinsäureimide, speziell um die Imide mit aliphatischen Polyaminen. Solche Polyisobutenyl-substituierten Bernsteinsäureimide werden vornehmlich als polare Kraftstoffadditiv-Komponente mit Detergenswirkung in Dieselkraftstoff eingesetzt. B) DemulgatorenDetergent additives from group (h) are particularly preferred in the process according to the invention. These are, in particular, polyisobutenyl-substituted succinimides, especially the imides with aliphatic polyamines. Such polyisobutenyl-substituted succinimides are primarily used as a polar fuel additive component with detergent action in diesel fuel. B) Demulsifiers
Demulgatoren sind Substanzen, welche die Entmischung einer Emulsion bewirken. Hierbei kann es sich sowohl um ionogene als auch um nicht-ionogene Subtanzen han- dein, die an der Phasengrenze wirksam sind. Dementsprechend sind grundsätzlich alle oberflächenaktiven Substanzen als Demulgatoren geeignet. Besonders geeignete Demulgatoren sind ausgewählt unter Anionen-aktiven Verbindungen, wie die Alkali- oder Erdalkalisalze von Alkyl-substituierten Phenol- und Naphthalinsulfonaten und die Alkalioder Erdalkalisalze von Fettsäuren, außerdem neutrale Verbindungen, wie Alkoholal- koxylate, z.B. Alkoholethoxylate, Phenolalkoxylate, z.B. tert-Butylphenolethoxylat oder tert-Pentylphenolethoxylat, Fettsäuren, Alkylphenole, Kondensationsprodunkte von Ethylenoxid (EO) und Propylenoxid (PO), z.B. auch in Form von EO/PO-Blockcopoly- meren, Polyethylenimine oder auch Polysiloxane.Demulsifiers are substances which cause the separation of an emulsion. These may be both ionogenic and non-ionic substances which are effective at the phase boundary. Accordingly, basically all surface-active substances are suitable as demulsifiers. Particularly suitable demulsifiers are selected from anion-active compounds such as the alkali or alkaline earth salts of alkyl-substituted phenol and naphthalenesulfonates and the alkali or alkaline earth salts of fatty acids, as well as neutral compounds such as alcohol alkoxylates, e.g. Alcohol ethoxylates, phenol alkoxylates, e.g. tert-butylphenol ethoxylate or tert-pentylphenol ethoxylate, fatty acids, alkylphenols, condensation products of ethylene oxide (EO) and propylene oxide (PO), e.g. also in the form of EO / PO block copolymers, polyethyleneimines or else polysiloxanes.
Die Additivzusammensetzung und der Kraftstoff können darüber hinaus mit weiteren üblichen Komponenten und Additiven kombiniert werden. Hier sind beispielsweise Trägeröle ohne ausgeprägte Detergenswirkung zu nennen, wobei diese insbesondere beim Einsatz in Otto kraftstoff zum Tragen kommen. Gelegentlich kommen sie aber auch in Mitteldestillaten zum Einsatz.The additive composition and the fuel can also be combined with other conventional components and additives. Here are, for example, carrier oils without pronounced detergent action to name, and these come in particular when used in petrol fuel to fruition. Occasionally, however, they are also used in middle distillates.
C) TrägeröleC) carrier oils
Trägeröle gelangen meist in Kombination mit Detergensadditiven zur Anwendung und üben mit diesen eine Lösungsmittel- oder Waschfunktion aus. Trägeröle sind in der Regel hochsiedende, viskose, thermostabile Flüssigkeiten, welche eine heiße Metalloberfläche überziehen und dadurch die Bildung oder Ablagerung von Verunreinigungen auf der Metalloberfläche verhindern.Carrier oils are usually used in combination with detergent additives and exercise with these a solvent or washing function. Carrier oils are typically high boiling, viscous, thermostable liquids which coat a hot metal surface and thereby prevent the formation or deposition of contaminants on the metal surface.
Geeignete mineralische Trägeröle sind bei der Erdölverarbeitung anfallende Fraktio- nen, wie Brightstock oder Grundöle mit Viskositäten wie beispielsweise aus der Klasse SN 500 - 2000; aber auch aromatische Kohlenwasserstoffe, paraffinische Kohlenwasserstoffe und Alkoxyalkanole. Brauchbar ist ebenfalls eine als "hydrocrack oil" bekannte und bei der Raffination von Mineralöl anfallende Fraktion (Vakuumdestillatschnitt mit einem Siedebereich von etwa 360 bis 5000C, erhältlich aus unter Hochdruck kataly- tisch hydriertem und isomerisiertem sowie entparaffiniertem natürlichen Mineralöl). Ebenfalls geeignet sind Mischungen oben genannter mineralischer Trägeröle.Suitable mineral carrier oils are fractions obtained in petroleum processing, such as bright stock or base oils with viscosities such as from class SN 500-2000; but also aromatic hydrocarbons, paraffinic hydrocarbons and alkoxyalkanols. Useful is also a technique known as "hydrocrack oil" and obtained in the refining of mineral oil fraction (vacuum distillate cut having a boiling range of about 360-500 0 C, available natural out catalytic high pressure table hydrogenated and isomerized and also deparaffinized mineral oil). Also suitable are mixtures of the abovementioned mineral carrier oils.
Beispiele für erfindungsgemäß verwendbare synthetische Trägeröle sind ausgewählt unter: Polyolefinen (Polyalphaolefine oder Polyintemalolefine), (Poly)estern, (Poly)alko- xylaten, Polyethem, aliphatischen Polyetheraminen, alkylphenolgestarteten Polyethem, alkylphenolgestarteten Polyetheraminen und Carbonsäureester langkettiger Alkanole. Beispiele für geeignete Polyolefine sind Olefinpolymerisate mit Mn = 400 bis 1800, vor allem auf Polybuten- oder Polyisobuten-Basis (hydriert oder nicht hydriert).Examples of synthetic carrier oils which can be used according to the invention are selected from polyolefins (polyalphaolefins or polyethylenemolefins), (poly) esters, (poly) acrylates, polyethers, aliphatic polyetheramines, alkylphenol-initiated polyethers, alkylphenol-initiated polyetheramines and carboxylic acid esters of long-chain alkanols. Examples of suitable polyolefins are olefin polymers having Mn = 400 to 1800, especially based on polybutene or polyisobutene (hydrogenated or non-hydrogenated).
Beispiele für geeignete Polyether oder Polyetheramine sind vorzugsweise Polyoxy-C2- C4-alkylengruppierungen enthaltende Verbindungen, welche durch Umsetzung von C2- Cβo-Alkanolen, Cβ-Cso-Alkandiolen, Mono- oder Di-C2-C3o-alkylaminen, Ci-C3o-Alkyl- cyclohexanolen oder Ci-C3o-Alkylphenolen mit 1 bis 30 mol Ethylenoxid und/ oder Pro- pylenoxid und/oder Butylenoxid pro Hydroxylgruppe oder Aminogruppe und, im Falle der Polyetheramine, durch anschließende reduktive Aminierung mit Ammoniak, Mono- aminen oder Polyaminen erhältlich sind. Derartige Produkte werden insbesondere in EP-A 310 875, EP-A 356 725, EP-A 700 985 und US-A 4 877 416 beschrieben. Beispielsweise können als Polyetheramine Poly-C2-C6-Alkylenoxidamine oder funktionelle Derivate davon verwendet werden. Typische Beispiele hierfür sind Tridecanol- oder Isotridecanolbutoxylate, Isononylphenolbutoxylate sowie Polyisobutenolbutoxylate und -propoxylate sowie die entsprechenden Umsetzungsprodukte mit Ammoniak.Examples of suitable polyethers or polyetheramines are preferably compounds containing polyoxy-C 2 -C 4 -alkylene groups, which are prepared by reacting C 2 -C 6 -alkanols, C 6 -C 50 -alkanediols, mono- or di-C 2 -C 30 -alkylamines, C 1 -C 30 -alkyl - Cyclohexanolen or Ci-C3o-Alkylphenolen with 1 to 30 mol of ethylene oxide and / or propylene oxide and / or butylene oxide per hydroxyl group or amino group and, in the case of polyether amines, by subsequent reductive amination with ammonia, mono amines or polyamines are available. Such products are described in particular in EP-A 310 875, EP-A 356 725, EP-A 700 985 and US-A 4,877,416. For example, as polyetheramines, poly-C 2 -C 6 -alkylene oxide amines or functional derivatives thereof can be used. Typical examples of these are tridecanol or Isotridecanolbutoxylate, Isononylphenolbutoxylate and Polyisobutenolbutoxylate and propoxylates and the corresponding reaction products with ammonia.
Beispiele für Carbonsäureester langkettiger Alkanole sind insbesondere Ester aus Mono-, Di- oder Tricarbonsäuren mit langkettigen Alkanolen oder Polyolen , wie sie insbesondere in der DE-A 38 38 918 beschrieben sind. Als Mono-, Di- oder Tricarbonsäuren können aliphatische oder aromatische Säuren eingesetzt werden, als Esteralkohole bzw. -polyole eignen sich vor allem langkettige Vertreter mit beispielsweise 6 bis 24 C- Atomen. Typische Vertreter der Ester sind Adipate, Phthalate, iso-Phthalate, Tereph- thalate und Trimellitate des Isooctanols, Isononanols, Isodecanols und des Isotrideca- nols, wie z.B. Di-(n- oder lso-tridecyl)-phthalat.Examples of carboxylic acid esters of long-chain alkanols are in particular esters of mono-, di- or tricarboxylic acids with long-chain alkanols or polyols, as described in particular in DE-A 38 38 918. As mono-, di- or tricarboxylic acids it is possible to use aliphatic or aromatic acids, especially suitable ester alcohols or polyols are long-chain representatives having, for example, 6 to 24 carbon atoms. Typical representatives of the esters are adipates, phthalates, isophthalates, terephthalates and trimellitates of isooctanol, isononanol, isodecanol and isotridecanol, such as e.g. Di (n- or iso-tridecyl) phthalate.
Weitere geeignete Trägerölsysteme sind beispielsweise beschrieben inOther suitable carrier oil systems are described, for example, in
DE-A 38 26 608, DE-A 41 42 241 , DE-A 43 09 074, EP-A 452 328 und EP-A 548 617, worauf hiermit ausdrücklich Bezug genommen wird.DE-A 38 26 608, DE-A 41 42 241, DE-A 43 09 074, EP-A 452 328 and EP-A 548 617, to which reference is hereby expressly made.
Beispiele für besonders geeignete synthetische Trägeröle sind alkoholgestartete Polyether mit etwa 5 bis 35, wie z.B. etwa 5 bis 30, C3-C6-Alkylenoxideinheiten, wie z.B. ausgewählt unter Propylenoxid-, n-Butylenoxid- und i-Butylenoxid-Einheiten, oder Gemischen davon. Nichtlimitierende Beispiele für geeignete Starteralkohole sind langkettige Alkanole oder mit langkettigem Alkyl substituierte Phenole, wobei der langkettige Alkylrest insbesondere für einen geradkettigen oder verzweigten C6-Ci8-Alkylrest steht. Als bevorzugte Beispiele sind zu nennen Tridecanol und Nonylphenol.Examples of particularly suitable synthetic carrier oils are alcohol-started polyethers having about 5 to 35, such as about 5 to 30, C 3 -C 6 alkylene oxide units, for example selected from propylene oxide, n-butylene oxide and i-butylene oxide units, or mixtures from that. Nonlimiting examples of suitable starter alcohols are long-chain alkanols or long-chain alkyl-substituted phenols, where the long-chain alkyl radical is in particular a straight-chain or branched C 6 -C 18 -alkyl radical. Preferred examples are tridecanol and nonylphenol.
Weitere geeignete synthetische Trägeröle sind alkoxylierte Alkylphenole, wie sie in der DE-A 10 102 913 beschrieben sind. D) Weitere AdditiveFurther suitable synthetic carrier oils are alkoxylated alkylphenols, as described in DE-A 10 102 913. D) Further additives
Weitere übliche Additive sind die Kälteeigenschaften des Kraftstoffs verbessernde Additive, z.B. Nukleatoren, Fließverbesserer, Paraffindispergatoren und deren Gemische, z.B. Ethylen-Vinylacetat-Copolymere; Korrosionsinhibitoren, beispielsweise auf Basis von zur Filmbildung neigenden Ammoniumsalzen organischer Carbonsäuren oder von heterocyclischen Aromaten im Falle von Buntmetallkorrosionsschutz; Dehazer; Anti- schaummittel, z.B. bestimmte Siloxanverbindungen; Cetanzahlverbesserer (Zündfähig- keitsverbesserer); Verbrennungsverbesserer; Antioxidantien oder Stabilisatoren, bei- spielsweise auf Basis von Aminen wie p-Phenylendiamin, Dicyclohexylamin oder Derivaten hiervon oder von Phenolen wie 2,4-Di-tert-butylphenol oder 3,5-Di-tert-butyl-4- hydroxyphenylpropionsäure; Antistatikmittel; Metallocene wie Ferrocen; Methylcyclo- pentadienylmangantricarbonyl; Schmierfähigkeitsverbesserer, z.B. bestimmte Fettsäuren, Alkenylbernsteinsäureester, Bis(hydroxyalkyl)fettamine, Hydroxyacetamide oder Ricinusöl; sowie Farbstoffe (Marker). Gegebenenfalls werden auch Amine zur Absenkung des pH-Wertes des Kraftstoffes zugesetzt.Further common additives are the cold properties of the fuel-improving additives, e.g. Nucleators, flow improvers, paraffin dispersants and mixtures thereof, e.g. Ethylene-vinyl acetate copolymers; Corrosion inhibitors, for example based on film-forming ammonium salts of organic carboxylic acids or of heterocyclic aromatics in the case of non-ferrous metal corrosion protection; dehazers; Anti-foaming agent, e.g. certain siloxane compounds; Cetane number improvers (ignitability improvers); combustion improvers; Antioxidants or stabilizers, for example based on amines such as p-phenylenediamine, dicyclohexylamine or derivatives thereof or of phenols such as 2,4-di-tert-butylphenol or 3,5-di-tert-butyl-4-hydroxyphenylpropionic acid; Antistatic agents; Metallocenes such as ferrocene; Methylcyclopentadienyl manganese tricarbonyl; Lubricity improver, e.g. certain fatty acids, alkenyl succinic esters, bis (hydroxyalkyl) fatty amines, hydroxyacetamides or castor oil; as well as dyes (markers). Optionally, amines are added to lower the pH of the fuel.
Geeignete Verdünnungs- und Lösungsmittel sind beispielsweise aromatische und aliphatische Kohlenwasserstoffe, beispielsweise Cs-Cio-Alkane, wie Pentan, Hexan, Heptan, Octan, Nonan, Decan, deren Konstitutionsisomere und Gemische; Petrolether, Aromaten, wie Benzol, Toluol, XyIoIe und Solvent Naphtha; Alkanole mit 3 bis 8 Kohlenstoffatomen, z. B. Propanol, Isopropanol, n-Butanol, sec-Butanol, Isobutanol und dergleichen, in Kombination mit Kohlenwasserstoff-Lösungsmitteln; und Alkoxyalkano- Ie. Geeignete Verdünnungsmittel sind beispielsweise auch bei der Erdölverarbeitung anfallende Fraktionen, wie Kerosin, Naphtha oder Brightstock. Bei Mitteldestillaten, insbesondere bei Dieselkraftstoffen und Heizölen bevorzugt verwendete Verdünnungsmittel sind Naphtha, Kerosin, Dieselkraftstoffe, aromatische Kohlenwasserstoffe, wie Solvent Naphtha schwer, Solvesso® oder Shellsol® sowie Gemische dieser Lösungsund Verdünnungsmittel.Suitable diluents and solvents are, for example, aromatic and aliphatic hydrocarbons, for example Cs-Cio-alkanes, such as pentane, hexane, heptane, octane, nonane, decane, their constitution isomers and mixtures; Petroleum ethers, aromatics such as benzene, toluene, xylene and solvent naphtha; Alkanols of 3 to 8 carbon atoms, e.g. Propanol, isopropanol, n-butanol, sec-butanol, isobutanol and the like, in combination with hydrocarbon solvents; and alkoxyalkanoethylene. Suitable diluents are, for example, fractions obtained in petroleum processing, such as kerosene, naphtha or bright stock. When middle distillates, especially in diesel fuels and heating oils preferred diluent used are naphtha, kerosene, diesel fuels, aromatic hydrocarbons such as Solvent Naphtha heavy, Solvesso ® or Shellsol ®, as well as mixtures of these solvents and diluents.
Wenn Detergensadditive, z.B. solche mit den polaren Gruppierungen (a) bis (i), im Kraftstoff, insbesondere in Dieselkraftstoff oder Ottokraftstoff, verwendet werden, so werden sie dem Kraftstoff üblicherweise in einer Menge von 10 bis 5000 Gew.-ppm, insbesondere 50 bis 1000 Gew.-ppm, zugegeben.When detergent additives, e.g. those with the polar groupings (a) to (i), in the fuel, in particular in diesel fuel or gasoline, are used, they are the fuel usually in an amount of 10 to 5000 ppm by weight, especially 50 to 1000 parts by weight. ppm, added.
Wenn Demulgatoren verwendet werden, so werden sie dem Kraftstoff üblicherweise in einer Menge von 0,1 bis 100 Gew.-ppm, insbesondere 0,2 bis 10 Gew.-ppm, zugegeben.When demulsifiers are used, they are usually added to the fuel in an amount of 0.1 to 100 ppm by weight, especially 0.2 to 10 ppm by weight.
Die sonstigen erwähnten Komponenten und Additive werden, wenn gewünscht, in hierfür üblichen Mengen zugesetzt. Weiterhin ist Gegenstand der vorliegenden Erfindung die Verwendung des beschriebenen Verfahrens zum qualitativen oder quantitativen Nachweis einer Kraftstoffadditiv- Komponente in einem die Kraftstoffadditiv-Komponente und gegebenenfalls weitere Kraftstoffadditiv-Komponenten enthaltenden Dieselkraftstoff oder Ottokraftstoff als Ana- lyten.The other components and additives mentioned are added, if desired, in customary amounts. Furthermore, the subject of the present invention is the use of the described method for the qualitative or quantitative detection of a fuel additive component in a diesel fuel or gasoline containing the fuel additive component and optionally further fuel additive components as analytes lyte.
Das erfindungsgemäße Verfahren ist ein einfach durchzuführendes Nachweisverfahren für eine Kraftstoffadditiv-Komponenten, insbesondere ein basisches Detergensadditiv, in einem Kraftstoffadditiv-Paket oder im Kraftstoff selbst und kann auch „vor Ort", d.h. in der Raffinerie oder an der Tankstelle, mit einfachen messtechnischen Mitteln durchgeführt werden. Das Nachweisverfahren ist dabei weitgehend unabhängig von der Herkunft der jeweiligen Kraftstoffsorte, d.h. die Zusammensetzung des jeweiligen Kraftstoffes hat keinen Einfluß auf durch die Wechselwirkung zwischen Kraftstoffadditiv-Komponente und Indikator hervorgerufene Änderung der Farbeigenschaften des Indikators im Analyten.The method according to the invention is a simple detection method for a fuel additive component, in particular a basic detergent additive, in a fuel additive package or in the fuel itself and can also be carried out "on site", ie in the refinery or at the filling station, with simple measuring instruments The detection method is largely independent of the origin of the respective fuel grade, ie the composition of the respective fuel has no influence on the interaction between the fuel additive component and the indicator caused change in the color properties of the indicator in the analyte.
Beispielexample
Quantitativer Nachweis eines Polyisobutenyl-substituierten Bernsteinsäureimid- Detergensadditivs in DieselkraftstoffQuantitative detection of a polyisobutenyl-substituted succinimide detergent additive in diesel fuel
Proben von handelsüblichem unadditiviertem Dieselkraftstoff aus verschiedenen Raffinerien und Raffinerieschnitten wurden mit jeweils den gleichen Mengen eines Deter- gensadditives auf Basis des Imides aus Polyisobutenylbemsteinsäureanhydrid (zahlen- gemitteltes Molekulargewicht des Polyisobutenyl-Restes: ca. 1000) und Tetraethylen- pentamin, welches in Form eines üblichen Diesel-Performance-Paketes zugesetzt wurde, in praxisnahen Mengen additiviert. Aus den mit den unterschiedlichen Dosierraten des Detergensadditivs in den einzelnen Dieselkraftstoff-Proben (Analyten) in einem handelsüblichen Photometer bestimmten Extinktionswerten wurde eine entsprechende Eichkurve für den Bereich von 0 bis 170 Gew.-ppm Detergensadditiv (bezogen auf Wirksubstanz) erstellt. Als Indikator für die photometrische Bestimmung wurden 1,0 ml einer ethanolischen Bromkresolgrün-Lösung (13 mg Bromkresolgrün in 100 ml Ethanol, rotorange Lösung) auf 10 ml additivierten Dieselkraftstoff zugegeben. Die Messungen wurden nach erfolgtem Farbumschlag im Analyten von gelb nach blau, welcher durch intensives Schütteln der Proben mit der Indikatorlösung in einem Meßkolben ausgelöst und vervollständigt wurde, in einer 1 ml-Küvette bei einer Wellenlänge von 620 nm durchgeführt.Samples of commercially available unadditized diesel fuel from various refineries and refinery cuts were each mixed with the same amounts of a detergent additive based on the imide of polyisobutenylsuccinic anhydride (number average molecular weight of the polyisobutenyl radical: about 1000) and tetraethylene pentamine, which is in the form of a conventional Diesel performance package was added, additized in practical quantities. From the extinction values determined with the different dosing rates of the detergent additive in the individual diesel fuel samples (analytes) in a commercially available photometer, a corresponding calibration curve for the range from 0 to 170 ppm by weight of detergent additive (based on active substance) was prepared. As an indicator for the photometric determination, 1.0 ml of an ethanolic bromocresol green solution (13 mg bromocresol green in 100 ml ethanol, red-orange solution) was added to 10 ml of additized diesel fuel. The measurements were carried out after a color change in the analyte from yellow to blue, which was initiated and completed by vigorously shaking the sample with the indicator solution in a volumetric flask, in a 1 ml cuvette at a wavelength of 620 nm.
Aus der Korrelation zu der erstellten Eichkurve konnten nun mit der oben geschilderten Meßmethode Dieselkraftstoff-Proben, die das oben genannte Detergensadditiv in unbekannter Menge neben weiteren Kraftstoffaddtiven enthielten, die Mengen dieses Detergensadditivs quantitativ mit einer Genauigkeit von ±10 % bestimmt werden. From the correlation to the established calibration curve, with the measurement method described above, diesel fuel samples containing the above-mentioned detergent additive in an unknown amount besides other fuel additives could quantitatively determine the amounts of this detergent additive with an accuracy of ± 10%.

Claims

Patentansprüche claims
1. Verfahren zum qualitativen oder quantitativen Nachweis einer Kraftstoffadditiv- Komponente, die Bestandteil eines Kraftstoff und/oder weitere Kraftstoffadditiv- Komponenten enthaltenden Analyten ist, dadurch gekennzeichnet, dass man den1. A method for the qualitative or quantitative detection of a fuel additive component which is part of a fuel and / or other fuel additive components containing analyte, characterized in that the
Analyten mit einem Indikator in Kontakt bringt und die durch die Wechselwirkung zwischen Kraftstoffadditiv-Komponente und Indikator hervorgerufene Änderung der Farbeigenschaften des Indikators im Analyten bestimmt.Analytes with an indicator in contact and determines the caused by the interaction between the fuel additive component and indicator change in the color properties of the indicator in the analyte.
2. Verfahren nach Anspruch 1 , dadurch gekennzeichnet, dass man als Indikator einen Säure-Base-Indikator einsetzt.2. The method according to claim 1, characterized in that one uses as indicator an acid-base indicator.
3. Verfahren nach Anspruch 2, dadurch gekennzeichnet, dass man als Säure-Base- Indikator Bromkresolgrün, α-Naphthylrot, 2,5-Dinitrophenyl, Mischindikator 5 oder Methylrot einsetzt.3. The method according to claim 2, characterized in that one uses as acid-base indicator bromocresol green, α-naphthyl red, 2,5-dinitrophenyl, mixed indicator 5 or methyl red.
4. Verfahren zum quantitativen Nachweis einer Kraftstoffadditiv-Komponente nach den Ansprüchen 1 bis 3, dadurch gekennzeichnet, dass man die Intensität der Färbung nach erfolgter Änderung der Farbeigenschaften im Analyten photomet- risch bestimmt.4. A method for the quantitative detection of a fuel additive component according to claims 1 to 3, characterized in that one determines the intensity of the color after changing the color properties in the analyte photometrically.
5. Verfahren nach den Ansprüchen 1 bis 4, dadurch gekennzeichnet, dass man als Analyten Dieselkraftstoff oder Ottokraftstoff einsetzt, welcher neben der nachzuweisenden Kraftstoffadditiv-Komponente gegebenenfalls weitere Kraftstoffadditiv- Komponenten enthält.5. The method according to claims 1 to 4, characterized in that one uses as an analyte diesel fuel or gasoline, which optionally contains further fuel additive components in addition to the fuel additive component to be detected.
6. Verfahren nach den Ansprüchen 1 bis 5 zum Nachweis einer polaren Kraftstoffadditiv-Komponente mit Detergenswirkung.6. Process according to claims 1 to 5 for the detection of a polar fuel additive component with detergent effect.
7. Verfahren nach den Ansprüchen 1 bis 6 zum Nachweis einer polaren Kraftstoffadditiv-Komponente mit Detergenswirkung mit aus Bernsteinsäureanhydrid abgeleiteten Gruppierungen mit Hydroxy- und/oder Amino- und/oder Am ido- und/oder Imidogruppen.7. Process according to claims 1 to 6 for the detection of a polar fuel additive component with detergent action with derived from succinic anhydride moieties having hydroxy and / or amino and / or amido and / or imido groups.
8. Verfahren nach Anspruch 7 zum Nachweis von Polyisobutenyl-substituierten8. The method according to claim 7 for the detection of polyisobutenyl-substituted
Bemsteinsäureimiden als polare Kraftstoffadditiv-Komponente mit Detergenswirkung.Succinimides as a polar fuel additive component with detergent action.
9. Verwendung des Verfahrens gemäß den Ansprüchen 1 bis 8 zum qualitativen oder quantitativen Nachweis einer Kraftstoffadditiv-Komponente in einem die9. Use of the method according to claims 1 to 8 for the qualitative or quantitative detection of a fuel additive component in a
Kraftstoffadditiv-Komponente und gegebenenfalls weitere Kraftstoffadditiv- Komponenten enthaltenden Dieselkraftstoff oder Ottokraftstoff als Analyten. Fuel additive component and possibly further fuel additive components containing diesel fuel or gasoline as the analyte.
EP06792588A 2005-08-03 2006-07-27 Method for detecting a fuel additive component Ceased EP1913369A1 (en)

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