EP0050289B1 - Gasoline compositions - Google Patents

Gasoline compositions Download PDF

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Publication number
EP0050289B1
EP0050289B1 EP81108217A EP81108217A EP0050289B1 EP 0050289 B1 EP0050289 B1 EP 0050289B1 EP 81108217 A EP81108217 A EP 81108217A EP 81108217 A EP81108217 A EP 81108217A EP 0050289 B1 EP0050289 B1 EP 0050289B1
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EP
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Prior art keywords
weight
gasoline
boric acid
water
carbon atoms
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EP81108217A
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German (de)
French (fr)
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EP0050289A1 (en
Inventor
Horst Lorke
Klaus Dr. Ulm
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Hoechst AG
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Hoechst AG
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/30—Organic compounds compounds not mentioned before (complexes)
    • C10L1/301—Organic compounds compounds not mentioned before (complexes) derived from metals
    • C10L1/303—Organic compounds compounds not mentioned before (complexes) derived from metals boron compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/12—Inorganic compounds
    • C10L1/1233—Inorganic compounds oxygen containing compounds, e.g. oxides, hydroxides, acids and salts thereof
    • C10L1/125—Inorganic compounds oxygen containing compounds, e.g. oxides, hydroxides, acids and salts thereof water
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/182—Organic compounds containing oxygen containing hydroxy groups; Salts thereof
    • C10L1/1822—Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms
    • C10L1/1824—Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms mono-hydroxy

Definitions

  • the invention relates to gasoline mixtures consisting essentially of gasoline and short-chain alcohols, the miscibility in the presence of water being achieved with the aid of water acceptors.
  • alcohol-containing fuels for internal combustion engines, in particular for motor vehicle engines, is increasing to an increasing extent. More or less large amounts of short-chain, straight or branched aliphatic alcohols are added to the gasoline.
  • Mixtures of petrol and alcohols can also contain more or less large amounts of water.
  • the water content results, for example, from the fact that the hydrophilic alcohols attract water from the air.
  • the air During the course of the distribution and storage of the fuel, there is usually contact with the air, so that a certain water content in an alcohol-containing gasoline is inevitable.
  • the alcohol-containing gasoline can also be absorbed here.
  • the miscibility of mixtures of gasoline and alcohols, and in particular the miscibility of gasoline and alcohols with water leaves something to be desired. In such mixtures, phase separation usually occurs more or less quickly depending on the temperature.
  • phase separation depends in particular on the amount of water and the temperature of the mixture. In winter, segregation can occur even with relatively low water contents, for example with less than 0.1% by weight of water.
  • the lowest possible segregation temperature (characterized by the cloud point of the mixture) is required for gasoline-alcohol-water mixtures, even at relatively high water contents.
  • attempts have already been made to lower the cloud point by adding a fourth component to the hydrocarbon-alcohol-water mixture.
  • European patent specification 0012345 recommends adding an adduct of ethylene oxide or propylene oxide to a carboxamide having 8 to 22 carbon atoms in an effective amount, which acts as an emulsifier, as a further component in water-containing alcohol-gasoline mixtures.
  • German Offenlegungsschrift 30 04 115 describes water-containing ethanol-gasoline mixtures which contain an effective amount of alkyl tert-butyl ether as the solvent-imparting component.
  • Gasoline-alcohol mixtures added to solve the phase separation problem should not only solve this problem, but also meet a number of other requirements. Among other things, they should at least not lower the octane number of the gasoline, should not separate even after a long storage period and, in particular, should not have a corrosive effect, especially on steel, cast iron and aluminum.
  • the object of the invention is therefore to propose substances which solve the problem of phase separation in gasoline-alcohol and in gasoline-alcohol-water mixtures and, moreover, meet the above-mentioned requirements, especially the requirement for anti-corrosivity.
  • the object of the invention is in particular to propose gasoline-alcohol mixtures in which no phase separation occurs even at a relatively high water content and at low temperatures.
  • boric acid esters of monohydric or polyhydric alcohols are particularly suitable for achieving the object.
  • a gasoline mixture consisting essentially of gasoline and short-chain alcohols, characterized in that it additionally contains at least one boric acid ester as an emulsifier and water serum acceptor in an effective amount which has been formed by reacting boric acid and monohydric to trihydric alcohols .
  • boric acid esters which have been formed by reacting boric acid and a mono- to trihydric alcohol in a molar ratio of 1: 0.5 to 1: 6.
  • OR 'groups are the same or different. In the case of mixed OR 'groups, those with oxethylene and oxpropylene are preferred.
  • the effective amount of boric acid esters to be used according to the invention is generally 0.05 to 5% by weight, preferably 0.1 to 2% by weight, based on the weight of the gasoline-alcohol mixture.
  • gasoline includes the gasolines which are generally customary for internal combustion engines.
  • gasolines consist essentially of a hydrocarbon mixture with a boiling range within 30 to 250 ° C.
  • the problems outlined above are particularly present in gasolines with no or only a low aromatic content, because the solubility of water-containing alcohols is particularly limited in these gasolines.
  • short-chain, straight or branched aliphatic alcohols are used for mixing with gasolines.
  • they are alcohols with 1 to 5 carbon atoms, preferably methanol, ethanol or mixtures thereof.
  • the amount of alcohol is more or less depending on the intended purpose. It is 10 to 30 wt .-%, based on the weight of the gasoline-alcohol mixture.
  • the amount of water that gasoline-alcohol mixtures can contain can vary within wide limits. It is generally from 0.01 to 10% by weight, preferably from 0.05 to 1% by weight, based on the weight of the gasoline-alcohol mixture.
  • the boric acid esters to be used according to the invention are prepared by reacting boric acid with the specified alcohols.
  • boric acid preferably orthoboric acid
  • the alcohol preferably alcohols of the formula RO- (R 1 O) x -H, where R, R 1 and x have the meaning given for formula I, in a molar ratio of 1: 0.5 to 1: 6, preferably 1: 1 to 1: 3, advantageously in a vessel equipped with a stirrer and optionally with a reflux condenser, the water of reaction formed being removed.
  • the reaction temperature is generally 50 to 150 ° C, preferably 110 to 140 ° C.
  • the removal of the water of reaction to the desired amount is preferably carried out continuously during the reaction with the aid of a vacuum (for example a water jet vacuum), which is generally about 500 to 1,500 Pa.
  • a vacuum for example a water jet vacuum
  • the removal of the water can also be carried out with the aid of an inert solvent which forms an azeotrope with water, for example toluene, xylene, methylene chloride and the like.
  • the solvent which may be used is removed from the reaction product by customary distillation and, if further purification should be necessary, it is expediently vacuum-stripped at a temperature of 90 to 150 ° C. (pressure about 1 to 500 Pa).
  • the gasoline mixtures according to the invention can also contain other useful components, for example the anti-knock agents and antioxidants customary for gasolines.
  • the gasoline mixtures according to the invention are produced simply by mixing the individual components. This can be done, for example, at room temperature in a container equipped with a stirrer.
  • the gasoline mixtures according to the invention have low cloud points even at high water contents and low temperatures, so they do not show any phase separation even at relatively low temperatures.
  • the boric acid esters according to the invention act as water acceptors and as emulsifiers. They also bind existing water chemically and not solely through physical forces, as the known emulsifiers and solvent-based substances do.
  • the unexpectedly advantageous effect of the boric acid esters proposed according to the invention is also evident in the fact that homogeneous gasoline-alcohol and gasoline-alcohol-water mixtures are achieved with comparatively small amounts.
  • These boric acid esters also have an anti-corrosive effect, so that the addition of such agents, which must be suitable for gasoline-alcohol mixtures, which is often not without problems, can be dispensed with.
  • Gasoline mixtures according to the invention were produced by mixing the components listed below and the cloud point (° C.) of these mixtures was measured.
  • the cloud point of this mixture is - 2.0 ° C.
  • the cloud point of this mixture is - 32.8 ° C.
  • the cloud point of this mixture is - 28.5 ° C.
  • the cloud point of this mixture is - 11.9 ° C.
  • the cloud point of this mixture is - 15.9 ° C.
  • the cloud point of this mixture is - 13.5 ° C.
  • the cloud point of this mixture is - 12.3 ° C.
  • the cloud point of this mixture is - 26.0 ° C.
  • the cloud point of this mixture is - 12.9 ° C.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Liquid Carbonaceous Fuels (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Preparation Of Compounds By Using Micro-Organisms (AREA)
  • Solid Fuels And Fuel-Associated Substances (AREA)

Abstract

1. Gasoline composition consisting essentially of gasoline as the main component, a smaller amount of aliphatic alcohols having from 1 to 5 carbon atoms and boric acid esters as an additive, characterised in that it contains the aliphatic alcohols in an amount of from 10 to 30% by weight and boric acid esters of the general formula (HO)-3-n B-[(OR**1 )x -OR]n wherein R is alkyl with from 1 to 18 carbon atoms, R**1 is alkylene with from 2 to 5 carbon atoms, the OR**1 groups being the same or different from one another, x is 0 or an integer of from 1 to 10 and n is an integer of from 1 to 3, as emulsifier and water acceptor additive in an amount of from 0.05 to 5% by weight, the percentages by weight being in each case relative to the weight of gasoline and alcohol.

Description

. Die Erfindung betrifft Benzin-Mischungen, bestehend im wesentlichen aus Benzin und kurzkettigen Alkoholen, wobei die Mischbarkeit in Gegenwart von Wasser mit Hilfe von Wasserakzeptoren erreicht wird.. The invention relates to gasoline mixtures consisting essentially of gasoline and short-chain alcohols, the miscibility in the presence of water being achieved with the aid of water acceptors.

In zunehmendem Maße wächst das Interesse an alkoholhaltigen Kraftstoffen (Benzinen) für Verbrennungskraftmaschinen, insbesondere für Kraftfahrzeugmotoren. Dabei werden dem Benzin mehr oder weniger große Mengen an kurzkettigen, geraden oder verzweigten aliphatischen Alkoholen zugesetzt.Interest in alcohol-containing fuels (petrol) for internal combustion engines, in particular for motor vehicle engines, is increasing to an increasing extent. More or less large amounts of short-chain, straight or branched aliphatic alcohols are added to the gasoline.

Gemische aus Benzin und Alkoholen können jedoch auch mehr oder weniger große Mengen Wasser enthalten. Der Wassergehalt resultiert beispielsweise daraus, daß die hydrophilen Alkohole Wasser aus der Luft anziehen. Im Laufe der Verteilung und Lagerung des Kraftstoffes kommt es in der Regel zu einem Kontakt mit der Luft, so daß ein gewisser Wassergehalt in einem alkoholhaltigen Benzin unvermeidlich ist. Ferner liegt am Boden von bereits genutzen Vorratstanks häufig Wasser in Form von flachen Pfützen, so daß auch hier eine Wasseraufnahme des alkoholhaltigen Benzins erfolgen kann. Nun läßt aber die Mischbarkeit von Gemischen aus Benzin und Alkoholen, und insbesondere die Mischbarkeit von Benzin und Alkoholen mit Wasser zu wünschen übrig. In derartigen Gemischen tritt in der Regel je nach Temperatur mehr oder weniger rasch eine Phasentrennung auf. Es liegt auf der Hand, daß sich dies sehr nachteilig auf die Anwendung der in Rede stehenden benzin-Mischungen auswirkt. Die Tendenz zur Phasentrennung ist insbesondere von der Menge an Wasser und von der Temperatur der Mischung abhängig. So kann im Winter eine Entmischung schon bei relativ kleinen Wassergehalten, beispielsweise schon bei weniger als 0,1 Gew.-% Wasser, auftreten.Mixtures of petrol and alcohols can also contain more or less large amounts of water. The water content results, for example, from the fact that the hydrophilic alcohols attract water from the air. During the course of the distribution and storage of the fuel, there is usually contact with the air, so that a certain water content in an alcohol-containing gasoline is inevitable. Furthermore, there is often water in the form of shallow puddles on the bottom of storage tanks that are already in use, so that the alcohol-containing gasoline can also be absorbed here. Now, however, the miscibility of mixtures of gasoline and alcohols, and in particular the miscibility of gasoline and alcohols with water, leaves something to be desired. In such mixtures, phase separation usually occurs more or less quickly depending on the temperature. It is obvious that this has a very disadvantageous effect on the use of the gasoline mixtures in question. The tendency towards phase separation depends in particular on the amount of water and the temperature of the mixture. In winter, segregation can occur even with relatively low water contents, for example with less than 0.1% by weight of water.

Im Hinblick auf die geschilderten Verhältnisse wird bei Benzin-Alkohol-Wasser-Gemischen eine möglichst niedrige Entmischungstemperatur (charakterisiert durch den Trübungspunkt der Mischung) auch bei relativ hohen Wassergehalten gefordert. Um dieser Forderung nachzukommen, ist bereits versucht worden, durch Zugabe einer vierten Komponente zu dem Kohlenwasserstoff-Alkohol-WasserGemisch eine Erniedrigung des Trübungspunktes zu erreichen.In view of the conditions described, the lowest possible segregation temperature (characterized by the cloud point of the mixture) is required for gasoline-alcohol-water mixtures, even at relatively high water contents. In order to meet this requirement, attempts have already been made to lower the cloud point by adding a fourth component to the hydrocarbon-alcohol-water mixture.

So wird in der europäischen Patentschrift 0012345 empfohlen, wasserhaltigen Alkohol-Benzin-Gemischen als weitere Komponente ein Anlagerungsprodukt von Ethylenoxid oder Propylenoxid an ein Carbonsäureamid mit 8 bis 22 C-Atomen in einer wirksamen Menge zuzusetzen, das als Emulgator wirkt.European patent specification 0012345, for example, recommends adding an adduct of ethylene oxide or propylene oxide to a carboxamide having 8 to 22 carbon atoms in an effective amount, which acts as an emulsifier, as a further component in water-containing alcohol-gasoline mixtures.

In der deutschen Offenlegungsschrift 30 04 115 werden wasserhaltige Ethanol-Benzin-Mischungen beschrieben, die Alkyl-tert.-butylether als lösungsvermittelnde Komponente in wirksamer Menge enthalten.German Offenlegungsschrift 30 04 115 describes water-containing ethanol-gasoline mixtures which contain an effective amount of alkyl tert-butyl ether as the solvent-imparting component.

Die Komponenten, die wasserhaltigen. benzin-Alkohol-Mischungen zur Lösung des Phasentrennproblems zugesetzt werden, sollen nicht nur dieses Problem lösen, sondern auch noch eine Reihe von anderen Forderungen erfüllen. Sie sollen unter anderem die Octanzahl des Benzins zumindest nicht erniedrigen, sich auch bei langer Lagerzeit nicht abscheiden und insbesondere nicht korrosiv wirken, vor allem auf Stahl, Gußeisen und Aluminium.The components that contain water. Gasoline-alcohol mixtures added to solve the phase separation problem should not only solve this problem, but also meet a number of other requirements. Among other things, they should at least not lower the octane number of the gasoline, should not separate even after a long storage period and, in particular, should not have a corrosive effect, especially on steel, cast iron and aluminum.

Aufgabe der Erfindung ist es daher, solche Substanzen vorzuschlagen, die das Problem der Phasentrennung in Benzin-Alkohol- und in Benzin-Alkohol-Wasser-Gemischen lösen und darüberhinaus die obengenannten Forderungen, vor allem die Forderung nach Antikorrosivität erfüllen. Aufgabe der Erfindung ist es insbesondere, Benzin-Alkohol-Mischungen vorzuschlagen, in denen auch bei einem relativ hohen Wassergehalt und bei niedrigen Temperaturen keine Phasentrennung eintritt.The object of the invention is therefore to propose substances which solve the problem of phase separation in gasoline-alcohol and in gasoline-alcohol-water mixtures and, moreover, meet the above-mentioned requirements, especially the requirement for anti-corrosivity. The object of the invention is in particular to propose gasoline-alcohol mixtures in which no phase separation occurs even at a relatively high water content and at low temperatures.

Es wurde überraschenderweise gefunden, daß Borsäureester von ein- oder mehrwertigen Alkoholen besonders geeignet sind, die gestellte Aufgabe zu lösen.It has surprisingly been found that boric acid esters of monohydric or polyhydric alcohols are particularly suitable for achieving the object.

Gefunden wurde demnach eine Benzin-Mischung, bestehend im wesentlichen aus Benzin und kurzkettigen Alkoholen, dadurch gekennzeichnet, daß sie zusätzlich mindestens einen Borsäureester als Emulgator und Wasserserakzeptor in einer wirksamen Menge enthält, der durch umsetzen von Borsäure und ein- bis dreiwertigen Alkoholen gebildet worden ist.Accordingly, a gasoline mixture was found, consisting essentially of gasoline and short-chain alcohols, characterized in that it additionally contains at least one boric acid ester as an emulsifier and water serum acceptor in an effective amount which has been formed by reacting boric acid and monohydric to trihydric alcohols .

Erfindungsgemäß werden vorzugsweise solche Borsäureester eingesetzt, die durch Umsetzen von Borsäure und einem ein- bis dreiwertigen Alkohol im Molverhältnis von 1 : 0,5 bis 1 : 6 gebildet worden sind.According to the invention, preference is given to using boric acid esters which have been formed by reacting boric acid and a mono- to trihydric alcohol in a molar ratio of 1: 0.5 to 1: 6.

Besonders bevorzugt sind Borsäureester der nachstehenden allgemeinen Formel I

Figure imgb0001
worin bedeuten

  • R eine Alkylgruppe mit 1 bis 18 C-Atomen,
  • - Rl eine Alkylengruppe mit 2 bis 5 C-Atomen, wobei die OR'-Gruppen gleich oder verschieden sein können,
  • X 0 oder eine ganze Zahl von 1 bis 10, und
  • n eine ganze Zahl von 1 bis 3.
Boric acid esters of the general formula I below are particularly preferred
Figure imgb0001
 in what mean
  • R is an alkyl group with 1 to 18 carbon atoms,
  • Rl is an alkylene group with 2 to 5 carbon atoms, where the OR 'groups can be the same or different,
  • X is 0 or an integer from 1 to 10, and
  • n is an integer from 1 to 3.

Die Alkylgruppe R und die Alkylengruppe R1 können geradkettig oder verzweigt sein.

  • R bedeutet vorzugsweise eine Alkylgruppe mit 1 bis 8 C-Atomen.
  • R1 bedeutet vorzugsweise Ethylen oder Propylen.
  • X bedeutet vorzugsweise 0 oder eine ganze Zahl von 1 bis 3.
  • n bedeutet vorzugsweise 3.
The alkyl group R and the alkylene group R 1 can be straight-chain or branched.
  • R preferably denotes an alkyl group with 1 to 8 carbon atoms.
  • R 1 is preferably ethylene or propylene.
  • X is preferably 0 or an integer from 1 to 3.
  • n is preferably 3.

Die OR'-Gruppen sind gleich oder verschieden. Im Falle von gemischten OR'-Gruppen sind solche mit Oxethylen und Oxpropylen bevorzugt.The OR 'groups are the same or different. In the case of mixed OR 'groups, those with oxethylene and oxpropylene are preferred.

Die wirksame Menge an erfindungsgemäß einzusetzenden Borsäureestern beträgt im allgemeinen 0,05 bis 5 Gew.-%, vorzugsweise 0,1 bis 2 Gew.-%, bezogen auf das Gewicht der Benzin-Alkohol-Mischung.The effective amount of boric acid esters to be used according to the invention is generally 0.05 to 5% by weight, preferably 0.1 to 2% by weight, based on the weight of the gasoline-alcohol mixture.

Der Begriff Benzin umfaßt im Rahmen der vorliegenden Erfindung die für Verbrennungsmotoren allgemein üblichen Benzine. Benzine bestehen bekanntlich im wesentlichen aus einem Kohlenwasserstoff-Gemisch mit einem Siedebereich innerhalb von 30 bis 250 °C. Die geschilderten Probleme liegen vor allem bei Benzinen mit keinem oder nur einem geringen Gehalt an Aromaten vor, weil in diesen Benzinen die Löslichkeit von wasserhaltigen Alkoholen besonders begrenzt ist.In the context of the present invention, the term gasoline includes the gasolines which are generally customary for internal combustion engines. As is known, gasolines consist essentially of a hydrocarbon mixture with a boiling range within 30 to 250 ° C. The problems outlined above are particularly present in gasolines with no or only a low aromatic content, because the solubility of water-containing alcohols is particularly limited in these gasolines.

Wie in den Ausführungen zum Stand der Technik bereits erwähnt worden ist, werden kurzkettige, gerade oder verzweige aliphatische Alkohole zur Abmischung mit Benzinen verwendet. im allgemeinen sind es Alkohole mit 1 bis 5 C-Atomen, vorzugsweise Methanol, Ethanol oder Gemische davon.As has already been mentioned in the comments on the prior art, short-chain, straight or branched aliphatic alcohols are used for mixing with gasolines. generally they are alcohols with 1 to 5 carbon atoms, preferably methanol, ethanol or mixtures thereof.

Die Menge an Alkohol ist je nach beabsichtigtem Zweck mehr oder weniger groß. Sie beträgt 10 bis 30 Gew.-%, bezogen auf das Gewicht der Benzin-Alkohol-Mischung.The amount of alcohol is more or less depending on the intended purpose. It is 10 to 30 wt .-%, based on the weight of the gasoline-alcohol mixture.

Die Menge an Wasser, die Benzin-Alkohol-Mischungen enthalten können, kann in weiten Grenzen variieren. Sie liegt im allgemeinen bei 0,01 bis 10 Gew.-%, vorzugsweise bei 0,05 bis 1 Gew.-%, bezogen auf das Gewicht der Benzin-Alkohol-Mischung.The amount of water that gasoline-alcohol mixtures can contain can vary within wide limits. It is generally from 0.01 to 10% by weight, preferably from 0.05 to 1% by weight, based on the weight of the gasoline-alcohol mixture.

Die erfindungsgemäß zu verwendenden Borsäureester werden durch Reaktion von Borsäure mit den angegebenen Alkoholen hergestellt. Dazu werden Borsäure, vorzugsweise Orthoborsäure, und der Alkohol, vorzugsweise Alkohole der Formel RO-(R1O)x-H, worin R, R1 und x die bei Formel I angegebene Bedeutung haben, im Molverhältnis von 1 : 0,5 bis 1 : 6, vorzugsweise 1 : 1 bis 1 : 3, zweckmäßigerweise in einem mit Rührer und gegebenenfalls mit Rückflußkühler ausgestatteten Gefäß umgesetzt, wobei das entstehende Reaktionswasser entfernt wird. Die Reaktionstemperatur beträgt im allgemeinen 50 bis 150 °C, vorzugsweise 110 bis 140 °C. Die Entfernung des Reaktionswassers bis zur gewünschten Menge erfolgt vorzugsweise kontinuierlich während der Reaktion mit Hilfe von Vakuum (z. B. Wasserstrahlvakuum), das im allgemeinen etwa 500 bis 1 500 Pa beträgt. Die Entfernung des Wassers kann auch mit Hilfe eines inerten, mit Wasser ein Azeotrop bildenden Lösungsmittels, beispielsweise Toluol, Xylol, Methylenchlorid und dergleichen, durchgeführt werden.The boric acid esters to be used according to the invention are prepared by reacting boric acid with the specified alcohols. For this purpose, boric acid, preferably orthoboric acid, and the alcohol, preferably alcohols of the formula RO- (R 1 O) x -H, where R, R 1 and x have the meaning given for formula I, in a molar ratio of 1: 0.5 to 1: 6, preferably 1: 1 to 1: 3, advantageously in a vessel equipped with a stirrer and optionally with a reflux condenser, the water of reaction formed being removed. The reaction temperature is generally 50 to 150 ° C, preferably 110 to 140 ° C. The removal of the water of reaction to the desired amount is preferably carried out continuously during the reaction with the aid of a vacuum (for example a water jet vacuum), which is generally about 500 to 1,500 Pa. The removal of the water can also be carried out with the aid of an inert solvent which forms an azeotrope with water, for example toluene, xylene, methylene chloride and the like.

Nach Beendigung der Umsetzung wird das gegebenenfalls verwendete Lösungsmittel durch übliche Destillation vom Reaktionsprodukt entfernt und dieses - sofern noch eine weitere Reinigung erforderlich sein sollte - zweckmäßigerweise bei einer Temperatur von 90 bis 150 °C vakuumgestrippt (Druck etwa 1 bis 500 Pa).After the reaction has ended, the solvent which may be used is removed from the reaction product by customary distillation and, if further purification should be necessary, it is expediently vacuum-stripped at a temperature of 90 to 150 ° C. (pressure about 1 to 500 Pa).

Bei den beschriebenen Herstellungsverfahren wird man in der Regel ein Gemisch von verschiedenen Borsäurestern erhalten. Durch entsprechende Wahl der Reaktionsparameter, wie Molverhaltnis, Temperatur und Umsetzungsgrad (gemessen an der Menge des Reaktionswassers), bei der Umsetzung der trifunktionellen Borsäure mit den mono- bis trifunktionellen Alkoholen ist die Möglichkeit gegeben, auf eine vollständige oder partielle Veresterung hinzusteuern und damit gleichsam strukturell maßgeschneiderte Borsäureester oder Borsäureestermischungen herzustellen.In the production processes described, a mixture of different boric acid esters is generally obtained. By appropriate selection of the reaction parameters, such as molar ratio, temperature and degree of conversion (measured by the amount of water of reaction), in the reaction of the trifunctional boric acid with the mono- to trifunctional alcohols, there is the possibility of controlling for a complete or partial esterification and thus, as it were, structurally to manufacture tailor-made boric acid esters or boric acid ester mixtures.

Die erfindungsgemäßen Benzinmischungen können noch weitere zweckmäßige Komponenten enthalten, beispielsweise die für Benzine üblichen Antiklopfmittel und Antioxidantien.The gasoline mixtures according to the invention can also contain other useful components, for example the anti-knock agents and antioxidants customary for gasolines.

Die Herstellung der erfindungsgemäßen Benzin-Mischungen erfolgt einfach durch Mischen der einzelnen Komponenten. Dies kann beispielsweise bei Raumtemperatur in einem mit Rührer ausgestatteten Behälter erfolgen.The gasoline mixtures according to the invention are produced simply by mixing the individual components. This can be done, for example, at room temperature in a container equipped with a stirrer.

Die erfindungsgemäßen Benzin-Mischungen weisen auch bei hohen Wassergehalten und niedrigen Temperaturen tiefe Trübungspunkte auf, sie zeigen also selbst bei relativ niedrigen Temperaturen keine Phasentrennung. Die erfindungsgemäßen Borsäureester wirken als Wasserakzeptor und als Emulgator. Sie binden vorhandenes Wasser auch chemisch und nicht allein durch physikalische Kräfte, wie es die bekannten Emulgatoren und lösungsvermitteinden Substanzen tun. Die unerwartet vorteilhafte Wirkung der erfindungsgemäß vorgeschlagenen Borsäureester zeigt sich auch darin, daß mit vergleichsweise geringen Mengen homogene Benzin-Alkohol- und Benzin-Alkohol-Wasser-Mischungen erzielt werden. Diese Borsäureester wirken darüberhinaus auch antikorrosiv, so daß ein häufig nicht unproblematischer Zusatz von derartigen Mitteln, die für Benzin-Alkohol-Gemische geeignet sein müssen, entfallen kann.The gasoline mixtures according to the invention have low cloud points even at high water contents and low temperatures, so they do not show any phase separation even at relatively low temperatures. The boric acid esters according to the invention act as water acceptors and as emulsifiers. They also bind existing water chemically and not solely through physical forces, as the known emulsifiers and solvent-based substances do. The unexpectedly advantageous effect of the boric acid esters proposed according to the invention is also evident in the fact that homogeneous gasoline-alcohol and gasoline-alcohol-water mixtures are achieved with comparatively small amounts. These boric acid esters also have an anti-corrosive effect, so that the addition of such agents, which must be suitable for gasoline-alcohol mixtures, which is often not without problems, can be dispensed with.

Die Erfindung wird nun durch die folgenden-Beispiele noch näher erläutert.The invention will now be explained in more detail by the following examples.

Es wurden erfindungsgemäße Benzin-Mischungen durch Mischen der nachstehend angeführten Komponenten hergestellt und der Trübungspunkt (°C) dieser Mischungen gemessen.Gasoline mixtures according to the invention were produced by mixing the components listed below and the cloud point (° C.) of these mixtures was measured.

Um einen Vergleich zu haben, wurde zunächst der Trübungspunkt der nachstehenden Mischung gemessen.To have a comparison, the cloud point of the mixture below was first measured.

VergleichsbeispielComparative example

  • 85 Gew.-Teile Benzin mit dem Siedepunktbereich von 40 bis 200 °C85 parts by weight of gasoline with a boiling point range of 40 to 200 ° C
  • 15 Gew.-Teile Methanol15 parts by weight of methanol
  • 0,25 Gew.-Teile Wasser0.25 parts by weight of water

Der Trübungspunkt dieser Mischung beträgt - 2,0 °C.The cloud point of this mixture is - 2.0 ° C.

Beispiel 1example 1

  • a) 85 Gew: Teile Benzin mit dem Siedebereich von 40 bis 200 °Ca) 85 parts by weight of gasoline with a boiling range of 40 to 200 ° C
  • b) 15 Gew.-Teile Methanolb) 15 parts by weight of methanol
  • c) 0,25 Gew.-Teile Wasserc) 0.25 part by weight of water
  • d) 1,5 Gew.-Teile Borsäureester: B-(O-ISO-C4H9)3·d) 1.5 parts by weight of boric acid ester: B- (O-ISO-C 4 H 9 ) 3

Der Trübungspunkt dieser Mischung beträgt - 32,8 °C.The cloud point of this mixture is - 32.8 ° C.

Beispiel 2Example 2

  • a) 85 Gew.-Teile Benzin mit dem Siedebereich von 40 bis 200 °Ca) 85 parts by weight of gasoline with a boiling range of 40 to 200 ° C.
  • b) 15 Gew.-Teile Methanolb) 15 parts by weight of methanol
  • c) 0,25 Gew.-Teile Wasserc) 0.25 part by weight of water
  • d) 1,5 Gew.-Teile Borsäureester : B―(O-iso-C8H17)3.d) 1.5 parts by weight of boric acid ester: B― (O-iso-C 8 H 17 ) 3 .

Der Trübungspunkt dieser Mischung beträgt - 28,5 °C.The cloud point of this mixture is - 28.5 ° C.

Beispiel 3Example 3

  • a) 85 Gew.-Teile Benzin mit dem Siedebereich von 40 bis 200 °Ca) 85 parts by weight of gasoline with a boiling range of 40 to 200 ° C.
  • b) 15 Gew.-Teile Methanolb) 15 parts by weight of methanol
  • c) 0,25 Gew.-Teile Wasserc) 0.25 part by weight of water
  • d) 1,0 Gew.-Teile Borsäureester: B-(OCH3)3,d) 1.0 part by weight of boric acid ester: B- (OCH 3 ) 3 ,

Der Trübungspunkt dieser Mischung beträgt - 11,9 °C.The cloud point of this mixture is - 11.9 ° C.

Beispiel 4Example 4

  • a) 85 Gew.-Teile Benzin mit dem Siedebereich von 40 bis 200 °Ca) 85 parts by weight of gasoline with a boiling range of 40 to 200 ° C.
  • b) 15 Gew.-Teile Methanolb) 15 parts by weight of methanol
  • c) 0,25 Gew,-Teile Wasserc) 0.25 part by weight of water
  • d) 1,5 Gew.-Teile Borsäureester: B-(OCH2CH2OCH3)3. d) 1.5 parts by weight of boric acid ester: B- (OCH 2 CH 2 OCH 3 ) 3 .

Der Trübungspunkt dieser Mischung beträgt - 15,9 °C.The cloud point of this mixture is - 15.9 ° C.

Beispiel 5Example 5

  • a) 85 Gew-Teile Benzin mit dem Siedebereich von 40 bis 200 °Ca) 85 parts by weight of gasoline with a boiling range of 40 to 200 ° C.
  • b) 15 Gew.-Teile Methanolb) 15 parts by weight of methanol
  • c) 0,25 Gew.-Teile Wasserc) 0.25 part by weight of water
  • d) 1,0 Gew.-Teil Borsäureester : -B-(OCH2CH2-OCH2CH2OCH3)3.d) 1.0 part by weight of boric acid ester: -B- (OCH 2 CH 2 -OCH 2 CH 2 OCH 3 ) 3 .

Der Trübungspunkt dieser Mischung beträgt - 13,5 °C.The cloud point of this mixture is - 13.5 ° C.

Beispiel 6Example 6

  • a) 85 Gew.-Teile Benzin mit dem Siedebereich von 40 bis 200 °Ca) 85 parts by weight of gasoline with a boiling range of 40 to 200 ° C.
  • b) 15 Gew.-Teile Methanolb) 15 parts by weight of methanol
  • c) 0,25 Gew.-Teile Wasserc) 0.25 part by weight of water
  • d) 0,5 Gew.-Teile Borsäureester: B-(O-iso-C9H19)3' d) 0.5 part by weight of boric acid ester: B- (O-iso-C 9 H 19 ) 3 '

Der Trübungspunkt dieser Mischung beträgt - 12,3 °C.The cloud point of this mixture is - 12.3 ° C.

Beispiel 7Example 7

  • a) 85 Gew.-Teile Benzin mit dem Siedebereich von 40 bis 200 °Ca) 85 parts by weight of gasoline with a boiling range of 40 to 200 ° C.
  • b) 15 Gew.-Teile Methanolb) 15 parts by weight of methanol
  • c) 0,25 Gew.-Teile Wasserc) 0.25 part by weight of water
  • d) 1,5 Gew: Teile Borsäureester: B-(O-iso-C13H27)3.d) 1.5% by weight: parts of boric acid ester: B- (O-iso-C 13 H 27 ) 3 .

Der Trübungspunkt dieser Mischung beträgt - 26,0 °C.The cloud point of this mixture is - 26.0 ° C.

Beispiel 8Example 8

  • a) 85 Gew.-Teile Benzin mit dem Siedebereich von 40 bis 200 °Ca) 85 parts by weight of gasoline with a boiling range of 40 to 200 ° C.
  • b) 15 Gew.-Teile Methanolb) 15 parts by weight of methanol
  • c) 0,25 Gew: Teile Wasserc) 0.25 wt: parts of water
  • d) 0,5 Gew.-Teile Borsäureester : B―(OC4H9)3.d) 0.5 part by weight of boric acid ester: B― (OC 4 H 9 ) 3 .

Der Trübungspunkt dieser Mischung beträgt - 12,9 °C.The cloud point of this mixture is - 12.9 ° C.

Claims (3)

1. Gasoline composition consisting essentially of gasoline as the main component, a smaller amount of aliphatic alcohols having from 1 to 5 carbon atoms and boric acid esters as an additive, characterised in that it contains the aliphatic alcohols in an amount of from 10 to 30 % by weight and boric acid esters of the general formula
Figure imgb0003
wherein
R is alkyl with from 1 to 18 carbon atoms,
R1 is alkylene with from 2 to 5 carbon atoms, the OR1 groups being the same or different from one another,
x is 0 or an integer of from 1 to 10 and
n is an integer of from 1 to 3,

as emulsifier and water acceptor additive in an amount of from 0.05 to 5 % by weight, the percentages by weight being in each case relative to the weight of gasoline and alcohol.
2. The gasoline composition as claimed in claim 1, wherein R is alkyl with from 1 to 8 carbon atoms, R1 is ethylene and/or propylene, x = 0 or an integer of from 1 to 3 and n is 3.
3. The gasoline composition as claimed in any of claims 1 and 2, wherein the quantity of boric acid ester is in the range of from 0.1 to 2 weight percent, calculated on the weight of gasoline and alcohol.
EP81108217A 1980-10-17 1981-10-12 Gasoline compositions Expired EP0050289B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT81108217T ATE7305T1 (en) 1980-10-17 1981-10-12 PETROL MIXTURES.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3039225 1980-10-17
DE19803039225 DE3039225A1 (en) 1980-10-17 1980-10-17 PETROL BLENDS

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EP0050289A1 EP0050289A1 (en) 1982-04-28
EP0050289B1 true EP0050289B1 (en) 1984-05-02

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EP (1) EP0050289B1 (en)
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AT (1) ATE7305T1 (en)
AU (1) AU7654381A (en)
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JP2582424B2 (en) * 1986-12-17 1997-02-19 ザ ルブリゾル コーポレーション Method of overbasing by forming metal borate
JP2509079B2 (en) * 1993-12-17 1996-06-19 株式会社東芝 Basic panel board unit and floor construction method using basic panel board unit

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DE539355C (en) * 1924-11-23 1931-11-27 Emilio Martin Flores Process for the production of a liquid fuel, particularly suitable as a propellant for engines
DE1033457B (en) * 1957-02-14 1958-07-03 Basf Ag Fuels
FR1199314A (en) * 1958-01-30 1959-12-14 Shell Res Ltd Advanced fuel compositions for internal combustion engines
DE1545482B1 (en) * 1964-12-16 1969-10-23 Aral Ag Improvement of the scavenging effect in leaded fuels for gasoline engines

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ZA817167B (en) 1982-10-27
EP0050289A1 (en) 1982-04-28
DE3039225A1 (en) 1982-04-29
AU7654381A (en) 1982-04-22
ATE7305T1 (en) 1984-05-15
BR8106689A (en) 1982-06-29
CA1181946A (en) 1985-02-05
DE3163413D1 (en) 1984-06-07

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