EP0263925A1 - Corrosion inhibitors for fuels - Google Patents

Corrosion inhibitors for fuels Download PDF

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Publication number
EP0263925A1
EP0263925A1 EP87110212A EP87110212A EP0263925A1 EP 0263925 A1 EP0263925 A1 EP 0263925A1 EP 87110212 A EP87110212 A EP 87110212A EP 87110212 A EP87110212 A EP 87110212A EP 0263925 A1 EP0263925 A1 EP 0263925A1
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EP
European Patent Office
Prior art keywords
corrosion inhibitor
methanol
fuels
ethanol
vol
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.)
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Application number
EP87110212A
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German (de)
French (fr)
Inventor
Charles Voegtlin
Hans Stettler
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Wintershall Dea International AG
Original Assignee
RWE Dea AG fuer Mineraloel und Chemie
Union Rheinische Braunkohlen Kraftstoff AG
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Publication of EP0263925A1 publication Critical patent/EP0263925A1/en
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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
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/04—Use of additives to fuels or fires for particular purposes for minimising corrosion or incrustation
    • 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
    • C10L1/1291—Silicon and boron containing 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
    • 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
    • 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
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
    • C10L1/2222—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates
    • 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
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/232—Organic compounds containing nitrogen containing nitrogen in a heterocyclic ring

Definitions

  • gasoline / alcohol mixtures as fuels for gasoline engines, in particular automobiles.
  • Such fuels can e.g. B. from 8o - 99 parts by volume of gasoline (hydrocarbons) and 2o - 1 parts by volume of alcohol, such as methanol and / or ethanol.
  • alcohol or a mixture consisting predominantly of alcohol e.g. B. methanol, or the z. B. up to 40 parts by volume of hydrocarbons are added to use as fuels.
  • Such mixtures generally contain only a little water (1.5 - 4%). Nevertheless, such alcohols or their mixtures with hydrocarbons cause corrosion problems, e.g. B.
  • the invention relates to phosphorus-free corrosion inhibitors for fuels containing a mixture of benzotriazole and / or derivatives of benzotriazole and tolyltriazole and / or derivatives of tolyltriazole, sodium boroheptonate and an alkylene oxide addition product of primary or secondary Aminen.Aethylenglycol and / or methanol and / or ethanol, may preferably also be included, but also other mono-, di- and polyalcohols such as C1 - C20 - alcohols, propylene glycol, butylene glycols, glycerol and others. Very suitable alkene oxides are ethylene oxide, propene oxide and their mixtures.
  • Talgaminopropylamine is preferably used as the amine and reacted with 25-30 mol of ethylene oxide, but other primary and secondary amines are also very suitable according to the invention, in particular longer-chain amines, di- and polyamines, also with branches.
  • a typical corrosion inhibitor according to the invention contains, for example, benzotriazole and tolyltriazole, sodium boroheptonate, an ethylene oxide addition product of primary and / or secondary amines, ethylene glycol and methanol and / or ethanol as a solvent.
  • These corrosion inhibitors can be easily dissolved in fuels and have a corrosion-preventing effect that is comparable to and partially superior to that of the phosphorus-containing inhibitors. They can be used in particular for automotive fuels with catalytic converters. Such fuels can contain, for example, 80% by volume of hydrocarbons, 1-10% by volume of ethanol, 1 to 10% by volume of methanol and 1 to 10% by volume of tert-butanol, and they can also be, for example, fuels which about 80-99% by volume of methanol and / or ethanol, and about 1-20% by volume of hydrocarbons, and 50-500 ppm (based on the alcohol content) of a corrosion inhibitor according to claims 1-8 or containing about 80- 99 vol .-% of an alcohol mixture consisting of at least 2 alcohols from the group of aliphatic C1 - C18 - alcohols, and about 1 - 20 vol .-% hydrocarbons and 50 - 500 ppm (based on the alcohol content) of a corrosion inhibitor according to the claims
  • the corrosion inhibitors are used in amounts of 50-500 ppm (based on the alcohol content), preferably in amounts of 50-300 ppm and particularly preferably 60-120 ppm.
  • the corrosion inhibitors preferably contain the various synergistic active ingredients in the following proportions: a mixture of benzotriazole or derivative and tolyltriazole or derivative in an amount of 10-15% by weight, sodium boroheptonate in an amount of 5-6% by weight, an adduct of ethylene oxide with tallow aminopropylamine (25-30 moles of ethylene oxide per Mol of amine), which also has a dispersing action, in an amount of 3 to 12% by weight and ethylene glycol, which also serves as a solvent, in an amount of 35 to 45% by weight. All in z.
  • Active ingredients dissolved in methanol or ethanol together make up, for example, an amount of 60 to 65% by weight.
  • weight ratios are also suitable according to the invention.
  • the various components of the corrosion inhibitors can simply be mixed together. In order to obtain a clear solution of the active ingredients in as little methanol or ethanol as possible, it is advisable, for example, without this process being necessary, first of all only a part of the mixture of benzotriazole and tolyltriazole (e.g. 8 parts and 2 parts), sodium boroheptonate ( 4 parts) and ethylene glycol (30 parts) in anhydrous methanol or ethanol (3o parts) to dissolve the ethylene oxide addition product of Add tallow aminopropylamine to this basic mixture and add further portions of the previously mentioned active ingredients, as well as methanol or ethanol, to the desired concentration.
  • the basic mixture consists of 30 g ethylene glycol, 4 g sodium boroheptonate, 30 g raw methanol, 8 g benzotriazole and 2 g tolyltriazole.
  • the basic mixture consists of 35g propylene glycol, 5g sodium boroheptonate, 3og ethanol, 8g 5-aminobenzotriazole and 3g tolyltriazole. 2 g of an ethylene propylene mixed oxide adduct of tallow aminopropylamine (25 moles of alkene oxide) are added to 8 g of this basic mixture.
  • a corrosion inhibitor contains: 22% by weight of the mixture contained 11 wt% benzotriazole 4% by weight sodium boroheptonate 32% by weight propylene glycol 31% by weight ethanol
  • the corrosion inhibitor corresponds to Example 4, but the adduct consists of octadecylamine and 26 moles of propylene oxide.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Combustion & Propulsion (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Liquid Carbonaceous Fuels (AREA)
  • Lubricants (AREA)
  • Anti-Oxidant Or Stabilizer Compositions (AREA)

Abstract

Phosphorus-free corrosion inhibitors for alcohol-containing motor fuels contain a mixture of benzotriazole and tolyltriazole, sodium boroheptonate, an alkylene oxide addition product of primary or secondary amines, ethylene glycol and methanol or ethanol.

Description

Es ist bekannt, Benzin/Alkohol-Gemische als Treibstoffe für Ottomotoren, insbesondere Automobile, zu verwenden. Solche Treibstoffe können z. B. aus 8o - 99 Volumenanteilen Benzin (Kohlenwasserstoffen) und 2o - 1 Volumenanteilen Alkohol, wie Methanol und/oder Aethanol, bestehen. Weiter ist es möglich, Alkohol oder eine Mischung, die vorwiegend aus Alkohol, z. B. Methanol, besteht, oder der z. B. bis zu 40 Volumenanteile an Kohlenwasserstoffen beigemischt sind, als Treibstoffe zu verwenden. Solche Mischungen enthalten im allgemeinen nur wenig Wasser (1,5 - 4%). Trotzdem verursachen solche Alkohole oder deren Mischungen mit Kohlenwasserstoffen Korrosionsprobleme, z. B. an Eisen-, Zink-, Magnesium- und Aluminiumteilen und Buntmetallen, insbesondere an Bauteilen, z. B. Armaturen, von Automobilen, Zapfsäulen und Treibstofftanks. Dies ist u. a. bedingt durch den Gehalt des Alkohols an Ameisensäure und Essigsäure, bedingt durch deren technische Herstellung.It is known to use gasoline / alcohol mixtures as fuels for gasoline engines, in particular automobiles. Such fuels can e.g. B. from 8o - 99 parts by volume of gasoline (hydrocarbons) and 2o - 1 parts by volume of alcohol, such as methanol and / or ethanol. It is also possible to use alcohol or a mixture consisting predominantly of alcohol, e.g. B. methanol, or the z. B. up to 40 parts by volume of hydrocarbons are added to use as fuels. Such mixtures generally contain only a little water (1.5 - 4%). Nevertheless, such alcohols or their mixtures with hydrocarbons cause corrosion problems, e.g. B. on iron, zinc, magnesium and aluminum parts and non-ferrous metals, especially on components, for. B. fittings, automobiles, petrol pumps and fuel tanks. This is u. a. due to the content of formic acid and acetic acid in the alcohol, due to their technical production.

Aus der DE - OS 34 33 554 ist es bekannt, diese Korrosion durch Verwendung von bestimmten Phosphorsäureestern zu verringern. Solche Phosphorsäureester können jedoch nicht bei Treibstoffen eingesetzt werden, die für Automobile benutzt werden, die mit Katalysatoren ausgerüstet sind. Es besteht daher weiterhin Bedarf für phosphorfreie Korrosionsinhibitoren welche die in Alkohol enthaltenden Treibstoffen auftretende Korrosion verhindern.From DE-OS 34 33 554 it is known to reduce this corrosion by using certain phosphoric acid esters. However, such phosphoric acid esters cannot be used in fuels used for automobiles that are equipped with catalysts. There is therefore still a need for phosphorus-free corrosion inhibitors which prevent the corrosion occurring in fuels containing alcohol.

Die Erfindung betrifft phosphorfreie Korrosionsinhibitoren für Treibstoffe, enthaltend eine Mischung von Benzotriazol und/oder Derivaten des Benzotriazols und Tolyltriazol und/oder Derivaten des Tolyltriazols, Natriumboroheptonat und ein Alkylenoxydanlagerungsprodukt von primären oder sekundären Aminen.Aethylenglykol und/oder Methanol und/oder Aethanol, können bevorzugt zusätzlich enthalten sein, aber auch andere Mono-, Di- und Polyalkohole wie z.B. C₁ - C₂₀ - Alkohole, Propylenglykol, Butylenglykole, Glycerin u. a. Sehr gut geeignete Alkenoxide sind Ethylenoxid, Propenoxid und ihre Gemische. Als Amin wird vorzugsweise Talgaminopropylamin eingesetzt und mit 25 - 30 Mol Aethylenoxyd umgesetzt, jedoch auch andere primäre und sekundäre Amine sind erfindungsgemäß sehr gut geeignet, insbesondere längerkettige Amine, Di- und Polyamine, auch mit Verzweigungen.The invention relates to phosphorus-free corrosion inhibitors for fuels containing a mixture of benzotriazole and / or derivatives of benzotriazole and tolyltriazole and / or derivatives of tolyltriazole, sodium boroheptonate and an alkylene oxide addition product of primary or secondary Aminen.Aethylenglycol and / or methanol and / or ethanol, may preferably also be included, but also other mono-, di- and polyalcohols such as C₁ - C₂₀ - alcohols, propylene glycol, butylene glycols, glycerol and others. Very suitable alkene oxides are ethylene oxide, propene oxide and their mixtures. Talgaminopropylamine is preferably used as the amine and reacted with 25-30 mol of ethylene oxide, but other primary and secondary amines are also very suitable according to the invention, in particular longer-chain amines, di- and polyamines, also with branches.

Ein typischer erfingungsgemäßer Korrosionsinhibitor enthält beispielsweise Benzotriazol und Tolyltriazol, Natriumboroheptonat, ein Ethylenoxidanlagerungsprodukt von primären und/oder sekundären Aminen, Ethylenglykol und Methanol und/oder Ethanol als Lösungsmittel.A typical corrosion inhibitor according to the invention contains, for example, benzotriazole and tolyltriazole, sodium boroheptonate, an ethylene oxide addition product of primary and / or secondary amines, ethylene glycol and methanol and / or ethanol as a solvent.

Diese Korrosionsinhibitoren lassen sich einwandfrei in Treibstoffen lösen und haben eine korrosionsverhindernde Wirkung, die denen der phosphorhaltigen Inhibitoren vergleichbar und teilweise überlegen ist. Sie können insbesondere eingesetzt werden bei Treibstoffen für Automobile mit Katalysatoren. Solche Treibstoffe können beispielsweise 80 Vol.- % Kohlenwasserstoffe, 1 - 10 Vol.- % Aethanol,1-1o Vol.-% Methanol und 1-1o Vol.% tert.Butanol enthalten, es kann sich auch beispielsweise um Treibstoffe handeln, die etwa 80 - 99 Vol.- % Methanol und/oder Ethanol, und etwa 1 - 20 Vol.- % Kohlenwasserstoffe enthalten, sowie 50 - 500 ppm (bezogen auf den Alkoholanteil) eines Korrosionsinhibitors gemäß Ansprüchen 1 - 8 enthalten oder die etwa 80 - 99 Vol.- % eines Alkoholgemisches, bestehend aus wenigstens 2 Alkoholen aus der Gruppe der aliphatischen C₁ - C₁₈ - Alkohole, und etwa 1 - 20 Vol.- % Kohlenwasserstoffe sowie 50 - 500 ppm (bezogen auf den Alkoholanteil) eines Korrosionsinhiibitors nach den Ansprüchen 1 - 8 enthalten.These corrosion inhibitors can be easily dissolved in fuels and have a corrosion-preventing effect that is comparable to and partially superior to that of the phosphorus-containing inhibitors. They can be used in particular for automotive fuels with catalytic converters. Such fuels can contain, for example, 80% by volume of hydrocarbons, 1-10% by volume of ethanol, 1 to 10% by volume of methanol and 1 to 10% by volume of tert-butanol, and they can also be, for example, fuels which about 80-99% by volume of methanol and / or ethanol, and about 1-20% by volume of hydrocarbons, and 50-500 ppm (based on the alcohol content) of a corrosion inhibitor according to claims 1-8 or containing about 80- 99 vol .-% of an alcohol mixture consisting of at least 2 alcohols from the group of aliphatic C₁ - C₁₈ - alcohols, and about 1 - 20 vol .-% hydrocarbons and 50 - 500 ppm (based on the alcohol content) of a corrosion inhibitor according to the claims 1 - 8 included.

In solchen Treibstoffen werden die Korrosionsinhibitoren in Mengen von 50 - 500 ppm (bezogen auf den Alkoholanteil), bevorzugt in Mengen von 50 - 300 ppm und besonders bevorzugt von 60 - 120 ppm eingesetzt.
Die Korrosionsinhibitoren enthalten am Beispiel f olgender Zusammensetzung die verschiedenen synergistisch wirkenden Wirkstoffe vorzugsweise in folgenden Anteilen:
eine Mischung von Benzotriazol bzw. Derivat und Tolyltriazol bzw. Derivat in einer Menge von 10 - 15 Gew.- %, Natriumboroheptonat in einer Menge von 5 - 6 Gew.- %, ein Anlagerungsprodukt von Aethylenoxyd an Talgaminopropylamin (25 -30 Mol Aethylenoxyd pro Mol Amin), das auch eine dispergierende Wirkung hat, in einer Menge von 3 bis 12 Gew.-% und Aethylenglykol, das auch als Lösungsmittel dient, in einer Menge von 35 bis 45 Gew.- %. Alle in z. B. Methanol bzw. Aethanol gelösten Wirkstoffe machen zusammen beispielsweise eine Menge von 60 bis 65 Gew.- % aus.In such fuels, the corrosion inhibitors are used in amounts of 50-500 ppm (based on the alcohol content), preferably in amounts of 50-300 ppm and particularly preferably 60-120 ppm.
Using the example of the following composition, the corrosion inhibitors preferably contain the various synergistic active ingredients in the following proportions:
a mixture of benzotriazole or derivative and tolyltriazole or derivative in an amount of 10-15% by weight, sodium boroheptonate in an amount of 5-6% by weight, an adduct of ethylene oxide with tallow aminopropylamine (25-30 moles of ethylene oxide per Mol of amine), which also has a dispersing action, in an amount of 3 to 12% by weight and ethylene glycol, which also serves as a solvent, in an amount of 35 to 45% by weight. All in z. B. Active ingredients dissolved in methanol or ethanol together make up, for example, an amount of 60 to 65% by weight.

Aber auch andere Gewichtsverhältnisse sind erfindungsgemäß geeignet. Die verschiedenen Bestandteile der Korrosionsinhibitoren können einfach miteinander vermischt werden. Um eine klare Lösung der Wirkstoffe in möglichst wenig Methanol oder Aethanol zu erhalten, empfiehlt es sich, beispielhaft, ohne daß dieses Verfahren zwingend ist, zunächst nur einen Teil der Mischung von Benzotriazol und Tolyltriazol (z.B. 8 Teile und 2 Teile), von Natriumboroheptonat (4 Teile) und Aethylenglykol (30 Teile) in wasserfreiem Methanol oder Aethanol (3o Teile) zu lösen, das Aethylenoxydanlagerungsprodukt von
Talgaminopropylamin zu dieser Grundmischung zu geben und weitere Anteile der vorher genannten Wirkstoffe sowie Methanol oder Aethanol bis zur gewünschten Konzentration dazu zu geben.However, other weight ratios are also suitable according to the invention. The various components of the corrosion inhibitors can simply be mixed together. In order to obtain a clear solution of the active ingredients in as little methanol or ethanol as possible, it is advisable, for example, without this process being necessary, first of all only a part of the mixture of benzotriazole and tolyltriazole (e.g. 8 parts and 2 parts), sodium boroheptonate ( 4 parts) and ethylene glycol (30 parts) in anhydrous methanol or ethanol (3o parts) to dissolve the ethylene oxide addition product of
Add tallow aminopropylamine to this basic mixture and add further portions of the previously mentioned active ingredients, as well as methanol or ethanol, to the desired concentration.

Die nachfolgenden Beispiele erläutern die Erfindung.The following examples illustrate the invention.

Beispiel 1example 1

Die Grundmischung besteht aus 30 g Aethylenglykol, 4 g Natriumboroheptonat, 30 g Roh-Methanol, 8 g Benzotriazol und 2 g Tolyltriazol.The basic mixture consists of 30 g ethylene glycol, 4 g sodium boroheptonate, 30 g raw methanol, 8 g benzotriazole and 2 g tolyltriazole.

Zu 8 g dieser Grundmischung werden 2 g eines Aethylenoxydanlagerungsproduktes von Talgaminopropylamin (28 Mol Aethylenoxyd) gegeben.2 g of an ethylene oxide adduct of tallow aminopropylamine (28 moles of ethylene oxide) are added to 8 g of this basic mixture.

Ein Korrosionsinhibitor enthält
20 Gew.-% der erhaltenen Mischung
11 Gew.-% Benzotriazol
4,5 Gew.-% Natriumboroheptonat
32 Gew.-% Aethylenglykol
32,5 Gew.-% Methanol (Wassergehalt 1,5-4 %)Contains a corrosion inhibitor
20% by weight of the mixture obtained
11 wt% benzotriazole
4.5% by weight sodium boroheptonate
32% by weight of ethylene glycol
32.5% by weight of methanol (water content 1.5-4%)

Beispiel 2Example 2

Zu 7 g der Grundmischung aus Beispiel 1 werden 3 g des gleichen Aethylenoxydanlagerungsproduktes gegeben.
Ein Korrosionsinhibitor enthält
30 Gew.-% der erhaltenen Mischung
9,5 Gew.-% Benzotriazol
4 Gew.-% Natriumboroheptonat
28 Gew.-% Aethylenglykol
28,4 Gew.-% Methanol (Wassergehalt 1,5-4 %)3 g of the same ethylene oxide addition product are added to 7 g of the base mixture from Example 1.
Contains a corrosion inhibitor
30% by weight of the mixture obtained
9.5% by weight benzotriazole
4% by weight sodium boroheptonate
28% by weight of ethylene glycol
28.4% by weight of methanol (water content 1.5-4%)

Beispiel 3Example 3

Die Grundmischung besteht aus 35g Propylenglykol, 5g Natriumboroheptonat, 3og Ethanol, 8g 5-Aminobenzotriazol und 3g Tolyltriazol.
Zu 8g dieser Grundmischung werden 2g eines Ethylenpropylenmischoxid-Anlagerungsproduktes von Talgaminopropylamin (25 Mol Alkenoxid) gegeben.The basic mixture consists of 35g propylene glycol, 5g sodium boroheptonate, 3og ethanol, 8g 5-aminobenzotriazole and 3g tolyltriazole.
2 g of an ethylene propylene mixed oxide adduct of tallow aminopropylamine (25 moles of alkene oxide) are added to 8 g of this basic mixture.

Ein Korrosionsinhibitor enthält:
22 Gew.-% der enthaltenen Mischung
11 Gew.-% Benzotriazol
4 Gew.-% Natriumboroheptonat
32 Gew.-% Propylenglykol
31 Gew.-% EthanolA corrosion inhibitor contains:
22% by weight of the mixture contained
11 wt% benzotriazole
4% by weight sodium boroheptonate
32% by weight propylene glycol
31% by weight ethanol

Beispiel 4Example 4

Zur Grundmischung von Beispiel 1 werden 2,5 g eines Ethylenoxidanlagerungsproduktes von 1,6-Diaminoethan (2o Mol Ethylenoxid) gegeben.2.5 g of an ethylene oxide adduct of 1,6-diaminoethane (20 mol of ethylene oxide) are added to the basic mixture of Example 1.

2o% dieser Mischung sind wie im Beispiel 1 in dem Korrosionsinhibitor enthalten.As in Example 1, 20% of this mixture is contained in the corrosion inhibitor.

Beispiel 5Example 5

Der Korrosionsinhibitor entspricht Beispiel 4, jedoch besteht das Anlagerungsprodukt aus Octadecylamin und 26 Mol Propylenoxid.The corrosion inhibitor corresponds to Example 4, but the adduct consists of octadecylamine and 26 moles of propylene oxide.

AnwendungsbeispieleExamples of use

Eine typische Treibstoffmischung enthält in Vol.-%

  • 1. 89-9o% Kohlenwasserstoffe
    5% Aethanol 96%
    3% Methanol 99,5-97,2%
    2% tertiäres Butanol
    <1% Korrosionsinhibitor gemäß Beispielen 1-5 (3oo ppm auf Alkohol bezogen)
  • 2. ca. 9o% Methanol
    ca. 1o% C₄ - C₇- Kohlenwasserstoffe
    1oo ppm Korrosionsinhibitor gemäß Beispielen 1-5
  • 3. ca. 85% Methanol
    ca. 15% Superbenzin
    35o ppm Korrosionsin itor gemäß Beispielen 1-5
  • 4. ca. 75% Methanol
    ca. 1o% Ethanol
    ca. 15% Superbenzin
    15o ppm Korrosionsinhibitor gemäß Beispielen 1-5
  • 5. ca. 75% Methanol
    ca. 1o% C₂-C₈-Alkohole
    8o ppm Korrosionsinhibitor gemäß Beispielen 1-5
A typical fuel mixture contains in volume%
  • 1. 89-9o% hydrocarbons
    5% ethanol 96%
    3% methanol 99.5-97.2%
    2% tertiary butanol
    <1% corrosion inhibitor according to Examples 1-5 (300 ppm based on alcohol)
  • 2. approx. 90% methanol
    approx. 10% C₄ - C₇ hydrocarbons
    100 ppm corrosion inhibitor according to Examples 1-5
  • 3. approx. 85% methanol
    approx. 15% premium gasoline
    35o ppm corrosion initiator according to Examples 1-5
  • 4. about 75% methanol
    about 10% ethanol
    approx. 15% premium gasoline
    15o ppm corrosion inhibitor according to Examples 1-5
  • 5. approx. 75% methanol
    about 1o% C₂-C₈ alcohols
    8o ppm corrosion inhibitor according to Examples 1-5

Bei den Anwendungsbeispielen wurde auch bei einjährigem Test in Testfahrzeugen keine Korrosion im Motorbereich festgestellt. In the application examples, no corrosion was found in the engine area even after a one-year test in test vehicles.

Claims (13)

1. Korrosionsinhibitor, enthaltend eine Mischung von Benzotriazol und/oder Derivaten des Benzotriazols ein Tolyltriazol und/oder Derivaten des Tolyltriazols Natriumboroheptonat und ein Alkylenoxydanlagerungsprodukt von primären und/oder sekundären Aminen.1. Corrosion inhibitor containing a mixture of benzotriazole and / or derivatives of benzotriazole, a tolyltriazole and / or derivatives of tolyltriazole sodium boroheptonate and an alkylene oxide addition product of primary and / or secondary amines. 2. Korrosionsinhibitor für Treibstoffe nach Anspruch 1, dadurch gekennzeichnet, daß die Mischung zusätzlich Mono-, und/oder Di- und/oder Polyole enthält.2. Corrosion inhibitor for fuels according to claim 1, characterized in that the mixture additionally contains mono-, and / or di- and / or polyols. 3. Korrosionsinhibitor für Treibstoffe nach den Ansprüchen 1 und 2, enthaltend eine Mischung von Benzotriazol und Tolyltriazol, Natriumboroheptonat, ein Aethylenoxydanlagerungsprodukt von primären und/oder sekundären Aminen, Aethylenglykol und Methanol und/oder Aethanol.3. Corrosion inhibitor for fuels according to claims 1 and 2, containing a mixture of benzotriazole and tolyltriazole, sodium boroheptonate, an ethylene oxide addition product of primary and / or secondary amines, ethylene glycol and methanol and / or ethanol. 4. Korrosionsinhibitor nach den Ansprüchen 1 bis 3, dadurch gekennzeichnet, daß die Mischung von Benzotriazol und/oder Benzotriazolderivaten und Tolyltriazol und/oder Tolyltriazolderivaten in einer Menge von 10 - 15 Gew.- % enthalten ist.4. Corrosion inhibitor according to claims 1 to 3, characterized in that the mixture of benzotriazole and / or benzotriazole derivatives and tolyltriazole and / or tolyltriazole derivatives is contained in an amount of 10-15% by weight. 5. Korrosionsinhibitor nach den Ansprüchen 1 bis 4, dadurch gekennzeichnet, daß Natriumboroheptonat in einer Menge von 5 - 6 Gew.- % enthalten ist.5. Corrosion inhibitor according to claims 1 to 4, characterized in that sodium boroheptonate is contained in an amount of 5-6% by weight. 6. Korrosionsinhibitor nach den Ansprüchen 1 - 5, dadurch gekennzeichnet, daß ein Aethylenoxydanlagerungsprodukt von Talgaminopropylamin in einer Menge von 3 bis 12 Gew.- % enthalten ist.6. Corrosion inhibitor according to claims 1-5, characterized in that an ethylene oxide addition product of tallow aminopropylamine is contained in an amount of 3 to 12% by weight. 7. Korrosionsinhibitor nach den Ansprüchen 1 bis 6, dadurch gekennzeichnet, daß Aethylenglykol in einer Menge von 35 bis 45 Gew.- % enthalten ist.7. Corrosion inhibitor according to claims 1 to 6, characterized in that ethylene glycol is contained in an amount of 35 to 45% by weight. 8. Korrosionsinhibitor nach den Ansprüchen 1 bis 7, dadurch gekennzeichnet, daß die Wirkstoffe nach Anspruch 1 in Ethylenglykol und/oder Methanol und/oder Ethanol gelöst sind.8. Corrosion inhibitor according to claims 1 to 7, characterized in that the active ingredients according to claim 1 are dissolved in ethylene glycol and / or methanol and / or ethanol. 9. Verfahren zur Herstellung eines Korrosionsinhibitors für Treibstoffe, dadurch gekennzeichnet, daß eine Mischung von Benzotriazol und Tolyltriazol, Natriumboroheptonat und Aethylenglykol in Methanol oder Aethanol gelöst werden, ein Aethylenoxydanlagerungsprodukt von Talgaminopropylamin zugesetzt wird und weitere Anteile der vorher genannten Wirkstoffe sowie Methanol oder Aethanol zugegeben werden.9. A process for the preparation of a corrosion inhibitor for fuels, characterized in that a mixture of benzotriazole and tolyltriazole, sodium boroheptonate and ethylene glycol are dissolved in methanol or ethanol, an ethylene oxide addition product of tallow aminopropylamine is added and further portions of the previously mentioned active ingredients and methanol or ethanol are added . 10. Treibstoffe für Verbrennungsmotoren, die Alkohol oder Alkohol/Kohlenwasserstoffgemische enthalten und einen Korrosionsinhibitor gemäß Ansprüchen 1 bis 8 enthalten.10. Fuels for internal combustion engines which contain alcohol or alcohol / hydrocarbon mixtures and contain a corrosion inhibitor according to claims 1 to 8. 11. Treibstoffe für Verbrennungsmotoren gemäß Anspruch 10, dadurch gekennzeichnet, daß sie etwa 80 Vol.- % Kohlenwasserstoffe, 1 - 10 Vol- % Ethanol, 1 - 10 Vol.- % Methanol und 1 - 10 Vol.- % tert. Butanol, sowie 50 -300 ppm (bezogen auf den Alkoholanteil) eines Korrosionsinhibitors gemäß Ansprüchen 1 bis 8 enthalten.11. Fuels for internal combustion engines according to claim 10, characterized in that they tert about 80 vol% hydrocarbons, 1-10 vol% ethanol, 1-10 vol% methanol and 1-10 vol%. Butanol, and 50-300 ppm (based on the alcohol content) of a corrosion inhibitor according to claims 1 to 8 contain. 12. Treibstoffe für Verbrennungsmotoren gemäß Anspruch 10, dadurch gekennzeichnet, daß diese etwa 80 - 99 Vol.- % Methanol und/oder Ethanol, und etwa 1 - 20 Vol.- Koh lenwasserstoffe enthalten, sowie 50 - 500 ppm (bezogen auf den Alkoholanteil) eines Korrosionsinhibitors gemäß Ansprüchen 1 bis 6 enthalten.12. Fuels for internal combustion engines according to claim 10, characterized in that these about 80-99 vol .-% methanol and / or ethanol, and about 1 - 20 vol .- Koh contain hydrogen and contain 50 - 500 ppm (based on the alcohol content) of a corrosion inhibitor according to claims 1 to 6. 13. Treibstoffe für Verbrennungsmotoren gemäß Anspruch 10, dadurch gekennzeichnet, daß diese etwa 80 - 99 Vol.- % eines Alkoholgemisches, bestehend aus wenigstens 2 Alkoholen aus der Gruppe der aliphatischen C₁ - C₁₈ - Alkohole, und etwa 1 - 20 Vol.- % Kohlenwasserstoffe sowie 50 - 500 ppm (bezogen auf den Alkoholanteil) eines Korrosionsinhibitors nach den Ansprüchen 1 bis 8 enthalten.13. Fuels for internal combustion engines according to claim 10, characterized in that these about 80-99 vol .-% of an alcohol mixture consisting of at least 2 alcohols from the group of aliphatic C₁ - C₁₈ - alcohols, and about 1 - 20 vol .-% Contain hydrocarbons and 50 - 500 ppm (based on the alcohol content) of a corrosion inhibitor according to claims 1 to 8.
EP87110212A 1986-07-22 1987-07-15 Corrosion inhibitors for fuels Withdrawn EP0263925A1 (en)

Applications Claiming Priority (2)

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DE19863624767 DE3624767A1 (en) 1986-07-22 1986-07-22 CORROSION INHIBITOR FOR FUELS
DE3624767 1986-07-22

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EP0263925A1 true EP0263925A1 (en) 1988-04-20

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JP (1) JPS6366291A (en)
CN (1) CN87104997A (en)
AU (1) AU7598887A (en)
DD (1) DD261371A5 (en)
DE (1) DE3624767A1 (en)
DK (1) DK380987A (en)
ES (1) ES2002250A4 (en)
GR (1) GR880300061T1 (en)
NO (1) NO873027L (en)
NZ (1) NZ221139A (en)
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Cited By (1)

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DE3724181A1 (en) * 1987-07-22 1989-02-16 Sandoz Ag Corrosion inhibitor for fuels

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Publication number Priority date Publication date Assignee Title
MY158617A (en) * 2009-10-14 2016-10-31 Palox Ltd Protection of liquid fuels
CN110066694A (en) * 2019-05-23 2019-07-30 金玖洲新能源有限公司 A kind of clean fuel and preparation method thereof

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FR2405987A1 (en) * 1977-10-13 1979-05-11 Lubrizol Corp COMPOSITIONS OF DEEMULSIONING ADDITIVES FOR LUBRICANTS AND FUELS AND COMPOSITIONS CONTAINING THEM
DE3433554A1 (en) * 1983-09-24 1985-04-11 Sandoz-Patent-GmbH, 7850 Lörrach Fuels for internal combustion engines
US4518395A (en) * 1982-09-21 1985-05-21 Nuodex Inc. Process for the stabilization of metal-containing hydrocarbon fuel compositions
US4595523A (en) * 1983-07-01 1986-06-17 Petrolite Corporation Corrosion inhibition in engine fuel systems

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US2759021A (en) * 1951-01-19 1956-08-14 Armour & Co Substituted trimethylene diamines
FR1211144A (en) * 1958-05-30 1960-03-14 Shell Res Ltd Fuel hydrocarbons
US3092475A (en) * 1958-12-22 1963-06-04 Sinclair Research Inc Fuel composition
US3574577A (en) * 1968-05-22 1971-04-13 Texaco Inc Method of preventing ice formation in a jet engine
FR2150703A1 (en) * 1971-07-15 1973-04-13 Mobil Oil Corp
FR2227318A1 (en) * 1973-04-28 1974-11-22 Basf Ag
FR2405987A1 (en) * 1977-10-13 1979-05-11 Lubrizol Corp COMPOSITIONS OF DEEMULSIONING ADDITIVES FOR LUBRICANTS AND FUELS AND COMPOSITIONS CONTAINING THEM
US4518395A (en) * 1982-09-21 1985-05-21 Nuodex Inc. Process for the stabilization of metal-containing hydrocarbon fuel compositions
US4595523A (en) * 1983-07-01 1986-06-17 Petrolite Corporation Corrosion inhibition in engine fuel systems
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ZA875282B (en) 1988-03-30
GR880300061T1 (en) 1988-10-18
NO873027D0 (en) 1987-07-20
DK380987A (en) 1988-01-23
AU7598887A (en) 1988-01-28
JPS6366291A (en) 1988-03-24
ES2002250A4 (en) 1988-08-01
NZ221139A (en) 1989-07-27
CN87104997A (en) 1988-11-30
NO873027L (en) 1988-01-25
DE3624767A1 (en) 1988-06-01
DK380987D0 (en) 1987-07-21
DD261371A5 (en) 1988-10-26

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