DE60028599T2 - FUEL SUPPLEMENT FOR VALVE SEAT BUTTON PREVENTION - Google Patents

Abstract

There is provided use of a composition for the prevention and/or inhibition of valve seat recession of an internal combustion engine, the composition comprising (i) (a) phosphorus and/or a phosphorus compound; and/or (b) potassium and/or a potassium compound; and (ii) iron and/or an iron compound.

Description

The The present invention relates to a use. The present Invention relates to additives for fuel, these containing fuel compositions and their use. In particular, the invention relates to additives that prevent in the a phenomenon, those skilled in the art as exhaust valve seat wear (VSR) well known, are effective.

Metal- or metal-containing additives have been incorporated into fuel compositions for many years. The additives can to provide a number of effects on the fuel. From Certain additives are known to have the combustion properties improve the fuel; For example, certain additives may Octane rating of petroleum fuels increase. The additives can even during the Burning, especially during combustion in an internal combustion engine, provide an effect. For example, you can Metal or metal containing additives during combustion metal or metal compounds on the surface of an internal combustion engine deposit. In particular, you can Metal or metal connections on the valves or valve seats of an internal combustion engine form deposits. Such deposits can protect these components of the engine from operational wear; for example can the deposits the valve seats from abrasion and the resulting Protect wear.

It gives one over for many years considerable History of technical documents, the lessons of the causes and to include means to prevent VSR.

In a Society document published in the Transactions for 1930 and 1931 of Automotive Engineers, Inc. of the United States of America A. T. Colwell the problems of operating engines with exhaust valve seats made of cast iron under conditions of high stress. These often involved trucks with gasoline engines and buses on long-distance highways. The operating problems are concentrated on education extremely hard excrescences or nodules on the surface the exhaust valve, where this is in contact with the valve seat. The presence of this hard nodules leads to a quick wear or Abrasion of the seat, especially at high temperatures of the exhaust valve, as when driving in conditions of persistently high speed can be found.

Colwell describes the whole phenomenon of the VSR exactly and with far-reaching insight into the probable Mechanism of the wear process and its possible Solution. He says, "There is more options, to remedy this condition (referring to VSR), ... In many cases alone is the use of ethylbenzene (which Tetraethylblei contains) the trouble put an end to it. This is probably due to the fact that the products the combustion of ethylbenzene a thin coating on the valve seat form an insulating material between the valve and the block. "Over many decades the use of tetraethyl lead-containing gasoline provided one almost complete Protection against VSR. Adjusting the uptake of tetraethyl lead in Gasoline, however, resulted in a search for alternative fuel additives, which provides protection against VSR in cast iron engines can provide.

Lots Researchers have since played the role of metallic fuel additives play a role in providing protection against VSR in gasoline engines, emphasized. Barker suggested in his document C291 / 73, presented the Tribotechnics Conference I. Mech. E. in London in 1973, an explanation for the Protection by lead additives. The explanation is similar to the one in the Document proposed by Colwell; it affects education a thin one Films between the exhaust valve and its seat. It is believed that metal salts, typically Oxides, form a strong lubricant with high melting point and provide, which prevents the contact of metal to metal.

In his document to the conference from the year 1973 gives Barker Indications of the effects of various metallic fuel additives in preventing VSR in gasoline engines. The considered Metals include lead, zinc, iron, sodium and vanadium. Lead with a processing rate of 13.0 mg Pb / l was very effective at Prevent VSR, followed by zinc, vanadium, sodium and iron. All the latter metals were significantly less effective than Lead, although with a metal processing rate of 18.5 mg M / l where M is the metal tested. investigations of wear-related Deposits showed that iron oxides were present on the valve seat. These aggressive materials stood with the wear process itself in connection, suggesting that the presence of iron in Petrol is not necessarily beneficial to VSR protection. The relatively poor performance of iron as an additive for protection before VSR is consistent with this view.

One later Document on McArragher VSR Additive Protection et al., presented on the occasion of a Conference of the Coordinating European Council in Birmingham in the year 1993, concerned the use of a number of chemical components, including Phosphorus and alkali metals. It has been shown that phosphorus compounds various types provide a significant level of protection from VSR. The document also mentions that phosphorus compounds are beneficial in preventing deposits on spark plugs. additionally the document showed that potassium at a processing rate of about 10 mg K / kg a limited, but acceptable level protection for Provides valve seats in gasoline engines. In the document by McArragher will be confirmed, that phosphorus a higher one compared to potassium Level of protection before valve seat wear supplies. Nevertheless, potassium has subsequently become commercially available in many European countries ver propelled fuel for Vehicles that were previously fueled with leaded gasoline used to to provide protection against VSR. The efficiency This metallic additive is well known to those skilled in the art. In similar Wise are its limitations as an additive to protect against VSR to those skilled in the industry.

ferrocene is a well-known metallic fuel additive with a significant Ability, the octane quality increase in unleaded gasoline. It is used in refineries as an additive used to adjust the octane number to the octane quality of gasoline to improve the specifications for the octane quality of gasoline comply. The efficiency this product as an additive to protect against VSR has been researched by Barker, as discussed above, and it turned out that they are a processing rate of 18.5 mg Fe / liter, which corresponds to 25 mg Fe / kg, is relatively bad. For purposes of improving octane quality is in the form ferrocene-added iron, typically at a processing rate of 9 mg Fe / kg. It is expected that this processing rate of the Additivs a very limited Protection against VSR supplies. It can be shown that this is indeed the Case is.

The VSV protection mechanism of the Valvemaster phosphorus additive is based on the formation of P ₂ O ₅ in the motor. Deposits occur between the exhaust valve and its seat, preventing metal-to-metal contact leading to erosion or abrasion of the valve seat. The deposition of such protective deposits has been postulated, as previously described by Colwell in 1931 and by Barker in 1973. The combustion products of PLUTOcen ^® are iron oxides, where it is slightly aggressive materials, one of which is not expected to provide protection from VSR.

The Applicants of the present invention have determined a composition the valve seat wear prevention / inhibition (VSR) allows.

In A first aspect is the use of a composition for Preventing and / or inhibiting valve seat wear of a Provided internal combustion engine, wherein the composition (i) a potassium compound from the group consisting of potassium sulfonates, potassium carboxylates and mixtures thereof, and (ii) a ferrocene and / or a substituted one Includes ferrocene.

In A second aspect is a fuel additive composition which comprises (i) a potassium compound selected from the group consisting of potassium sulfonates, potassium carboxylates and mixtures and (ii) a ferrocene and / or a substituted ferrocene includes.

The Composition is present in an amount with which the desired improvement combustion characteristics and prevention of valve seat wear can be.

VSR Is the abbreviation of valve seat wear. In this context, the term generally means the valve seat wear in one Internal combustion engine, such as a gasoline engine / gasoline engine.

The Iron and / or the iron compound can with potassium and / or a Potassium compound can be combined, and there are unexpected benefits to observe. It is well known that VSR prevents performance of potassium at a metal processing rate of 8 mg K / kg is mediocre. However, we have found that the combination of the two Metals when mixed with iron in the form of ferrocene, its VSR poor performance, as described above, combined, a level of protection VSR provides, which is surprising and unexpected. In addition, the combination of potassium increases with Ferrocene octane quality of the mixture to which the combination is added.

In addition to the considerable Advantage of improved protection against VSR unexpectedly by The combination of iron and potassium is achieved are certain additional To observe advantages.

The so available lower processing rates allow adequate protection before VSR with metalworking rates at which it is less likely is, that you Problems with regard to cases of Deposits on spark plugs or cause the general build-up of deposits within the cylinder. Furthermore, any alkali-induced corrosion risks minimized.

Frequently becomes regarding the effects of additives to protect against VSR 3-way catalysts or the lambda sensors used to control them are misdirected Expressed concern. Each with a 3-way catalyst equipped Vehicle is for designed an operation with unleaded fuel and therefore with hardened Valve seats equipped. It does not require a VSR additive in the fuel, and the distributor nozzles are designed so that misfires avoided, which should therefore only be able to occur if a later added additive used in an inappropriate way. If the additive is a combination contains iron and phosphorus, can protection due to the reduced phosphorus content of the combination before VSR and various other benefits to be achieved with accompanied by a further reduction of this already low risk.

• • Die katalytische Oxidation von kohlenstoffhaltigem Material verhindert die Ansammlung von Ablagerungen,
• • Reaktionen, die zur Ablagerung von kohlenstoffhaltigem Material führen, werden unterdrückt,
• • ansonsten schädliche Ablagerungen werden weich und bröckelig gemacht.

It is believed that the additive combination (s) act by depositing lubricating thin films at high temperatures on and around the valve face and valve seat. Without wishing to be bound by theory, it is believed that the mechanism (s) that make the additive combinations so successful consists of:

• • The catalytic oxidation of carbonaceous material prevents the accumulation of deposits,
• • Reactions that lead to the deposition of carbonaceous material are suppressed,
• • otherwise harmful deposits are made soft and friable.

POTASSIUM

Preferably the potassium and / or the potassium compound is a potassium compound.

One very broad range of compounds has been considered suitable agents for providing alkali metals, in particular potassium, in one suitable, soluble in gasoline Form claimed for use as VSR additives.

The used potassium salts can acidic, neutral or alkaline (i.e., overbased, hypercalcified or superalkalized).

Acid salts can be prepared with an excess of organic acid over potassium, neutral salts convert substantially stoichiometric amounts of acid and base, and alkaline salts contain excess cations and are typically prepared by "blowing in" a suspension of a metal base into a solution of a catalyst organic acid produced with gaseous CO ₂ .

In Aspects of the present invention may include colloidal suspensions inorganic salts of potassium are used.

suitable organic acids for use in the preparation of the potassium compound are described in the WO 87/01126 to Johnston et al. discussed in detail. These include sulfuric acids, carboxylic acids and phosphoric acids.

Some Workers have expressed their concern about that one Poisoning of the catalyst can limit the usefulness of the phosphoric acids.

In In one aspect, the potassium compound is prepared from a sulfuric acid.

Include sulfuric acids Sulfonic, sulfamic, thiosulfonic, sulfenic, sulfinic, partially esterified Sulfuric, sulphurous and thiosulphuric acid. The sulfuric acids can be aliphatic or be aromatic, including mono- or polynuclear aromatic acids or cycloaliphatic compounds. Sulfonates of by-products Detergent production is also common.

Carboxylic acids include aliphatic, cycloaliphatic and aromatic mono- and polybasic carboxylic acids, naphthene, alkyl or Alkenylcyclopentan- and hexanoic acid and the corresponding aromatic acids. Branched chain carboxylic acids, including 2-ethylhexanoic acid and propylene tetramer sub It is also possible to use substituted maleic acids. Carboxylic acid fractions containing various mixed hydrocarbon chains, such as tall oil and rosin resins, are also found.

Salts of phenols (commonly referred to as phenates) can be used. These have the general formula: (R *) a- (Ar *) - (OH) m wherein R * is an aliphatic group having 4 to 400 carbon atoms, a is an integer of 1-4, Ar * is a polyvalent aromatic hydrocarbon nucleus of up to 14 carbon atoms, and m is an integer of 1-4, with the proviso that at least about 8 C atoms per acid equivalent are provided by the R * groups. The R * groups may be substituted provided that this does not alter the substantial hydrocarbon character of the groups.

Phosphoric acids can also be used such as the phosphonic and thiophosphonic acids prepared by reacting P ₂ S ₅ with petroleum fractions such as Brightstock or with polymeric materials made from C ₂ to C ₆ monoolefins such as polybutenes. A suitable technique for preparing a series of phosphorus additives is described in WO 87/01126.

The EP 207 560 and the EP 555 006 describe a series of succinic acid derivatives substituted on at least one of the alpha carbon atoms with a C ₂₀ to C ₂₀₀ hydrocarbyl group and optionally linked to the other alpha carbon atom through a hydrocarbon radical of 1 to 6 carbon atoms. Such derivatives can be further derivatized by reacting a carboxyl group with an alcohol or an amine to produce the hemiester or amide, respectively.

preferred acid salts are the salts of potassium with the succinic derivatives, as they are direct or alkylbenzenesulfonic acids, in particular Dodecylbenzenesulfonic acid, from of detergent production.

preferred neutral salts are overbased Salts. Salts that can withstand extraction into the aqueous phase prefers.

The Alternative of providing a fuel stable colloidal Suspension of a metal salt with an average particle size of 1 Microns, preferably 0.5 microns or less, is disclosed in US-A-5,090,966 by Crawford et al. described. An emulsion of a solution of a suitable metal salt, such as potassium borate, carbonate, bicarbonate or acetate, is prepared; optionally it will be using an emulsifier prepared in some carrier oil. The solvent is then typically by heating with simultaneous rapid shake away. The patent discloses suitable in situ methods of preparation metal borate products, preferred carrier oils and preferred emulsifiers described. Such colloidal suspensions are also preferred Sources for Potassium for use according to the invention.

mixtures any or all of the above acids can be used become a fuel-soluble one and stable source for Provide potassium ions. Potassium ions can be used as a mixture of sources in the form of solutions or colloidal suspensions.

IRON

Preferably the iron and / or iron compound is an iron compound.

Preferably the iron compound is a ferrocene and / or a substituted one Ferrocene.

Preferably For example, the iron compound is an iron complex selected from dicyclopentadienyl and substituted dicyclopentadienyl.

The iron compound may be an iron complex of dicyclopentadienyl or substituted dicyclopentadienyl, which substituents may be, for example, one or more C _1-5 alkyl groups, preferably C _1-2 alkyl groups. A combination of such iron complexes can also be used.

Suitable alkyl-substituted dicyclopentadienyl iron complexes are cyclopentadienyl (methylcyclopentadienyl) iron, cyclopentadienyl (ethylcyclopentadienyl) iron, bis (methylcyclopentadienyl) iron, bis (ethylcyclopentadienyl) iron, bis (1,2-dimethylcyclopentadienyl) iron, iron pentacarbonyl and bis (1-methyl-3-ethylcyclopentadienyl) iron. These iron complexes can be prepared by the methods described in US-A-2,680,756, US-A-2,804,468, GB-A-0733129 and GB-A-0763550.

suitable Iron complexes are dicyclopentadienyliron and / or bis (methylcyclopentadienyl) iron.

A most preferred Iron complex is ferrocene (i.e., dicyclopentadienyliron).

The for the solubilization of transition metals, including Iron, in hydrocarbon solvents, e.g. Diesel fuel, relevant coordination chemistry is professionals well known in the art (see for example WO-A-87/01720 and WO-A-92/20762).

A wide range of so-called "substituted ferrocenes" are known and can be used in the present invention (see, eg, Comprehensive Organic Chemistry, Ed. Wilkinson et al., Pergamon 1982, Vol. 4: 475-494 and Vol. 8: 1014-1043). Substituted ferrocenes for use in the invention include those wherein substitution may be on either or both cyclopentadienyl groups. Suitable substituents include, for example, one or more C _1-5 alkyl groups, preferably C _1-2 alkyl groups.

Especially suitable alkyl-substituted dicyclopentadienyl iron complexes (substituted Ferrocenes) include cyclopentadienyl (methylcyclopentadienyl) iron, bis (methylcyclopentadienyl) iron, bis (ethylcyclopentadienyl) iron, bis (1,2-dimethylcyclopentadienyl) iron and 2,2'-diethylferrocenylpropane.

Further suitable substituents present on the cyclopentadienyl rings can, include cycloalkyl groups such as cyclopentyl, aryl groups such as tolylphenyl, and acetyl groups, e.g. present in diacetylferrocene. One especially useful Substituent is the hydroxyisopropyl group, the (-hydroxyisopropyl) ferrocene supplies. As disclosed in WO-A-94/09091, (-hydroxyisopropyl) ferrocene is at room temperature, a liquid.

Other organometallic complexes of iron may also be used in the invention as far as they are soluble and stable in fuel. Such complexes include, for example, iron pentacarbonyl, diisone nonacarbonyl, (1,3-butadiene) iron tricarbonyl, (cyclopentadienyl) iron dicarbonyl dimer and the diisobutylene complex of iron pentacarbonyl. Salts such as dietetralinenetetraphenylborate (Fe (C ₁₀ H ₁₂ ) ₂ (B (C ₆ H ₅ ) ₄ ) ₂ ) can also be used.

As a result of the combination of their solubility, stability, high iron content, and especially their volatility, the substituted ferrocenes are particularly preferred iron compounds for use in the invention. Ferrocene itself is a particularly preferred iron compound on this basis. Ferrocene suitable purity is in a number of suitable forms as PLUTOcen ^®, and in the form of solutions, such satacen ^®, both available sold by Octel Germany GmbH.

The Iron compounds for use in the invention need no Have iron-carbon bonds, to dissolve in fuel and to be stable. It can Salts are used; these can neutral or overbased be. So can for example overbased Soaps containing iron stearate, iron oleate and iron naphthenate, be used. Methods for producing metal soaps are in The Kirk-Othmer Encyclopaedia of Chemical Technology, 4th ed., Volume 8: 432-445, John Wiley & Sons, 1993, described. Suitable stoichiometric or neutral iron carboxylates for use in the invention the so-called "drier Iron "species, such as iron tris- (2-ethylhexanoate) [19583-54-1].

Iron complexes which have no metal-carbon bonds and not through Carbonization can be made in the invention also be used, with the proviso that she in a suitable degree soluble in fuel and are stable. Examples include complexes with diketonates, such as Tetramethyl.

• • Aromatische Mannich-Basen, wie diejenigen, die durch Umsetzen eines Amins mit einem Aldehyd oder Keton, gefolgt von einem nukleophilen Angriff auf eine aktive Wasserstoff enthaltende Verbindung hergestellt werden, z.B. das Produkt der Reaktion zweier Äquivalente von (Tetrapropenyl)phenol, zweier Äquivalente von Formaldehyd und eines Äquivalents von Ethylendiamin,
• • Hydroxyaromatische Oxime, wie (Polyisobutenyl)salicylaldoxim. Diese können durch Umsetzen von (Polyisobutenyl)phenol, Formaldehyd und Hydroxylamin hergestellt werden.
• • Schiff-Basen, wie diejenigen, die durch Kondensationsreaktionen zwischen Aldehyden oder Ketonen (z.B. (6-t-Butyl)-salicylaldehyd) und Aminen (z.B. Dodecylamin) hergestellt werden. Ein vierzähniger Ligand kann unter Verwendung von Ethylendiamin (ein halbes Äquivalent) anstelle von Dodecylamin hergestellt werden.
• • Substituierte Phenole, wie 2-substituierte 8-Chinolinole, beispielsweise 2-Dodecenyl-8-chinolinol oder 2-N-Dodecenylaminomethylphenol.
• • Substituierte Phenole, wie diejenigen, bei denen der Substituent NR₂ oder SR ist, wobei R eine langkettige (z.B. 20–30 C-Atome) Kohlenwasserstoffgruppe ist. Im Falle von sowohl α- als auch β-substituierten Phenolen können die aromatischen Ringe in vorteilhafter Weise mit Hydrocarbylgruppen, z.B. niederen Alkylgruppen, weiter substituiert sein.
• • Carbonsäureester, insbesondere Bernsteinsäureester, wie diejenigen, die durch Umsetzen eines Anhydrids (z.B. Dodecenylbernsteinsäureanhydrid) mit einem einzigen Äquivalent eines Alkohols (z.B. Triethylenglycol) hergestellt werden.
• • Acylierte Amine. Diese können mittels einer Vielzahl von Verfahren hergestellt werden, die Fachleuten auf dem Gebiet gut bekannt sind. Besonders geeignete Chelate sind jedoch diejenigen, die durch Umsetzen von alkenylsubstituierten Succinaten, wie Dodecenylbernsteinsäureanhydrid, mit einem Amin, wie N,N'-Dimethylethylendiamin oder Methyl-2-methylaminobenzoat, hergestellt werden.
• • Aminsäuren, beispielsweise diejenigen, die durch Umsetzen eines Amins, wie Dodecylamin, mit einem α,β-ungesättigten Ester, wie Methylmethacrylat, hergestellt werden. In Fällen, bei denen ein primäres Amin verwendet wird, kann dieses anschließend acyliert werden, wie z.B. mit Ölsäure oder Oleylchlorid.
• • Hydroxamsäuren, wie diejenigen, die aus der Umsetzung von Hydroxylamin mit Ölsäure hergestellt werden.
• • Gebundene Phenole, wie diejenigen, die aus der Kondensation von alkylierten Phenolen mit Formaldehyd hergestellt werden. Wenn ein Verhältnis von Phenol:Formaldehyd von 2:1 verwendet wird, ist die Bindungsgruppe CH₂. Wenn ein Verhältnis von 1:1 verwendet wird, ist die Bindungsgruppe CH₂OCH₂.
• • Alkylierte, substituierte Pyridine, wie 2-Carboxy-4-dodecylpyridin.
• • Borierte acylierte Amine. Diese können durch Umsetzen eines Bernsteinsäureacylierungsmittels, wie Poly(isobutylen)bernsteinsäure, mit einem Amin, wie Tetraethylenpentamin, hergestellt werden. Diesem Verfahren folgt dann die Boronierung mit einem Boroxid, Borhalogenid oder Boronsäure, -amid oder -ester. Ähnliche Reaktionen mit Phosphorsäure führen zur Bildung von phosphorhaltigen acylierten Aminen, die auch zur Bereitstellung eines in Öl löslichen Eisenchelats zur Verwendung in der Erfindung geeignet sind.
• • Pyrrolderivate, in denen ein alkyliertes Pyrrol an der 2-Position mit OH, NH₂ substituiert ist.
• • NHR, CO₂H, SH oder C(O)H. Besonders geeignete Pyrrolderivate umfassen 2-Carboxy-t-butylpyrrole.
• • Sulfonsäuren, wie diejenigen mit der Formel R¹SO₃H, wobei R¹ eine C₁₀- bis etwa C₆₀-Hydrocarbylgruppe, z.B. Dodecylbenzensulfonsäure, ist.
• • Organometallische Komplexe von Eisen, wie Ferrocen, substituierte Ferrocene, Eisennaphthenat, Eisensuccinat, stöchiometrische oder überalkalisierte Metallseifen (Carboxylat oder Sulfonat), Eisenpikrat, Eisencarboxylat und Eisen-Diketonat-Komplexe.

Iron complexes of the following chelating ligands are also suitable for use in the invention:

• Aromatic Mannich bases, such as those prepared by reacting an amine with an aldehyde or ketone, followed by nucleophilic attack on an active hydrogen-containing compound, eg, the product of the reaction of two equivalents of (tetrapropenyl) phenol, two equivalents of Formaldehyde and one equivalent of ethylenediamine,
• • Hydroxyaromatic oximes, such as (polyisobutenyl) salicylaldoxime. These can be prepared by reacting (polyisobutenyl) phenol, formaldehyde and hydroxylamine.
• Schiff bases, such as those produced by condensation reactions between aldehydes or ketones (eg (6-t-butyl) -salicylaldehyde) and amines (eg dodecylamine). A tetradentate ligand can be prepared using ethylenediamine (half an equivalent) in place of dodecylamine.
• Substituted phenols, such as 2-substituted 8-quinolinols, for example 2-dodecenyl-8-quinolinol or 2-N-dodecenylaminomethylphenol.
• Substituted phenols, such as those in which the substituent is NR ₂ or SR, where R is a long chain (eg 20-30 C-atoms) hydrocarbon group. In the case of both α- and β-substituted phenols, the aromatic rings may be further advantageously substituted with hydrocarbyl groups, eg, lower alkyl groups.
• Carboxylic acid esters, especially succinic acid esters, such as those prepared by reacting an anhydride (eg, dodecenylsuccinic anhydride) with a single equivalent of an alcohol (eg, triethylene glycol).
• • Acylated amines. These can be prepared by a variety of methods well known to those skilled in the art. However, particularly suitable chelates are those prepared by reacting alkenyl substituted succinates such as dodecenylsuccinic anhydride with an amine such as N, N'-dimethylethylenediamine or methyl 2-methylaminobenzoate.
• Amino acids, for example those prepared by reacting an amine such as dodecylamine with an α, β-unsaturated ester such as methyl methacrylate. In cases where a primary amine is used, it may then be acylated, such as with oleic acid or oleyl chloride.
• Hydroxamic acids, such as those made from the reaction of hydroxylamine with oleic acid.
• Bonded phenols, such as those made from the condensation of alkylated phenols with formaldehyde. When a ratio of phenol: formaldehyde of 2: 1 is used, the linking group is CH ₂ . When a ratio of 1: 1 is used, the linking group is CH ₂ OCH ₂ .
• Alkylated, substituted pyridines, such as 2-carboxy-4-dodecylpyridine.
• Borated acylated amines. These can be prepared by reacting a succinic acylating agent such as poly (isobutylene) succinic acid with an amine such as tetraethylene pentamine. This process is then followed by boronation with a boron oxide, boron halide or boronic acid, amide or ester. Similar reactions with phosphoric acid lead to the formation of phosphorus-containing acylated amines, which are also suitable for providing an oil-soluble iron chelate for use in the invention.
• Pyrrole derivatives in which an alkylated pyrrole is substituted at the 2-position by OH, NH ₂ .
• • NHR, CO ₂ H, SH or C (O) H. Particularly suitable pyrrole derivatives include 2-carboxy-t-butylpyrroles.
• Sulfonic acids, such as those of the formula R ¹ SO ₃ H where R ^{1 is} a C ₁₀ to about C ₆₀ hydrocarbyl group, eg dodecylbenzenesulfonic acid.
• Organometallic complexes of iron such as ferrocene, substituted ferrocenes, iron naphthenate, iron succinate, stoichiometric or overbased metal soaps (carboxylate or sulfonate), iron picrate, iron carboxylate and iron diketonate complexes.

suitable Iron picrates for use in the invention include those those in US-A-4,370,147 and US-A-4,265,639.

Further Iron-containing compounds for use in the invention include those having the formula M (R) x .nL where M is an iron cation R, the radical of an organic compound RH, wherein R is an organic Is a group containing an active hydrogen atom H, which replaceable by the metal M and to an O, S, P, N or C atom in the group R attached is, is, x is 2 or 3, n is 0 or a positive integer, which indicates the number of donor ligand molecules that is a dative Make bond with the metal cation, and L is a species that can act as a Lewis base.

FUEL

In A third aspect provides a fuel composition, which is (i) a potassium compound selected from the group consisting of potassium sulfonates, potassium carboxylates and mixtures thereof, (ii) a ferrocene and / or a substituted ferrocene and (iii) a Fuel includes.

In the context of VSR, the term "fuel" covers compositions containing a large amount of gasoline as the base fuel suitable for use in gasoline engines. This includes hydrocarbon base fuels boiling in the so-called gasoline boiling range of 30 to 230 ° C. This ba Sulfur fuels may include mixtures of saturated, olefinic and aromatic hydrocarbons. They may be derived from straight-run gasoline, synthetically produced aromatic hydrocarbon mixtures, thermally or catalytically cracked hydrocarbon feedstocks, hydrocracked petroleum fractions or catalytically-reformed hydrocarbons. Engine gasoline is defined by ASTM D-439-73, jet fuels typically have a narrower boiling range of 37 to 165 ° C. The gasoline may also contain various blending components designed to provide a good octane number, such as MTBE, TAME or ETBE as non-limiting examples. Some of the hydrocarbons may also be replaced by, for example, alcohols, ethers (as above), esters or ketones. In general, the octane number of the gasoline is greater than 65.

In In a preferred aspect, the iron compound provides elemental Iron in an amount of at least 5 mg per kg of fuel. preferred The iron compound provides elemental iron in an amount of at least 30 mg per kg of fuel or in an amount of 7 to 10 mg per kg of fuel.

Preferably the fuel is gasoline.

Of the Fuel may still contain performance enhancing additives. A non-limiting Listing included Corrosion inhibitors, rust inhibitors, stabilizers, antioxidants, solvent oils, antistatic agents, Dyes, anti-icing agents, ashless dispersants and detergents.

The Fuel additives according to the invention can added to the fuel as part of a package prior to combustion become. This can be at some stage in the fuel supply chain (for example, at the refinery or at the delivery point), or the additives can have one Dosing device on board the vehicle either to the fuel or even separately directly into the combustion chamber or intake system be added. The fuel additives may be the fuel in the fuel tank be added by the user of the vehicle, in the frame a so-called treatment "after the Sale".

The Invention furthermore an additive solution for the Add to a fuel. Such an additive could be up any stage in the fuel supply chain before combustion of the fuel are metered. The fuel additives of the invention can at any stage in the fueling chain to the fuel be dosed. Preferably, each additive is near the engine or the combustion system, in the fuel storage system of the engine in the refinery, at the delivery point or on any other Stage in the fuel supply chain, including the application after the Sale, added to the fuel.

The Kind, like an additive solution to use is affected the optimal formulation in a significant way. For example The fuel may be in the refinery or at the delivery point too be added to the fuel. Here are the iron and potassium components providing valuable added flexibility in use be added together or individually. If they are added together, they are made according to the need of providing a pumpable solution and avoiding any crystallization / separation of any the components at low temperatures, e.g. about -30 ° C, in the Minimum amount of solvent compatible with fuel.

When the advantages are desired, a separate addition, the ferrous material, as PLUTOcen ^®, added at the refinery as a blending component for adjusting the octane quality to meet the required product octane quality, whereby the well known and valuable role of the octane quality enhancing agent as Finisher is met. The potassium component may be added to the final fuel at the point of discharge to produce a product known to those skilled in the industry as "lead replacement gasoline" (LRG) or "lead replacement fuel" (LRP).

However, if the additive combination is to be added in the form of a "post-sale" treatment, the amount of solvent used is such as to provide a non-viscous solution suitable for use in a dispenser bottle or syringe package. The concentration of iron and potassium is such that a suitable and easily reproducible processing rate (eg, about 1 cm ³ per liter of fuel) is required. In any case, the solvents to be used should dissolve well in and be compatible with fuel, also in terms of boiling point range, and preferably have flashpoints above 62 ° C for ease of storage.

The additive solution may optionally have additional components beyond the iron and potassium compounds contain nents. These components include, as part of a nonlimiting list, corrosion inhibitors, rust inhibitors, stabilizers, antioxidants, solvent oils, antistatic agents, dyes, anti-icing agents, ashless dispersants and detergents. If any additional component is used, the use of detergents, especially poly (butenyl) succinimide based detergents, is preferred.

The Invention will now be described by way of example only with reference to FIGS accompanying drawing in more detail described.

1 is a diagram showing the measurement of the valve seat height.

EXAMPLES

The Tests were conducted by the Motor Industry Research Association (MIRA) under the auspices of the Federation of British Historic Vehicle Clubs (FBHVC). The tests were documented according to the Method No. FBHVC 98/01 performed. Details of this Methods are given in Annex I.

The Test protocol used a 1.3-liter four-cylinder engine with one cast iron Cylinder head without valve seat inserts. The engine was operated for a total of 70 hours, of which 50 hours at 3,800 rpm and 23 kW load and 20 hours at 5,500 rpm and 42 kW load. In practice, this corresponds to full throttle (WOT) operation. Before the start of the two test stages, the engine was used over a "run-in" period of about one hour powered by unleaded gasoline. This process became a purpose consistency and to allow the engine to recover after reinserting the engine Cylinder head to put. The removal and reinstatement of the Kopfs was after completion of each separate test run required. The distance between the valves was while the first 50-hour Operating time every ten hours and during the second 20 hours of operation all five Hours checked.

Example 1 - Iron and potassium

vehicle testing be using an engine of the Rover "A" series with a cast-iron cylinder head carried out. cast iron cylinder heads are for their vulnerability across from Valve seat wear known. Before the start of each test, the cylinder head is repaired and the valve seats are resized to ensure that no Traces of lead deposits that can influence the results. Of the Reassembly is done according to the standard specification. The car will then be on a dynamometer at speeds from 50-70 km / h for 1,000 km operated to allow the exhaust valves themselves embed. Experience from previous tests indicates that that at To observe these speeds only little or no valve seat wear (See M.W. Vincent and T.J. Russell, "A Review of World-wide Approaches to The Use of Additives to Prevent Exhaust Valve Seat Recession ", 4th Annual Fuels and Lubes Asia Conference, 14.-16. January 1998). Details of the engine are as below:

• Gesamtdauer 65 Minuten.
• Mittlere Geschwindigkeit insgesamt 98,5 km/h.

The test vehicle is operated according to the cycle shown below. The valve stem to toggle block distances are checked every 4 hours during the actual test. The total test time is 100 cycles, but the tests are prematurely ended when a significant valve seat wear is required is observed. The total abrasion and abrasion rates per hour for the additive fuels are compared to those obtained with gasoline containing 0.03 to 0.15 g / l lead in the form of tetraethyl lead. Tests using unleaded gasoline without additives are of a shorter duration.

• Total duration 65 minutes.
• Average speed overall 98.5 km / h.

• Gesamtdauer 50 Minuten.
• Mittlere Geschwindigkeit insgesamt 83 km/h.

Although this cycle is realistic, it is also tough. Tests were also carried out using a modified cycle as shown below.

• Total duration 50 minutes.
• Average speed overall 83 km / h.

The Results of the tests are summarized in the table below:

In In any case, the efficiency is the combination of additives of those that one compares the efficiency the individual components with or in the range of used Dose rates would be superior. This means, Signs of a synergistic effect are observed.

Example 2 - Iron and potassium

Testing were using an engine of the Rover "A" series, performed as described above. The test cycle was as follows:

• • Basisbenzin plus 9 ppm Fe in Form von Ferrocen
• • Basisbenzin plus 8 ppm K in Form eines kommerziell erhältlichen Produkts
• • Basisbenzin plus 9 ppm Fe in Form von Ferrocen und 8 ppm K in Form eines kommerziell erhältlichen Produkts

The following fuel compositions were tested:

• Base gasoline plus 9 ppm Fe in the form of ferrocene
• Base gasoline plus 8 ppm K in the form of a commercially available product
• Base gasoline plus 9 ppm Fe in the form of ferrocene and 8 ppm K in the form of a commercially available product

Each Pass followed the replacement of the valve seat inserts in the Cylinder head by cast iron constant hardness.

The the following data was obtained:

Of the Mean and, more importantly, the critical worst Show value with the iron and Potassium combination of the present invention a much lower Wear. These data demonstrate a synergy when iron and potassium in a VSR inhibiting additive can be combined.

Various Modifications and variations of the described methods and of the Systems of the invention are for Professionals in the field at hand. Although the invention is related has been described with specific preferred embodiments, it is understood that the Invention, as claimed herein, not in improper Ways to be limited to such specific embodiments.

ANNEX I FEDERATION OF BRITISH HISTORIC VEHICLE CLUBS DOCUMENTED PROCEDURE NO. FBHVC 98/01 MEASUREMENT OF THE EXHAUST VALVE SEAT FRAME USING AN ENGINE OF THE ROVER "A" SERIES

AUSLASSVENTILSITZVERSCHLEISS TEST PROCEDURE FEDERATION OF BRITISH HISTORIC VEHICLE CLUBS

1. SCOPE

This Document defines a test method for the evaluation of claimed Devices and fuel additives to allow one for leaded Petrol engine with permanent fuel unleaded gasoline can be operated.

2. AIM

The The aim of the test procedure is to reduce the exhaust valve seat wear at every device or fuel additive tested is to quantify and measure. From the recorded measurements can be an assessment of the protection of the engine, by candidate devices or Fuel additives is achieved, and their possible suitability to a valve seat wear in the made to prevent permanent use of unleaded gasoline become.

3. Definitions

• 3.1 engine - on Internal combustion engine with piston ignition
• 3.2 engine system - either Part of the engine assembly, including fuel, intake, ignition, Lubrication, cooling, outlet and control systems
• 3.3 device - any Device or any apparatus associated with the engine system, the fuel storage tank or piping
• 3.4 Additive - in Fuel soluble Medium leading to unleaded gasoline in the fuel storage tank or the piping is added
• 3.5 unleaded petrol - fuel, containing less than 0,013 g Pb / l and the specification EN 228 or BS7070
• 3.6 Leaded petrol - fuel, containing lead alkyl additives as an anti-knock agent and specification BS4040 Fulfills
• 3.7 Should - called a mandatory requirement

4. Test motors

Of the Test engine should have the following specification:

5. Preparation of the engine

• • nicht für den Betrieb mit unverbleitem Benzin modifiziert wurde
• • nicht mit Ventilsitzeinsätzen ausgestattet wurde
• • keinen Ventilsitzverschleiß aufweist.

The engine should be checked before use during testing to ensure that the cylinder head used

• • has not been modified for use with unleaded petrol
• • not equipped with valve seat inserts
• • has no valve seat wear.

N.B .: There are no new cylinder heads available are, can under exercise greater Care in the selection and preparation for the fulfillment of the above-mentioned requirements renewed units are used.

• • Einlaß- und Auslaßventile
• • Ventilschaftabdeckungen
• • Zylinderkopf- und andere Dichtungen nach Bedarf

The engine should be refitted with the following new components before use in tests:

• • intake and exhaust valves
• • Valve stem covers
• • Cylinder head and other gaskets as needed

All Valves should be ground to remove lead deposits from the previous operation with leaded gasoline from the valve seats sure.

To The reassembly is intended to drive the engine over a range of speeds and load conditions to be normal To ensure operation. preignition and excessive amounts at CO should be checked and opened the manufacturer's specifications are adjusted. As part of a final review should a power curve to be performed at full load.

• • nach dem Wiederzusammenbau des Motors und vor dem Starten. Dies wird als "Anfangs"-Zustand bezeichnet.
• • nach Einlaufen des Motors und einer Leistungsprüfung, wobei 30 Minuten nach dem Ausschalten zum Abkühlen des Motors gestattet werden. Dies wird als Zustand "nach Leistungsüberprüfung" bezeichnet.

The position of the valve tip should be measured using a gauge in combination with a micrometer gauge. Please refer 1 , The distance "a" is called the valve height. The valve heights can be measured as follows, and the measurements are recorded:

• • after reassembly of the engine and before starting. This is called an "initial" state.
• • after the engine has run down and after a performance test, allowing it to cool down for 30 minutes after switching it off. This is referred to as "after performance verification".

6. Operating conditions of the motor

The valve seat wear test should be carried out in two stages as follows:
step 1
Operation for 50 hours at 3800 rpm and 23 kW power
Level 2
Operation for 20 hours at 5500 rpm and 42 kW power

The following operating conditions should be maintained during the test: Coolant outlet 90 ± 2 ° C Temperature of the oil distribution gallery 100 ± 2 ° C Auslaßrückflußdruck 133 mbar at 5500 rpm

7. Measurement the valve seat wear

For details on measuring the position of the valve tip before starting the test, see section 5. The same technique is used to measure valve seat wear at intervals during the test. The valve height after 30 minutes of cooling should be measured and recorded at the following intervals:
Level 1: every 10 hours and after 50 hours
Stage 2: every 5 hours and after 20 hours

To Each measurement of the position of the valve tip should be checked the valve distances and on the manufacturer's specifications are adjusted.

8. Test fuel

Of the Test fuel should consist of a batch of unleaded gasoline in enough to test all candidate devices or fuel additives using the same type of fuel to allow. If a device is to be tested, no should add another additive to the fuel unless the additive forms an integral part of the device. If a fuel additive should be tested, it should be using of the mixing procedure defined in Annex A before the start of the test be added to the test fuel.

9. Test Protocol

Of the Test engine to be disassembled (removal of the cylinder head) and according to the requirements of Section 5 will be prepared to put him to the test with each candidate device or prepare any fuel additive.

Motor oil should as Part of the preparation for each test is drained and refilled.

The Piston parts of the engine ("lower End ") should be between The tests should be checked at least after every 4th test to obtain a satisfactory mechanical condition, e.g. Pass by, ensuring piston rattle. Spare pistons should be installed and holes should be ground, to keep the engine in a satisfactory state of operation.

To Completion of the Testing of candidate devices and fuel additives a test fuel containing 0.03 g Pb / L was used for another test to determine relative valve seat wear performance. This test fuel should be added by adding the required amount to lead alkyl additive to the unleaded test fuel for the previous ones Tests used was generated.

10. Criteria for success / failure

• (i) Ideally, at all stages of the Tests no significant wear of the exhaust valves to be recorded.
• (ii) Borderline success is a result with no single valve in Stage 1 Has wear and not a single valve in stage 2 has a wear greater than 0.25 mm or twice the value recorded with leaded gasoline, whichever is greater.
• (iii) a failure is a result where any valve shows valve wear, which is bigger as in (ii).

11. Results 11.1 Total valve wear (mm)

11.2 Wear of the surface of the seat after 70 hours (mm)

12. Summary operation

Appendix A

mixing process

1. Fuel / additive mixing process

• a) Verwendung eines sauberen und trockenen 205 Liter-Kraftstoffasses, Füllen mit 200 Liter Basiskraftstoff
• b) Entnehmen einer Probe von 1 Liter aus der Trommel
• c) Berechnen der erforderlichen Menge an Additiv, um die richtige Dosis zu erzielen
• d) Abmessen der erforderlichen Menge an Additiv
• e) Zugeben des Additivs zu dem Basiskraftstoff. Falls notwendig, Zugeben von etwas Kraftstoff zu dem Additiv aus der 1 Liter-Probe, um das Mischen zu unterstützen. Spülen des Additivbehälters mit Kraftstoff, um sicherzustellen, daß das gesamte Additiv in die Trommel überführt wurde
• f) Schütteln des Gemischs unter Verwendung eines pneumatischen Rührers für 10 Minuten
• g) Entnehmen einer Kraftstoffprobe von 1 Liter

The following procedure is used to prepare the fuel for the test:

• a) Using a clean and dry 205 liter fuel gauge, filling with 200 liters of basic fuel
• b) Take a 1 liter sample from the drum
• c) Calculate the amount of additive required to achieve the correct dose
• d) measuring the required amount of additive
• e) adding the additive to the base fuel. If necessary, add some fuel to the additive from the 1 liter sample to aid in mixing. Rinse the additive tank with fuel to ensure that all of the additive has been transferred to the drum
• f) Shake the mixture using a pneumatic stirrer for 10 minutes
• g) Take a fuel sample of 1 liter

Of the Basic fuel for The test should be unleaded gasoline, which meets the requirements Sections 3.5 and 8.

2. Results of fuel analysis

A Fuel sample should routinely off each one for barrels used in the test be removed. The samples can for analysis, if necessary.

Claims (12)

Use of a composition for preventing and / or inhibiting valve seat wear in an internal combustion engine, the composition comprising: (i) a potassium compound, selected from the group consisting of potassium sulfonates, potassium carboxylates and Mixtures thereof, and (ii) a ferrocene and / or a substituted Ferrocene. A fuel additive composition which comprises comprising: (I) a potassium compound from the group consisting of potassium sulfonates, potassium carboxylates and Mixtures thereof, and (ii) a ferrocene and / or a substituted Ferrocene. A fuel composition comprising: (I) a potassium compound from the group consisting of potassium sulfonates, potassium carboxylates and Mixtures thereof, (ii) a ferrocene and / or a substituted Ferrocene and (iii) a fuel. Use or composition according to any one of the preceding Claims, wherein the potassium compound comprises a potassium sulfonate. Use or composition according to claim 4, wherein the potassium sulfonate is an acid salt of potassium with alkyl benzene sulfonic acid. Use or composition according to claim 5, wherein the potassium sulfonate is an acidic salt of potassium with dodecylbenzenesulfonic acid. Use or composition according to any one of the preceding Claims, wherein the potassium compound comprises a potassium carboxylate. Use or composition according to claim 7, wherein the potassium carboxylate is an acid salt of potassium with a succinic acid derivative is. Use or composition according to any one of the preceding claims, wherein the ferro and / or the substituted ferrocene is an iron complex selected from dicyclopentadienyl and substituted dicyclopentadienyl. Use or composition according to any one of the preceding Claims, wherein the ferrocene and / or the substituted ferrocene elemental Provides iron in an amount of at least 5 mg per kg of fuel. Use or composition according to any one of the preceding Claims, wherein the ferrocene and / or the substituted ferrocene elemental Provides iron in an amount of at least 30 mg per kg of fuel. Use or composition according to any one of claims 1 to 10, wherein the ferrocene and / or the substituted ferrocene elemental Provides iron in an amount of 7 to 10 mg per kg of fuel.