DK1615985T3

DK1615985T3 - Fuel composition

Info

Publication number: DK1615985T3
Application number: DK04726498.1T
Authority: DK
Inventors: Harald Schwahn; Dietmar Posselt; Erich K Fehr
Original assignee: Basf Se
Priority date: 2003-04-11
Filing date: 2004-04-08
Publication date: 2014-03-03
Also published as: WO2004090079A1; KR20060006781A; AU2004227095B2; CA2520578A1; CL2004000766A1; BRPI0409171A; CN100545244C; ES2443993T3; JP2010013665A; JP2006522846A; PL2270119T3; RU2005134823A; JP4452712B2; CA2810284A1; CA2520578C; PT1615985E; SI1615985T1; EP1615985A1; MY162483A; AR044001A1

Description

The present invention relates to a fuel composition comprising a major amount of a specific lower alkanol-containing gasoline fuel and a minor amount of selected gasoline fuel additives.

Carburetors and intake systems of gasoline engines, and also injection systems for fuel metering, are contaminated to an increasing degree by impurities which are caused by dust particles from the air, uncombusted hydrocarbon residues from the combustion chamber and the crankcase vent gases conducted into the carburetor.

These residues shift the air-fuel ratio when idling and in the lower partial load range, so that the mixture becomes leaner, the combustion more incomplete and in turn the proportions of uncombusted or partially combusted hydrocarbons in the exhaust gas become higher and the gasoline consumption increases.

It is known that these disadvantages can be prevented by using fuel additives to keep valves and carburetors or injection systems of gasoline engines clean (cf., for example: M. Rossenbeck in Katalysatoren, Tenside, Mineraloladditive [Catalysts, surfactants, mineral oil additives], Eds.: J. Falbe, U. Hasserodt, p. 223, G. Thieme Verlag, Stuttgart 1978).

Moreover, in gasoline engines of older design, the problem of valve seat wear occurs on operation with lead-free gasoline fuels. To counteract this, valve seat wear-inhibiting additives have been developed which are based on alkali metal or alkaline earth metal compounds.

For trouble-free use, modern gasoline engines require fuels having a complex profile of properties which can only be ensured in combination with appropriate gasoline fuel additives. Such gasoline fuels generally consist of a complex mixture of chemical compounds and are characterized by physical quantities. However, the interplay between gasoline fuels and appropriate additives is still in need of improvement in the known fuel compositions with regard to the action of cleaning and keeping clean, and the valve seat wear-inhibiting action. WO 01/85874 discloses a fuel composition comprising a gasoline fuel having a sulfur content of max. 150 ppm, an olefin content of max. 21% by volume, a benzene content of max. 1.0% by volume, and aromatics content of max. 42% by volume, a carrier oil mixture and a detergent additive. The fuel composition may comprise alcohols such as methanol (maximum of 3% by volume), ethanol (maximum of 5% by volume), isopropanol (maximum of 10% by volume), t-butanol (maximum of 7% by volume) or isobutanol (maximum of 10% by volume).

Comparable maximum alcohol contents have been disclosed in the prior WO 03/074637 for gasoline fuel compositions which have been additized with specific mixtures of detergent additive and carrier oil. DD 140 359 describes low-lead fuels comprising 5-30% by volume of an additive composed of a mixture of methanol, methyl tert-butyl ether and an alcohol fraction which boils between 373 and 473 Kelvin.

The prior WO 03/076554 describes the use of specific hydrocarbylamines for reducing injector deposits in gasoline engines, wherein the lead-free gasoline fuels used may comprise 0.1-15 % by volume of additives such as methanol, ethanol and MTBE.

It is an object of the present invention to find a more effective gasoline fuel-gasoline fuel additive composition. In particular, the intention is to find more effective additive formulations .

We have found that this object is achieved by a gasoline composition according to claim 1, comprising at least one gasoline fuel additive having detergent action, wherein this gasoline fuel additive has at least one hydrophobic hydrocarbon radical having a number-average molecular weight (MN) of from 85 to 20 000 and at least one polar moiety, and wherein the fuel composition also has a content of methanol, ethanol and mixtures thereof of from 10 to 75% by volume, and wherein the polar moiety is selected from: (a) mono- or polyamino groups having up to 6 nitrogen atoms, of which at least one nitrogen atom has basic properties; (f) polyoxy-C2- to -C4-alkylene groups which are terminated by hydroxyl groups, mono- or polyamino groups, in which at least one nitrogen atom has basic properties, or by carbamate groups; (h) moieties derived from succinic anhydride and having hydroxyl and/or amino and/or amino and/or imido groups; and (i) moieties obtained by Mannich reaction of substituted phenols with aldehydes and mono- or polyamines.

The alkanol content, based on the total volume of the fuel composition, is from 10 to 75% by volume, preferably from 10 to 65% by volume, in particular from 20 to 55% by volume, for example 30 - 40% by volume or 40 - 50% by volume.

The content of further alcohols and ethers in the gasoline fuel is normally relatively low. Typical maximum contents are 7% by volume for tert-butanol, 10% by volume for isobutanol and 15% by volume for ethers having 5 or more carbon atoms in the molecule.

The maximum aromatics content of the gasoline fuel is preferably 40% by volume, in particular 38% by volume. Preferred ranges for the aromatics content are from 20 to 42% by volume, in particular from 25 to 40% by volume.

The maximum sulfur content of the gasoline fuel is preferably 100 ppm by weight, in particular 50 ppm by weight. Preferred ranges for the sulfur content are from 0.5 to 150 ppm by weight, in particular from 1 to 100 ppm by weight.

In a preferred embodiment, the gasoline fuel has a maximum olefin content of 21% by volume, preferably 18% by volume, in particular 10% by volume. Preferred ranges for the olefin content are from 6 to 21% by volume, in particular from 7 to 18% by volume.

In a further preferred embodiment, the gasoline fuel has a maximum benzene content of 1.0% by volume, in particular 0.9% by volume, Preferred ranges for the benzene content are from 0.5 to 1.0% by volume, in particular from 0.6 to 0.9% by volume.

In a further preferred embodiment, the oxygen content of the gasoline fuel is a maximum of 2.7% by weight, and is preferably from 0.1 to 2.7% by weight, in particular from 1.0 to 2.7% by weight, especially from 1.2 to 2.0% by weight.

Particular preference is given to a gasoline fuel which at the same time has a maximum aromatics content of 38% by volume, a maximum olefin content of 21% by volume, a maximum sulfur content of 50 ppm by weight, a maximum benzene content of 1.0% by volume and an oxygen content of from 1.0 to 2.7% by weight.

The above percentages by volume for all of them, benzene, aromatics and oxygen content are each based on the volume of the mineral gasoline fuel component, i.e. without additives and without alkanol.

The summer vapor pressure of the gasoline fuel is typically a maximum of 70 kPa, in particular 60 kPa (each at 370C).

The research octane number ("RON") of the gasoline fuel is generally from 90 to 100. A typical range for the corresponding motor octane number ("MON") is from 80 to 90.

The specifications mentioned are determined by customary methods (DIN EN 228) .

The hydrophobic hydrocarbon radical in the gasoline fuel additives, which ensures sufficient solubility in the fuel, has a number-average molecular weight (Mn) of from 85 to 20 000, especially from 113 to 10 000, in particular from 300 to 5 000. Typical hydrophobic hydrocarbon radicals which can be used, in particular in conjunction with the polar moieties (a) , (c) , (h) and (i) are the polypropenyl, polybutenyl and polyisobutenyl radical each having Mn = from 300 to 5 000, especially from 500 to 2 500, in particular from 750 to 2 250.

Individual gasoline fuel additives having detergent action include the following:

Additives comprising mono- or polyamino groups (a) are preferably polyalkenemono- or polyalkenepolyamines based on polypropene or on highly reactive (i.e. having predominantly terminal double bonds, usually in the alpha- and beta- position) or conventional (i.e. having predominantly internal double bonds) polybutene or polyisobutene having Mn = from 300 to 5000. Such additives based on highly reactive polyisobutene, which can be prepared from the polyisobutene which may comprise up to 20% by weight of n-butene units by hydroformylation and reductive amination with ammonia, monoamines or polyamines, such as dimethylaminopropylamine, ethylenediamine, diethylenetriamine, triethylenetetramine or tetraethylenepentamine, are disclosed in particular in EP-A 244 616. When polybutene or polyisobutene having predominantly internal double bonds (usually in the beta and gamma position) are used as starting materials in the preparation of the additives, a possible preparative route is by chlorination and subsequent amination or by oxidation of the double bond with air or ozone to give the carbonyl or carboxyl compound and subsequent amination under reductive (hydrogenating) conditions. The amines used here for the amination may be the same as those used above for the reductive amination of the hydroformylated highly reactive polyisobutene. Corresponding additives based on polypropene are described in particular in WO-A 94/24231.

Further preferred additives comprising monoamino groups (a) are the hydrogenation products of the reaction products of polyisobutenes having an average degree of polymerization P = from 5 to 100 with nitrogen oxides or mixtures of nitrogen oxides and oxygen, as described in particular in WO-A 97/03946.

Further preferred additives comprising monoamino groups (a) are the compounds obtainable from polyisobutene epoxides by reaction with amines and subsequent dehydration and reduction of the amino alcohols, as described in particular in DE-A 196 20 262.

Additives comprising polyoxy-C2~ to C4-alkylene moieties (f) are preferably polyethers or polyetheramines which are obtainable by reaction of C2- to C6o-alkanols, Ce~ to C3o-alkanediols, mono- or di-C2-C3o_alkylamines, C1-C30-alkylcyclohexanols or Ci-C3o-alkylphenols with from 1 to 30 mol of ethylene oxide and/or propylene oxide and/or butylene oxide per hydroxyl group or amino group and, in the case of the polyetheramines, by subsequent reductive amination with ammonia, monoamines or polyamines. Such products are described in particular in EP-A 310 875, EP-A 356 725, EP-A 700 985 and US-A 4 877 416. In the case of polyethers, such products also have carrier oil properties. Typical examples of these are tridecanol butoxylates, isotridecanol butoxylates, isononylphenol butoxylates and polyisobutenol butoxylates and propoxylates and also the corresponding reaction products with ammonia.

Additives comprising moieties derived from succinic anhydride and having hydroxyl and/or amino and/or amido and/or imido groups (h) are preferably corresponding derivatives of polyisobutenylsuccinic anhydride which are obtainable by reacting conventional or highly reactive polyisobutene having Mn = from 300 to 5 000 with maleic anhydride by a thermal route or via the chlorinated polyisobutene. Particular interest attaches to derivatives with aliphatic polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine or tetraethylenepentamine. Such gasoline fuel additives are described in particular in US-A 4 849 572.

Additives comprising moieties obtained by Mannich reaction of substituted phenols with aldehydes and mono- or polyamines (i) are preferably reaction products of polyisobutene-substituted phenols with formaldehyde and mono- or polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine or dimethylaminopropylamine, The polyisobutenyl-substituted phenols may stem from conventional or highly reactive polyisobutene having Mn = from 300 to 5 000. Such "polyisobutene-Mannich bases" are described in particular in EP-A 831 141.

For a more precise definition of the gasoline fuel additives detailed individually, reference is explicitly made here to the disclosures of the abovementioned prior art documents.

The fuel composition according to the invention may additionally comprise further customary components and additives. These include primarily carrier oils without marked detergent action, for example mineral carrier oils (base oils) , in particular those of the viscosity class "Solvent Neutral (SN) 500 to 2 000", and synthetic carrier oils based on olefin polymers having Mn = from 400 to 1800, in particular based on polybutene or polyisobutene (hydrogenated or nonhydrogenated), on poly-alpha-olefins or poly(internal olefin)s.

Useful solvents or diluents (when providing additive packages) are aliphatic and aromatic hydrocarbons such as Solvent

Naphtha .

Further customary additives are corrosion inhibitors, for example based on ammonium salts of organic carboxylic acids, said salts tending to form films, or of heterocyclic aromatics for nonferrous metal corrosion protection, antioxidants or stabilizers, for example based on amines such as p-phenylenediamine, dicyclohexylamine or derivatives thereof or of phenols such as 2,4-di-tert-butylphenol or 3,5-di-tert-butyl-4-hydroxyphenylpropionic acid, demulsifiers, antistats, metallocenes such as ferrocene or methylcyclopentadienylmanganese tricarbonyl, lubricity additives such as certain fatty acids, alkenylsuccinic esters, bis(hydroxyalkyl) fatty amines, hydroxyacetamides or castor oil and also markers. Amines are also optionally added to lower the pH of the fuel.

Also useful for the fuel composition according to the invention are in particular combinations of the gasoline fuel described with a mixture of gasoline fuel additives having the polar moiety (f) and corrosion inhibitors and/or lubricity additives based on carboxylic acids or fatty acids which may be present as monomeric and/or dimeric species. Typical mixtures of this type comprise polyisobutanamines in combination with alkanol-started polyethers such as tridecanol or isotridecanol butoxylates or propoxylates, polyisobutenamines in combination with alkanol-started polyetheramines such as tridecanol or isotridecanol butoxylate-ammonia reaction products and alkanol-started polyetheramines such as tridecanol or isotridecanol butoxylate reaction products in combination with alkanol-started polyethers such as tridecanol or isotridecanol butoxylates or propoxylates, used together with the corrosion inhibitors and/or lubricity additives mentioned.

The gasoline fuel additives having the polar moieties (a) , (f) , (h) and (i) mentioned, and also the other components mentioned, are metered into the gasoline fuel and exhibit their action there. The components and/or additives may be added to the fuel individually or as a concentrate prepared beforehand ("additive package").

The gasoline fuel additives having the polar moieties (a) , (f) , (h) and (i) mentioned are added to the gasoline fuel typically in an amount of from 5 to 5 000 ppm by weight, especially from 5 to 3 000 ppm by weight, in particular from 10 to 1 000 ppm by weight. The other components and additives mentioned are, if desired, added in amounts customary for this purpose .

In the fuel composition according to the invention, it is surprisingly possible with distinctly less detergent or valve seat wear inhibitor to achieve the same action of cleaning or keeping clean, or valve seat wear-inhibiting action as for comparable fuel compositions without lower alkanol addition. Moreover, the use of the same amounts of detergent or valve seat wear inhibitor in the fuel composition according to the invention, compared to conventional fuel compositions, surprisingly results in a distinctly better action of cleaning or keeping clean, and valve seat wear-inhibiting action.

In addition, the fuel composition according to the invention additionally exhibits advantages to the effect that fewer deposits are formed in the combustion chamber of the gasoline engine and that less additive is entrained into the engine oil via the fuel dilution.

The invention further relates to i) the use of a lower alkanol in low-sulfur gasoline fuels to improve the action of an additive having detergent action as defined in the claims and ii) the use of a combination of lower alcohol and at least one additive having detergent action to reduce combustion chamber deposits and/or to reduce deposits in the intake system of a gasoline engine; as defined in the claims and

The examples which follow are intended to illustrate the invention without restricting it.

Examples:

The gasoline fuel additive used was a commercial additive package comprising 60% by weight of detergent additive, polyisobutenamine (Mn = 1 000 g/mol) , and 32% by weight of carrier oil (tridecanol etherified with 22 units of butylene oxide).

The gasoline fuels used were those listed below with the particular specification stated, and GF 1 (parameters see Table 1) is a typical commercially available fuel.

Table 1

GF 2 = GF 1 + 10% by vol. of EtOH GF 3 = GF 1 + 50% by vol. of EtOH Preparation of the fuel compositions Example 1 (comparative experiment) 150 or 200 mg of additive package were dissolved in 1 kg of GF 1 according to Table 1.

Example 2 (inventive)

Example 1 was repeated except that GF 2 was used instead of GF 1.

Example 3 (inventive)

Example 1 was repeated except that GF 3 was used instead of GF 1

Performance investigations Example 4

Gasoline fuels according to Examples 1 to 3 were investigated for their influence on the intake valve deposits (IVD) and on the total combustion deposits (TCD). This was effected with the aid of engine tests which were carried out in test rig experiments with a Mercedes-Benz engine M102 E according to CEC F-05-A-93. The IVD values for additized and nonadditized fuels are compiled in the following Table 2.

In addition, the amount of total combustion deposits (TCD) was determined in the same experimental series for each of the four cylinders of the engine. The particular average value is likewise quoted in Table 2. To determine the TCD value, the procedure was similar to the method CEC F-20-A-98.

Table 2

2) Intake Valve Deposits 2) Total Combustion Deposits

As is evident from Table 2, the admixing of relatively large amounts of ethanol (i.e. > 10%) to the gasoline fuel results in surprisingly little formation of valve or combustion chamber (cylinder) deposits being observed.

Claims

A gasoline composition having a maximum sulfur content of 150 wt ppm containing 5 to 5,000 wt ppm of at least one gasoline additive with detergent action, said gasoline additive having at least one hydrophobic hydrocarbon group having a number average molecular weight (Mn) of 85 to 20,000 and at least one polar group, the fuel composition further having a methanol, ethanol or mixtures thereof of 10 to 75% by volume, and the polar group being selected from: (a) mono or polyamino groups having up to 6 nitrogen atoms; (at least one nitrogen atom having basic properties, (f) polyoxy-C 2 -C 4 alkylene groups terminated by hydroxyl groups, mono- or polyamino groups, at least one nitrogen atom having basic properties, or by carbamate groups, (h) groupings derived from succinic anhydride with hydroxy and / or amino and / or amido and / or imido groups and (i) groupings produced by Mannich reaction of substituted phenols with aldehydes and mono or polyamines.

The gasoline composition of claim 1, containing as a gasoline additive with polar groupings (a) polyalkene mono or polyalkene polyamines based on polypropylene, polybutene or polyisobutene having Mn = 300 to 5,000.

The gasoline composition of claim 1, containing as a gasoline additive with polar groupings (f) polyethers or polyetheramines obtainable by reaction of C -C30 alkylcyclohexanols or C1-C30 alkyl phenols having 1 to 30 moles of ethylene oxide and / or propylene oxide and / or butylene oxide per hydroxyl group or amino group and, in the case of polyetheramines, by subsequent reductive amination with ammonia, monoamines or polyamines.

The gasoline composition of claim 1, containing as a petrol additive with polar groupings (h) derivatives of polyisobutenyl succinic anhydride, obtainable by reaction of conventional or highly reactive polyisobutene with Mn = 300 to 5,000 with maleic anhydride in a thermal manner or via the chlorinated polyisobutene.

The gasoline composition of claim 5, containing as a gasoline additive with polar groupings (i) reaction products of polyisobutene-substituted phenols with formaldehyde and mono- or polyamines.

A gasoline composition according to any one of claims 1 to 5, containing a gasoline having an olefin content of a maximum of 21% by volume based on the volume of the non-added non-alcoholic gasoline.

A gasoline composition according to any one of claims 1 to 6, containing a gasoline having a maximum gasoline content of 1.0 vol% based on the volume of the non-added non-alcoholic gasoline.

The gasoline composition according to any one of claims 1 to 7, containing a gasoline having an oxygen content of a maximum of 2.7% by weight based on the volume of the non-added non-alcoholic gasoline.

The gasoline composition according to any one of claims 1 to 8, containing a gasoline having a maximum aromatic content of 42% by volume based on the volume of the non-added non-alcoholic gasoline.

Use of at least one C 1 -C 6 monoalkanol or mixtures thereof in a proportion of 10 to 75% by volume in low sulfur gasoline having a maximum sulfur content of 150% by weight ppm to improve the effect of an additive with detergent effect, the additive have at least one hydrophobic hydrocarbon group having a number average molecular weight (Mn) of 85 to 20,000 and at least one polar group selected from (a) mono- or polyamino groups having up to 6 nitrogen atoms, at least one nitrogen atom having basic properties, (f) polyoxy C 2 -C 4 alkylene groups terminated by hydroxyl groups, mono or polyamino groups, having at least one nitrogen atom having basic properties, or by carbamate groups, (h) groupings derived from succinic anhydride with hydroxy groups. and / or amino and / or amido and / or imido groups and (i) the groupings produced by Mannich reaction of substituted phenols with aldehydes and mono- or polyamines; the additive effect can be determined according to CEC F-05-A-93 or CEC F-20-A-98, and the additive being contained in an amount of 5 to 5,000 weight ppm.

Use of a combination of at least one C1-C6 monoalkanol or mixtures thereof and at least one detergent action additive as defined in claim 1 for reducing deposits in the combustion chamber which can be determined according to CEC F-20-A. 98, and / or to reduce deposits in the intake system of a gasoline engine and / or to reduce which can be determined according to CEC F-05-A-93, adding the additive with detergent to a gasoline in an amount of 5 to 5,000 weight -ppm, and the alkanol is added in a content of 10 to 75% by volume.