WO2004090079A1

WO2004090079A1 - Fuel composition

Info

Publication number: WO2004090079A1
Application number: PCT/EP2004/003811
Authority: WO
Inventors: Harald Schwahn; Dietmar Posselt; Erich K. Fehr
Original assignee: Basf Aktiengesellschaft
Priority date: 2003-04-11
Filing date: 2004-04-08
Publication date: 2004-10-21
Also published as: MXPA05010183A; EP1615985B1; CA2810284C; CN100545244C; AR044001A1; MY162483A; EP1615985A1; ZA200509086B; CA2810284A1; JP4452712B2; PT1615985E; CA2520578A1; JP2013209664A; RU2005134823A; CN1802425A; DE10316871A1; ES2443993T3; NO20054374L; PL1615985T3; BRPI0409171A

Abstract

Disclosed is a fuel composition containing a major quantity of gasoline having a maximum sulfur content of 150 ppm by weight, and a minor quantity of at least one gasoline additive having a detergent effect or a valve seat wear-inhibiting effect. Said gasoline additive comprises at least one hydrophobic hydrocarbon radical having an average molecular weight of 85 to 20,000, and at least one polar group. The fuel composition further contains at least one low alkanol at a moiety of about 5 to 75 percent by volume.

Description

Fuel composition

description

The present invention relates to a fuel composition containing, in a larger amount, a specific low alkanol-containing gasoline fuel and a smaller amount of selected gasoline additives.

Carburetors and intake systems of gasoline engines, but also injection systems for fuel metering, are increasingly burdened by impurities caused by dust particles from the air, unburned hydrocarbon residues from the combustion chamber and the crankcase vent gases fed into the gasifier.

These residues shift the air-fuel ratio at idle and in the lower part-load range, making the mixture leaner, incomplete combustion and, in turn, increasing the proportion of unburned or partially combusted hydrocarbons in the exhaust gas and increasing gasoline consumption.

It is known that in order to avoid these disadvantages, fuel additives are used for keeping valves and carburetors or injection systems of gasoline engines clean (cf., for example: M. Rossbach in Catalysts, Surfactants, Mineral Oil Additives, Ed. J. Falbe, U. Hasserodt, S. 223, G. Thieme Verlag, Stuttgart 1978).

Furthermore emerges in gasoline engines of older design, the problem of valve seat wear when operating with unleaded gasoline. For this purpose, valve seat wear-inhibiting additives based on alkali metal or alkaline earth metal compounds have been developed.

Modern gasoline engines require for a trouble-free use fuels with a complex property profile, which can be guaranteed only in combination with appropriate gasoline additives. Such gasoline fuels usually consist of a complex mixture of chemical compounds and are characterized by physical quantities. However, the interaction between gasoline fuels and corresponding additives is still in need of improvement in the case of the known fuel compositions with regard to the cleaning and / or retention effect and the valve seat wear-inhibiting effect. It was therefore an object of the present invention to find a more effective gasoline / gasoline fuel additive composition. In particular, more effective additive formulations should be found.

Accordingly, a fuel composition has been found which contains in a greater amount a gasoline having a sulfur content of at most 150 ppm by weight, and in a smaller amount at least one gasoline additive with detergent effect or valve seat wear-inhibiting effect, said gasoline fuel additive having at least one hydrophobic hydrocarbon radical having a number average molecular weight (MN) of 85 to 20,000 and at least one polar moiety, and wherein the fuel composition further has a content of at least one lower alkanol of about 5 to 75% by volume.

The polar grouping is selected under:

(a) mono- or polyamino groups having up to 6 nitrogen atoms, at least one nitrogen atom having basic properties,

(b) nitro groups, optionally in combination with hydroxyl groups,

(c) hydroxyl groups in combination with mono- or polyamino groups, where at least one nitrogen atom has basic properties,

(d) carboxyl groups or their alkali metal or alkaline earth metal salts,

(e) sulphonic acid groups or their alkali metal or alkaline earth metal salts,

(f) polyoxy-C 2 to C 4 -alkylene groups terminated by hydroxyl groups, mono- or polyamino groups, wherein at least one nitrogen atom has basic properties, or terminated by carbamate groups,

(g) carboxylic ester groups,

(h) succinic anhydride-derived moieties having hydroxy and / or amino and / or amido and / or imido groups and

(i) moieties generated by Mannich reaction of substituted phenols with aldehydes and mono- or polyamines The lower alkanol used according to the invention is preferably a straight-chain or branched, saturated C ₁ -C 6 mono- or diol, in particular a C ₁ -C ₃ mono- alkanol, such as methanol, ethanol, n- or i-propanol, or a mixture of several of these alkanols.

The alkanol content is, based on the total volume of the fuel composition a maximum of 75 vol .-%, such as. B. 5 to 75 vol .-%, preferably 10 to 65 vol .-%, in particular 20 to 55 vol .-%, such as. B. 30 - 40 vol .-% or 40 - 50 vol .-%.

The content of other alcohols and ethers in gasoline is usually 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 C atoms in the molecule.

The aromatic content of the gasoline is preferably not more than 40% by volume, in particular not more than 38% by volume. Preferred ranges for the aromatic content are from 20 to 42% by volume, in particular from 25 to 40% by volume.

The sulfur content of the gasoline is preferably not more than 100 ppm by weight, in particular not more than 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 has an olefin content of not more than 21% by volume, preferably not more than 18% by volume, in particular not more than 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 has a benzene content of not more than 1, 0 vol .-%, in particular not more than 0.9 vol .-%, on. Preferred ranges for the benzene content are from 0.5 to 1, 0 vol .-%, in particular 0.6 to 0.9 vol .-%.

In a further preferred embodiment, the gasoline has an oxygen content of at most 2.7% by weight, preferably from 0.1 to 2.7% by weight, especially from 1, 0 to 2.7% by weight. , in particular from 1, 2 to 2.0 wt .-%, on.

Particularly preferred is a gasoline fuel which at the same time has an aromatics content of not more than 38% by volume, an olefin content of not more than 21% by volume, a sulfur content of not more than 50 ppm by weight, a benzene content of not more than 1.0% by volume and a Has oxygen content of 1, 0 to 2.7 wt .-%. The above vol .-% - for olefin, benzene, aromatics and oxygen content are in each case based on the volume of the mineral gasoline component, ie without additives and without alkanol.

The summer vapor pressure of the gasoline is usually not more than 70 kPa, in particular 60 kPa (each at 370C).

The research octane number ("RON") of the gasoline is typically 90 to 100. A common range for the corresponding engine octane number ("MOZ") is 80 to 90.

The specified specifications are determined by conventional methods (DIN EN 228).

The hydrophobic hydrocarbon radical in the gasoline fuel additives, which provides sufficient solubility in the fuel, has a number average molecular weight (Mn) of 85 to 20,000, especially from 113 to 10,000, especially from 300 to 5000. As a typical hydrophobic hydrocarbon radical, in particular Compound with the polar groups (a), (c), (h) and (i), the Polypropenyl-, Polybu- tenyl- and Polyisobutenylresl come with in each case Mn = 300 to 5000, in particular 500 to 2500, especially 750 to 2250 , considering.

As individual gasoline additives with detergent effect or with valve seat wear-inhibiting effect, the following may be mentioned.

Mono- or polyamino (a) -containing additives are preferably polyalkene mono- or Polyalkenpolyamine based on polypropene or highly reactive (ie with predominantly terminal double bonds - usually in the alpha and beta position) or conventional (ie with predominantly middle double bonds Polybutene or polyisobutene having Mn = 300 to 5000. Such additives based on highly reactive polyisobutene, which from the polyisobutene, which may contain up to 20 wt .-% of n-butene units, by hydroformylation and reductive amination with ammonia, monoamines or polyamines, such as dimethylaminopropylamine, ethylenediamine, diethylenetriamine, triethylenetetramine or tetraethylenepentamine, are known in particular from EP-A 244 616. If one starts with the preparation of the additives of polybutene or polyisobutene with predominantly central double bonds (usually in the beta and gamma position), the preparation route by chlorination and subsequent amination or by oxidation of the double bond with air or ozone to carbonyl or Carboxyl compound and subsequent amination under reductive (hydrogenating) conditions to. For amination, the same amines as described above for the reductive amination of the hydroformylated highly reactive polyisobutene can be used here. Corresponding additives based on polypropene are described in particular in WO-A 94/24231.

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

Further preferred monoamino groups (a) containing additives 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.

Nitro groups, optionally in combination with hydroxyl groups, (b) containing additives are preferably reaction products of polyisobutenes of average degree of polymerization P = 5 to 100 or 10 to 100 with nitrogen oxides or mixtures of nitrogen oxides and oxygen, as described in particular in WO-A 96/03367 and WO-A 96/03479. These reaction products typically are mixtures of pure nitropolyisobutanes (e.g., alpha.beta.-dinitropolyisobutane) and mixed hydroxynitropolyisobutanes (e.g., alpha-nitro-beta-hydroxypolyisobutane).

Hydroxyl groups in combination with mono- or polyamino groups (c) containing additives are in particular reaction products of polyisobutene epoxides obtainable from preferably predominantly terminal double bonds polyisobutene having Mn = 300 to 5000, with ammonia, mono- or polyamines, as described in particular in EP-A 476 485 are described.

Carboxyl groups or their alkali metal or alkaline earth metal salts (d) containing additives are preferably copolymers of C ₂ -C ₄₀ olefins with maleic anhydride having a total molecular weight of 500 to 20 000, the carboxyl groups wholly or partially to the alkali metal or alkaline earth metal salts and a remaining Rest of the carboxyl groups are reacted with alcohols or amines. Such additives are known in particular from EP-A 307 815. Such additives serve primarily to prevent valve seat wear and, as described in WO-A 87/01126, may advantageously be used in combination with conventional fuel detergents such as poly (iso) butenamines or polyetheramines. Sulphonic acid groups or their alkali metal or alkaline earth metal salts (e) containing additives are preferably alkali metal or alkaline earth metal salts of a sulfosuccinic acid alkyl ester, as described in particular in EP-A 639 632. Such additives are mainly used to prevent valve seat wear and can be used to advantage in combination with conventional fuel detergents such as poly (iso) butenamines or polyetheramines.

Polyoxy-C ₂ - to C ₄ -alkylene (f) additives are preferably polyethers or polyetheramines which are obtainable by reaction of C ₂ - to C ₆₀ alkanols, C ₆ - to C ₃₀ alkanediols, mono- or di-C ₂ C ₃₀ -alkylamines, -CC ₃₀ -alkylcyclohexanols or CC ₃₀ -alkylphenols with 1 to 30 moles of ethylene oxide and / or propylene oxide and / or butylene oxide per hydroxyl group or amino group and, in the case of polyetheramines, by subsequent reductive amination with ammonia, monoamines or polyamines are available. Such products are 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 polyethem, such products also fulfill carrier oil properties. Typical examples of these are tridecanol or Isotridecanolbutoxylate, Isononylphenolbutoxylate and Polyisobutenolbutoxylate and propoxylates and the corresponding reaction products with ammonia.

Carboxylic ester groups (g) containing additives are preferably esters of mono-, di- or tricarboxylic acids with long-chain alkanols or polyols, especially those having a minimum viscosity of 2 mm2 / s at 100oC, as described in particular in DE-A 38 38 918. Aliphatic or aromatic acids can be used as the mono-, di- or tricarboxylic acids, and the ester alcohols or polyols which are suitable are above all long-chain representatives with, for example, 6 to 24 C atoms. Typical representatives of the esters are adipates, phthalates, isophthalates, terephthalates and trimellitates of iso-octanol, iso-nonanol, iso-decanol and of isotridecanol. Such products also meet carrier oil properties.

Succinic anhydride-derived groupings containing hydroxyl and / or amino and / or amido and / or imido groups (h) are preferably corresponding derivatives of polyisobutenyl succinic anhydride obtained by reacting conventional or highly reactive polyisobutene having Mn = 300 to 5000 with maleic anhydride thermal ways or via the chlorinated polyisobutene are available. Of particular interest here are derivatives with aliphatic polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine or tetraethylenepentamine. Such gasoline additives are described in particular in US Pat. No. 4,849,572. By Mannich reaction of substituted phenols with aldehydes and mono- or polyamines generated groupings (i) containing additives are preferably reaction products of polyisobutene-substituted phenols with formaldehyde and mono- or polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine or dimethylaminopropylamine. The polyisobutenyl-substituted phenols may be derived from conventional or highly reactive polyisobutene having Mn = 300 to 5,000. Such "polyisobutene-Mannich bases" are described in particular in EP-A 831 141.

For a more detailed definition of the individual listed petrol additives, reference is made here expressly to the disclosures of the abovementioned prior art documents.

The fuel composition of the invention may further contain other conventional components and additives. Carrier oils without pronounced detergent action should be mentioned here in the first place, for example mineral carrier oils (base oils), in particular those of the viscosity class "Solvent Neutral (SN) 500 to 2000", and synthetic carrier oils based on olefin polymers with Mn = 400 to 1800, above all based on polybutene or polyisobutene (hydrogenated or unhydrogenated), polyalphaolefins or polyinteralalefins.

Suitable solvents or diluents (when providing additive packages) are aliphatic and aromatic hydrocarbons, e.g. Solvent naphtha, into consideration.

Further customary additives are corrosion inhibitors, for example based on film-forming ammonium salts of organic carboxylic acids or of heterocyclic aromatics in the case of non-ferrous metal corrosion protection, antioxidants or stabilizers, for example based on amines such as p-phenylenediamine, dicyclohexylamine or derivatives thereof or on phenols such as 2,4 -Di-tert-butylphenol or 3,5-di-tert-butyl-4-hydroxyphenylpropionic acid, demulsifiers, antistatic agents, metallocenes such as ferrocene or methylcyclopentadienyl manganese tricarbonyl, lubricity improvers such as certain fatty acids, alkenyl succinic acid esters, bis (hydroxyalkyl ) fatty amines, hydroxyacetamides or castor oil as well as dyes (markers). Sometimes amines are also added to lower the pH of the fuel.

For the fuel composition according to the invention, in particular, combinations of the described gasoline with a mixture of gasoline fuel additives with the polar grouping (f) and corrosion inhibitors and / or lubricity improvers based on carboxylic acids or fatty acids, which as monomeric and / or dimeric species may be considered. Typical mixtures of this type include polyisobutene amines in combination with alkanol-initiated polyethers such as tridecanol or isotridecanol butoxylates or propoxylates, polyisobutene amines in combination with alkanol-initiated polyetheramines such as tridecanol or isotridecanol butoxylate ammonia reaction products and alkanol-initiated polyether amines such as tridecanol or isotridecaol butoxylate ammonia reaction products Combination with alkanol-initiated polyethers, such as tridecanol or isotridecanol butoxylates or propoxylates, in each case together with the abovementioned corrosion inhibitors or lubricity improvers.

The aforementioned gasoline additives with the polar groups (a) to (i) and the other components mentioned are added to the gasoline and unfold their effect there. The components or additives can be added to the gasoline fuel individually or as a previously prepared concentrate ("additive package").

The above gasoline additives with the polar groups (a) to (i) are added to the gasoline usually in an amount of 1 to 5000 ppm by weight, in particular 5 to 3000 ppm by weight, especially 10 to 1000 ppm by weight , The other components and additives mentioned are added, if desired, in customary amounts.

Surprisingly, with the fuel composition of the present invention, with significantly less detergent or valve seat wear-inhibiting agent, the same cleaning or valve seat wear-inhibiting effect can be achieved as in comparable fuel compositions without low alkanol addition. Furthermore, when using the same amounts of detergent or valve seat wear-inhibiting agent in the inventive fuel composition compared to conventional fuel compositions surprisingly results in a significantly better cleansing or reinhaltende or valve seat wear-inhibiting effect kung.

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

Further objects of the invention relate to i) the use of a lower alkanol in low-sulfur gasoline fuels to improve the effect of a detergent-effect additive or valve seat wear-inhibiting effect as defined above; (ii) a method of improving the additive effect of a detergency-enhancing or valve-seat wear-inhibiting additive as defined above in low-sulfur gasoline fuels by adding an effective amount of a lower alcohol to the gasoline;

(iii) the use of a combination of a lower alcohol and at least one detergency-enhancing or valve-seat wear-inhibiting additive as defined above to reduce combustion chamber deposits and / or to reduce deposits in the intake system of a gasoline engine.

iv) the use of a combination of low alcohol and valve seat wear-inhibiting additive as defined above as a valve seat wear inhibitor for gasoline fuels.

The following examples are intended to illustrate the invention without, however, limiting it.

Examples:

The gasoline additive used was a commercial additive package comprising 60% by weight of detergent additive polyisobuteneamine (Mn = 1000 g / mol) and 32% by weight of carrier oil (tridecanol etherified with 22 units of butylene oxide).

As gasoline fuels, those listed below were used with the specified specification, with OK 1 (parameters see Table 1) representing a typical commercial fuel.

Table 1

OK 2 = OK 1 + 10 vol% EtOH OK 3 = OK 1 + 50 vol% EtOH

Production of Fuel Compositions

Example 1 (comparative experiment)

150 or 200 mg of additive package were dissolved in 1 kg of OK 1 according to Table 1.

Example 2 (according to the invention)

Example 1 was repeated, but using OK 2 instead of OK 1.

Example 3 (according to the invention)

Example 1 was repeated but using OK 3 instead of OK 1.

Application studies

Example 4

Gasoline fuels according to Examples 1 to 3 were examined for their influence on the intake system cleanliness (IVD) and on the combustion chamber deposits (TCD). This was done with the help of engine tests, which were carried out in Mercedes-Benz engine M102 E according to CEC F-05-A-93. The IVD values for additized and non-additized fuels are summarized in Table 2 below.

Further, in the same series of experiments, the amount of combustion chamber deposits (TOD) for each of the 4 cylinders of the engine was determined. The respective average value is also given in Table 2. To determine the TCD value, the procedure was analogous to the procedure CEC F-20-A-98. Table 2

¹⁾ Intake Valve Deposits

²⁾ Total Combustion Deposits

As can be seen from Table 2, when larger quantities of ethanol (ie> 10%) are added to the gasoline, a surprisingly small formation of valve or combustion chamber (cylinder) deposits is observed.

Claims

claims

1. A fuel composition containing in a larger amount a gasoline fuel with a sulfur content of at most 150 ppm by weight, and in a smaller

An amount of at least one gasoline detergent or valve seat wear inhibiting gasoline additive, said gasoline fuel additive having at least one hydrophobic hydrocarbon radical having a number average molecular weight (MN) of 85 to 20,000 and at least one polar moiety, and wherein said fuel composition also has a content of at least one lower alkanol of about 5 to 75% by volume.

2. A fuel composition according to claim 1, wherein the polar moiety is selected from:

(b) nitro groups, optionally in combination with hydroxyl groups,

(d) carboxyl groups or their alkali metal or alkaline earth metal salts,

(e) sulphonic acid groups or their alkali metal or alkaline earth metal salts,

(g) carboxylic ester groups,

(i) moieties generated by Mannich reaction of substituted phenols with aldehydes and mono- or polyamines.

3. A fuel composition according to claim 2, containing as gasoline additive with polar groups (a) Polyalkenmono- or Polyalkenpolyamine based on polypropene, polybutene or polyisobutene with Mn = 300 to 5000.

4. Fuel composition according to claim 2, containing as gasoline additive with polar groups (b) reaction products of polyisobutenes of average degree of polymerization P = 5 to 100 with nitrogen oxides or mixtures of nitrogen oxides and oxygen.

5. A fuel composition according to claim 2, containing as a gasoline additive with polar groups (c) reaction products of polyisobutene epoxides obtainable from predominantly terminal double bonds having polyisobutene with Mn = 300 to 5000, with ammonia, mono- or polyamines.

6. A fuel composition according to claim 2, comprising as gasoline additive with polar groups (d) copolymers of C ₂ -C ₄₀ olefins with maleic anhydride having a total molecular weight of 500 to 20,000, the carboxyl groups wholly or partly to the alkali metal or alkaline earth metal salts and a remaining radical of the carboxyl groups are reacted with alcohols or amines.

7. A fuel composition according to claim 2, containing as gasoline additive with polar groups (e) alkali metal or alkaline earth metal salts of a sulfosuccinic acid alkyl ester.

8. A fuel composition according to claim 2, containing as a gasoline additive with polar groups (f) polyether or polyether amines obtainable by reaction of C ₂ -C ₃₀ alkanols, C ₆ -C ₆ o-alkanediols, mono- or di- C ₂ -C ₃₀ -alkylamines, CC ₃₀ -alkylcyclohexanols or CrC ₃ o-alkylphenols with 1 to 30 moles of ethylene oxide and / or propylene oxide and / or butylene oxide per hydroxyl group or amino group and, in the case of polyetheramines, by subsequent reductive amination with ammonia, monoamines or polyamines.

9. A fuel composition according to claim 2, containing as gasoline additive with polar groups (g) esters of mono-, di- or tricarboxylic acids with long-chain alkanols or polyols.

10. A fuel composition according to claim 2, comprising as petrol additive with polar groups (h) derivatives of polyisobutenyl succinic anhydride, obtainable by reaction of conventional or highly reactive polyisobutene with Mn = 300 to 5000 with maleic anhydride by thermal means or via the chlorinated polyisobutene.

11. A fuel composition according to claim 2, containing as gasoline additive with polar groups (i) reaction products of polyisobutene-substituted

Phenols with formaldehyde and mono- or polyamines.

12. A fuel composition according to any one of claims 1 to 11, containing a gasoline with an olefin content of not more than 21 vol .-% based on the volume of the non-additive low alkanol-free gasoline.

13. A fuel composition according to any one of claims 1 to 12, containing a gasoline with a benzene content of not more than 1, 0 vol .-% based on the volume of the non-additive low alkanol-free gasoline.

14. A fuel composition according to any one of claims 1 to 13, containing a gasoline having an oxygen content of at most 2.7 wt .-% based on the volume of the non-additive low alkanol-free gasoline.

15. A fuel composition according to any one of claims 1 to 14, containing a gasoline having an aromatic content of not more than 42 vol .-% based on the volume of the non-additive low alkanol-free gasoline.

16. A fuel composition according to claims 1 to 15, containing the gasoline fuel additives with the polar groups (a) to (i) in an amount of 1 to

5000 ppm by weight.

17. Use of a low alkanol in low-sulfur gasoline fuels to improve the effect of a detergent-effect additive or valve seat wear-inhibiting effect as defined in claim 1.

18. A method for improving the additive effect of a detergent effect or with valve seat wear inhibiting effect as defined in claim 1 in low-sulfur gasoline fuels, wherein the gasoline is added with an effective amount of a lower alcohol.

19. Use of a combination of a lower alcohol and at least one additive with detergent action or valve seat wear-inhibiting effect as defined in claim 1 for reducing combustion chamber deposits and / or for reducing deposits in the intake system of a gasoline engine.

Use of a combination of lower alcohol and valve seat wear-inhibiting additive as defined in claim 1 as a valve seat wear inhibitor for gasoline fuels.