DE1959388A1 - Fuel additive of an ether and group 2a metal salt - Google Patents

Abstract

The additive is a mixture of an ether, a group (IIA) metal-salt of an organic acid and a group (IIA) metal sulphonate or a group (IIA) metal carbonate. The purpose is the suppression of smoke and the reduction of rust.

Description

Fuel additive The invention relates to new fuel additions It particularly relates to new fuel additives that reduce smoke and soot during the operation of internal combustion engines, in particular internal combustion engines with compression ignition, decrease.

The petroleum industry faces serious problems, middle distillate and to supply heavy oil fuels that are suitable for injection in through compression Ignited engines are suitable and which do not have any significant pollution of the atmosphere due to smoke and soot build-up. Bs is not just a need for one Diesel fuel mixture with reduced smoke formation, but also for hydrocarbon fuel mixtures with improved combustion properties found in spark ignition and jet engines be used.

Attempts have been made to reduce the amount of visible smoke and to reduce soot in the exhaust gases generated during the oxidation of liquids Hydrocarbon fuels form, for example, have been used in compression ignition engines certain metallic smoke suppression mixtures have been used, but these mixtures do not residues back in the engine crankcase (a consequence of the between the cylinder wall and pistons of forced gas, and they are expensive to manufacture and to package, and ultimately they can put unwanted combustion products in a It is still known to form an amount depending on its metal content. in fuels incorporate various materials to reduce their tendency to form soot and Prevent sediments and their tendency to clog0 Some of these materials however, exhibit a tendency, and in some cases, to emulsify upon storage Tendency to decrease or decrease in the cetane number of diesel fuels the octane number of gasoline, while others oppose the stability of the fuel Reduce oxidation during storage, these and other additives also impart the fuels generally have no other favorable properties, such as zoBe a corrosion protection for the engine surfaces, or a surface activity for Support cleaning the injection pumps of diesel engines or a more uniform one Injection behavior, accordingly, there is an urgent need for the production of multifunctional hydrocarbon fuel additives that reduce smoke and soot formation suppress when operating combustion engines and improve the combustion process, with no side effects and disadvantages, as they are with the known additives Have occurrence, So according to the invention there is a smoke and soot formation propose suppressive additive for liquid hydrocarbon fuels, which consists of a mixture, that results from (i) an ether and (2) a Group IIA metal salt of an organic acid, a Group IIA metal sulfonate or a Group IIA metal carbonate.

According to the invention, a fuel additive is also proposed, which is composed of an ether and a Group IIA metal salt of an organic acid a Group IIB metal salt of an organic acid. .additional combinations from barium and zinc salts of alkanoic acids, which are branched in the alpha position and glycol ethers, particularly alkyl ethers of ethylene glycol, give one particular strong reduction in the also and soot formation of the Kraftsotffe. A particularly effective one Addition is a mixture of the monomethyl ether of ethylene glycol and of barium and zinc 2-ethylhexanoate, wherein the weight ratio of barium metal to zinc metal about 10: 1 and the weight ratio of ether to carboxylates about 2: 1-1 5: 1 is.

The above fuel additives can also contain Group IIA metal sulfonates, in particular a barium alkaryl sulfonate.

A particularly preferred additive is a mixture of 1-methoxy-2-propanol, a barium alkaryl sulfonate with a molecular weight of approximately 1000, barium 2-ethylhexanoate and zinc-2-ethylhexanoat0 A fuel mixture with a reduced smoke and Soot is formed when using the above mixture of carboxylates, ether and sulfonate dispersed or dissolved in liquid hydrocarbon fuels. A preferred one Fuel blend is a diesel fuel that contains approximately 0.2-0.5 wt% barium alkaryl sulfonate 0.1-0.6% by weight barium and zinc 2-ethylahexanoate and approximately 0.2-0.5% by weight 1 methoxy-2-propanol contains.

In general, the Group IIA and Group IIB metals combined with any organic acids to produce salts that used according to the earth connection can be. Such salts can be aliphatic or aromatic carboxylates, such as. B. alkyl, aryl, alkaryl, Alkenyl, alkynyl or alicyclic carboxylates. Some examples of special Acids are: methacrylic, ethane, propane, butane, 2-ethylhexane, decane, eicosane, Tricontane, Benzoe, Naphthoe, 2-Phenylethane, 3-Propylbenzoe, Cyclobutane, Cyclodecane, Glycol, propyne.

Fumaric, and other similar acids. It should be noted that in each case the acid anion of the group IIA metal salt with the acid anion of the Group IIB metal salt may be identical or different. Furthermore can a mixed (unsymmetrical) salt of a Group IIA and / or Group IIB metal be used. The mixed (unsymmetrical) salts of group IIA and / or Group IIB metals are used, for example, together with symmetrical salts or unsymmetrical salts of the same or different group IIA and / or group IIB retals used.

Specific examples of salts used to make the smoke suppression mixtures Can be mixed with ethers are: barium and cadmium-2-ethylhexanoate; Strontium decanoate and cadmium 3-methylnonanoate; Barium and cadmium o-propyl benzoate; Calcium and Cadmium cyclobutanoate; Magnesium methyl cycloheptanoate and zinc 2-ethyl pentanoate; Strontium hexanoate and mercury 2-ethylbutanoate; Strontium hexanoate and mercury 2-ethylbutanoate; Beryllium and zinc oleate or linoleate; and barium fumarate and zinc octanoate. Some special mixed salt combinations are e.g. E.g .: barium 2-ethylhexanoate-2,2-dimethylpropanoate and zinc 2-methyl decanoate; Barium methactylate pentanoate and cadmium glycolate tridecanoate.

The ethers used according to the invention generally have the following structural formulas: R (O-R '-) nOR ", where n is an integer which is preferably between approximately 0 and 10; R is a hydrocarbon radical; R" is hydrogen or a hydrocarbon radical where, when n is an integer, R "is hydrogen or hydrocarbon, and when n is O, R" is hydrocarbon; R 'denotes a divalent hydrocarbon radical such as methylene, ethylene or the like; and the total number of carbon atoms in a molecule is preferably less than about 30; and wherein n 'is an integer which preferably has a value of 1 or 2; R 'and R "' represent divalent hydrocarbon radicals; and preferably the molecule contains fewer than about 30 carbon atoms.

If R and R "represent hydrocarbon radicals, then it can for example alkyl, alkenyl, aryl, alkaryl, aralkyl, or alicyclic Act radicals. Examples of suitable hydrocarbon radicals are; ethyl, Ethyl, propyl, butyl, 2-ethylhexyl, neodecyl, dodecyl, octadecyl, eicosyl, nonacosyl, Phenyl, naphthyl, benzyl, tolyl, ethylphenyl, phenylhexyl, propylphenyl, cyclohexyl, Cyclopropyl, cyclopentyl, butenyl, octenyl, linoleyl, etc. When R 'and R "are divalent Mean hydrocarbon radicals, then it can be, for example, alkylene Act arylene, alkarylene, aralkylene, alkenylene or slicyclic radicals. Examples for suitable divalent hydrocarbon radicals are: methylene, ethylene, propylene, Isohexylene, decylene, phenylene, cyclohexylene, pentenylene, etc. are examples of simple Ethers which can be used according to the invention are: diethyl ether, isopropyl ether, Methyl tert-butyl ether, ethyl n-butyl ether, decyl butyl ether, nonacosyl methyl ether, Allyl ethyl ether, vinyl isobutyl ether, cyclopropyl methyl ether, dicyclobutyl ether, Ethyl ethyl ether, benzyl methyl ether, benzyl ethyl ether, diphenyl ether, anisole, Bis (2-chloroisopropyl) ether and the like.

Examples of heterocyclic ethers used according to the invention are: heterocyclic monoethers such as tetrahydrofuran, ethylene oxide, Propylene oxide furan; heterocyclic dieters such as p-dioxane, m-dioxane, dioxolane, 2- (3-heptyl) -1,3-dioxolane, 2- (3-heptyl) -1,3-dioxan-5-ol.

2- (3-heptyl) -1,3-dioxolane-4-methanol; and heterocyclic triethers such as sym-trioxane, ethyltrioxane and the like an improved reduction in smoke and Soot formation during fuel combustion occurs when barium and zinc salts are used of organic acids are used., Low molecular weight alkanoic acids, in particular Alkanoic acids of about 4-12 carbon atoms are particularly preferred dies The acids used are preferably soluble in the fuels.

In general, acyclic alkanoic acids have the tendency that they result in fewer combustion residues and lighter than unsaturated or cyclic ones Acids are oxidized; accordingly, they are preferred.

A further improvement in smoke suppression is achieved if the Group IIA and Group IIB salts of organic acids, especially of alkanoic acids with 4-12 carbon atoms, and especially the barium and zinc salts thereof, are branched in the alpha position.

Examples of suitable salts are those obtained by combination of metals of Group IIA and Group IIB with those given in the following table Acids are obtained whereby symmetrical or asymmetrical salts are formed: group IIA Group IIB Acid Barium Zinc 2-Nethylpropanoic Acid Strontium Cadmium 3-Methylbutanoic Acid Calcium Mercury 2-Methylpentanoic Acid Magnesium 2,2-Dimethylhexanoic Acid Beryllium 2-Ethyloctanoic acid, 2-Propylnonanoic acid, 2-Methylundecanoic acid, 2,2-Diethylheptanoic acid 2,2-Dimethyldecanoic acid A particularly preferred additive consists of a combination from group I1A and group IIB salts of 2-ethylhexanoic acid, especially barium and zinc 2-ethylhexanoate and barium and cadmium-2-ethylhexanoate.

It should be noted that the di- and polycarbonate homologues of Monocarboxylates already described can be used for this purpose. Examples for such homologues are: barium and zinc adipate, Stront @@@ @koctadecandioat, barium and cadmium pimelate and the like.

The group of Itt salts of carbonic acids can, for example, thereby be prepared by mixing 2 moles of carboxylic acid with 1 Elol of powdered dry Group IIA metal hydroxide reacts in a hydrocarbon solvent and the Temperature then heated above 100 ° C in order to drive off the water formed0 A combination from group IIA and group IIB salts of carboxylic acids, / one can for example in one reaction stage by adding 2 moles of one or in a similar manner several carboxylic acids with (1-x) Nol dry group IIA hydroxide and x moles dry Group IIB-hydroxy converts, wherein x was calculated stoichiometrically so that a desired Weight percentage of Group IIB metal is present in the product. The metal carboxylate products are usually solids, but preferably they come as clear solutions all in one Petroleum solvents used0 The solubility of salts in petroleum solvents can by heating, adding a small amount of an oxygenated coordinating agent Increased dissolution and / or use of ultrasound, it should be noted that derivatives of the above-mentioned carboxylates with groups that are preferably polar and which are present instead of hydrogen, also in hydrocarbon fuels can be incorporated.

Such substituents are practically not allowed in relation to the fuel be reactive, examples are polar groups such as halogen, amino, Nitro, Nitrate Hydroxyl and dglo The preferred ethers are the normally liquid ones Mono- or dieters of polyols which are soluble in fuel.

Examples of these ethers are: the monomethyl ether of diethylene glycol, the monoethyl ether of diethylene glycol, the dimethyl ether of propylene glycol, the Monoethyl ether of triethylene glycol, the diethyl ether of dipropylene glycol, the Alkylphenoxy-polyethyleneoxyethanols and the like. The alkyl ethers of polyoxyalkylene glycols, where the glycol ether has 3-10 carbon atoms are particularly preferred.

Particularly suitable ethers are the monoalkyl ethers of glycols and in particular of Ethyxlenglykol, such. E.g .: the monoethyl ether of ethylene glycol, the monopentyl ether of ethylene glycol, the mono (2-ethylbutyl) ether of ethylene glycol, the monopropyl ether of ethylene glycol and the nonopropyl ether of propylene glycol; and the dieters of glycols and in particular of ethylene glycol, such as e.g. B. the dibutyl ether of ethylene glycols Ether, which is particularly good at reducing soot and smoke in fuels are the monomethyl ethers of ethylene glycol and 1-methoxy-2-propanol.

The fuel mixtures, which dialkyl ethers of ethylene glycol and especially the dimethyl ether of ethylene glycol (this is commonly called glyme labeled), show compared to diesel fuels that contain this ether not included, improved cetane numbers as well as effective soot and smoke reduction. This improvement is also used in dialkyl ethers of polyalkyleneoxyglycols, such as. B.

the dimethyl ether of diethylene glycol, the diethyl ether of diethylene glycol and the dimethyl ether of triethylene glycol, found Accordingly, these ethers make represent another particularly preferred class of ethers.

It is pointed out that the derivatives of the above-mentioned ethers, in which hydrogen atoms have been replaced by groups, preferably polar groups, can also be incorporated into the fuels, these substituents are allowed be practically non-reactive towards the fuel, examples of such polar groups are halogen, amino, nitro, nitrate, hydroxyl and the like.

Typical fuel additives according to the invention for internal combustion engines are those obtained by combining Group IIA carboxylates and Group IIB carboxyl species can be obtained with an ether as indicated below.

Group IIA salt Group IIB salt Ether Beryllium isobutanoate Mercury 2-ethyl Diethyl ether pentanoate barium-2-ethyldecane-zinc-2,2-dimethyl-hexalpentyloate octanoate ether strontium linoleate cadmium-2-heptenoate dipropyl ether clay propylene glycol barium-3-methyltetra- Zinc 2,4-dibutyl methyl ethyl decanoate 2,3-di-benzoate ether of ethyl undecanoate Ethylene glycol Magnesium-2-phenyl-zinc-3-phenyldecan-monoethyl ether ethanoate oat-2-ethyl nonanoate of decylene glycol calcium cyclopent- cadmium cyclobutanoate dibenzyl ether anoate barium-2-methyl- Mercury 3-propyl benzyl ethyl benzoate ether preferred according to the invention Fuel additives are the following additives 1.6, with the last three being special to be favoured.

1. Barium 2-methylpropanoate, zinc 2-methylpropanoate, monomethyl ether of propylene glycol 2. barium-2-ethylbutanoate zinc-2-ethyloctanoate diethyl ether of Pentylene glycol 3. barium 2-methylundecanoate-2-ethylpropanoate zinc-2-methylundecanoate Monomethyl ether of triethylene glycol 4. Barium 2-ethylhexanoate Zinc 2-ethylhexanoate Monomethyl ether of ethylene glycol 50 barium-2-ethylhexanoate zinc-2-ethylhexanoate Dimethyl ether of ethylene glycol 6. Barium 2-ethylhexanoate Zinc 2-ethylhexanoate 1 -Nethoxy-2-propanol As mentioned above, a Group IIA metal sulfonate those are incorporated into the abovementioned carboxylate / ether additive mixtures Sulphonates can also be used alone in a mixture with the Xthers0 The sulphonic acids, from which the sulfonates used according to the invention are derived can by the following structural formula can be shown: R - SO3H, where R is a hydrocarbon radical represents.

R can be an alkyl, alkenyl, aryl, alkaryl, alkynyl, aralkyl or be alicyclic radical. Examples of suitable groups R are: methyl, propyl, 2-ithylhe yl, neodecyl, dodecyl, octadecyl, eicosyl, pentacosyl, phenyl, naphthyl, Benzyl, tolyl, ithylphenyl, phenylhexyl, cyclohexyl, cyclopropyl, butenyl, linoleyl, Propynyl, hexynyl and the like.

Examples of sulfonic acids that can be present in the sulfonates are: methanesulfonic acid, decanesulfonic acid, 2-ethylhexanesulfonic acid, pentanesulfonic acid, Phenyl methanesulfonic acid, decylbenzenesulfonic acid, naphthalenesulfonic acid, octene sulfonic acid, Cyclohexanesulfonic acid and the like, and mixtures thereof.

Other mixed (asymmetrical) sulfonates can be used, to increase or decrease the metal content, if so desired.

Some specific sulfonates used in accordance with the invention can, are; Barium nonanesulfonate; Strontium 2-ethylheptanesulfonate; Calcium o-propylbenzenesulfonate; Magnesium cyclooctanesulfonate; Beryllium oleyl sulfonate; Barium 2,2-dimethyl undecanesulfonate; Barium hexanesulfonate p-toluenesulfonate; Calcium napthalene-1,6-disulfonate; and mixtures from it.

Improved smoke suppression is obtained when using barium sulfonates be used.

In general, it is preferred that sulfonates be used, which are soluble in fuel, such as. B. high molecular weight petroleum sulfonates, for example "Mahogany Acid" Sulphonates.

Naturally occurring alkaryl hydrocarbons, such as. B.

those found in mixed kerosene fractions of petroleum can be used as hydrocarbon substituents of the sulfonic acids. The sulfonic acids can be prepared by methods described in US patents 2,395,713 and 2,388,677 are ei.

can be refined by methods described in U.S. Patent 2,387,866 are described0 Synthetically produced mixed alkaryl sulfonates of group IIA metals, especially of barium, the two alkyl groups each aromatic Group included are well suited.

It is particularly preferred that each alkyl group be included in the mixed sulfonates is a linear group of about 14-18 carbon atoms, the aforesaid Sulphonate has a molecular weight of 800-1500, preferably 900-1100.

Examples of preferred sulfonates are: barium 2-hexadecyl-3-heptadecylbenzenesulfonate; Barium 2- (3-methylpentadecyl) -6-octadecylbenzenesulfonate; Barium 2-octadecyl-8- (2-ethylhexadecyl) naphthalene sulfonate; Barium 2-ethyltetradecyl-8- (3-methyltetradecyl) naphthalene sulfonate; as well as mixtures thereof and especially those with a molecular weight of about 1000.

It is further noted that derivatives of the above-mentioned Sulphonates, in which hydrogen atoms are replaced by groups, preferably polar groups, are replaced, in which hydrocarbon fuels can be incorporated. Such Substituents must be practically non-reactive with the fuel. Examples of such polar groups are halogen, amino, nitro, nitrate and hydroxyl and the like. An additive according to the invention for fuels consists of an ether and a Group IIA metal carbonate. A preferred additive consists of barium carbonate and an alkyl ether of an alkylene glycol having 3-10 carbon atoms. A particularly effective additive is a mixture of barium carbonate and dimethyl ether of ethylene glycol, the weight ratio of the ether to barium carbonate being approximately 2: 1-1: 2 is.

A fuel mixture with reduced smoke and soot formation is obtained when the above-mentioned mixtures of Group IIA carbonate and ether dispersed or dissolved in liquid hydrocarbon fuels. Am the preferred fuel mixture is a diesel fuel, which is approximately 0.1-1% by weight Barium carbonate and about 0.1-1% by weight of an alkyl ether of an alkylene glycol, which has about 3-10 carbon atoms, contains Typical Group IIA metal carbonates are beryllium carbonate, calcium carbonate, magnesium carbonate and strontium carbonate.

Basic Group IIA metal carbonates can also be used Example vest are basic beryllium carbonate and basic magnesium carbonate suitable. Weer can also use hydrated forms of Group IIA metal carbonates and basic group IIA metal carbonates can be used, e.g. B. artinite and hydromagnesite. If desired, mixtures of the various Group IIA metal carbonates, basic carbonates and / or hydrated carbonates can be used, Typical ones Additive mixtures of the first mentioned embodiment of the invention which are used in fuels are those obtained by using a Group IIA carboxylate, a group IIB carboxylate, an ether and a group IIA sulfonate combined, such as which is given below, Group IIA Salt Group IIB Salt Ether Group IIA Sulphonate Beryllium-2-mercury-2-diethyl-barium-tridecanmethylporpanoate ethyl pentanoate ether sulfonate barium-2-ethyl-zinc-2,2-di-hexyl-strontium-hexadecanoate methyloctanoate pentyl decylbenzene ether sulfonate strontium cadmium 2 dipro calcium cyclohexane linoleate heptanoate pylether sulfonate undecanoate of propylene glycol magnesium zinc 2-phenyl Monoethyl magnesium decenphenylethanolate decanoate ether of sulfonate decylene glycol Calcium-cyclo-cadmium-cyclo-dibenzyl- beryllium pentanoate butanoate ether naphthylpropane sulfonate Barium 2-methyl mercury 2-benzyl barium nonadecane benzoate propyl benzoate ethyl sulfonate ether motor phenyl ether of ethylene glycol Preferred according to the invention Mixtures containing sulfonates are the following additives 1-6, with the the latter three are preferred.

1. Barium 2-methylpropanoate, zinc 2-methylpropanoate, monomethyl ether of propylene glycol 2. barium-2-ethylbutanoate zinc-2-ethyloctoate diethyl ether of Pentylene glycol barium 1,2,3-tridodecylnaphthalene sulfonate 3. barium 2-methylundecanoate Zinc-2-methylundecanoate, monomethyl ether of triethylene glycol, barium-2-octadecylanthracene sulfonate 4. Barium 2-ethylhexanoate, zinc 2-ethylhexanoate, monomethyl ether of ethylene glycol Barium-2-undecyl-3-dodecylbenzenesulfonate 5. barium-2-ethylhexanoate zinc-2-ethylhexanoate Dimethyl ether of ethylene glycol barium-2-heptadecyl-8-decylnaphthalene sulfonate 6. Barium-2-ethylhexanoate zinc-2-ethylhexanoate dimethyl ether of diethylene glycol barium-2-tridecyl-4-pentadecyl @@@ Preferred mixtures according to the invention with sulfonates that are not a group IIA or Group IIB metal salts containing organic acids are: 1. Monomethyl ether of propylene glycol barium 2- (2-ethylheptyl) benzenesulfonate diesel fuel 2. diethyl ether of pentylene glycol barium 1,2,3-tridodecylnaphthalene sulfonate diesel fuel 3. Monomethyl ether of triethylene glycol Barium-3-octadecylanthracene sulfonate Diesel fuel Particularly suitable diesel fuel blends of the invention are: 1. 1-methoxy-2-propanol, barium-3-decyl-4-nonylbenzenesulfonate Diesel fuel 2. Monomethyl ether of ethylene glycol Barium-2-dodecyl-3-dodecylbenzenesulfonate Diesel fuel 3. Dimethyl ether of ethylene glycol Barium-2-heptadecyl-8-decylnaphthalene sulfonate Diesel fuel 4. Dimethyl ether of diethylene glycol Barium-2-tridecyl-4-pentadecylbenzenesulfonate Diesel fuel.

Bs it is preferred that the weight ratio of ether to total combined weight of Group IIA and Group IIB carboxylates between approximately 4-1.0 parts of ether per part of carboxylate. In the case of mixtures consisting of barium and Zinc alkanoate and glycyl ether exist, the weight ratio of ether to combined weight of barium and zinc alkanoate preferably between about 3-1.5 parts of ether per part of carboxylates.

In the case of the particularly preferred additional mixtures of barium and zinc 2-ethylhexanoate and monomethyl ether of ethylene glycol have been found to give the best results if the weight ratio of ether to total weight of barium and zinc carboxylate about 2.0-1.5 parts of ether per part of carboxylate is 0 A synergistic effect, which gives an improved Ranohyd soot reduction is observed when the The proportion of Group IIA metal carboxylates is greater than the proportion of Group IIB metal carboxylates. This effect is particularly evident when the Group IIA carboxylate is a barium salt and the Group IIB carboxylate is a zinc salt. Further reductions are observed, when the ratio of Group IIA metal to Group IIB metal (in the carboxylates ) and especially from barium metal to zinc metal about 5: 1 to 30: 1 and especially is about 8: 1 to 12: 1 (weight ratio). For best results it will particularly preferred that the weight ratio be about 10 parts barium per part Zinc amounts.

There is also a synergistic effect between the ether and the above mentioned carboxylate mixture can be seen. This effect is particularly evident when alkyl glycol ethers, especially the hono- and dialkyl ethers of ethylene glycol, and especially the monomethyl ether of ethylene glycol, can be used in general the sulfonates in the above-mentioned mixtures of salts and ethers give one additional smoke suppression, and they also improve the favorable features these additives, such as B. the cleaning effects and the corrosion-inhibiting effects.

For these and other purposes, the weight ratio is generally from carboxylates and ethers to sulfonates in additives about 1-3 parts Carboxylates and about 1-2 parts of ether 1-2 parts of sulfonate each and preferably of about 1-2 parts of ether and 1-2 parts of sulfonate per part of total carboxylates.

In the case of the particularly preferred additives of barium and zinc 2-ethylhexanoate, to 1-methoxy-2-propanol and a barium alkaryl sulfonate with a molecular weight of about 100 have been found to give the best results when the weight ratio of the additional components approximately, 4 parts ether and 1.4 parts Sulphonate per part is barium and zinc carboxylate.

In general, the additive mixtures are used in amounts that a significant reduction in the build-up and soot formation of hydrocarbon fuels result. For this purpose, at least about 0.05% by weight should generally Additional mixture can be used. Although amounts of more than about 5 wt .-% can be used, but practical soot and smoke reduction will generally be anoh obtained smaller amounts with X.

Improved smoke reduction is usually achieved when the Total concentration of that present as the carboxylate salt and optionally as the sulfonate Group IIA metal in the fuel mixture 0.04-0.08 wt%, preferably about 0.07 wt%.

In general, the mixtures of Group IIA and Group liB salts of the present invention used in amounts that provide effective smoke and soot suppression result. For this purpose, a smaller amount of salt, usually whole, should be used at least 0.05% by weight can be used. It is true that larger quantities can also be used but in general it is not necessary to use more than about 5% by weight.

For best results it is preferred that the salts can be used in total concentrations of about 0.1-2% by weight.

In the case of the particularly preferred diesel fuel mixtures, the barium and zinc 2-ethylhexanoate have been found to give the best results are used when a total of about 0.1-0.6 wt% salts are used. Mixtures from Diesel fuels and made from about 0.3-2 wt. Barium 2-ethylhexanoate or about 0.1-2% by weight calcium 2-ethylhexanoate are particularly effective.

In general the ethers are used in amounts necessary a significant reduction in the formation of belly and soot in fuel mixtures to achieve. In general, at least 0.05% by weight of ether should be used for this purpose be used. Although amounts in excess of about 5% by weight can be used, is a practical soot and smoke reduction usually even with smaller amounts achieved0 The best results are obtained when the ethers in concentrations from about 0.1-1% by weight can be used.

In the case of the particularly preferred diesel fuel mixtures, the barium and zinc-2-ethylhexanoate and glycol ether contained, it was found that the beds Results are obtained using about 0.2-0.5 wt% ether and about 0.1-0.6 Wt .-% salts used.

Another preferred mixture is a mixture of diesel fuel and from about 0.1-0.5% by weight of barium 2-ethylhexanoate and from about 0.3-0.6% by weight of the monomethyl ether of ethylene glycol.

The weight percentages of the additives are based on the weight of the Addition compared to the total weight of the fuel mixture.

Mm the amount of black soot and smoke visible from internal combustion engines The Group IIA metal sulfonates will decrease significantly in minor amounts, at least about 0.05% by weight, in combination with the groups II-metal salts used by organic acids.

Generally no more than about 1 weight percent sulfonate is based based on the total weight of the fuel mixture. If larger quantities are used no substantial visible smoke and soot reduction is obtained.

for best results, it is preferred that the Group IIA metal sulfonates in amounts of approximately 0.1-0.8% by weight, based on the total weight of the fuel mixture including Group II salts of organic acids can be used.

When used without Group IIA metal salts of organic acids then the Group IIA metal sulfonates are used in smaller amounts, at least about 0.07 wt% Group IIA metal used. When amounts are below a 0.007 wt% Group IIA metal is used then there will be no practical smoke reduction achieved.

Generally no more than about 0.1 wt.% Group IIA metal will be used which is present as a Group IIA metal sulfonate is used. If larger quantities are used then there will be no further significant visible smoke and soot reduction achieved. When the Group IIA metal is in the form of the sulfonate in amounts greater than about 0.1 wt% is used, it will be detrimental to the performance of the engine Effects observed such. B. Jerking and stopping.

For best results, it is preferred that the Group IIA metal sulfonates, especially the barium alkaryl sulfonates, are used in such amounts that about 0. X4 to 0.08 weight percent Group IIA metal is present.

A particularly preferred fuel mixture is a diesel fuel in admixture with about 0.2-0.5% by weight 1-methoxy-2-propanol and about 0.04-0.08 Wt .-% barium metal, which as barium alkaryl sulfonate with a molecular weight is available from approximately 900-1100. Improved results are also obtained when the ether is the dimethyl ether of ethylene glycol.

Preferred fuel additives according to the invention which contain carbonates are the following: 1. Barium carbonate monomethyl ether of propylene glycol 2. Barium carbonate Diethyl ether of pentylene glycol 3. Barium carbonate Monomethyl ether of triethylene glycol Particularly suitable additives according to the invention are: 1. Barium carbonate monomethyl ether of ethylene glycol 2. Barium carbonate, dimethyl ether of ethylene glycol In general is the weight ratio of the individual Group IIA metal carbonates in the inventive Additions between about 5: 1 and 1: 5, and preferably between 3: 1 and 1: 3 im Case of the barium carbonate and glycol ether additive.

mixture, it is preferred that the weight ratio of ether to ionic carbonate is between about 2: 1 and 1: 2.

In general, the additive mixtures are used in an amount which significantly reduces smoke and soot formation from the hydrocarbon fuel results. Generally about 0.05-5 wt.% Group IIA metal carbonate is used for this purpose and about 0.05-5 wt% ether is used.

It is true that amounts of more than 5% by weight of Group IIA metal carbonate can be used can be used, but practical smoke and soot reductions are already provided at smaller amounts achieved.

Generally less than about 5 wt% ether is used, although larger amounts can be used. Preferably the is Concentration of Group IIA metal carbonates about 0.1-1% by weight and the concentration of the ether about 0.1-1% by weight.

In the case of barium carbonate and alkyl ethers of alkylene glycols it is preferred that the barium carbonate be used in amounts of about 0.2-0.5% by weight and the Ether is used in amounts of approximately 0.2-0.5% by weight. The above weight percent are based on the weight of the metal carbonate or ether compared to the total weight the fuel mixtures.

In the case of the particularly preferred diesel fuel mixtures, the Containing barium and zinc alkanoates, as well as glycol ethers, will give the best results achieved when the sulfonates, especially barium alkaryl sulfonates, in amounts of approximately 0.2 to 0.5% by weight based on the total weight of the fuel mixture, be used.

The alkanoates are used to produce the new carboxylate / ether mixtures mixed with the ether by conventional means. If necessary, a resolver can be added to the new additive mixtures in effective amounts to ensure a homogeneous liquid concentrate with improved solubility in liquid hydrocarbon fuels to manufacture.

To produce fuel mixtures /, the carboxylates, ethers and Containing sulfonate, one can advantageously first the metal carboxyltes dissolve in the fuel, whereupon the ether is added to the carboxylate / fuel mixture and Finally, the sulfonate can be added0 The mixture of additives can also be added directly to the Fuel can be added or a dissolver can be added to the additive mixture whereupon the obtained composition is mixed with a fuel In general, the above-mentioned triggers are inert petroleum solvents, such as B. Petroleum ether, hydrocarbon fuels, varsol, white oil, alcohols, in particular glycols and d8Lo and mixtures thereof If a dissolver is used for additives consisting of zen, ether and sulfona, then will it is preferred that the proportion of the salts be between about 10 and 30% by weight of the proportion the ether between 15 and 40% by weight, the proportion of sulfonates between 15 and 25 % By weight and the proportion of the solvent is between approximately 60 and 5% by weight, where the stated weight percentages are based on the total weight of salts, ethers, Sulfonate and solvent are related.

In general, all liquid hydrocarbon fuels, including heating fuels, and in particular fuels for internal combustion engines used as fuels to which the new additives are added. It will it is preferred that the liquid hydrocarbon fuel include a diesel fuel an ignition point of approximately 149 ° C and a final distillation point of approximately 396 ° C.

Diesel fuel with a boiling range of about 204 to about 357 ° C, such as B. Diesel fuel No. 2 are particularly preferred.

The invention is explained in more detail using the following examples.

Beise1 1 To test the new smoke suppression mixtures, a Solution of barium 2-ethylhexanoate in an earth solvent (33% barium salt and 67% inert solvent) added to a diesel fuel in suitable quantities.

The diesel fuel used was a diesel fuel llr, 2, the 110 ppm of a 1, 1-dimethylalkylamine, used as a color stabilizer and antioxidant served during storage. Diesel fuel No. 2 had the following properties: 1. Cetane number, minimum 43 2nd flash point, ° C minimum 60 ° C 3rd distillation, 90% recovered, ° C maximum 71 ° C 4 viscosity, centistoke at 3800 251 - 4? 3 5o carbon residue (10% soil products) 0.25 The smoke suppressants were in a single cylinder diesel engine (Cetane-Type), which was equipped with a Hartridge Smoke Meter. In the Exhaust gas was inserted through a probe approximately four feet from the exhaust manifold.

The probe was connected to a 2-way stopcock on the smoke meter, The typical engine temperatures were: intake air 65 ° C lubricating oil 49 - 600C (Gallery Oil) Coolant 10000 First, the engine was using the base fuel up to conditions heated, with no visible black smoke to be found in the exhaust gases The fuel flow was increased until it reached approximately 13 cc / min, at which point Worth visible black smoke in the exhaust and a Hartridge smoke Number (HSN) of approximately 40 is reached, upon which the base fuel was carried out a mixture according to the invention which contained the smoke suppressant replaced, and the engine was run for an additional 5 minutes to allow stabilization enable. The smoke meter was then read, The base fuel change and the fuel added was repeated two more times.

The following table explains the effectiveness of the new diesel fuel blends. In the table is the Hartridge Smocke Number (HSN) as average indicated by three consecutive attempts.

Results of the tests for smoke suppression additive in wt .-% HSN, HSN, basic basic fuel of the additive basic fuel set fuel with additive Barium 2-ethyl hexanoate 0.24 55 36 Calcium 2-ethyl hexanoate 0.16 45 19 Calcium 2-ethyl hexanoate 1 3 42 9 A value of 100 on the Hartridge Smoke Number scale means you are complete black smoke. A value of 30 and below means a clear exhaust gas that is below is acceptable to all running conditions. The weight percentage of the additive is on based on the weight of the salt compared to the total weight of the diesel fuel mixture, specified.

Example II A diesel fuel mixture was prepared as follows: about 60 parts by weight of a liquid solution containing about 19 parts by weight of barium 2-ethylhexanoate, about 3 parts by weight of zinc 2-ethylhexanoate and about 38 parts of inert petroleum solvent were mixed with approximately 40 parts of a specific glycol ether The ratio of ether to salts was approximately 1.8: 1. Certain amounts of this concentrate were mixed with # 2 diesel fuel as described in Example I.

The fuel mixture containing the smoke suppressant was then used in place of the base fuel, and the engine became roughly Run for 5 minutes to allow stabilization as shown in Example I. is described. The smoke meter was then read.

A mixture of a base fuel and 0.7% by weight was then a commercially available smoke suppressant instead of the mixture with the one according to the invention Addition used as a 3 reference. After 5 minutes (by then the motor had stabilized) the smoke meter was read; The sequence basic force, stoff9 fuel with the invention The additive and reference fuel were repeated two more times.

The following table explains the effectiveness of the new additional mixtures. In this table, the Hartridge Smoke Number (HSN) values are an average of indicated three consecutive attempts. The value "% efficiency" is indicated by the following equation: [HSNwithout - HSNaddition] x 100% [HSNwithout - HSNreference] and is a measure of the effectiveness of the new fuel blends compared to the fuel mixtures with conventional smoke suppressants. The weight percent The additive is based on the weight of the component compared to the total weight of the fuel mixture.

Results of the smoke suppression tests Addition in wt .-% HSN, HSN, HSN,% effective-basic- the basic- with reference to fuel fuel rate In the substance fuel Er.1 barium-2-ethylhexanoate 0.13 zinc-2-ethylhexanoate 0.01 monomethyl ether of ethylene glycol 0.26 32 5 5 100 total 0.40 # 2.

Barium-2-ethylhexanoate ° R34 zinc-2-ethylhexanoate 0.03 monomethyl ether of ethylene glycol 0.50 38 8 9 103 total 0.87 No. 3 barium-2-ethylhexanoate 0.23 55 57 6 38 No. 4 zinc 2-ethylhexanoate 0.39 67 65 10 3 No. 05 monomethyl ether of ethylene glycol 0.50 42 38 8 12 A value of 100 on the Hartridge Smoke Number scale means a completely black soot. A value of 30 and below means clear exhaust gases that are acceptable under all operating conditions0 The use of zinc 2-ethylhexanoate as the only additive resulted in concentrations of 0-0.39 % By weight in the base fuel has a percentage effectiveness in reducing noise from zero.

The above results show that the addition of barium * and zinc 2-ethylhexanoate as well as glycol ethers for fuels a reduction the smoke and soot formation results. The results also show the synergistic interaction between the beard and zinc salts, which is especially evident when that The ratio of arium to zinc metal is approximately 10: 1.

The results of the above examples also prove that the add-on of alkyl ethers of ethylene glycol (in particular the ionomethyl ether of ethylene glycol) and of barium and zinc salts of low molecular weight alkanoic acids (in particular such acids, which are branched in the alpha position) to fuels which smoke and Soot formation reduced.

It should also be emphasized that the components of the fuel mixtures in this example, when tested individually in diesel fuel, a far cause less reduction in soot and smoke formation than the combinations used This shows that multiple synergies are obtained9 when the metal salt / fuel mixtures also contain etherO Example III For further demonstration the smoke and soot suppression achieved by the additives according to the invention in hydrocarbon fuels is achieved, a diesel fuel mixture was obtained according to the procedure of Example 1 manufactured. Selected amounts of a concentrate, which, the same proportions on carboxylates and ethers as in the first group of results in Example I. were mixed with a No. 2 diesel fuel whose properties were similar to those of the fuel described in Example I.

The smoke suppression was in a Cummins A-175 rotor with natural Intake determines which engine was equipped with a Hartridge Smoke Meter. In the test, the engine was heated with untreated base fuel, and so was the fuel supply was set so that the engine delivered approximately 140 Brake Horsepower (BHO). Here the Hartridge Smoke Meter values were measured. Next up was the fuel supply slightly reinforced so that the engine made about 150 BHP. Subsequently was the fuel supply increased so that the engine delivered approximately 155 BHP. at The smoke meter readings were taken at both exposures. Next, a Fuel mixture according to the invention, which contained smoke suppressing additives, used in place of the base fuel, and the smoke meter readings were at The following table determined the three power outputs of the engine given above explains the effectiveness of the new additional mixtures Results of the Smoke suppression tests Addition wt .-% Brake- HSN, HSN,% reduction in the basic force- of the horse basic additive in the substance additive Power Kraft basic force smoke substance substance barium-2-ethylhexanoate 0.13 140 26 17 35 zinc-2-ethylhexanoate 0.01 150 37 22 40 1-methoxy-2-propanol 0.26 155 52 31 40 total 0.40 No. 2 barium-2-ethylhexanoate 0.064 140 30 25 17 zinc 2-ethylhexanoate 0.006 150 37 32 14 1-methoxy-2-propanol 0.130 155 50 43 14 total 0.200 The reduction in smoke is given by the following Expression shown: [HSNwithout - HSNAdditional] x 100 [HSNwithout] Example IV For demonstration the 'smoke and soot reduction in mixtures of hydrocarbon fuels, Metal salts and ethers, a diesel fuel mixture was produced as follows: About 33 parts by weight of barium 2-ethylhexanoate were mixed with about 66.7 parts by weight of the monomethyl ether of ethylene glycol mixed. Selected amounts of this concentrate were mixed with # 2 diesel fuel as described in Example I. and into a cetane engine according to the method by example 1 introduced. A mixture of the diesel fuel No. 2 from Example I and 0.7 Weight percent of a commercially available smoke suppressant was tested as a reference This mixture was used instead of the additional mixtures after each test in the Cetane engine used. The "% Efficacy" is as expressed in Example II.

Results of the smoke suppression tests Addition in% by weight HSN, HSN, HSN,% effective base fuel of the additional basic with additional reference rate fuel in the basic fuel 1.

Solution of barium 2-ethylhexanoate in monoethyl ether of ethylene glycol 0.64 52 7 10 107 2.

Solution of barium 2-ethylhexanoate in the monoethyl ether of ethylene glycol , 0.41 37 7 5 91 Monomethyl ether of ethylene glycol 0.50 42 38 8 12 4.

Barium 2-ethylhexanoate 0.27 55 36 67 38 It should be noted that that the components of the fuel mixtures of this example, if they are individually in Diesel fuels are tested as having a much lower effectiveness the Smoke and soot reduction gave as the combinations. This shows that there is a synergism is obtained when the metal salt / fuel mixtures additionally contain ether.

Example V To determine the smoke suppression effect of the invention Mixtures of carboxylates, ethers and sulfonate, selected amounts of barium and Zinc-2-ethylhexanoate, the monomethyl ether of ethylene glycol and a synthetic one Barium alkaryl sulfonate (14.6% Ba metal) with a molecular weight of approximately 1000 individually dissolved in the # 2 diesel fuel of Example I to form a fuel mixture to manufacture.

The fuel mixture was prepared by the procedure described in Example I. tested. The mixture contained a weight ratio of additional components of about 1.4 parts of ether ru 1.4 parts of sulfonate per part of carboxylate0 The weight ratio the barium carboxylate to zinc carboxylate was approximately 10: 1. the barium and zinc carboxylate components the additives were added to the fuel as a liquid. This liquid composition contained approximately 37 parts by weight of carboxylates per 63 parts by weight of inert petroleum solvent. The reference standard of Example I was also tested for soot and roughness reductions could be compared.

The following table shows the effectiveness of these according to the invention Additions 0 Smoke Suppression Test Results. Test Results Component and weight% HSN, HSN, with addition HSN,% action of each ingredient The basic fuel principle in the base fuel is fuel no.1 barium-2-ethylhexanoate 0.11 33 5 5 100 zinc 2-ethylhexanoate 0.01 monomethyl ether of ethylene glycol 0.17 Barium dialkaryl sulfonate 0.17 total 0.46 No. 2 barium 2-ethylhexanoate 0.16 66 7.7 7 98 Zinc 2-ethylhexanoate 0.02 Monomethyl ether of ethylene glycol 0.25 Barium dialkaryl sulfonate 0.25 total 0.68 No. 3 barium-2-ethylhexanoate 0.16 53 21 11 76 zinc-2-ethylhexanoate 0.02 Monomethyl ether of ethylene glycol 0.50 including 0p68 The smoke and soot reduction, which are obtained in fuels when the additives are salts, ethers and sulfonates used are demonstrated when considering the unexpectedly increased effectiveness of the Compare addition # 2 with the effectiveness of addition # 3 in this example. The difference between the two additions was that with Addition No. 2, starting from addendum no.3 a part of the ether by a group IIA metal sulfonate was replaced.

Example VI To further illustrate the new carbon black and smoke suppressant additive mixtures, which consist of carboxylates, ether and sulfonate became mixtures of the same Components prepared in the same proportions as mixture No. 1 in Example V, with the difference that the 1-methoxy-2-propanol by the monomethyl ether of Ethylene glycol has been replaced. Selected amounts became that described below Diesel fuel # 2 added.

Diesel fuel No. 2 had the following characteristics: 1. Cetane number 51 2nd distillation, 10% point, 212.2 ° C 90% point, 294.5 C 3rd total Sulfur 0.072 4th weight, ° API at 15.6 ° C 36.9 5th FIA aromatics,% 25 olefins,% 0 Saturated,% 75 The smoke suppressants were used under simulated conditions at a constant speed in a six cylinder four stroke rubber NH-220 engine naturally aspirated tested in a 1965 International Harvester DC OF-405 dual axle drive tractor was built in 0 to actual operating conditions To simulate the tractor was modified on a Clayton chassis dynamometer mounted that could simulate the inertia caused by the movement of the tractor is generated under actual operating conditions0 um that during operation To measure the smoke and soot generated by the engine was a light extinction full flow Smokemeter used by the United States Public Health Service will, attached directly to the tractor's exhaust pipe. The smoke meter was 14.0 cm above of the exhaust pipe so that a light source is attached to an endo of a collimator tube was arranged to send a beam of light directly through the exhaust gas. One photoelectric collecting cell arranged at the other end of the collimator tube was wet the light that passed through the exhaust gases, being the percentage Light transmission could be read. In general, one classification corresponds of 20% opacity (or light darkening) of a Ringlemann number of 1e Der Gummins NH-220 engine and the tractor were simulated at constant speed conditions operated according to the following engine speed and vehicle speed.

Operating conditions engine speed simulated vehicle rpm. km / h A 1500 41.6 B 1700 46.4 C 1900 51.2 D 2100 56.0 To determine the effect of the smoke suppressing additives during the operation of the tractor became the following Method used.

The smoke meter was set to 0 with air to meet the conditions without faking smoke. The engine was thrown off and on ijtufe 7 (7th gear) accelerated and operated under operating conditions A. After 30 seconds it was a smoke meter reading was taken. Then the speed was set to operating conditions B increased and another smoke meter reading was taken after 30 seconds. The procedure was also repeated for operating conditions C and D, Of the entire cycle was repeated twice 3 the results are the mean values of three attempts.

The reduction in smoke is represented by the following expression: [Opacity without - additional opacity] x 100% [Opacity without] Additional smoke tests at constant speed component and% by weight of operating% opaque% opaque percentage components in the basic condition, activity, with tuale fuel gen basic Addition of smoke fuel in the basic fuel no.1 barium-2-ethylhexanoate 0.13 A 24 14 41 zinc 2-ethylene hexanoate 0.01 B 25 13 48 monomethyl ether of ethylene glycol 0.26 C 28 16 43 total 0.40 No. 2 barium-2-ethylhexanoate 0.064 A 24 16 33 zinc-2-ethylhexanoate 0.006 B 25 17 32 Monomethyl ether of ethylene glycol 0.130 D 30 22 27 total 0.200 No. 3 barium-2-ethylhexanoate 0.11 A 24 10 58 zinc-2-ethylhexanoate 0.01 25 10 60 1-methoxy-2-propanol 0.17 C 28 12 57 barium alkaryl sulfonate 0.17 D 30 13 57 total 0.46 No. 4 barium 2-ethylhexanoate 0.055 A 24 13 46 zinc 2-ethylhexanoate 0.005 B 25 14 44 1-methoxy-2-propanol 0.085 C 28 16 43 barium alkaryl sulfonate 0.085 D 30 18 40 total 0.230 No. 5 barium 2-ethylhexanoate 0.14 A 16 3 81 zinc 2-ethylhexanoate 0.01 B 20 4 80 1-methoxy-2-propanol 0.22 C 22 4 82 barium alkaryl sulfonate 0.22 D 23 5 78 No. 6 barium 2-ethylhexanoate 0.27 A 16 3 81 zinc 2-ethylhexanoate 0.03 B 20 4 80 1-methoxy-2-propanol 0.44 B 20 4 80 barium alkaryl sulfonate ° 0.44 D 23 6 74 total 1.18 The "operating conditions" refer to the previous table in which the simulated vehicle speed and the speed of the motor are given.

For the L Light Extinction Smoke Meter, a reading means 100% opacity means total absorption of light and an opacity of 0% means 100% Light passage.

In the diesel fuel mixtures explained, the concentration was of Group IIA metals about 0.05-0.15 wt% and the concentration of zinc metal 0.002-0.009% by weight, based on the fuel mixture.

The best smoke suppression was obtained when the barium concentration in the fuel was approximately 0.07 wt%.

The results of this example further demonstrate the effectiveness of the smoke and soot suppressant additives of the present invention. Similar results are to be expected when the additives in other hydrocarbon fuels, e.g. Gasoline, jet fuel and heating fuel can be used.

Example VII In order to determine the tolerance of the new fuel additive mixtures of the To test the present invention against water, selected amounts of Additives specified in the following table in 100 ml of diesel fuel no.2, the is described above in Example I, after which 10 ml of water were added, the Diesel fuel blends were room temperature when tested. The water and the diesel fuel additives were shaken vigorously and allowed to settle. The mixtures were examined at periodic intervals of 10 days.

The results of the tests obtained after 15 minutes are described in the following table.

Additive component and% by weight of the oil / water boundary oil phase additive in the base fuel area ~~~~~~~ barium-2-ethylhexanoate 0.13 sharp clear zinc-2-ethylhexanoate 0.01 monomethyl ether of ethylene glycol 0.26 total 0.40 barium 2-ethylhexanoate zinc 2-ethylhexanoate 0.12 sharp clear monomethyl ether of ethylene glycol 0.17 barium alkaryl sulfonate 0.17 0.46 total base fuel was sharp clear after 10 days of standing no haze observed in the oil phases.

Example VIII To determine the effect of the new additives on the Cetane number of diesel fuels was a fuel mixture, welobes ans that Diesel fuel no.2 from Example 1 and from the additives given in Example Y. tested against diesel fuel No. 2 from Example I. The cetane number of diesel fuel # 2 and the new fuel mixtures were determined by that a single cylinder Cetane test engine was operated in accordance with ASTM D-613. The cetane number the # 2 base diesel fuel was approximately 43, while the cetane numbers were the Base fuels containing the additives mentioned above, Likewise was about 43. The results show that the new additives. in fuels do not adversely affect the .aetane number.

Example IX For Determining the Relative Stability of Fuel Additives of the present invention under aging conditions exposed to air and to determine the effectiveness of the additives in preventing the The formation of residues and the deterioration in color, diesel fuel mixtures, which are described in the previous example, the Accelerate4 Fuel Oil Stability Subjected to test by DuPont (149 ° C).

50 ml of diesel fuel mixtures were each aged in an oil bath, which was held at 14900 for 90 minutes. The samples were then placed under vacuum (40.6 cm Hg) through a 4.25 cm Whatman paper 4.25 cm in diameter, which is in in the Millipore filter holder, filtered. The test tubes that the aged Samples containing were rinsed with 3 ml portions of n-heptane. Any washing liquid was transferred to the filter holder. The filter holder and papers were under Vacuum washed with n-eeptane until free of fuel oil. The filters were dried in air under vacuum and compared with reference standards. A fuel which equals a standard of ErO 7 or gives a lower value, will referred to as "useful". The results of the test show that the base fuel had a pad rating of 7 while the base fuel / additive blends respectively had a rating of 9.

Example X To demonstrate corrosion inhibition against copper, which add smoke suppressant additives to fuels, especially diesel fuel, grant were the additions of example VII with the diesel fuel of Example 1 mixed and tested according to ASTM D-130.

The classifications of the individual additive / fuel mixtures and the Base fuel were IA.

Example XI To demonstrate the corrosion-inhibiting effect of Fuel blends containing the smoke suppressant additives of the invention compared to carbon steel under highly corrosive conditions were 2 mm thick Carbon steel strips separated into the additive mixes of Example I, the were in 400 ml of diesel fuel and 10 ml of 4% sodium chloride solution immersed at a temperature of 37.8 ° C. The mixtures were stirred at 1000 rpm, and measurements of the voltage drop between the strips were made at intervals performed. The percent corrosion was calculated from these measurements using previously obtained relationships between the voltage drop versus the percentage Corrosion obtained, which was measured on a carbon steel coupon, which was tested under pipeline conditions0 The following table shows the results of tests obtained after 24 hours of immersion.

Percentage corrosion of carbon steel after 24 hours - number 1 Barium and zinc 2-ethyl-5,5 hexanoate monomethyl ether of ethylene glycol No. 2 barium and zinc 2-ethyl-0.0 hexanoate monomethyl ether of ethylene glycol barium alkaryl sulfonate No.3 base fuel (without antioxidant 15.0) The results show the improved corrosion-inhibiting properties of fuel mixtures, containing the smoke suppressants of the invention. The accessories were present in diesel fuel at a concentration of approximately 0.007% by weight, for example XII In order to show the surface-active properties, the fuels by the Smoke suppressants according to the invention are issued, the additives were containing Fuel blends of Example VII tested according to ASTM D-971 for interfacial tension to investigate. In general, the lower the voltage, the greater it is the surface-active property of the fuel. The following table shows the decrease in interfacial tension at 25 ° C compared to a diesel fuel mixture distilled water.

Interfacial tension, dyn / cm No. 1 barium-2-ethylhexanoate 32.2 zinc-2-ethylhexanoate Monomethyl ether of ethylene glycol # 2 barium 2-ethylene hexanoate 26.5 zinc 2-ethyl hexanoate Monomethyl ether of ethylene glycol Barium alkaryl sulfonate No. 3 Base fuel 36.6 Example XIII To test the sulfonate smoke suppressant mixtures, 0.3% by weight Dimethyl ether of ethylene glycol and 0.3% by weight of barium alkaryl sulfonate (14.5% by weight Ba: molecular weight about 1000) consecutively in a diesel fuel dissolved at room temperature with mechanical stirring.

The diesel fuel used was diesel fuel # 2, which is the had the following characteristics: 1. severity, ° API 32.9 2. flash point, ° C 42.2 3rd distillation- 10% point, ° C 215.0 90% point, ° C 302.5 residue 1.5% 4th FIA% Aromatics 31.0% Olefins 0.0% Saturates 69.0 The New Smoke Suppression Blends were determined in a 4 cylinder John Deere Model 3020 tractor engine, which was equipped with a Hartridge smoke meter.

An exhaust probe was in the exhaust pipe approximately four feet from the exhaust manifold removed removed. The probe was connected to a two-way stopcock on the smoke meter.

Initially, the engine was warmed up on the base fuel in conditions serene, with no visible smoke in the exhaust gases. The fuel flow was increased until it was approximately 9.98 kg / st, a value where the more visible black Smoke occurs in the exhaust gases The table below shows the effectiveness of the new Fuel mixtures explained 0 The table shows the Adjusted Hartridge Smoke Numbers (HSN) given as the mean values of three consecutive tests.

Addition in wt .-% wt .-% HSN of the HSN of the% reduction in basic strength Addition of metal basic fuel of the visible substance in the fuel smoke fuel Fuel mixture barium alkaryl sulfonate 0.3 0.04 31 6 81 dimethyl ether of ethylene glycol total 0.6 barium alkaryl sulfonate 0.3 0.04 35 14 60 Dimethyl ether of ethylene glycol 0.3 - 32 30 6 It should be noted that that the components of the fuel mixture, when tested individually, have a less effective in reducing visible soot and smoke than the combinations thereof. This shows that there is a synergistic promotion smoke and soot suppression is obtained when Group IIA metal sulfonates and Ether can be mixed in fuels.

Example XIV Selected amounts of that used in Example XIII synthetic barium alkaryl sulfonate and 1-methoxy-2-propanol were used in diesel fuel # 2 of Example = 11 mixed in and then in a Jobn Deere four cylinder engine tested according to the procedure of 'Example XIII. The smoke reductions are through the equation in the example above has been determined and given in the following table: Results of the smoke suppression tests Addition in wt .-% wt .-% HSN of the fuel percentage basic force addition metal basic mixture reduction in the fuel of the visible fuel barium alkaryl sulfonate 0.05 0.007 43 39 9 1-methoxy-2-propanol 0.05 total 0.10 barium alkaryl sulfonate 0.1 0.014 44 37 16 1-methoxy-2-propanol gerrorat barium alkaryl sulfonate 0.4 0.058 43 21 51 1-methoxy-2-propanol 0.4 Barium alkaryl sulfonate 0.05 0.007 45 42 7 1-Methoxy-2-propanol 0.2 - 40 40 0 If the barium alkaryl sulfonate alone in Tested the above procedure at concentrations of 0.014% and 0.058 * barium metal n the smoke reductions observed were considerably less than for the sulfonate / ether fuel mixtures tested above that contain the same metal concentrations contained0 The ether used, 1-methoxy-2-propanol, gave a classification of 0 in terms of smoke reduction, there, the smoke meter obviously no decrease of visible smoke and soot.

These results show that fuel blends contain Group IIA metal sulfonates and ether, which suppress visible smoke and soot formation during combustion.

Example XV A diesel fuel blend was prepared which about 0.2% by weight of the dimethyl ether of ethylene glycol and about 0.208% by weight a commercially available smoke suppressant, a mixture of barium and calcium carbonate (21.6% Ba, 1.1% Ca). The ethers and carbonates were separated from diesel power added substance.

Diesel fuel No. 2 was used as in Example 13. The experiments were carried out as in Example XIII.

The following table shows the effectiveness of the new fuel blends. The table shows the Adjusted Hartridge Smoke Numbers (HSN) as average values of three consecutive Try indicated.

Addition in% by weight% by weight Adjusted Adjusted percentage basic strength Addition of metal RSN HSN Reduction of material in the basic of the power of the visible power Fuel fuel-heavier smoke material mixed metal carbonates (21.1% Ba 1.1% Ca) 0.208 0.04 33 10 70% dimethyl ether of ethylene glycol, metal carbonates 0.208 0.04 31 12 61% Dimethyl ether of ethylene glycol 0.200 - 33 33 0 It is on it noted that the components of the fuel mixtures when tested individually were less effective in reducing visible soot and smoke than their combinations. This shows the unexpected promotion of smoke and soot suppression, which is obtained when Group IIA metal carnonates and ethers are mixed into fuels will.

Example XVI When the monomethyl ether of ethylene glycol instead of the dimethyl ether was replaced by ethylene glycol in the above fuel mixture and the resulting mixture was tested according to the procedure of Example XIII, then the following results were obtained: Addition in% by weight Wt .-% Adjusted Adjusted percentage base addition metal HSN HSN of the reduction power in the in the fuel the visible substance basic smoke power power power Mixtures of substances of substances of metal carbonate (21.1% Ba 1.1% Ca) 0.208 0.04 32 10 69% Monomethyl ether of ethylene glycol 0.200 0.408 Metal carbonates 0.208 0.04 31 12 61% Monomethyl ether of ethylene glycol 0.2 - 33 34 0 in the above examples resulted a rating of 0 for smoke reduction when used individually became.

Selected amounts of a commercially available barium carbonate abdominal suppressant (22.5% Ba) and an ether were separated with the diesel fuel no.2 from example XIII and tested according to the procedure of Example XIII. There were get the following results: Addition in wt .-% wt .-% adjusted Adjusted HSN percentage basic addition metal HSN of the force reduction force in the smoke that can be mixed in the basic material of the face of fuel material material material metal carbonate (22.5% Ba) 0.2 0.04 34 13 62% monomethyl ether of ethylene glycol 0.2 0.4 metal carbonate (22.5% Ba) 0.2 0.04 33 13 61% dimethyl ether of ethylene glycol 0.2 0.4 metal carbonate 0.2 0.04 34 15 56% The ethers used gave a smoke reduction of 0%.

These results clearly show that one unexpected. Improvement of Smoke suppression for fuel mixtures containing Group IIA metal carbonates, is achieved when ether, especially glycol ether, with 3-10 carbon atoms, be used.

If desired, the fuel compositions of the invention can in addition, oxidation inhibitors, corrosion inhibitors, anti-foaming agents, others Smoke suppressants, sediment inhibitors, color stabilizers and other additives that improve fuels in one or more ways. Furthermore, other detergents, such as e.g.

Metal salts of monoesters of sulfuric acid obtained from n-aliphatic Alcohols with 8-18 carbon atoms are made, metal salts of di (2-ethylhexyl) sulfosuccinic acid and especially group IIA salts, preferably barium salts, and mixtures thereof can also be incorporated into the additives.

Claims (21)

P a t e n t a n s p r ü c h e 1. The use of a mixture of (1) an ether and T2) one Group II & metal salt of an organic acid, a Group IIA metal sulfonate or a Group IIA metal carbonate as a smoke and soot suppressant additive for liquid hydrocarbon fuels. 2o Use according to claim 1, characterized in that there are no t t that the ether is an ether of a polyol with up to about 30 carbon atoms is, 3. Use according to claim 1, characterized in that the g e k e n n z e i c h -n e t Ether an alkyl ether of a glycol, for example the monomethyl or dimethyl ether of ethylene glycol or 1-methoxy-2-propanol. 4. Use according to one of the preceding claims, characterized g e k e n n z e 5 c h n e t that the fuel is a fuel for internal combustion engines, especially diesel engines. 5. Use according to one of the preceding claims, characterized g e it is not noted that the Group IIA metal is calcium or barium 6. Use according to one of the preceding claims, characterized in that the Group IIA metal salt of an organic acid in the fuel in an amount of about 0.01-2% by weight, preferably 0.05-1% by weight, and the ether in an amount from about 0.05-5% by weight, preferably 0.1 to 1% by weight, based on the total weight of the fuel, 7. Use according to claim 6, dir g e k e n n z z i o h -ne t * that the Group IIA salt in an amount of 0.2-5 % By weight and the ether is present in an amount of 0.3-0.6% by weight. 8. Use according to one of claims 1 to 5, characterized in that g e k e n It is noted that the mixture is a Group IIB metal salt of an organic Contains acid in addition to the Group IIA metal salt of an organic acid. 9. Use according to claim 8, characterized in that g e k e n n z e i c h -n e t that the group IIA metal salt is a barium salt and the group IIB metal salt is a Zinc salt is. 100 Use according to claim 9, characterized in that there are no Z e i c h -, n e t that the ratio of barium salt to zinc salt is approximately 8: 1 to 12: 1. 110 Use according to one of claims 8 to 10, characterized in that it is It should be noted that the mixture contains a Group IIA metal sulfonate. 1 2 'Use according to one of claims 8 to 11, characterized in that g e k e It is noted that the total amount of Group IIA and IIB metal salts of the organic acids in fuel is approximately 0.05-5% by weight, the amount of ether is about 0.05-5 weight percent and the amount of the Group IIA metal sulfonate, if this is present at all, is approximately 0.05-1% by weight, based in each case on the Total weight of fuel. 130 Use according to one of the preceding claims, characterized in that g It is not noted that the organic acid is a monoalkanoic acid with approximately Is 4-12 carbon atoms. 14. Use according to claim 13, characterized in that g e k e n n z e i c h -n e t that the alkanoic acid is branched in the alpha position and, for example, from 2-ethylhexanoic acid consists. 15. Use according to one of claims 1 to 5, characterized g e k e n It should be noted that the Group IIA metal sulfonate is present in the fuel in an amount of 0.007-0.1% by weight, preferably 0.04-0.08% by weight, based on the Total weight of fuel. 16. Use according to claim 15, characterized in that it is e k e n n z e i c h -n e t that the ether in an amount of 0.05-5 wt .-%, preferably 0.01-1 wt .-%, is present. 17. Use according to one of the preceding claims, characterized in that g It is not noted that the sulfonate is a barium hydrocarbon sulfonate is. 18. Use according to claim 17, thereby g e k e n n n z e i c h -n e t that the sulfonate is a barium aralkyl sulfonate with a molecular weight of approximately 900-1100 is. 19. Use according to one of claims 1 to, thereby g e k e n It is noted that the Group IIA metal carbonate in an amount of 0.05-5 % By weight, preferably 0.1-1% by weight, and the ether in an amount of 0.05-5% by weight, preferably 0.1-1% by weight, based on the total weight of the fuel. 20. Use according to claim 19, characterized in that g e k e n n -z e i c h n e t that barium carbonate in an amount of 0.2-0.5 wt. and the ether in one Amount of 0.2-0.5% by weight is present. 21. Use according to claim 19 or 20, characterized in that g e k e n n -z e i c h e t that the weight ratio of carbonate to ether is 5: 1 to 1: 5.