DE1272041B - Low-smoke burning diesel oil containing an oil-soluble, overbased metal salt - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. CL.

ClOl

German class: 46 a6 - 7

Number: 1272041

File number: P 12 72 041.1-44 (L 51521)

Filing date: August 31, 1965

Open date: 4th July 1968

In the work of diesel engines, the incomplete combustion of diesel oil is a difficult one Problem. The incomplete combustion of the diesel oil causes excessive wear on the machine parts and reduces the efficiency of the engine. It also leads to the formation of black exhaust smoke, especially when the engine accelerates rapidly. The black one formed by a diesel engine Smoke pollutes the air.

US Pat. No. 3,124,435 describes diesel oils which contain an organometallic compound preferably an organic lead compound, such as tetraethyl lead, and a wetting and dispersing agent, preferably an oil-soluble alkali or alkaline earth metal sulfonate. Draw such diesels are characterized by improved combustion properties and reduced formation of black smoke.

Diesel oils known from the German Auslegeschrift 1071867 should burn with particularly little smoke, the two or more sulfonates of metals of Groups II, IV, V, VIb or VIII of the Periodic System of elements included, with smoke development, in particular by a combination of Sulphonates of tin and lead, should be greatly reduced.

However, normal sulfonic acid salts are regularly detergents and act as a detergent in oil-water systems Emulsifiers. Furthermore, the use of many organometallic compounds is prohibited, in particular that of lead, because of its toxicity and / or the toxicity of the resulting from it when burned Products that get into the breathing air with the exhaust gases.

Since, as has been established, the smoke development is also the best known in this regard Diesel oils, namely those with a combination of tin sulfonate and lead sulfonate as an additive contain, is still unsatisfactorily high, it is desirable to include other less harmful, more effective in improving the combustion properties and the other properties to use additives that do not adversely affect diesel oils.

The invention relates to a low-smoke, oil-soluble overbased alkaline earth metal salt Containing diesel oil, which is characterized by a content of 0.1 to 5 percent by weight an oil-soluble overbased alkaline earth metal salt of a bright stock sulfonic acid, which by treating of a mixture

a) a bright stock sulfonic acid,

Low-smoke burning, an oil-soluble,
Diesel oil containing overbased metal salt

Applicant:

The Lubrizol Corporation,

Cleveland, Ohio (V. St. A.)

Representative:

Dr. E. Jung and Dr. V. Vossius, patent attorneys,

8000 Munich 23, Siegesstr. 26th

Named as inventor:
William Monroe LeSuer,
Cleveland, Ohio (V. St. A.)

Claimed priority:
V. St. v. America September 3, 1964
(394 337)

b) an alcohol, phenol, calcium phenate, mercaptan, an aci-nitro compound or a Enol compound as a promoter and

c) more than 1 equivalent of a basic alkaline earth metal compound per equivalent of bright stock sulfonic acid

with carbon dioxide at a temperature of about ⁰ C to the decomposition point of the mixture and subsequent separation of volatile constituents by methods known per se. The overbased alkaline earth metal salts used as additives in the diesel oils according to the invention are characterized by a pronounced degree of basicity, which is determined according to the so-called reflux basicity procedure. In this method, a solution of the overbased metal salt in a solvent mixture of toluene-isopropanol-water (volume ratio: 49: 0.5) and a measured excess of aqueous hydrochloric acid is refluxed and the excess acid is back-titrated with potassium hydroxide solution of known normality. The basicity of the metal compounds is expressed by the amount of KOH in milligrams, which is equivalent to 1 g of the compound. In the description, the basicity determined by this method of operation is referred to as "reflux base number". The in the diesel oils according to the invention

809 568/464

3 4

Applied overbased alkaline earth metal salts have in most cases about 1.5 to a reflux base number of at least about 10. 25 equivalents of the basic alkaline earth metal compound

Such overbased oil-soluble metal salts were produced per equivalent of the bright stock sulfonic acid. That in very small amounts of a maximum of 0.06 weight equivalent weight of an alkaline earth metal oxide or percent already diesel oils as stabilizers, antioxy- 5 »hydroxyds is half of its molecular weight, as an accelerator, a hydroxy-

plug of the fuel feed is added (see USA compound, such as an alcohol or phenol used, Patents 2,781,403 and 3,031,284). z. B, methanol, ethanol, isopropanol, cyclohexanol,

In these very small amounts their smoke- dodecanol, behenyl alcohol, ethylene glycol, and diethylene formation-reducing Effect, however, so low, io glycol, triethylene glycol, the monomethyl ether of the that she was not noticed. Ethylene Glycol, the Monobutyl Ethylene

The oil-soluble over-glycol, hexamethylene glycol, glycerol, pentaerythritol, basic alkaline earth metal salts are derived from a benzyl alcohol, 2-phenylethyl alcohol, phenol, naph- "Brightstock sulfonic acid". Brightstock is a relatively thol, cresol, pyrocatechol, p-tert-butylphenol, by viscous petroleum fraction which is obtained when one is polyisobutene "with a molecular weight of 350 substiparaffin-basic Distilled oils and the paraffin-like phenol, ο, ρ-didodecylphenol, a-hexyl / 3-naph residue deasphalted, dewaxed and refined. thol, m-cyclohexylphenol, 4,4'-methylene-bis-phenol, They are high molecular weight, isoparaffinic 2,2'-methylene-4,4'-dioctyl-bis-phenol, aminoethylal hydrocarbons. The molecular weight can be in the alcohol, o-chlorophenol, m-nitrophenol, o-methoxy range from about 500 to 2000 or even higher ao phenol, hexatriacontanyl alcohol and furfuryl alcohol, lie. Are alcohols of up to about 12 carbon atoms

Brightstock usually has a viscosity of particularly useful as an accelerator. Phenols and at least about 80 SUS (Saybolt Universal Seconds) alkylated phenols may be with one to three alkyl groups of at 99 ⁰ C, where each has more often from about 85 SUS to about 250 SUS to about 50 carbon atoms, are 99 ° C. sulfonic from Brightstock after 25 also preferred. Mixtures of alcohols are prepared as known processes, such as treating mixtures of methanol and n-pentanol, mixtures of the bright stock with sulfuric acid, sulfur trioxide, of methanol, isobutanol, n-pentanol and cyclo-oleum, chlorosulphonic acid or another sulfonic acid, mixtures of methanol and glycerine and f oning agents. Brightstock sulfonic acids, mixtures of methanol and isooctanol can also be obtained, especially by using a mixture of 30.

Brightstock, sulfur dioxide and chlorine irradiated. The accelerator can also be a calcium phenate,

Bright stock sulfonic acids with a molecular weight of mercaptan, an aci-nitro compound or enolic from about 500 to about 2000 are required for making connection, e.g. B. ethyl acetoacetate, acetylder acetone, nitromethane, nitropropane, nitrodecane, nitro oil soluble in the diesel oil according to the invention, overbased alkaline earth metal salts be benzene, nitrotoluene, m-nitrophenol, o-methoxyphenol, especially suitable. Thiophenol, methyl mercaptan, dodecyl mercaptan,

The overbased alkaline earth metal salts of bright isooctyl mercaptan and benzyl mercaptan. As Stock sulfonic acids can lead to the calcium phenates which can be used in the USA accelerators Patents 2,915,517 and 3,001981 are known to discard alkylphenols and alkylphenol-aldehyde processes getting produced. 40 condensation products in which the alkyl radical or

One convenient method is treating the alkyl radicals in total at least 6 carbons of a mixture of the bright stock sulfonic acid containing atoms. The terms "phenol" and promoter and more than 1 equivalent of a basic "phenol", as used here, are intended to include alkaline earth metal compounds per equivalent of the bright phenols as well as mononuclear and polynuclear phenols. stock-sulfonic acid with carbon dioxide at a tem- 45 Similarly, the term "alkyl" is intended to both temperature up to the decomposition point of the open-chain of about 25 ⁰ C as well as cyclic alkyl groups introduced premix, close. In most cases this is alkylphenol,

The carbonation is preferably carried out in the presence of the directly converted into the calcium phenate a diluent carried out, which usually or initially condenses with an aldehyde and is a flowable solvent in which at least 50 is then converted to calcium phenate one of the reactants or the product is mononuclear monoalkylphenol in which the alkyl radical is soluble. Examples of solvents that can be used are about 3 to about 150, preferably about 4 to about 50 are benzene, toluene, chlorobenzene, heavy gasoline, contains carbon atoms. Generally contains a Dodecane, xylene and mineral oil. no further such mononuclear monoalkylphenol

The basic alkaline earth metal compound can have one more substituent, albeit for some purposes Alkaline earth metal oxide, hydroxide, bicarbonate, sulfide, substituents such as chlorine, bromine, nitro, sulfide, di- mercaptide, hydride, alcoholate or phenolate. sulfide, ether, amino, nitroso, in the alkyl radical and / or It is preferably an oxide, alcoholate or hy- the aromatic nucleus can be present, hydroxide of calcium or barium, because specific examples of alkylphenols are o, p-diethylthese Products derived from metal bases as especially 60 phenol, n-propylphenol, p-isopropylphenol, diisoproactive pylphenol, n-butylphenol, p-tert, -butylphenol, and Cyclo were found for the purposes of the invention. It appears in the amount to be used of hexylphenol, methylcyclohexylphenol, sec-hexyl metal base no upper limit to exist. From phenol, heptylphenol, tert-octylphenol, n-decylpractical Reasons, however, exceed the amount of phenol, cetylphenol, oleylphenol, wax-alkylated of the metal base to be used rarely 35 equivalents 65 phenol, polyisobutene-substituted phenol, in which per equivalent of bright stock sulfonic acid. One of the polyisobutene radicals is about 20 to about 150 or more larger amount of metal base can be used, contains carbon atoms; alkylated aryl substituted but this does not seem to offer any particular advantages. Phenols, such as heptylphenylphenol, isooctyldiphenyl

5 6

phenol, and di-tert-amylnaphthylphenol; alkylated One particularly useful accelerator is a

polyhydroxyaromatic compounds, such as a heptyl mixture of a calcium phenate and a alizarin, n-octylquinizarin, octylpyrocatechol, Hep alcohol or alcohols. For example, are mixtures tylpyrogallol and substituted phenols such as heptyl from one of the calcium phenates described above p-nitrophenol, isododecylpipric acid, p-n-octyl-5 with an alcohol or with alcohols in weight o-chlorophenol, Octylphenol monosulphide, heptylphenol ratio 2: 1 to 1: 4 useful accelerators for disulfide, the condensation product of heptyl- Production of strong alkaline earth metal salts of phenol and formaldehyde in the molar ratio of bright stock sulfonic acids with metal ratios of 2: 1, the condensation product of tert-octylphenol 5 to 40. A more specific example of such a genus and formaldehyde in a molar ratio of 1: 1 io mix is one which consists of 150 parts of methanol, and the condensation product of tertiary amylphenol, 250 parts of isooctyl alcohol and 200 parts of one and acetaldehyde in a molar ratio of 2: 1. Calcium phenate consists, which the latter produced

The preparation of the calcium phenolates of alkyl was known by 10 hour condensation of an alkylphenol, alkylphenol sulfide and alkylphenol-alde- phenol with an aldehyde in a molar ratio of hyd-condensation products and is 15 1: 1 at 50 to 200 ^° C in the presence of a small example in the USA. patents 2,197,833, quantity (1 to 2 ° / ₀₎ of hydrochloric acid and subsequent order-2,228,654, 2,228,661, 2,362,289, 2,250,188, 2,280,419, conversion of the condensation product in the CaI -2 331 448 and 2 252 663. Generally ciumphenolat.

the calcium phenates are made by reacting the amount of accelerator to be used

Low stoichiometric phenolic compound is best expressed as a chemical equimetric excess of a calcium base such as calcium valent per equivalent of the bright stock sulfonic acid. The ciumoxide or hydroxide, calcium methylate or amount can be 0.1 to 10 equivalents or more per equivalent of the bright stock sulfone ethylate, or calcium carbide, for 30 minutes to acidic. The 10 hours at a temperature of about 50 to preferred amount is made 200 ⁰ C to about 5 Äquietwa about 0.25. Solvents, such as mineral oil, are 25 valents per equivalent of the bright stock sulfonic acid. Benzene, toluene, and alcohols, accelerator equivalent weight, can be used to facilitate the reaction. on the number of alcoholic or phenolic

The calcium phenolates hydroxyl groups or mercapto radicals in the molecule, the alkylphenol-aldehyde condensation products, are particularly useful. In the case of aci-nitro compounds, the equation is. B. the calcium phenolates of the condensation pro- valent weight equal to the molecular weight. For the result of formaldehyde with a mononuclear illustration, it should be stated that the equivalent monoalkylphenol in which the alkyl radical is about 3 to by weight of a monohydric alcohol equal to its about 150, more often about 4 to about 50 carbon atoms molecular weight; has the equivalent weight of one. Instead of formaldehyde, one can use other trihydric alcohols one third of its lower molecular weight aldehydes with 2 to about 10 carbon atoms; use the equivalent weight of a bis-phenol, such as acetaldehyde, propionaldehyde, butyr- is half its molecular weight, and the aldehyde, furfural or benzaldehyde, although the equivalent weight of a mercaptan with a mer-formaldehyde due to its low cost and capto group is equal to its molecular weight.
Responsiveness is preferred. The calcium pheno- The use of a combination of the

late of the alkylphenol-aldehyde Kondensationsproduk- 40 called promoters with about 0.1 to about 5 ° / ₀ can be prepared by known methods th based on the weight of the Carbonisierungsgemisches be, for example, an inorganic halide is particularly favorable.

The halide can be ammonium chloride, ammonium

(a) Condensation of the alkylphenol and aldehyde in bromide or an alkali or alkaline earth halide, such as a molar ratio of about 4: 1 to about 1: 4 45 sodium chloride, calcium chloride, potassium chloride, Na for 30 minutes to 15 hours and at 50 to trium bromide, potassium iodide , Barium chloride, Magne-200 ⁰ C in the presence of a small amount, in the sium chloride or sodium iodide. The halide generally 0.5 to 5%, of a basic or facilitates carbonization and enables acidic catalysts such as aqueous ammonia to incorporate an unusually large amount of metal or hydrochloric acid, with subsequent conversion to the carbonized product.

of the condensation product formed in the The carbonization temperature also depends on the

Calcium phenate; used accelerator. Used as an accelerator

/ -1-N in x t. Ic *· j τ-ι. *,. m, ■ a phenol is used, the temperature is usually

^(b) Ä *? * ^b r ¹⁵ T ^{dlgeS e} r ι 'I lh * ** range of about 80 to about 300 ° C, preferably-200 C a mixture of a calcium base, _{yon about m big 2QQ0} ^ _{m Verwend' dn} ^S _it

such as calcium oxide or hydroxide * f, - _{alcohol wirddieTemperatur usually about} l ₀ 0 ° C

Alkylphenol and an aldehyde which _{do not exceed} . _The carbonization temperature

Calcium base _fe as a catalyst for the condensation _{kh 2QaQ}

acts sationsreaktion while providing calcium mixing the alkaline earth metals, which for the phenation needed _{6q compound having a} bright stock sulfonic acid is

are formed oüer _{a metal salt} , so that the mixture a

(c) Heating a mixture of an alkylphenol metal salt of a bright stock sulfonic acid and a calcium base for 30 minutes to a large excess of the metal base. Such 15 hours at 50 to 200 ⁰ C for the preparation of the mixture is mainly due to the presence of calcium phenate and subsequent condensation 65 large excess of unöslicher metal base heterosation the intermediate obtained with gene. With the progress of carbonation is an aldehyde for 30 Minutes to 5 hours, the metal base dissolved in the organic phase, at 50 to 200 ° C. and the carbonized product finally becomes a

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homogeneous mass, which contains an unusually large amount of heptylphenol and 384 parts of water to 80 ⁰ C amount of metal. The mechanism by which it is heated, resulting in 1480 parts (19.2 equivalents) of the homogeneous product, is unknown. Barium oxide is believed to be added to the carbonization within a 0.6 hour period, however. The reaction is exothermic, and the excess metal base in a carbonate or 5 temperature of the reaction mixture reaches 100 ⁰ C. Bicarbonate converts, which with the metal salt of the The mixture is heated to 150 ° C and carbonized a homogeneous complex temperature with this bright stock sulfonic acid. Formed during the carboni. This complex is in solvents, such as 24 parts of barium chloride to the benzene, xylene, heavy gasoline and mineral oil, easily added mixture. Soluble from the reaction mixture. It is not possible for the entire metal base to remove oil during the carbonization. The necessary, so converted to carbonization by carbonization, is continued at this temperature, in order to form a soluble, homogeneous product until the mixture has a base number (phenolphthalein). In many cases a homogeneous product of 80 will be found. Then the mixture obtained 164 parts if already 75 ° / ₀ of the excess metal octyl alcohol and a filter aid added, are base carbonized. The expression "carbonized," 15 and the mixture is filtered while hot. The filtrate denotes a basic alkaline earth metal compound, which is a solution of the desired overbased orbomogeneous carbonized product without special reference to bright stock sulfonate with a barium sulfate increase in the degree of conversion of the excess ash content of 26.42, a metal ratio of 4.6 metal base by carbonization. and a reflux base number of 104.

After carbonization, the accelerator can be used at 20 C. A calcium phenate is prepared from the product according to the following procedure, if it is a volatile compound. A mixture of 2250 parts can be removed by distillation. If the loading of mineral oil, 960 parts (5 moles) of heptylphenol, and is speedy relatively non-volatile, so leaving him to 50 parts of water is stirred at 25 ⁰ C. The mixture usually with no adverse effect in the product. is then heated to 40 ⁰ C and 7 parts of CAI Usually, it is expedient, the carbonized, 25 ciumhydroxyd and 231 parts (7 moles) of 91 ° / _o sodium Paraüberbasische alkaline earth metal salt of formaldehyde in a solvent within a period of 1 hour medium produce so that a product is put into solution. Is obtained after heating the mixture to 8O ⁰ C, which can be easily mixed with diesels further 200 parts of calcium hydroxide (which can be a whole. 207 parts or 5 moles) over a period of

The amount of metal which is added to the carbonized product for 1 hour, after which the mixture is incorporated into the product, is more than that heated to stoichio-150 ° C and calculated on a metric basis for 12 hours at this temperature, i.e. more than is kept by, while nitrogen is blown by looking at neutral metal salts of the bright stock mixture, the removal of water to sulfonic acids can be calculated. Support in the product. If the mixture foams, the amount of metal present is expediently measured as the “metal-a few drops of polymerized dimethyl silicone oil ratio”. Add the expression "metal ratio". The reaction mass is then filtered, as used herein, is meant the ratio of the filtrate, a 33.6 ° / _o oil solution of the desired total chemical equivalents of the metal in calcium phenate of heptyl phenol-formaldehyde-metal salt to the chemical equivalents of the metal condensation product containing 7.56 ° / ₀ Calciumbezeichnen, the 40 sulfate ash in the form of a normal salt.

d. H. a neutral salt of sulfonic acid is present. A mixture of 1000 parts of the neutral calcium

For example, a metal salt with 5 equivalents of bright stock sulfonate from B has 1207 parts of mineral oil Metal per equivalent of the organic acid residue and 158 parts of the calcium pheno-metal ratio established above of 5. A neutral salt has a lats, 240 parts of a mixture of isobutanol and Metal ratio of 1. 45 amyl alcohol (65:35 mol percent), 108 parts metha-

Instructions for the Preparation below are nol and 170 parts of calcium hydroxide is contained in the inventive diesel oil, stirred at 45 ⁰ C, and 50 parts of carbon dioxide are within oil-soluble overbased Erdalaklimetallsalze gege- a period of 2 hours initiated. Then practice. Unless otherwise stated, three additional servings of calcium hydroxide are all parts of the information based on weight. 50 of 114 parts each added, and on each one

A. A mixture of 730 parts (0.5 equivalents) of such additive is reintroduced carbon dioxide, a neutral calcium bright stock sulfonate, 58 parts A fourth portion of 114 parts calcium hydroxide len (0.3 equivalents) heptylphenol, 57 parts water is then added, and then 100 parts and 300 parts of toluene is heated to 7O ⁰ C, after which carbon dioxide introduced. Then another 123 parts (1.6 equivalents) of barium oxide within 55 114 parts of calcium hydroxide and 75 parts of carbon are added over a period of 15 minutes. The dioxide added. The mixture is then in 3.5 stun mixture is then heated to 150 ⁰ C and heated at a the at 15O ⁰ C and kept at this temperature rate of 4251 per hour of carbon dioxide, while four hours nitrogen carbonized by until carbon dioxide passes from the reaction mixture mixture. After adding a filter aid, it is no longer absorbed. The mixture is filtered. 60 the mixture is filtered. The filtrate is the desired one. The filtrate is a solution of the desired over-product with a calcium sulfate ash content of basic barium sulfonate with a barium sulfate 39.4% and a metal ratio of 28.4. ash content of 17.3%, a metal ratio of D. A mixture of 1360 parts of a mineral oil-2.9 and a reflux base number of 58. solution, the 550 parts (1 equivalent or 0.5 mol) of a

B. A mixture of 5846 parts (4.0 equivalents) of 65 neutral calcium bright stock sulphonate, 300 parts of a neutral calcium sulphonate of a bright stock luene, 100 parts of methyl alcohol, 100 parts of isooctyl sulphonic acid with a calcium sulphate ash content of alcohol and 260 parts (7 equivalents) Calciumhydro-4.68 ° / ₀ (66% mineral oil), 464 parts (2.4 equivalents) xyd contains, is carbonized at 35 to 47 ° C until

9 10

no further carbon dioxide is heated by the reaction mixture and is no longer absorbed to remove the volatile substances. The mixture is then blown with nitrogen for 3 hours. Then, 10 g of a 50 ° / ₀ aqueous sodium hydroxide mixture added Filtrierhifsmittel and filtered, and added 10 g ammonium chloride in 20 g The filtrate is a solution of the desired water is dissolved. The resulting mixture is carbonized with 5 basic calcium bright stock sulfonate at 62 ° C until its base number (phenol calcium sulfate ash content of 36.9 and a metal phthalein indicator) has decreased to 32. The ratio of 35.

The mixture is filtered and the filtrate to remove I. It is a concentrate of a carbonized,

volatile components heated at 160 ° C / 15 mm Hg. overbased calcium salt according to the method described in B

The residue is a concentrate of the carbonized, io benen working method produced with the exception

overbased calcium bright stock sulfonate with an applied ratio of equivalents of

Calcium sulphate ash content of 18 ° / ₀ and a metal calcium hydroxide to neutral calcium bright stock

ratio of 3.9. _ Sulphonate is 15.5: 1 and the calcium hydroxide in

E. A mixture of 5049 parts (3.5 equivalents) of four parts to the reaction mixture of the neutral calcium bright stock sulfonate from B, 15 is added, with a carbonation step of 401 parts (2.1 equivalents) of heptylphenol and 342 parts for each part. follows. The filtered product has a Calciumlen water is heated to 70 ⁰ C, after which sulfated ash content of 27 ° / ₀ and a metal ratio of 1725 parts (22.4 equivalents) of barium oxide within the sixteenth

added over a period of 2.5 hours. The K. A mixture of 700 parts (0.5 equivalents) mixture is heated to 150 ⁰ C and carbonized to 20 of the neutral calcium bright stock sulfonate from B, its base number (phenolphthalein) to 300 parts of mineral oil, 54 parts of water and 27 parts reduced 8.4. Of isooctyl alcohol (170 parts) and 1-nitropropane is heated to 5O ⁰ C, whereupon 1000 parts of mineral oil are added to the mixture hinzu- 145 parts (1.9 equivalents) of barium oxide used slowly, which then contributes to the removal of water. Allowing the temperature of the mixture to 105 ° C with stirring at 170 ⁰ C is heated. The mixture will reach 25. The mixture is filtered at this temperature. The filtrate is stirred a solution of the desired 1 hour and then overbased to remove barium bright stock sulfonate having heated the water to 15O ⁰ C. A barium sulphate ash content of 23.7, a metal and carbon dioxide at a rate of 4.3 and a reflux base number of 91.851 per hour are introduced into the mixture until it reacts neutrally.

F. It is 30 After further heating lstündigem produced a concentrate of a carbonized exceeded at 150 to basic calcium sulphonate by 160 ⁰ C is added to the reaction mixture with a carbon dioxide-said filtration in a mixture of 700 parts (0.5 equidistant auxiliaries and filtered. the filtrate is the valence) of a 40 ° / ₀ oil solution of neutral desired overbased barium bright stock sulfonate calcium bright stock sulfonate having a molecular with a Bariumsulfataschegehalt of 17.7 ° / ₀ and weight of 1100, 900 parts of Mineral oil, 296 parts 35 with a metal ratio of 3.6.

(8 equivalents) calcium hydroxide, 100 parts methyl L. A mixture of 1160 parts (1.0 equivalent)

alcohol, 75 parts isooctyl alcohol, 2.5 g calcium of the neutral calcium bright stock sulfonate from B, chloride and 2.5 g of water. Carbonization 232 parts of water and 56 parts (1.5 equivalents)

is continued at 50 to 58 ° C until the mixture is ^{heated to 7O 0} C, then with a calcium hydroxide

Base number of 43 (phenolphthalein indicator) to 40 282 parts (3 equivalents) phenol added and 2.5 hours

shows. The mixture is then refluxed to remove any. After that the water

volatile components heated ^{to 150 0 C.} The distilled off by heating to 15O ⁰ C and that

The residue is filtered, and the filtrate has a mixture carbonized by adding carbon dioxide

Calcium sulfate ash content of 19.7 ° / ₀ and a metal at a rate of 85 per 1 Hour 2 Hours

ratio of 10.7. 45 introduces. The mixture becomes more volatile for removal

G. A carbonized, overbased CaI compound is heated to 230 ° C./30 mm Hg and cium salt prepared by carbon filtration at 45 to 60 ° C. The filtrate is the desired overbased one Dioxide in a mixture of a mineral oil solution of calcium bright stock sulfonate with a calcium neutral Calcium bright stock sulphonate (0.5 equisulphate ash content of 11.81% and a metal valent) of D, 370 parts (10 equivalents) calcium 50 ratio of 2.1.

hydroxyd, 200 parts of methyl alcohol and 100 parts.

Octyl alcohol is introduced until the mixture against phenol- ten prevents overbased alkaline earth metal salts

phthalein indicator reacts slightly acidic. The ge the deposition of sludge or paint-like

mixture is then heated to 15O ⁰ C and filtered. The substances in the engine in which the diesel oil is used

Filtrate is a 42% oil solution of the salt with a 55 will. They also facilitate the burning of the

Calcium sulfate ash content of 10.4 ° / ₀ and a diesel oil.

Metal ratio of 5.3. Diesel oils containing these overbased alkaline earth metal

H. An overbased calcium bright stock sulfonate salts may contain other common additives

with a barium sulphate ash content of 28.5 and one containing, such as color stabilizers, antioxidants

Metal ratio of 17.6 is made according to C. 60 agents, rust inhibitors and dispersants. In many

A mixture of 2000 parts of this basic sulfonates cases can diesels 0.001 ° / ₀ to about 2 weight

126 parts of isooctyl alcohol, 168 parts of methanol and percent contain one or more such additives.

134 parts of calcium hydroxide are heated to 46 ° C. Specific examples of such additives are metal-containing

and carbonized with 50 parts of carbon dioxide inside detergents, such as the calcium salt of the hydrolyzate

a period of 2 hours. There are an additional 65 acidic product of polyisobutene with a

134 parts of calcium hydroxide were added, resulting in a molecular weight of 1000 and phosphorus pentasulfide.

Carbonization with 100 parts of carbon dioxide follows. Examples of other additives are tert-dodecylamm and

The mixture is then at 157 ° C / 13-46 mm Hg the imidazoline, which is produced by the reaction of oleic acid

obtained with diethylenetriamine or triethylenetetramine will.

The overbased alkaline earth metal salts can be incorporated into diesel oils by mixing a desired amount of the additive with the diesel oil. You can also prepare a concentrate by dissolving the additive in a solvent such as xylene, toluene or mineral oil and then mixing the concentrate with the diesel oil. The concentrate can / longer contain 5 weight percent or less, or 90 ° or ₀ of the solvent. The diesel oil usually contains about 0.1 to 5%, preferably 0.1 to 2% of the additive.

The improved combustion properties of the diesel oils according to the invention are shown by a remarkably reduced tendency of the engine to form black exhaust smoke. These advantages are demonstrated by the following machine test, in which a single cylinder four-stroke diesel engine is operated with a compression ratio of 19: 1 under the following conditions: number of revolutions 1500 ± 10 rpm; Fuel consumption 1.2 ± 0.018 kg per hour; Machine load about 6 brake horsepower; Air to fuel ratio about 19: 1; and oil sump temperature 55 ± 1.7 ⁰ C. The motor is equipped with a "smoke-tube" apparatus, for measuring the black exhaust Qualms, in which the exhaust gases pass through a glass tube having an outer diameter of 18 mm, in which the smoke on the inside wall of the pipe precipitates. The effectiveness of the additive in preventing black smoke formation is assessed by comparing the pipe with a set of standard pipes having varying amounts of rainfall and rating on a number scale from 0 to 10, with 0 indicating no rainfall and 10 indicating heavy rainfall . The engine is also equipped with another device ("smoke stain" device) for measuring black exhaust smoke, in which the exhaust gases pass through a white filter paper. The amount of black precipitate on the filter paper is also an indication of the effectiveness of the additive. The precipitate is scored in the same way by comparing the filter paper with a set of standard samples, ie papers showing various amounts of precipitation and rated on a number scale from 0 to 10, with 0 indicating no precipitation and 10 indicating heavy precipitation. The fuel used is a common diesel oil with a sulfur content of 1 percent by weight. After a break-in period to establish equilibrium conditions, the engine is run on the diesel oil until the smoke stain rating is within the range of 8.5 to 9.0 and the smoke tube rating is within the range of 6.0 to 6.5. The engine is then run on the test fuel (made by incorporating the additive into the diesel oil) until the operational equilibrium conditions are restored. The smoke tube rating and the smoke spot rating are recorded at the end of 15 seconds and 30 seconds after equilibrium conditions have been reached. The results of the test are shown in Table I below.

Table I smoke test

additive
from Weight percent
in diesel oil Smoke stain
valuation Flue pipe
valuation Regulation 30 seconds 15 seconds none 8.5 9.0 6.0 6.5 C. 0.32 8.0 3.5 0.64 6.5 1.5 B. 0.42 5.0 2.5 0.95 6.5 2.0

The overbased alkaline earth metal salts contained in the diesel oil according to the invention also have the Property that they do not emulsify water in diesel oils.

As noted above, diesel oils often come with water during storage and transportation in touch. If the diesel oil emulsifies water slightly, it carries the emulsified water with it when it is used in engines. Water causes corrosion of the metallic parts that come with the diesel oil come into contact. It also has an adverse effect on the combustion properties of the Diesel oil.

It is obvious that the low emulsifiability of the alkaline earth metal salts used according to the invention is an important benefit. The emulsifying ability of the overbased alkaline earth metal salts is shown by the results of an emulsification test shown in Table II in which a mixture homogenized from 100 ml of a diesel oil and 1 ml of water in a square 113 g glass bottle 44.5 x 44.5 mm and then left to stand at room temperature in order to separate the water from the To enable diesel oil. The turbidity of the sample is measured after 5 minutes, 3, 6 and 24 hours, by bringing a newspaper print behind the bottle and this through the diesel oil layer considered. The turbidity is then rated on a number scale from 0 to 3, with 0 being a clear sample indicates (i.e. complete separation of the water layer from the diesel oil layer) and 3 severe turbidity of the sample (newsprint print completely illegible). A lower rating indicates a lower one Ability to emulsify. A common diesel oil is used in this test. For comparison purposes a commercially available barium mahogany

6g sulfonate wetting agent tested, and its great tendency to emulsify water and diesel oil is shown by the results in Table II.

Table II Water Emulsification Test

additive
from Weight percent 5 minutes Test results 6 hours 24 hours Regulation in diesel oil Obisl 3 hours 0 0 none 2 to 3 0 3 3 basic barium 0.5 3 Magonisulfonate 1 0 0 A. 0.5 Ibis 2 0 0 0 0.25 1 Obisl 0 0 B. 0.5 Ibis 2 0 0 Obisl E. 0.5 0 0 0 0 H 0.5 1 0 0 0 C. 0.5 Obisl 0 0 0 0.25 0

The comparative tests, the results of which are given in Table III below, are as follows carried out:

A four-stroke diesel engine with 12.18 l installed in an intercity tractor is used as the test engine Stroke volume used. The power transferred to the drive wheels when the load changes is determined by means of a dynamometer, with a constant engine speed of 1950 rpm is adhered to.

The already mentioned smoke spot device is used to determine the exhaust smoke every measurement sucks a certain amount of exhaust gases through a filter paper disk. The determination the blackening of the soot stain remaining on the filter paper is carried out by measuring the Photoelectric reflectivity of the soot triangle. The evaluation takes place in the already described on a numerical scale from 0 to 10.

First, the so-called base oil, i. H. a diesel oil without reducing soot development Additives tested and then one after the other the diesel oils to be compared, which are produced by mixing the base oil are made with the various additives in appropriate proportions.

After each attempt, the fuel system is completely flushed by turning the engine on first with the base oil and then with the next diesel oil to be tested.

Table III

Diesel oil 60 I 80 3.6
3.8
3.3
3.1
2.4
2.6
2.3 Load (hp)
100 I 120
Smoke stain value 4.9
4.9
4.3
4.0
3.5
4.3
3.7 140 I Max. 7.4
7.1
6.8
6.2
6.0
6.6
5.2 Base oil 1 2.9
3.3
3.0
2.8
2.0
2.2
1.9 4.3
3.8
3.8
3.5
2.9
3.4
2.7 6.1
6.1
5.6
5.2
4.6
4.9
4.0 Base oil 2 1. German publication 1 071 867
2. German publication 1 071 867
3. U.S. Patent 2,781,404 4. U.S. Patent 3,031,284 5. Diesel oil X (according to the invention)

All additive quantities in percent by weight state the content of active additive, exclusively optionally through the production of solvents and / or diluents present in the additive (Mineral oil).

1. Diesel oil according to the German Auslegeschrift 1071867 (Base oil 2, the 0.25 mg atom of tin and lead per kilogram of oil in the form of sulfonates contains, corresponding to an additive content of about 0.05 percent by weight)

2. Diesel oil in accordance with the German Auslegeschrift 1 071 867

(Base oil 2, which contains 1 mg atom of tin and lead in the form of sulfonates per kilogram of oil, corresponding to an additive content of about 0.2 percent by weight)

3. Diesel oil according to US Pat. No. 2,781,403 (base oil 1 with a content of 0.06 percent by weight of an overbased barium salt according to Example 4 of this USA patent)

4. Diesel oil according to US Pat. No. 3,031,284 (base oil 1 with a content of 0.06 percent by weight an overbased barium sulfonate)

5. Diesel oil according to the invention

(Base oil 1 with a content of 0.2 percent by weight of an overbased calcium brightstock sulfonate, which is produced according to the procedure described under C)

As can be seen from the values in Table III, the diesel oils according to the invention are not only those Base oils, but also all known diesel oils containing metal compounds with regard to the superior to low smoke development.

Claims (2)

Patent claims: 1. Low-smoke burning diesel oil containing an oil-soluble overbased alkaline earth metal salt, characterized by a content of 0.1 to 5 percent by weight of an oil-soluble overbased alkaline earth metal salt of a bright stock sulfonic acid, which is produced by treating of a mixture a) a bright stock sulfonic acid, b) an alcohol, phenol, calcium phenolate, mercaptan, an aci-nitro compound or an enol compound or a mixture of these compounds as accelerators and c) more than 1 equivalent of a basic alkaline earth metal compound per equivalent of bright stock sulfonic acid, optionally in the presence of an organic hydrocarbon solution or diluent, optionally in the presence of an alkali, ammonium or Alkaline earth halide, with carbon dioxide at a temperature of about 25 ⁰ C up to the decomposition point of the mixture and subsequent separation of volatile constituents by methods known per se. 2. Diesel oil according to claim 1, characterized in that it is an oil-soluble overbased Contains the calcium or barium salt of a bright stock sulfonic acid. Considered publications:
German Auslegeschrift No. 1121 617;
U.S. Patent Nos. 3,001,981, 2,915,517. 809 568/464 6.68 © Bundesdruckerei Berlin