JPS5920656B2 - Method for producing oil-dispersible metal salt-organic acid metal salt complex - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing an oil-dispersible metal salt-organic acid metal salt complex (hereinafter referred to as the complex).

More specifically, the present invention relates to a method for producing a composite material having a high content of iron, manganese, nickel, and cobalt. As is well known, organic acid metal salts of iron, manganese, nickel, and cobalt are useful as lubricating oil additives, fuel oil additives, synthetic resin additives, synthesis catalysts, paint additives, rust preventives, etc. It is something.

As examples of these organic acid metal salts, metal salts such as naphthenic acid, 2-ethylhexylic acid, ricinoleic acid, and neodecanoic acid are widely known, but the metal content is also 4% to 10%.
All of them are solid or highly viscous, and are usually diluted with a diluent before use. In that case, the metal content further decreases to about several percent, and when these diluted additives are used, there are many disadvantages such as an increase in the amount added and a decrease in the original physical properties of the liquid to be added. Katta. As a result of repeated research in order to solve these problems, the present inventors discovered that a certain kind of organic carboxylic acid or organic sulfonic acid metal neutral salt and a certain water-soluble inorganic metal salt and a certain kind of organic carboxylic acid or organic sulfonic acid metal salt in an organic solvent. The present invention was accomplished by discovering a method for producing a complex with a high metal content, low viscosity, and easy handling by reacting alkali hydroxide with oxygen and/or hydrogen peroxide. did. To describe the method for producing the composite of the present invention in more detail, each metal neutral salt of an organic carboxylic acid and an organic sulfonic acid is prepared by reacting the above acid with a metal oxide or metal hydroxide, or by reacting the above acid with a metal oxide or metal hydroxide. It can be produced by a double decomposition reaction between an alkali salt and a water-soluble inorganic metal salt.

This is reacted with a water-soluble inorganic metal salt and an alkali hydroxide, and this is oxidized with oxygen and/or hydrogen peroxide to produce metals such as oxides and hydroxides that are converted to higher valence by oxidation. By dispersing the compound in colloidal form, a composite with a high metal content can be produced. In addition, without making the metal neutral salt of the organic carboxylic acid or organic sulfonic acid in advance, it is possible to combine the organic carboxylic acid or organic sulfonic acid in the same system with the amount necessary to make the organic acid into a neutral salt, and also the metal. Alkaline hydroxide and water-soluble inorganic metal salt as materials for increasing concentration are simultaneously mixed and reacted,
A step of oxidizing this with oxygen and/or hydrogen peroxide can also be taken. Taking ferrous metals as an example, iron is 2
In this process, valent and trivalent salts are produced, and divalent iron is converted to trivalent iron through oxygen oxidation in the subsequent process. The organic carboxylic acid used in the present invention is naphthenic acid or carbon number 8-1.
A saturated or unsaturated aliphatic carboxylic acid having 8 carboxylic acids, examples of which include naphthenic acid, octylic acid, lauric acid, ricinoleic acid, oleic acid, and the most preferred example is naphthenic acid. Can be done.

The organic sulfonic acids used in the present invention are petroleum sulfonic acid,
Monoalkylbenzenesulfonic acid or dialkylbenzenesulfonic acid having 15 to 30 carbon atoms, examples of which are monononylbenzenesulfonic acid, monodecylbenzenesulfonic acid, monododecylbenzenesulfonic acid, monohexylmonododecylbenzenesulfonic acid, Examples include dinonylbenzenesulfonic acid, didecylbenzenesulfonic acid, didodecylbenzenesulfonic acid, and the most preferred examples include monododecylbenzenesulfonic acid and petroleum sulfonic acid having a molecular weight of 350 to 520. Examples of the metal of the metal neutral salt of organic carboxylic acid or organic sulfonic acid used in the present invention include sodium, barium, calcium, magnesium, iron, manganese, nickel, and cobalt. Preferred examples include iron, Manganese can be mentioned. The acid group that binds to these metals needs to be oil-soluble by binding to the metal, and is appropriately selected depending on each metal. The water-soluble inorganic metal salts used in the present invention are chlorides, sulfates, nitrates, bromides, and iodides of divalent iron, manganese, nickel, and cobalt, and examples thereof include:
Ferrous chloride, manganese chloride, nickel chloride, cobaltous chloride, ferrous sulfate, manganous sulfate, nickel sulfate, cobaltous sulfate, ferrous nitrate, manganous nitrate, Examples include nickel nitrate, cobaltous nitrate, ferrous bromide, manganese bromide, ferrous iodide, manganese iodide, etc., and preferred examples include ferrous chloride, manganous chloride, nickel chloride,
Mention may be made of cobaltous chloride, ferrous sulfate, manganous sulfate, nickelous sulfate, ferrous nitrate, manganous nitrate, and cobaltous nitrate. These water-soluble inorganic metal salts can also be used in the form of an aqueous solution.
The amount of the water-soluble inorganic metal salt to be used should be determined appropriately depending on the concentration of the final complex, but it is 1 to 15 times the molar amount of the metal neutral salt of the organic carboxylic acid or organic sulfonic acid. Preferably, it is particularly preferably 2 to 10 times the molar amount. If it exceeds this range, unreacted substances remain and it is also uneconomical. Examples of the alkali hydroxide used in the present invention include sodium hydroxide, potassium hydroxide, ammonium hydroxide, etc., and it is preferable to add it to the reaction system in the form of an aqueous solution, but water may already be present in the reaction system. If present, it can be used without being dissolved in water.

Usually, the concentration of alkali hydroxide is preferably 20 to 50%,
The amount of alkali hydroxide used is 2 times the amount of water-soluble inorganic metal salt.
The amount necessary for conversion to the valent oxide or hydroxide or a slight excess is used. Examples of the solvent used in the present invention include nonpolar solvents such as benzene, toluene, xylene, kerosene, normal heptane, and normal octane, and if necessary, a small amount of a polar solvent such as alcohol may be used in combination. be able to.

In the present invention, there are no particular restrictions on the mixing order, mixing temperature, etc. of metal neutral salts of organic carboxylic acids or organic sulfonic acids, water-soluble inorganic metal salts, alkali hydroxides, organic solvents, etc.; Alternatively, it is preferable to add the metal neutral salt of organic sulfonic acid, the water-soluble inorganic metal salt, and the alkali hydroxide in this order, and preferably to stir the mixture.

The mixing temperature is preferably 50 to 130°C. In the present invention, the oxidation reaction is carried out using oxygen and/or hydrogen peroxide, but air can also be used as the oxygen source.

The amount of oxygen required for the oxidation reaction is the minimum amount required to convert the valence of the divalent metal used in the present invention from divalent to trivalent, etc., and is usually used in large excess, but hydrogen peroxide In this case, it may be too much.

The reaction temperature of this oxidation reaction is 40 to 150°C, preferably 60 to 90°C, and the oxidation can be carried out by blowing oxygen or air into the reaction system, or by dropping hydrogen peroxide. can. After this oxidation reaction is completed, water present in the reaction system is removed from the system by liquid separation or distillation. When removing water by liquid separation, the lower aqueous layer in which the by-produced alkali salts such as sodium chloride or sodium sulfate are dissolved is separated by liquid separation, and a small amount remaining in the upper oil layer is removed. Water is removed by distillation, and then the alkali salts dissolved in a small amount of water in the oil layer precipitate and can be removed by filtration. In addition, in the case of distillation, the complex, which is liquid at room temperature, is removed by removing it from the system by azeotropic distillation with a solvent and distillation under reduced pressure, and removing a large amount of alkali salts precipitated in the system by filtration. can get. This liquid contains an organic solvent and can normally be used as an additive as is, but it is possible to adjust the concentration or change the solvent composition by adding more solvent or replacing part or all of the solvent with another solvent. It can also be prepared. Next, the method of the present invention will be specifically illustrated with examples.

The metal ratio in the examples was determined by the following formula. Example 1 A 100-ton reactor was charged with 141<g of kerosene, 6.0 kg (9.4 mol) of iron naphthenate neutral salt, and ferrous chloride. Tetrahydrate salt 6.1
kg (30.6 moles) and 13.0 kg (65 moles) of a 20% aqueous sodium hydroxide solution were charged with stirring, mixed, and air was added to this solution at 80 to 90°C at a rate of 25 to 28 t/Mm.
The oxidation reaction was carried out by blowing at a rate of 3 hours.

After the reaction was completed, the water was distilled off, then filtered using a filter aid, and 7.0 kg of kerosene in the liquid was distilled off under reduced pressure, resulting in an Fe content of 16.5% and a metal ratio of 3. 97 complexes are 1
2.7 kg was obtained. The yield was 92.0%. Example 2 10.9k9 (1
7.1 mol) Toluene 20.0 kg, ferrous sulfate heptahydrate 14.1 kg (50.7 mono(c), 30% sodium monohydroxide aqueous solution 14.9 kg (111.7 mol) while stirring After charging and mixing, air was blown into the solution at a rate of 25 to 27 t/Mm at 80 to 90°C for 3 hours to carry out an oxidation reaction.

After the reaction was completed, the water was distilled off, and then the water was filtered using a deep filter aid, and the entire amount of toluene in the liquid was distilled off under reduced pressure. When 7 kg of spray kerosene was added, the Fe content was 15. 7%,
21.9 kg of a composite with a metal ratio of 3.68 was obtained. The yield was 90.8%. Example 3 3.3 kg of iron naphthenate neutral salt (5.2
mole), toluene 6.0kg, spray kerosene 2.4kg
, ferrous sulfate heptahydrate 7.31<9 (26.3 mol),
20% sodium hydroxide aqueous solution 11.5 kg (57.5
mol) with stirring, mixed for 30 minutes at 80-90°C, and then added 17.5% hydrogen peroxide at 60-70°C.
．． 01<g was gradually added dropwise to carry out an oxidation reaction.

After the reaction, the water was separated, the oil layer was dehydrated, filtered using a filter aid, and all the toluene in the bottom liquid was distilled off under reduced pressure, resulting in a Fe content of 19.4% and a metal ratio of 5.20. 7.6 kg of the complex was obtained. The yield was 93.7%. Example 4 7.5 kg of naphthenic acid (24,95 kg
Mono(c), toluene 31.41<g, spray kerosene 5
．． 21<9, sodium hydroxide 6.5 kg (162.5
mole), water 19.8 kg, ferrous sulfate heptahydrate 22.1
1<g (79.5 mol) was charged with stirring, and after reacting for 1 hour under reflux, 12.6 kg of 7.5% hydrogen peroxide was added to 40
The oxidation reaction was carried out dropwise in minutes.

After the completion of the reaction, the aqueous layer was separated, and the oil layer was dehydrated and filtered using a deep-filtering aid, and the entire amount of toluene in the liquid was distilled off under reduced pressure. 18.0 kg of a composite with a ratio of 5.27 was obtained. The yield was 90.0(f). Example C kerosene 20.0k in 5100t reactor
g, iron monododecylbenzenesulfonate 10.4 kg (
16.3 mol), ferrous chloride tetrahydrate 10.71 < 9 (
53.8 monomer, 30% sodium hydroxide aqueous solution 16.
Prepare 0 kg (120.0 mono(c)) while stirring,
Mix and heat this solution at 80-90°C for 25-27 seconds. ．． /M
The oxidation reaction was carried out by blowing air at a rate of m for 4 hours.

After the reaction is complete, water is distilled off, filtered using a fuchi filter aid, and 7.5 kg of kerosene in the liquid is distilled off under reduced pressure.F
A composite with an e content of 14.8% and a metal ratio of 4.00 is 24.6
kg was obtained. The yield was 90.5f6. Example
6 Toluene 10.0kf, manganese naphthenate neutral salt 5.0kg (7.9 mol), manganese chloride tetrahydrate 3.6k in a 30t reactor! ? (18.2 mol) and 8.0 kg (40.0 mol) of a 20% aqueous sodium hydroxide solution were added with stirring, mixed, and added to this solution at 80 to 90°C.
Air was blown at a rate of 5 to 27 t/U for 3 hours to perform an oxidation reaction.

After the reaction was completed, water was distilled off, filtered using a filter aid, toluene in the liquid was distilled off under reduced pressure, and sprayed with 3.4 kf of kerosene.
When replaced with I, Mn content 13.9% metal ratio 3.12
9.7 kg of the complex was obtained. The yield was 90.2%. Example In a 730t reactor, 12.0 kg of kerosene, 6.0 kf (9.4 mol) of neutral salt of nickel naphthenate, and 3.3 kf of nickel sulfate hexahydrate! (12.6 moles)
, 20% sodium hydroxide aqueous solution 5.4 kg (27.0
After mixing for 30 minutes at 70-80℃, add 2.6k of 17% hydrogen peroxide at 65-75℃.
The oxidation reaction was carried out by gradually dropping 1.

After the reaction is completed, the water is distilled off, and 5.5 kg of kerosene in the liquid is distilled off using a filter aid, and the Ni content is 1.
10.6 kg of a composite with a metal ratio of 0.0% and a metal ratio of 2.10 was obtained. The yield was 83.3%. Example 8 In a 30-ton reactor, 8.0 kg of toluene, 6.4 kg (10.1 mol) of neutral cobalt naphthenate salt, 5.6 kg (19.2 monoli) of cobaltous nitrate hexahydrate, 2.0 kg of water
(11.1 mol), 40% aqueous sodium hydroxide solution4.
4 kg (44.0 mol) was charged and mixed with stirring, and air was blown into the solution at a rate of 23 to 25 t/11 for 3.5 hours at 80 to 90°C to carry out an oxidation reaction.

After the reaction was completed, the water was distilled off, filtered using a fuchi filter aid, and all toluene in the liquid was distilled off under reduced pressure, and replaced with 4.5 kg of spray kerosene, resulting in a CO content of 12.596,
11.76 kg of a composite with a metal ratio of 2.49 was obtained. The yield was 78.1%. Example 9 10.0 kg of kerosene and 4.5 kg (5.4 monoliths, ferrous sulfate heptahydrate) of petroleum sulfonate calcium neutral salt (molecular weight 840) were placed in a 301 reactor. 4.5 kg (16.2 mol), 2
096 Sodium hydroxide aqueous solution 7.0 kf (35.0 mol) was charged with stirring, mixed, and added to this solution.
An oxidation reaction was carried out at 00°C by blowing air at a ratio of 25 to 271/fin for 3 hours.

Claims (1)

[Claims] 1 Organic carboxylic acids selected from naphthenic acids, saturated and unsaturated aliphatic carboxylic acids with 8 to 18 carbon atoms, petroleum sulfonic acids, mono- or dialkylbenzene sulfonic acids with 15 to 30 carbon atoms in organic solvents. or neutral salts of metals selected from sodium, barium, calcium, iron, manganese, nickel, and cobalt of organic sulfonic acids, and chlorides, sulfates, nitrates, and bromides of divalent iron, manganese, nickel, and cobalt; An oil-dispersible metal salt-organic acid metal salt complex characterized by mixing a water-soluble inorganic metal salt selected from iodides and an alkali hydroxide, and reacting the mixture with oxygen and/or hydrogen peroxide. manufacturing method.