JPS6041980B2 - A method for dispersing fine particles of metal compounds in organic solvents at high concentrations - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for dispersing finely divided metal compounds in an organic solvent at a high concentration.

More specifically, the present invention relates to a method of dispersing fine particles of iron, manganese, nickel, and cobalt oxides and/or hydroxides in an organic solvent at a high concentration. As is well known, oil-soluble iron, manganese, nickel, and cobalt compounds are used as lubricating oil additives, fuel oil additives, synthetic resin additives, paint additives, antirust oil additives, synthesis catalysts, etc. It is useful.

As these oil-soluble metal compounds, metal salts of organic acids such as naphthenic acid, 2-ethylhexylic acid, ricinoleic acid, and neodecanoic acid are widely known, but the metal content is also several percent.
All of them are solid or highly viscous, and are usually diluted with an organic solvent before use. In this case, the metal content will further decrease, and the amount used will have to be increased to achieve the desired effect, and the organic solvent used for dilution will have an adverse effect on the desired performance. There were many aspects to it. Under these circumstances, additives containing metal compounds in high concentrations have been desired.

As a method for obtaining such additives, a method of dispersing metal oxides etc. in the form of fine particles in an organic solvent has conventionally been proposed. Methods such as mechanical pulverization, ultrasonic irradiation, or a combination of these have been used, but these methods are inefficient for mass production on an industrial scale, and in addition, the sizes of the fine particles produced are uneven. As a result, the particles settled over time, making it difficult to uniformly disperse the particles. As a result of repeated research to solve these problems, the present inventors found that
An inorganic acid of iron, manganese, nickel or cobalt is used as a dispersant using a neutral salt of a naphthenic acid and/or an organic sulfonic acid and an alkenylcarboxylic acid such as sodium, barium, calcium, magnesium, iron, manganese, nickel or cobalt. We have discovered that fine particles of metal oxides, etc. can be stably dispersed at high concentrations in organic solvents by reacting salts with alkali hydroxide and then reacting them with oxygen and/or hydrogen peroxide. Completed the invention.

To describe the method of the present invention in more detail, a neutral salt of a metal such as sodium, barium, magnesium, iron, manganese, nickel, cobalt, etc. of naphthenic acid and/or organic sulfonic acid and alkenylcarboxylic acid is used as a dispersant in an organic solvent. After reacting a divalent inorganic acid salt of iron, manganese, nickel or cobalt with an alkali hydroxide to form a hydroxide and/or metal oxide of divalent iron, manganese, nickel or cobalt, These divalent metal hydroxides and metal oxides are oxidized with oxygen and/or hydrogen peroxide, and the resulting fine particles of metal oxides and hydroxides are converted to higher valence by oxidation. It can be stably dispersed at high concentrations in organic solvents.

The metal neutral salts of naphthenic acid, organic sulfonic acid, and alkenyl carboxylic acid used in this method may be prepared in advance, but when using the metal neutral salts of organic acids such as manganese, nickel, and cobalt, is not prepared in advance, but the organic acid is combined with a divalent inorganic acid salt of iron, manganese, nickel or cobalt in an amount necessary to convert the organic acid into a neutral metal salt, an alkali hydroxide, and further increases the metal concentration. It is also possible to take a step in which the inorganic acid salt of the divalent metal and the alkali hydroxide as materials for the reaction are simultaneously reacted in the same system, and this is oxidized with oxygen and/or hydrogen peroxide. When using a neutral salt of an organic acid metal of iron, manganese, nickel, or cobalt as a dispersant, this neutral salt is once oxidized, and then a divalent inorganic salt of iron, manganese, nickel, or cobalt is added to the neutral salt. The metal compound can be dispersed more stably by adding and reacting the acid salt and alkali hydroxide, and then oxidizing it again with oxygen and/or hydrogen peroxide.

Taking ferrous metals as an example, iron produces divalent and trivalent salts, but
In this method, a valent iron compound is converted into a trivalent iron compound through oxidation in a subsequent step. The organic sulfonic acids used in the present invention include petroleum sulfonic acids, carbon atoms of 15 to 3C@. Preferred are monoalkyl or dialkyl benzenesulfonic acids having
Examples include monodecylbenzenesulfonic acid, monododecylbenzenesulfonic acid, monohexylmonododecylbenzenesulfonic acid, dinonylbenzenesulfonic acid, didecylbenzenesulfonic acid, didodecylbenzenesulfonic acid, and the most preferred examples include: Mention may be made of monododecylbenzenesulfonic acid and petroleum sulfonic acid having a molecular weight of 350 to 520.

Examples of alkenylcarboxylic acids used in the present invention include:
Alkenylcarboxylic acids having 11 to n carbon atoms are suitable, and in particular undecylenic acid, oleic acid, ricinoleic acid, erucic acid, etc. can be mentioned, and oleic acid can be mentioned as the most preferable example.

When the carbon number is outside this range, the metal compound has poor particle dispersibility and is not stable. The ratio of naphthenic acid and/or organic sulfonic acid to alkenylcarboxylic acid should be determined appropriately depending on the purpose, but 0.0.
The range of 1 to 1 mol is preferred.

When the amount of alkenylcarboxylic acid exceeds 1 mol, liquid separation will be poor in the separation and dehydration steps described later, and during dehydration, foaming will be very strong and reaction will be difficult. When the amount is less than mol, fine particles of the metal compound cannot be stably dispersed at a high concentration.

Examples of the metals constituting the metal neutral salts of naphthenic acids, organic sulfonic acids, and alkenylcarboxylic acids used as dispersants in the present invention include sodium, barium, calcium, magnesium, iron, manganese, nickel, and cobalt. Preferred examples include iron, manganese, nickel, and cobalt. The inorganic acid salts of divalent metals used in the present invention include ferrous chloride, manganous chloride, nickel chloride, cobaltous chloride, ferrous sulfate, manganous sulfate, and nickel sulfate. ,
Cobaltous sulfate, ferrous sulfite, manganese sulfite, ferrous nitrate, manganese nitrate, nickel nitrate, cobaltous nitrate, nickel nitrite, ferrous phosphate, manganous phosphate, Examples include cobaltous phosphate, ferrous phosphite, manganous phosphite, ferrous bromide, manganous bromide, ferrous iodide, manganese iodide, etc., and preferred examples include are ferrous chloride, manganese chloride, nickel chloride, cobaltous chloride, ferrous sulfate,
Mention may be made of manganous sulfate, nickel sulfate, ferrous nitrate, manganous nitrate, and cobaltous nitrate.

This metal salt of an inorganic acid can also be used in the form of an aqueous solution;
Although the metal of the metal neutral salt of organic sulfonic acid and alkenyl carboxylic acid can be different from that of the metal, it is easier to prepare the metal of the same type. The amount of the metal salt of an inorganic acid to be used should be determined appropriately depending on the purpose, but it is preferably 1 to 15 mol, particularly preferably 2 to 15 mol, per 1 mol of the metal neutral salt of these organic acids.
It is 10 moles. When the amount of the metal salt of the inorganic acid used is less than 1 mole per 1 mole of the metal neutral salt of the organic acid, the metal content is less than the metal content of the metal neutral salt of the organic acid. When it is not very expensive and is used in excess of 15 mol,
It is undesirable to stabilize the dispersion of finely divided metal compounds in organic solvents. 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; If present, it can be used without being dissolved in water.

Usually, the concentration of alkali is preferably 20 to 50%, and the amount of alkali used is the amount necessary to convert inorganic acid salts of divalent iron, manganese, nickel, or cobalt into divalent oxides or hydroxides. or) an excess amount is used.
Examples of organic solvents used in the present invention include benzene,
Examples include nonpolar solvents such as toluene, xylene, kerosene, normal heptane, normal octane, and carbon tetrachloride, and if necessary, polar solvents such as alcohol can be used in combination. In the present invention, the reaction temperature between the inorganic acid salt of the divalent metal and the alkali hydroxide is not particularly limited depending on the organic solvent used, but is preferably 50%
~110°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 metal neutral salt of an organic acid and the metal salt of an inorganic acid used in the present invention from divalent to a higher valence. Usually, it is used in large excess, but in the case of hydrogen peroxide, it may be used in excess. The reaction temperature of this oxidation reaction is 20-150℃
The temperature is preferably 50 to 110°C, and the oxidation can be carried out by blowing oxygen or air into the reaction system, or dropping hydrogen peroxide. Once this oxidation reaction is complete, most of the aqueous layer containing dissolved alkali salts such as by-product sodium chloride or sodium sulfate is separated by liquid separation, and the small amount of water remaining in the oil layer is removed by distillation. Therefore, a liquid in which fine particles of a metal compound are dispersed in an organic solvent at a high concentration is obtained. This liquid contains an organic solvent, and can be used as an additive (usually as is), but the concentration can be adjusted by adding more organic solvent or replacing part or all of the organic solvent with another organic solvent. It is also possible to prepare the organic solvent composition. 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 After 100e reaction, toluene 28.0k9, spray kerosene 6.5kg, naphthenic acid 7.8kg (25.2 mol)
, 1.2k9 (4.3 mol) of oleic acid, and 4.2k9 (31.5 mol) of a 30% aqueous sodium hydroxide solution were charged with stirring, and reacted for 2 min at a liquid temperature of 70 to 80'C. 4.2k9 (15.1 mol) of ferrous heptahydrate was added and a double decomposition reaction was carried out at 70-80'C.

Next, while keeping the reaction temperature at 60-70°C, 35%
After adding 0.8k9 hydrogen peroxide and carrying out the oxidation reaction,
Ferrous sulfate heptahydrate 17.5 kg (62.9 mol), 3
0% sodium hydroxide aqueous solution 17.3k9 (129.8
mol) with stirring, and at a liquid temperature of 70 to 80'C.
8. Perform a powder reaction while maintaining the reaction solution temperature at 60 to 70°C.
An oxidation reaction was carried out by adding 8.5k9 of 8% hydrogen peroxide. Next, after stopping the stirring and separating the liquid into a water layer and an oil layer, the small amount of water remaining in the oil layer and the used toluene were completely distilled off, and the iron content was 19.7% and the metal ratio was 4. 20.0k9 of a dispersion of .9 was obtained. The yield was 99.5%. This liquid stably dispersed the metal compound even after three months had passed. Example 2 In a 100e reactor, xylene 2
8.0k9, spray kerosene 6.5k9, naphthenic acid 7.
8 kg (25.2 mol), oleic acid 1.2 k9 (4.
3 mol), 30% aqueous sodium hydroxide solution 21.5k9
(161.3 mol), ferrous sulfate heptahydrate 21.5k9
(77.4 mol) was added while stirring, and the liquid temperature was 70 to 8.
React at 0°C for 6 minutes.

Next, while keeping the reaction temperature at 60-70°C, 8.8%
10.5 kg of hydrogen peroxide was added to carry out an oxidation reaction.
Next, stirring was stopped, the liquid was separated into a water layer and an oil layer, and the small amount of water remaining in the oil layer and the xylene used were completely distilled off.The iron content was 19.7%, and the metal ratio was 4. A dispersion of 19.9k9 was obtained. The yield was 99.4%. This liquid stably dispersed the metal compound even after three months had passed. Example 3 A 100f reactor was charged with toluene 28.
0kg, spray kerosene 6.5k9, naphthenic acid 6.6k
9 (21.3 mol), oleic acid 1.2 kg (4.3 mol), sodium hydroxide 1.0k9 (25.0 mol),
Add 2.3k9 of water while stirring and bring to a boiling temperature of 70-800.
4 Gin reaction with C, to which ferrous sulfate heptahydrate 3.4k
9 (12.2 mol) was added, and a double decomposition reaction was carried out at 70-80°C.

Next, while maintaining the reaction temperature at 60 to 70°C, 0.8k9 of 35% hydrogen peroxide was added to carry out an oxidation reaction, and then 20.3k9 (73.0 mol) of ferrous sulfate heptahydrate, Sodium hydroxide 5.9kg (147.5 mol), water 12.2k
9 was prepared with stirring, and after three reactions were carried out at a liquid temperature of 70 to 80'C, 8 was added while maintaining the reaction liquid temperature at 60 to 70'C.
．． An oxidation reaction was carried out by adding 9.9k9 of 8% hydrogen peroxide at 60 to 70°C. Next, stirring was stopped, the liquid was separated into a water layer and an oil layer, and the small amount of water remaining in the oil layer and the used toluene were completely distilled off, resulting in an iron content of 21.9% and a metal ratio of 6. A dispersion of 20.2k9 of No. 2 was obtained. The yield was 99.5%. This liquid stably dispersed the metal compound even after three months had passed. Example 4 To a 1001 reactor, toluene 30.0k9, spray kerosene 6.5k9, and iron dodecylbenzenesulfonate 3.9k
9 (5.5 mol), iron naphthenate 3.3k9 (5.2 mol), iron oleate 1.3k9 (2.1 mol), ferrous sulfate heptahydrate 20.0k9 (71.9 mol) ), sodium hydroxide 5.8 kg (145.0 mol), water 12.2 k
Add 9 while stirring, react with 3 powders at a liquid temperature of 70 to 80'C, and then add 9 while keeping the reaction liquid temperature at 60 to 70'C.
．． An oxidation reaction was carried out by adding 10.5k9 of 4% hydrogen peroxide.

Next, after stopping the stirring and separating the water layer and the oil layer, the small amount of water remaining in the oil layer and the used toluene were completely distilled off, and the iron content was 22.6% and the metal ratio was 5. 21.3 kg of a dispersion of .7 was obtained. The yield was 99.6%. This liquid stably dispersed the metal compound even after three months had passed. Example 5 In a 100f reactor, xylene 29.0k9, spray kerosene 5.4kg, naphthenic acid 6.4k9 (23.2 mol)
, 0.9k9 (3.2 mol) of oleic acid, 6.2k9 (155.0 mol) of sodium hydroxide, 23.1 kg of water,
12.4k9 (73.4 mol) of manganous sulfate monohydrate was charged while stirring, and reacted for 8 minutes at a liquid temperature of 70 to 80°C. ．．
17.6 kg of 5% hydrogen peroxide was added to carry out an oxidation reaction.

Next, after stopping the stirring and separating the liquid into a water layer and an oil layer, the small amount of water remaining in the oil layer and the xylene used were completely distilled off, resulting in a manganese content of 19.9% and a metal ratio of 4. ．．
16.3 kg of a dispersion of No. 5 was obtained. Yield is 95.0%
It was hot. This liquid stably dispersed the metal compound even after three months had passed. Example 6 To a 100e reactor, 33.0 kg of toluene, 16.5 k9 (26.1 mol) of manganese naphthenate, and 2 manganese oleate were added.

2 kg (3.6 mol), manganous chloride tetrahydrate 11
．． 9k9 (60.1 mol) and 20% aqueous sodium hydroxide solution 26.4k9 (132.0 mol) were added with stirring, and the liquid temperature was 70 to 80°C and the mixture was heated to 8 to 90 e/] FOF! The oxidation reaction was carried out by blowing air at a rate of 3 hours.

Next, after stopping the stirring and separating the liquid into a water layer and an oil layer, the small amount of water remaining in the oil layer and the used toluene are completely distilled off, and 11.3k9 of spray kerosene is added. 13.6%, metal ratio 3.0 dispersion is 35.9
The yield of k9 was 95.0%. This liquid is
The metal compound was stably dispersed even after 3 months had passed. Example 7 In a 100e reactor, 40.0 kg of white kerosene, 20.0 kg (31.3 mol) of nickel naphthenate, 2.7 kg (4.4 mol) of nickel oleate, and 11.0 kg of nickel sulfate hexahydrate were added. 0 kg (41.3 mol) and 20% sodium hydroxide aqueous solution 18.4 k9 (92.0 mol) were charged with stirring, and after reacting for 4 minutes at a liquid temperature of 70 to 80°C, the reaction liquid temperature was raised to 60 to 7σC. While maintaining the temperature, 8.7 kg of 17.0% hydrogen peroxide was added to carry out an oxidation reaction.

Next, after stopping the stirring and separating the water layer and the oil layer, a small amount of water and white kerosene 18.3k9 remaining in the oil layer were distilled off, resulting in a nickel content of 10.0% and a metal ratio of 1. 43.0 kg of a dispersion of .8 was obtained. The yield was 94.0%. This liquid stably dispersed the metal compound even after three months had passed. Example 8 In a 100e reactor, 27.0 kg of toluene, 15.0 k9 of white kerosene, 21.3 k9 (33.7 mol) of cobalt naphthenate, 0.9 k9 (1.5 mol) of cobalt oleate, and 6 cobaltous nitrate were added. 18.7 kg (64.3 mol) of hydrated salt and 13.4 k9 (134.0 mol) of 40% aqueous sodium hydroxide solution were charged with stirring, and the liquid temperature was adjusted to 70-80°C to 77-83 e/Wm.
The oxidation reaction was carried out by blowing air at a rate of 35%.

Next, stirring was stopped, the water layer and the oil layer were separated, and the small amount of water remaining in the oil layer and the used toluene were distilled off, resulting in a cobalt content of 12.5% and a metal ratio of 2. 45.2k9 of a dispersion of No. 3 was obtained. The yield was 85.0%. This liquid stably dispersed the metal compound even after three months had passed. Example 9 Into a 100f reactor, 33.3 kg of white kerosene and calcium petroleum sulfonate (molecular weight 840) 15.0k9 (18.0
mol), iron oleizate 3.0k9 (4.9 mol), ferrous sulfate 27.0k9 (97.2 mol), and 20% aqueous sodium hydroxide solution 41.9k9 (209.5 mol) were prepared while stirring. , 83.3-90 at a liquid temperature of 80-90°C
．． An oxidation reaction was carried out by blowing air at a ratio of 0'/WL for 3 hours.

Next, stirring was stopped and the liquid was separated into a water layer and an oil layer, and a small amount of water remaining in the oil layer and 13.3 kg of white kerosene were distilled off. Content 1
A 1.9% dispersion of 44.4k9 was obtained. Yield is 92
．． It was 0%. This liquid stably dispersed the metal compound even after three months had passed. Example 10 In a 100f reactor, xylene 26.0kg, spray kerosene 7.0k9, dinonylbenzenesulfonic acid 8.9k9
(23.5 mol), ricinoleic acid 1.2k9 (4.0
mol), 3.67 kg of 30% aqueous sodium hydroxide solution (
27.5 mol) was added while stirring, and the liquid temperature was 70-80 mol.
React at 3°C.

Furthermore, ferrous sulfate heptahydrate 17.0k9 (61.2 mol)
, 30% aqueous sodium hydroxide solution 16.8k9 (126.
2 mol) was added thereto, and three powders were reacted at a liquid temperature of 70 to 80°C. Next, 10.0 kg of 9% hydrogen peroxide was added to carry out an oxidation reaction while maintaining the temperature of the reaction solution at 60 to 70°C. Next, after stopping the stirring and separating the liquid into a water layer and an oil layer, a small amount of water remaining in the oil layer and the xylene used were completely distilled off, and the sodium content was 2.7%, iron content was Amount 14.6%
A dispersion of 22.8k9 was obtained. The yield was 98.5%. This liquid stably dispersed the metal compound even after three months had passed. Example 11 In a 100e reactor, toluene 2.7k9, spray kerosene 8.3k9, naphthenic acid 5.9k9 (19.9 mol),
1.0k9 (2.9 mol) of erucic acid, 1.1 kg (2.9 mol) of dinoylbenzenesulfonic acid, and 4.1 kg (12.9 mol) of barium hydroxide octahydrate were charged with stirring, and the liquid was prepared. The four powders were reacted at a temperature of 70 to 80°C.

Claims (1)

[Claims] 1. In an organic solvent, in the presence of each metal neutral salt of naphthenic acid and/or organic sulfonic acid and alkenyl carboxylic acid, 2.
A fine particle metal compound characterized by reacting an inorganic acid salt of iron, manganese, nickel, or cobalt with an alkali hydroxide and reacting this with oxygen and/or hydrogen peroxide at a high concentration in an organic solvent. How to disperse. 2 The organic sulfonic acid is petroleum sulfonic acid or has 15 or more carbon atoms.
The method according to claim 1, wherein the alkenyl carboxylic acid is a monoalkyl or dialkyl benzenesulfonic acid having 30 carbon atoms, and the alkenyl carboxylic acid is a carboxylic acid having 11 to 22 carbon atoms. 3. Divalent inorganic acid salts of iron, manganese, nickel, or cobalt are divalent iron, manganese, nickel, or cobalt chlorides, sulfates, sulfites, nitrates, nitrites, phosphates, and phosphites. , bromide or iodide.