JPS5822138B2 - Method for producing naphthenic acid - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to petrochemical synthesis, and more particularly to a method for producing saftenoic acid.

Naphthenic acids are widely used in the production of lacquers and varnishes.

It is actually a salt of metals with various valences and is the starting material for obtaining naphthenate driers, which are used as additives for paints and varnishes.

Naphthenic acids are also used to make alkyd resins, which are the starting materials for the production of nitroenamels and paints.

Lead naphthenate is effectively used in printing paint production.

Cobalt, manganese, nickel, copper and iron naphthenates are used as catalysts in synthesis and oxidation.

A process for preparing naphthenic acids by oxidation with oxygen of a petroleum fraction with a boiling point range of 250-500° C. in the presence of a catalyst, namely finely dispersed potassium permanganate, is known (USSR Inventor's Certificate No. 137). No. 515).

According to this method, the following components naphthenic hydrocarbons
79 weight line paraffinic hydrocarbon
A cut comprising 12% by weight of aromatic hydrocarbons and 3% by weight is oxidized.

The acid value of said fraction is 32.2 ■KOH for fraction 11, and its viscosity is 59.4 centistokes at 50°C.

This petroleum fraction was heated at 150° C. for 1 hour at 0.0%.
It is oxidized with an oxygen consumption of 25 cyyf.

This reaction lasted for 32 hours and the catalyst consumption was 0.2 of the raw material.
%.

Oxidation yields a complex mixture of oxygen-containing organic compounds.

This mixture includes aromatic, naphthenic and aliphatic acids,
Included are their peroxides: oxyacids, ether acids, ketoacids, lactones and lactides.

The resulting mixture of oxygen-containing compounds is treated with a 20% aqueous alkali solution, resulting in a mixture of unsaponifiable oxygen-containing organic compounds and alkaline salts of oxygen-containing organic compounds.

The unsaponifiable oxygen-containing compounds are separated from the mixture thus obtained, for example by extraction with an organic solvent.

The remaining mixture of alkali salts of oxygen-containing organic compounds is 30
The mixture of oxygen-containing organic compounds is separated by treatment with sulfuric acid.

The mixture includes aromatic, naphthenic and paraffinic mono-, di- and poly-acids, as well as non-oxidizing materials.

The main drawback of the process is that the finely dispersed catalyst used in the process is not selective for the naphthenic acid production process.

Furthermore, another disadvantage is that naphthenic acid, which is a component of a complex mixture of oxygen-containing organic compounds, cannot be obtained with this method of high quality.

. The object of the present invention is achieved by the following method for producing naphthenic acid.

a) Under conditions where a catalyst of a naphthenate mixture consisting of 30-40% by weight of manganese naphthenate and 60-70% by weight of potassium naphthenate is present in an amount of 1.5-2.5% by weight based on the weight of the starting petroleum fraction. oxidizing a petroleum fraction with a boiling point range of 250 to 350 °C at a temperature of ~140 °C to 0.06 to 0.065 da/h per hour with oxygen,
b) The mixture of oxygen-containing organic compounds thus obtained (including naphthenic acid and hydroxynaphthenic acid) is treated with an inert organic solvent (organic solvent:the mixture weight ratio is 1:1 to 1.5). C) precipitate and separate the hydroxynaphthenic acid from this diluted solution; d) remove the remaining mixture of oxygen-containing organic compounds in the solvent;
treatment with an aqueous sodium hydroxide solution at the boiling point temperature of the organic solvent; e) separating the solution of the unsaponifiable oxygen-containing organic compound in the organic solvent from the aqueous sodium naphthenate solution thus obtained; Ethyl naphthenate is isolated by treatment with diethyl sulfate at a temperature of
Boiling point range 75-170 g by rectification under reduced pressure
f) treating the isolated fraction with an aqueous sodium naphthenate solution by the action of a mineral acid; Isolate the acid product.

This method is carried out as follows.

Petroleum fractions with a boiling point range of 250 to 350°C are used as starting materials.

The properties of this fraction are as follows: molecular weight, 220~
240; specific gravity, 0.8520-0.8560; refractive index,
1.46-1.47; freezing point 50-55°C below zero; flash point 110-120°C.

This fraction comprises the following main hydrocarbons:

Aromatic hydrocarbons: 0.1-2 weight ratio Naphcene hydrocarbons: 70-75 weight ratio: Paraffinic hydrocarbons: 23-29.2 weight ratio: Each petroleum fraction from 135-20%
Oxidize with oxygen at 140°C.

The amount of oxygen used in this reaction is 0.06 per hour.
~o, O65icy/kg.

The oxidation is carried out in the presence of a catalyst, namely a naphthenate mixture consisting of 30-40% by weight of manganese naphthenate and 60-70% by weight of potassium naphthenate.

The mixture is used in an amount of 1.5 to 2.5 times the weight of the starting petroleum fraction.

The oxidation step is allowed to last for 4-4.5 hours.

The products thus obtained are mixtures of oxygen-containing organic compounds consisting of naphthenic acids, aromatic and aliphatic acids, their peroxides, oxyacids, ether acids, ketoacids, lactones and lactides.

The acid value of the oxygen-containing organic mixture is iyζ 25
~30711 g KOH.

Said mixture of oxygen-containing organic compounds comprises the following main compounds: naphthenic acid 15-16% by weight hydroxynaphthenic acid 0.1-1% by weight unsaponifiable oxygen-containing compound 78-92% by weight.

The mixture of oxygen-containing organic compounds is diluted with an organic solvent inert to the mixture in a weight ratio of 1:1 to 1.5 (with respect to the mixture).

The inert solvent may be, for example, benzine or petroleum ether with a boiling point range of 80 to 170°C.

On dilution with an organic solvent, the hydroxynaphthenic acid precipitates and is separated by known methods, for example by filtration.

The remaining mixture solution of oxygen-containing organic compounds from which the naphthenic acid has been removed is treated with a preferably 10% aqueous solution of Sourium hydroxide at the boiling point temperature of the solvent for 1 hour with stirring.

At the end of the alkali treatment, the reaction mixture is allowed to stand, and the solution of the unsaponifiable oxygen-containing organic compound in the organic solvent and the obtained aqueous sodium naphthenate solution are separated.

The solvent is then separated from the unsaponifiable oxygen-containing organic compound by distillation, and this solvent is returned to the dilution step of the mixture of oxygen-containing organic compounds.

The aqueous sodium naphthenate solution is treated with diethyl sulfate for 90-120 minutes at 90-95° C. with constant stirring of the mixture.

The mixture is then allowed to stand and the precipitated sulfuric acid is separated from the ethyl naphthenate by known methods.

Ethyl naphthenate is distilled under reduced pressure of 3 rran Hg and a fraction with a boiling point range of 75-170°C is collected.

This fraction is preferably treated with a 10% aqueous sodium hydroxide solution and the ethyl alcohol formed is distilled off at the same time.

Naphthenic acid is isolated in the form of a mixture from an aqueous sodium naphthenate solution by the action of mineral acids.

Sodium naphthenate is treated with mineral acid and free naphthenic acid is isolated.

The naphthenic acid thus obtained has the following properties: purity (purity test) 96.5-97%; unsaponifiable oxygen-containing organic compound 1.0-1.6% by weight; acid value 230-260 (
(Number of potassium hydroxide per 12 naphthenic acids): Color development by iodometric titration 20-22 (Amount of iodine in 1L of 1.00 Ti 10 aqueous solution of potassium chloride): Specific gravity 0.952
1-0.9698; refractive index 1.4530-1.4649
o The yield of naphthenic acid calculated on the basis of the starting petroleum fraction is 2.73-3.988% by weight.

The catalyst used in this process (a mixture of manganese naphthenate and potassium naphthenate) is a mixture of solid salts that are readily soluble in petroleum hydrocarbons.

The catalyst was G-S, Petrov, A, I-
Danilevich and A. Y. Rabin.
1. Development of methods for oxidizing petroleum and mineral oils and industrial use of the products obtained, by F. Goskhimiz.
dat, Leningrad, 1933).

The catalyst preparation method is illustrated by the following reaction.

RCOOH+KOH-A C00K+H20l2RC00
+Mn504-+(RCOO)2Mn+2So4I
In formula I, RooH is naphthenic acid.

According to the above reaction, naphthenic acid is neutralized with a 20-thialkali aqueous solution at 80-90°C for 1 hour.

The mixture thus obtained containing potassium naphthenate (to which a previously calculated amount of manganese sulfate is added) and the exchange reaction is carried out at the same temperature for 90 minutes.

The product obtained is manganese naphthenate.

The present invention has the following advantages.

The naphthenic acid obtained according to the invention is very pure (96.5-97% purity).

Low content of unsaponifiable oxygen-containing organic substances (1,0~
1.6% by weight).

The resulting naphthenic acid is a clear, homogeneous liquid suitable for use in the paint and lacquer industry.

The catalyst used in the process is selective for the process and ensures the production of naphthenic acids with a carbon number of 12 to 15.

In order to better understand the present invention, the present invention will be further described with reference to the following examples.

Example 1 A petroleum fraction with a boiling point range of 250 to 350°C having the following properties was used.

Molecular weight 224 Specific gravity 0.8550 Refractive index 1.468 Freezing point
-50℃ Flash point 115℃ Composition of hydrocarbons: Aromatic hydrocarbons 1.6% by weight Naphthenic hydrocarbons 73.2% by weight Paraffinic hydrocarbons 25.2% by weight This fraction 200 contains 9 to 13
Oxidation was carried out with oxygen at temperatures between 5 and 140°C.

The oxygen consumption rate is o per hour relative to the starting material, o
It was 6kq/ky.

Oxidation is. Catalyst, namely manganese naphthenate (35%
) and potassium naphthenate (65%) (1.5% by weight of starting material) for 4 hours.

The oxidation product obtained is a mixture (187,7 kg) of oxygen-containing organic compounds consisting of naphthenic acids, aromatic acids and fatty acids, their peroxidation products, oxyacids, ether acids, ketoacids, lactones and lactides. there were.

Is the acid value of this oxygen-containing mixture 1'? 28 ■KOH per
Met.

The mixture of oxygen-containing organic compounds thus obtained had the following composition.

Naphthenic acid 15% by weight Droxynaphthenic acid 0.9% by weight Unsaponifiable oxygen-containing organic compound 79% by weight This mixture of oxygen-containing organic compounds was added to benzine 18 with a boiling point range of 80 to 170°C.
It was diluted with 7.7 kg.

The hydroxynaphthenic acid was precipitated and separated from the remaining solution of the oxygen-containing organic compound mixture.

The hydroxynaphthenic acid may be separated by any known method, such as by filtration.

The amount of hydroxynaphthenic acid isolated was 1.7@.

The remaining benzene solution of the oxygen-containing organic compound/mixture (3
75.4 kg) was treated with 8.04 #10 aqueous sodium hydroxide solution.

Alkali treatment was performed at 80 to 90°C for 1 hour.

The reaction mixture was allowed to stand.

A benzene solution of unsaponifiable oxygen-containing organic compounds was separated from an aqueous sodium naphthenate solution.

The benzene solution was distilled to recover benzine 185.5 and 9.

This was reused in the dilution step of the oxygen-containing organic compound mixture.

Another distillation product is an unsaponifiable oxygen-containing organic compound (14
8.3 Ay).

The yield was 79% by weight, based on the total weight of the oxygen-containing organic compound mixture obtained in the oxidation step of the starting materials.

Sodium naphthenate aqueous solution is diethyl sulfate 15.7
The mixture was treated with @ and allowed to react at 90-95°C for 90 minutes.

The reaction product was separated from the sodium sulfate precipitate by standing.

The reaction product was ethyl naphthenate and its amount was 29.4 kf.

This ethyl naphthenate was rectified under reduced pressure of 3 rrrm Hg to separate a fraction with a boiling point range of 75-170°C.

The amount of distilled product was 8.82 kf.

This fraction was dissolved in a 10% sodium hydroxide aqueous solution 1.43A-
7 and at the same time the ethyl alcohol formed was distilled off (2.9 kg).

Then, 1.74 kf of sulfuric acid was added to the remaining aqueous sodium naphthenate solution to form a naphthenic acid with the following properties:
47 kf were isolated.

Purity (purity test) 96.5% unsaponifiable oxygen-containing organic compound 1.3 weight multi-oxidation (
TII! KOH/g) 245 Color (Iodometric Titration) 20 Specific Gravity 0.9679 Refractive Index 1.4638 The yield of naphthenic acid calculated based on the starting petroleum fraction was 2.73%.

Example 2 A petroleum fraction with a boiling point range of 250 to 350°C having the following properties was used.

Molecular weight 240 Specific amount 0.856 Refractive index 1.47 Freezing point
-53°C Flash point 120°C Hydrocarbon composition: Aromatic hydrocarbons 2.0% by weight Naphthenic hydrocarbons 75% by weight Paraffinic hydrocarbons 23% by weight This fraction 200@ was oxidized at a temperature of 136°C.

Oxygen consumption rate is o per hour, 061 try/kg
Met.

The oxidation was carried out using a catalyst, namely manganese naphthenate (30%
) and potassium naphthenate (70%) (1.82% by weight of the starting petroleum fraction) for 4.5 hours.

The obtained oxidation product was an oxygen-containing organic compound mixture (190 Ay) with an acid value of 25 ■KOH/P.

The mixture of oxygen-containing organic compounds thus obtained had the following composition.

Naphthenic acid: 16% by weight Hydroxynaphthenic acid: 1% by weight Unsaponifiable oxygen-containing organic compound: 78% by weight It was separated in

Benzine solution of a mixture of oxygen-containing organic compounds (378,1
Ay) was treated with an aqueous solution of 8.12A-7 10 thiosodium hydroxide.

A sulfur hydroxide treatment was carried out at 80 to 90° C. for 1 hour.

The resulting reaction mixture was allowed to stand to separate the benzene solution of the unsaponifiable oxygen-containing organic compound from the aqueous sodium naphthenate solution.

Distill the benzine solution to obtain benzine 185.7A-9 (
The unsaponifiable oxygen-containing organic compound (156Ay) was further separated.

A sodium naphthenate aqueous solution has a temperature of 2
time, treated with 15.82 kf diethyl sulfate,
29.7 kf of ethyl naphthenate was obtained.

This ethyl naphthenate was then rectified under reduced pressure of 3 mm Hg to isolate a fraction with a boiling point range of 75-170°C.

This fraction (10.4 Ay) was treated with 1.7 to 9 ml of a 10% aqueous solution of sulfur hydroxide.

Ethyl alcohol (3.4 kg) was separated from the reaction product.

Then, 21 kf of phosphoric acid was added to the aqueous sodium naphthenate solution to isolate 6.76 kf of naphthenic acid.

The naphthenic acid obtained had the following properties.

Purity (purity test) Section 97 unsaponifiable oxygen-containing organic compound 1.58% by weight acid value (■KOH
/7) 230 Color development (iodometric titration) 22 Specific gravity 0.9698 Refractive index 1.4649 The yield of naphthenic acid calculated based on the starting material was 3.38% by weight.

Example 3 A petroleum fraction with a boiling point range of 250 to 350°C having the following properties was used.

Molecular weight 220 Specific gravity 0.852 Refractive index 1.461 Freezing point
-55℃ Flash point 110℃ Composition of hydrocarbons: Aromatic hydrocarbons 0.4% by weight Naphthenic hydrocarbons 70.4% by weight Paraffinic hydrocarbons 29.2% by weight This petroleum fraction 200%
Oxidized at a temperature of 8°C.

The oxygen consumption rate is 0.065 #/7 per hour;
The oxidation was carried out using a catalyst consisting of manganese naphthenate (40%) and potassium naphthenate (60%) (1.9% of the starting material).
6% by weight) for 4.5 hours.

As a result, a mixture of oxygen-containing organic compounds with an acid value of 307,721 iIKOH/g was obtained. A-9 was obtained.

The mixture of oxygen-containing organic compounds thus obtained had the following composition.

Naphthenic acid 15% by weight Hydroxynaphthenic acid 0.8% by weight Unsaponifiable oxygen-containing organic compound 80% by weight The mixture thus obtained was diluted with benzene 189A-9 to precipitate hydroxynaphthenic acid 1.5%, and then This was separated.

A benzene solution of oxygen-containing organic compounds (376,5#) was treated with an aqueous solution of 10 sodium thihydroxide (8,02Ay) at 80-90<0>C for 1 hour.

The resulting reaction mixture was allowed to stand, and the benzine solution of the unsaponifiable oxygen-containing organic compound was separated from the aqueous sodium naphthenate solution.

The benzine solution was distilled to recover 185.2 Ay of benzine (to be reused), and an unsaponifiable oxygen-containing organic compound (151.2 Ay) was further obtained.

The sodium naphthenate aqueous solution is 90°C at 90-95°C.
Treated with 15.6 iy diethyl sulfate for 0 min.

The reaction product was ethyl naphthenate (29.2 kg).

Next, this was rectified under reduced pressure of 3 mmHg to separate a fraction with a boiling point range of 75 to 170°C (9.34 Ay), which was further added to a 1.46 A-7 aqueous solution of sodium hydroxide.
Processed with.

2.9@ of ethyl alcohol was recovered from this reaction product.

An aqueous solution of sodium naphthenate was mixed with 1.64 A-9 hydrochloric acid to isolate 5.5 h of naphthenic acid.

The properties of the naphthenic acid thus obtained were as follows.

Purity (purity test) 97% unsaponifiable oxygen-containing organic compound 1.1% by weight acid value (TIII
KOH/g) 260 color (iodine titration) 2
2 Specific gravity 0.9528 Refractive index 1.4532 The yield of naphthenic acid calculated on the basis of the starting petroleum fraction was 2.75% by weight.

Example 4 A petroleum fraction with a boiling point range of 250 to 350°C having the following properties was used.

Molecular weight 228 Specific amount 0.856 Refractive index 1.4708 Freezing point
-55℃ Flash point 115℃ Composition of hydrocarbons: Aromatic hydrocarbons 1.4% by weight Naphthenic hydrocarbons 74.6% by weight Paraffinic hydrocarbons 24.0% by weight This petroleum fraction 200@1
Oxidation was carried out at 35-140°C.

The oxygen consumption rate was 0.06 ky/ky per hour.

The oxidation was carried out using a catalyst consisting of manganese naphthenate (35% by weight) and potassium naphthenate (65% by weight) (two of the starting materials).
．． 5%).

The oxidation reaction product was a mixture of oxygen-containing organic compounds (139.7 bu) with an acid value of 25 KOH/P.

The mixture of oxygen-containing organic compounds thus obtained had the following composition.

Naphthenic acid 15% by weight Droxynaphthenic acid 0.1% by weight Unsaponifiable oxygen-containing organic compound 82% by weight The mixture thus obtained was diluted with 209.5% petroleum ether by 7% to give 0.2% hydroxynaphthenic acid; i was precipitated, which was then isolated by known methods.

At the boiling temperature of petroleum ether, a solution of an oxygen-containing organic compound in petroleum ether (349.2 Ay) was treated continuously for 1 hour with 3.98 @/ of a 10% aqueous sodium hydroxide solution.

The resulting reaction mixture was left standing to separate the unsaponifiable oxygen-containing organic compound solution from the sodium naphthenate aqueous solution.

The solution of the organic unsaponifiables thus separated in petroleum ether is distilled and 185 kg of solvent is recovered and reused).
And 174.5 kf of unsaponifiable oxygen-containing organic compounds were isolated.

Sodium naphthenate aqueous solution at 90-95℃
Treatment with 9 in 15.6 of diethyl sulfate for 0 min isolated 9 in 29.2 of ethyl naphthenate.

This ethyl naphthenate was rectified under a reduced pressure of 3 rrvn Hg to obtain a fraction (9,4
A-9) was isolated, and this fraction was further treated with 1.5@ of a 10% aqueous sodium hydroxide solution.

Ethyl alcohol 3 was separated from this reaction product.

An aqueous sodium naphthenate solution was mixed with 1.7 kli of sulfuric acid to isolate 7.97 kq of naphthenic acid.

The properties of the naphthenic acid thus obtained were as follows.

Purity (purity test) 96.8 unsaponifiable oxygen-containing organic compound 16 weight coefficient acid value (77v
KOH/7) 230 Color development (iodometric titration) 22 Specific gravity 0.9521 Refractive index 1.4530 Yield of naphthenic acid calculated based on starting petroleum fraction is 3.98% by weight
Met.

Claims (1)

Claims: 1 a) A catalyst of a naphthanate mixture consisting of 30-40% by weight of manganese naphthenate and 60-70% by weight of potassium naphthenate, based on the weight of the starting petroleum fraction.
1 of petroleum fractions in the boiling range of 250-350°C at a temperature of 135-140°C in the presence of ~2.5% by weight.
oxidizing with an amount of 7 kg of oxygen for 0.06 to 0.065 hours, and b) adding the mixture of oxygen-containing organic compounds thus obtained (including naphthenic acids and hydroxynaphthenic acids) to said mixture in an inert manner. diluting with an organic solvent (organic solvent: weight ratio of the mixture is 1:1 to 1.5), C) precipitating and separating hydroxynaphthenic acid from this diluted solution, and d) removing hydroxynaphthenic acid. e) treating a solution of the oxygen-containing organic compound mixture in an organic solvent with an aqueous sodium hydroxide solution at the boiling point temperature of the organic solvent; The aqueous sodium naphthenate solution was treated with diethyl sulfate at a temperature of 90-95°C to isolate ethyl naphthenate, and then 3 mm
Boiling point range 75-17 by rectification under reduced pressure of Hg
separating an ethyl naphthenate fraction at 0° C. and further f) treating said fraction with an aqueous sodium hydroxide solution and isolating the final product from the resulting aqueous sodium naphthenate solution by the action of a mineral acid. Characteristic method for producing naphthenic acid.