PL149930B1 - Method for manufacturing a mixture having a low solidification temperature - Google Patents

Description

PATENT DESCRIPTION

149 930

POLAND

REPUBLIC

FOLK

P * additional tent to patent no. Reported: 86 0 7 03 / P. 260440 /

Priority ——

Copy

Int. A. ⁴ COOK 3/18

OFFICE

PATENT

PRL

Application announced: 88 05 12

Patent description published: 1990 06 30

Inventors of the invention: Stanisław Rygiel, Antoni Oanuaz Oucwa, Marian Paciorek

The holder of the patent 1 Zakłady Azotowa Im. F. Dzierżyński, Tarnów / Polaka /

METHOD OF PREPARING THE MIXTURE WITH LOW COOLING POINT

The subject of the invention is the preparation of a mixture with a low freezing point, etoated to prevent the freezing of fossil products and freezing them to the hard surfaces, using the product formed in the process of cyclohakaan oxidation to cyclohakaanol and cyclohakaanone in the stage of acidic hydrolysis of asters. It is known from the Polish patent specification No. 132,732, consisting in the neutralization with sodium hydroxide solution at a temperature of 60-100 ° C of a mixture of dicarboxylic and hydrocarbokeyl aatra 1 with an acid number of 150-300 mg KOH / g and a saponification number of 200-400 mg KOH / g, which is a by-product of the oxidation of cyclohakaan to cyclohakaanol and cyclohakaanone. Neutralization is carried out with 25-40% sodium hydroxide solution. The mixture obtained as a result of neutralization contains 1-5% free NaOH. About the mixture is added 0.1-0.9% mineral oil to protect the mixture against air and secondary reactions. However, the mixture obtained in this way changes the quality during storage, it is considered, it forms a skin on the surface of the eggs, and sediment falls out, which makes it difficult to use. Mlaazonlna also has a fairly high viscosity, which also makes it difficult to use, despite the introduction - according to Polish patent No. 132 731 - among other propylene glycols.

According to the invention, the preparation of a mixture with a low pour point, in which the mixture of aaters 1 of dicarboxylic acids 1 of hydroxycaproic acid and their derivatives with an acid number of 150-300 mg KOH / g and a saponification number of 200-450 mg KOH / g, is a by-product of in the stage of acidic hydrolysis of the esters of the cyclohakaan oxidation process to cyclohakaanol and cyclohakaanone, it neutralizes it with sodium hydroxide solution at a temperature of about 100 ° C to obtain an excess of free NaOH, it consists in the fact that this mixture, adjusted to a water content of 5-35% by weight, is mixed before neutralization in a ratio of 0.4-2.7 t 1 with a mixture of sodium salts of C ^ -C? cadicarboxylic acids, mainly composed of

149 930

149 930 from sodium salts of valeric and caproic acids, containing 30-70% of water and 0.1-5% of NaOH, which is a by-product of the saponification of esters in the vapor-clechy phase of the oxidation of cyclohexane to cyclohexanol and cyclohexanone, and neutralization is carried out with lye sodium at a concentration of more than 40% by weight, preferably 42-45%, to obtain an excess of free NaOH in the reaction mixture of 0.01-0.9% by weight, preferably 0.15-0.5% by weight, with both component mixtures or with one of them introduces small amounts of cyclohexanol and cyclohexanone. These amounts may be 0.05-5, preferably 0.09-0.5 parts of cyclohexanol and cyclohexanone in total for 100 parts of the reaction mixture. By the method according to the invention, a homogeneous mixture of low viscosity and a pour point of -32 ° C is obtained, which is stable during storage.

Example. To a stirred reactor added 200 dm ^{3 of} mixtures of esters and dicarboxylic acids C 2 ^-C 8 carboxylic acid ^and hydroxycaproic and derivatives thereof having an acid number of 190 mg KOH / g and a saponification number of 250 mg KOH / g, which is a by-product from stage acidic hydrolysis of the ester oxidation process of cyclohexane to cyclohexanol and cyclohexanone. 0.5% by weight of cyclohexanol and cyclohexanone were introduced into this mixture. With stirring and ut rzymujęc temperature below 100 ° C was added 400 dm ^{3 of} a mixture of monocarboxylic acids, _C1-C7, mostly, i.e. 70% of s, valeric and caproic acids content of 60% by weight of water. 0.3% by weight of cyclohexanol and cyclohexanone in total were introduced into this mixture. Then the contents of the reactor were neutralized with a 44% by weight sodium hydroxide solution to obtain 0.3% by weight of free NaOH. A mixture with a freezing point of -31 ° C was obtained.

Claims (2)

Patent claims 1. Process for the preparation of a low-freezing point mixture, in which the mixture of esters and dicarboxylic acids and hydroxycaproic acid and their derivatives with an acid number of 150-300 mg KOH / g and a saponification number of 200-450 mg KOH / g, which is a by-product of the acid stage hydrolysis of esters of the cyclohexane oxidation process to cyclohexanol and cyclohexanone, neutralized with sodium hydroxide solution at a temperature of about 100 ° C to obtain an excess of free NaOH, characterized in that this mixture, adjusted to a water content of 5-35%, is mixed before neutralization in a ratio of 0.4 -2.7: 1 with a mixture of sodium salts of monocarboxylic acids C 1 -C 6, composed mainly of sodium salts of valeric and caproic acids, containing 30-70% water and 0.1-5% NaOH, which is a by-product of the ester saponification step in the vapor-liquid phase of the oxidation of cyclohexane to cyclohexanol and cyclohexanone, and neutralization is carried out with sodium hydroxide with a concentration above 40%, preferably 42-4 5% to obtain an excess of free NaOH in the reaction mixture of 0.01-0.9% by weight, preferably 0.15-0.5% by weight, where small amounts of cyclohexanol and cyclohexanone are introduced with both of the component mixtures or with one of them. 2. The method according to p. The process of claim 1, characterized in that the amount of cyclohexanol and cyclohexanone used is in total 0.05-5, preferably 0.09-0.5, parts per 100 parts of the reaction mixture. Printing House of the Polish Patent Office. Circulation 100 copies Price 1500 PLN