DE1443989A1 - Process for the sulfonation of fatty acids or their derivatives, in particular fatty acid esters - Google Patents

Description

"Process for the sulfonation of fatty acids or their derivatives, in particular of fatty acid esters "addition to the patent (patent application H 43 358 IVb / 12 o (D 1743)) The patent (patent application A 43 358 IVb / 12 o (D 1743)) describes a safekeeping for the sulfonation of fatty acids or their derivatives, especially fatty acid esters, this consists in adding the starting material to be sulfonated in a first sulfonation stage at temperatures of not more than 700 ° C. not more than 65 to 90% of the total to be used Add sulfur trioxide and the remaining sulfur trioxide in a second sulfonation stage to be added at a higher temperature. Both stages are divided into several individual stages , each individual stage being stirred in a separate reaction vessel can.

On further processing of the process it has now been found that one the starting material to be sulfonated advantageously in finely divided form with the sulfur trioxide-containing gas stream brings together.

This process can be carried out in various ways. The starting material to be sulfonated can, for example, be according to known methods Atomize process in an inert gas stream and gaseous sulfur trioxide into this gas stream bring in, or merge the gas flow with a sulfur trioxide-containing gas flow. But you can also use the sulfur trioxide-containing gas stream itself to atomize sulfonierande base material, and finally you can through the atomization of the starting material to be sulfonated creates a negative pressure, which sucks in an inert gas stream containing sulfur trioxide.

For example, the one shown in the figure is suitable for sulfonation Apparatus. The material to be sulfonated is circulated by the gear pump 1 through the cooler 2, the nozzle 3, the reaction vessel 5 and the pipeline 8. The nozzle 3 works on the principle of the water jet pump: that from the narrowed Material to be sulfonated from the pipeline creates a negative pressure and sucks the sulfur trioxide-inert gas mixture through the pipe socket 4. This will be the Reactants intimately mixed with one another, and the sulfur trioxide dissolves in the material to be sulfonated.

This collects itself in the reaction vessel 5, where it passes through the temperature control jacket 6 can be heated or cooled as required, and then goes to gear pump 1 return. Sulfur trioxide-containing or sulfonated material can be withdrawn from the connector 9 and unsulfonated starting material can be fed into the pipe socket 10.

The one claimed here in combination with the process of the main patent Method of mixing material to be sulfonated and sulfur trioxide needs not to be used in all procedural stages. This is preferably done in or first and in a few more sulfonation stages, i.e. everywhere there. Where m @ h take advantage of the intimate contact between the material to be sulfonated and the inert gas wants to give birth in large quantities, especially at the beginning of the reaction Heat of reaction with the essentially sulfur trioxide-free exiting at nozzle 7 Remove inert gas. Also in the reaction vessel 5, where the product that may accumulate if necessary can linger with stirring, and in the heat exchanger 2 can. Remove heat of reaction.

The pumping of the product to be sulfonated through the described Apparatus made possible by varying the pumping speed, the amount of sulfur trioxide supplied and the temperature control an optimal reaction process.

Example 1; The sulfonation was carried out in one apparatus made of four devices connected in series according to Figure duration. These devices had a downward outlet in the reaction vessel 5 Overflow pipe 11, which led into the reaction vessel of the downstream apparatus.

The methyl ester of a hardened coconut fatty acid served as the starting material (JZ = 0.5). The four reaction vessels were each filled with 5 kg of ester and the irritation adjusted so that the reaction mixture in the vessels during the whole experiment had the following temperatures increasing from vessel to vessel: 50, 60, 70, 800 C. Then the gear pump 1 was put into operation and so long on 5 vol .-% S03 containing air flow is sucked in until the in the individual vessels the following amounts of ester present, in percent of that for a quantitative conversion stoichiometrically necessary amounts of S0) had absorbed: 55, 80, 105 and 130. Then 20 kg of ester was pumped into vessel 1 per hour and the Amount of the SO3-air mixture adjusted so that in the reaction vessel 1 40% and the reaction vessels 2 to 4 each 20 ffi of the total supplied SO3-air mixture was introduced. The total amount of sulfur trioxide applied was 1.3 moles per mole of ester fed. That which flows out of the fourth vessel The reaction product was cooled and, after the addition of 2 wt. H2O2 (as 30% aqueous Solution) for two hours at 50 to 600 C and then bleached with 8% NaOH neutralized.

The degree of sulfonation of the product thus obtained was 94%; one with respect to crude acidic sulfonation product, had 5% solution of the sulfonate The following color values measured in a Lovibond tintometer in a 4 "cuvette: yellow = 8; red = 0.6; blue = O, G.

Example 2.

The experiment described in this example was carried out in a device carried out according to the figure, but not provided with the overflow pipe 11 was. The starting material was kept in this apparatus until the sulfonation was complete pumped over.

A mixture of 20 kg of the ethyl ester of a hardened palm kernel fatty acid and 22 kg of a hardened palm kernel fatty acid (IV of the mixture = 0.5) was added 500 C heated and through Circulation in the apparatus in finely divided Form atomized in an air stream containing 5 vol .-% SO3. After .30 minutes Circulation had taken up 0.5 mole of SO3 per mole of mixture. The temperature of the Product was then increased to 65 ° C and over a further 10 minutes per mole A further 0.4 ol 503 was added to the mixture. Then the temperature of the product was up 830 C increased and in the course of another 20 minutes sucked in as much SO3-air mixture as until a total of 1.3 mol SO3 had been absorbed per mol of fatty acid. The whole The reaction time was therefore 70 minutes.

The sulfonation product was cooled after adding 3% of its Weight of H2O2 (as 40% aqueous solution) for two hours at 50 to 60 ° C and then neutralized with 10 C / o sodium hydroxide solution. The degree of sulfonation of the product was 92%; a 5% solution showed under the @edingunen given in Example 1 the following color values; yellow = 6.0; red = 1.0; blue = 0.0.

Example 3: A mixture of 22 kg hardened material was used as the starting material Coconut fat and 25 kg of the ethyl ester of a hardened coconut fatty acid (JZ of the mixture = 0.4). This mixture was sulfonated under the conditions given in Example 2 and bleached with 2.5% by weight H202. Neutralization was carried out using 15% strength NaOH. In the Lovibond tintometer were under the conditions given in Example 1 the following color values measured: yellow = 2; red = 0.2; blue = 0.0.

Claims (5)

P a t e n t a n s p r ü c h e 1. Further development of the procedure for sulfonating fatty acids or their derivatives, especially fatty acid esters, by means of excess amounts of gaseous sulfur trioxide in the absence of solvents, which are capable of forming adducts with sulfur trioxide, resulting in the starting material no more in a first sulfonation stage at temperatures of at most 700 ° C than 65 - 90% of the total sulfur trioxide to be used and the rest Sulfur trioxide is added in a second sulfonation stage at higher temperatures, according to patent (patent application H 43 358 IVb / 12 o (D 171F3)) characterized that the material to be sulfonated in a finely divided state with the sulfur trioxide-containing Bringing inert gas stream together. 2. The method according to claim 1, characterized in that one Inert gas stream, which contains the material to be sulfonated in finely divided form, brings together with an inert gas stream containing the gaseous sulfur trioxide. 3. The method according to claim 1, characterized in that the Material to be sulfonated with the aid of an inert gas stream containing sulfur trioxide distributed in the inert gas. 4. The method according to claim 1, characterized in that one by Relax a stream of the material to be sulfonated with simultaneous atomization the same creates a negative pressure and through this negative pressure the sulfur trioxide-containing Sucks in inert gas stream. 5. The method according to claim 1 to 4, characterized in that one the work is limited to a material whose degree of sulfonation is 70 unc preferably 50% not yet exceeded nat and the rest of the S @@ wereltrioxyd in other Way admits. @@ L e r s e i t e