DE1568603A1 - Process for the production of straight-chain aliphatic and cycloaliphatic sulfonic acids - Google Patents

Description

Process for the production of straight-chain aliphatic and cycloaliphatic sulfonic acids

According to DBP 735 096, the production of sulfonic acids from paraffinic hydrocarbons by exposing a mixture of the hydrocarbons with sulfur dioxide and oxygen by means of photoactive rays is known. DBP 9O3 815 is known to produce long-chain aliphatic sulfonic acids from paraffinic hydrocarbons by introducing sulfur dioxide and oxygen under the action of ozone. According to 0BP 887 503, the reaction also takes place when organic peroxides are added. What all these processes have in common is that when long-chain hydrocarbons are converted, the energy must be supplied continuously in the form of UV light, ozone or peroxides. According to F * Asinger "Chemie und Technologie der Paraffinkohlenwasserstoffe, Berlin 1956 a distinction is made between two groups of paraffin hydrocarbons, one of which comprises hydrocarbons, the reaction of which with sulfur dioxide and oxygen to form sulfonic acids continues automatically as soon as it has been initiated by exposure to light, gassing in of ozone or the addition of peroxides ; This group includes cyclohexane, methylcyclohexane and heptane.

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other group, including in particular the higher molecular weight Paraffinkohlenwasserstoffθ belong, need to be implemented with sulfur dioxide and oxygen constantly one of the above listed measures

Furthermore, according to DBP 1 139 Il6, it is known to produce aliphatic and cycloaliphatic sulfonic acids by the simultaneous reaction of corresponding hydrocarbons with sulfur dioxide and oxygen under the action of ^ rays. According to DBP 1 206 89Ο it is also known that the reaction also takes place with intermittent irradiation. It has also already been proposed (patent application F k $ I31 IVb / 12 o -Fw 4695) “to start the reaction only by the action of energy-accumulating rays and then to continue it without supplying energy. In all such processes, nan receives sulfonic acids with varying levels of disulfonic acids; especially when using 2Γ radiation, the content of disulfonic acids is often so high that the detergent properties of the sodium sulfonates produced from them are impaired.

There has also been a method of making long chain Proposed sulfonic acids with a low content of disulfonic acids, the liquid reaction mixture of long-chain paraffin hydrocarbons, SO and O continuously one ^ - Radiation is exposed and the concentration of sulfonic acids in the reaction vessel by a «continuous extraction is kept low with an aqueous sulfonic acid extract CF 49 753 IVb / 12o - Fw 512%).

Finally, a process for the production of sulfonic acids by reacting straight-chain "saturated " hydrocarbons with sulfur dioxide and oxygen has already been proposed, in which the hydrocarbons are first cleaned in a special way, followed by the reaction through the action of high-energy rays or ultraviolet light | »/ | S /

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or starts by adding ozone or peroxides and then continues without adding radiation or compounds suitable for chain starting (F k6 302 VIb / 12 ο - Fw 4792).

There has now been a continuous process for the production of straight chain aliphatic and cycloaliphatic !! Sulphonic acids with 10 to 3 ^ carbon atoms found by reacting the corresponding hydrocarbons with sulfur dioxide and oxygen, which is characterized in that ozone is first added to the mixture of the three Auegangestoffe ι until the formation of sulphonic acid has started, after which the ozone supply is switched off and the three starting materials are continuously fed, while the reaction mixture is continuously transferred to an extraction vessel containing a mixture of 15 to 50 % sulfonic acids, 5 to KO% water, 20 to 60 % hydrocarbons and 3 to 10 % sulfuric acid and in so much water flows into the upper part that the water content of the mixture is retained, while the mixture flows out at the lower end and the excess paraffin flows back into the reaction vessel at the upper end of the extraction vessel.

The reaction is expediently carried out in such a way that the required oxygen or part of it is passed through an ozonizer, after which ozone concentrations between 1 and 10 % are generally achieved; lower or higher ozone concentrations are possible; their use only leads to a longer or shorter start-up time for the reaction. The duration of the ozone supply depends on the purity of the hydrocarbons used and is generally between 2 and 30 hours.

It is advisable to do this during the initial .0zohzufu.hr The oil formed dark sulphonic acid, which was difficult to separate

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and to remove it from the reaction mixture.

The preparation according to the invention of sulfonic acids can be carried out at temperatures between 0 and 80 ° C., preferably between 10 and 40 ° C. Prints between 0 and 50 atmospheres, in special cases even more than this are used, preferably prints between 0 and 5 atmospheres.

The gas mixture of sulfur dioxide and oxygen is expediently used in large excess, the volume of the gas mixture passed through per hour being 10 to 1500 times the volume of the hydrocarbons used; preferably 100 to 1000 times the volume is used. The ratio of sulfur dioxide to oxygen should be 2: 1 according to the reaction equation; however, gas mixtures with a higher sulfur dioxide content in a ratio of between 3 ^: 1 and 20: 1 are advantageously used. Particularly favorable results are achieved with mixtures between 8: 1 and 14: The gas mixture is expediently finely divided, e.g. initiated the reaction mixture.

The extraction can be between 0 and 50 ⁰ C, preferably between 10 and be made k0 C. Particularly advantageous is ee, the composition of the extracts :; to be chosen so that a separation between the extract and the protruding paraffin is perceptible in the extraction vessel.

The composition of the extract depends on the process conditions such as temperature, concentration of sulfonic acid and pump speed. In general, the procedure is such that a mixture of 15 to 50 % sulfonic acids, 5 to 40 % water, 20 to 60 % hydrocarbons and 3 to 10 % sulfuric acid is present in the extraction vessel. Is preferred

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an extract with a content of 20 to 40 % sulfonic acids, 10 to 30 % water, 25 to 45 % hydrocarbons and 4 to 8 % sulfuric acid. This extract is then largely freed from sulfuric acid in a separator at an elevated temperature, preferably at 80 to 120 ° C., after which the resulting mixture, which consists essentially of sulfonic acids and aliphatic hydrocarbons, is sulfonic acids or their salts such as sodium salts, calcium salts and ammonium salts processed. is.

If the reaction rate drops, this will result Reduction of the ratio 50: 0 in the raw action mix can be seen, by reducing the speed of the reaction mixture pumped into the column, the formation of sulfonic acids can be brought back to the normal reaction rate without the addition of ozone, after which the pumping speed can also be brought back to normal. If desired, the reaction rate can be can also be increased by another short-term addition of ozone.

One embodiment of the method according to the invention is shown in the diagram in FIG. The straight-chain aliphatic or cycloaliphatic hydrocarbons with 10 to 30 carbon atoms are fed to the reaction vessel (1) via line (2). The gaseous sulfur dioxide is introduced via line (3) and the oxygen via line Ci) first into the ozonizer and then, after combining with the sulfur dioxide, into the reaction vessel (1) by means of a gassing ring; The concentration of the ozone in the oxygen depends on the amount of oxygen introduced, on the dwell time in the ozonizer and on the voltage applied to the ozonizer. The gas mixture of sulfur dioxide and oxygen is with

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With the help of another pump (8) circulated through the reaction vessel. At the beginning of the ozone supply, a dark, sulfonic acid-containing, specifically heavy oil is produced, which is deposited in the ball (lk) and drawn off at (19), while the remaining reaction mixture is conveyed via lines (15) and (16) with the aid of the pump (5 ) is undepumped. The lines (l8) and (17) are closed here. When the dark oil no longer forms and the sulfonic acid content in the reaction vessel has reached the desired value between 1 and 50% , the ozonizer is switched off and the reaction mixture with the pump (5) via lines (18) and (17) into the extraction vessel ( 6) promoted. The water required for the extraction is fed into the upper end (7) of the extraction vessel (6) in such an amount that a mixture of the desired proportions of sulfonic acid, water, hydrocarbon and sulfuric acid is formed. The hydrocarbon above the extract is taken off at the top of the extraction vessel and fed continuously to the reaction vessel (1) via line (9) without further treatment. The extract is continuously drawn off at the lower end of the extraction vessel (10) and then largely freed from sulfuric acid in a separator (II) at an elevated temperature. The resulting mixture is processed further at (13).

With the help of the method according to the invention can continuously biologically in a particularly economical manner degradable sulfonic acids are produced. It is particularly advantageous and at the same time surprising that the contents of the process products of disulfonic acids are so small that the washing performance of the products is not impaired.

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Example 1

In a reaction vessel with a capacity of 100 1, 90 1 of a straight-chain aliphatic hydrocarbon with Carbon numbers between 10 and 20 sulfur dioxide and. Oxygen in a ratio of 10: 1 was introduced at a rate of 16 cbffl / hour by means of a gassing ring. By an ozonizer with a primary voltage of 170 volts are operated, an hourly .100 1 Oxygen passed, which amount is increased to 200 1 oxygen over 10 hours. With an ozone content of 4 vol. # the oxygen is then introduced into the gas circuit and Introduced into the reaction vessel. The need for oxygen increases themselves in the course of the reaction; the oxygen supply will be chosen so that the gas composition always the The above ratio of 10: 1 corresponds to * The gas pressure in the reaction vessel is 0.2 atu, the temperature 17 ° C.

The reaction mixture is first over the ball (l4) with Help the pump (5) via the lines (15) and (l6) in a circle pumped. Lines £ 18) and (17) remain closed. During the ozone supply, the reaction mixture is initially cloudy, then dark brown. The sulphonic acid formed in the process separates itself as a specific heavy oil in the sphere (l4) and can be deducted at (19). If the separation of the oil has reached a rate of 2 kg / hour, the Reaction mixture via lines (18) and (17) with the aid of the pump (5) into the extraction vessel (6) at one speed pumped at 30 l / hour. The ball {l4) and the line (15) remain closed. The ozonizer will then switched off.

The steady state of the reaction mixture is reached after a total of 50 hours of operation. The concentration of the sulfonic acid in the reaction mixture is between 5 and 95 » at a pumping speed of 2h l / hour. The oxygen supply is 220 l / hour, the sulfur dioxide supply 600 l / hour. 2.0 liters of water per hour must be poured into the

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Extraction vessel are introduced.

At the lower end of the extraction vessel (10), 6 liters of a mixture of 31-6 hydrocarbons, 25.3% water, 6.3 # sulfuric acid, 27.894 mono-sulfonic acids and 9 % disulfonic acids are drawn off per hour. The mixture is heated in the separator (II) with a mean residence time of half an hour at 110 C to give 6.% Of a 57 # aqueous sulfuric acid volume to be deposited. This gives 2.5 kg of sulfonic acid per hour. After 310 hours the reaction is still going on unchanged; it can be ended by interrupting the gas supply.

Example 2

The experiment described in Example 1 is continued in the same apparatus at a temperature of 26 ° C. The oxygen supply increases to 240 l / hour. After increasing the pumping speed to 50 l / hour, a stationary sulfonic acid concentration of 3 to 5 ^ is established in the reaction vessel. The reaction mixture consists of 92.6% hydrocarbons, 0.7 % sulfuric acid, 4.9 % monosulfonic acids and 0.7 % disulfonic acids, which corresponds to a ratio of 87.5 % monosulfonic acids to 12.5 % disulfonic acids. At the lower end of the extraction vessel, when 2.4 liters of water are fed in per hour, 9 liters of extract, consisting of 35.6 % hydrocarbons, 26.9 % water, 7.2 % sulfuric acid, 25.8 % monosulfonic acids and 4.5% % Disulfonic acids removed; the sulfonic acid mixture accordingly consists of 85.2 % monosulfonic acids and 14.8 % disulfonic acids. Dar extract is heated in the separator (II) with an average residence time of 20 minutes at 11O ⁰ C to give 6.% Of a 51 # sulfuric acid volume to be deposited. 3 kg of sulfonic acids are obtained per hour. The experiment was arbitrarily ended after 25 hours by interrupting the gas supply.

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Claims (1)

Fy 520 * 5 -9 - "68603 Claims l) Continuous process for the production of straight-chain aliphatic and cycloaliphatic sulfonic acids with 10 to 30 carbon atoms by reacting the corresponding hydrocarbons with sulfur dioxide and oxygen, characterized in that ozone is added to the mixture of the three starting materials until the formation of sulfonic acid has started is, after which the ozone supply is switched off and the three starting materials are continuously added, while the reaction mixture is continuously transferred into an extraction vessel, which is a mixture of 15 to 50 % sulfonic acids, 5 to kO% water, 20 to 60 % hydrocarbons and 3 to IQ % Sulfuric acid and in the upper part of the water so much that the water content of the mixture is retained, while at the lower end the mixture flows off and the supernatant paraffin flows back into the reaction vessel at the upper end of the extraction vessel. 2) Method according to claim 1, characterized in that the temperature of the reaction mixture is between 0 and 80.degree. C., preferably between 10 and ± 0.degree. 3) Method according to claim 1, characterized in that the extract running out of the reaction vessel in a separator at an elevated temperature of part of the sulfuric acid and freed of the water and then in known Way is processed in the sulfonic acids or their salts. ^l t) Process according to claim 1, characterized in that the volume of the amount of gas passed through the reaction mixture every hour is 10 to 1500 times, preferably 100 to 1000 times the volume of the liquid. *) as an extract 0 0 9 8 2 0/1 9 0 A Fw 5205 5) Method according to claim I _1, characterized in that the reaction gas, sulfur dioxide and oxygen in a ratio between 3 ^: 1 and 20: I ₁ preferably between 8: 1 and ΐΛ: 1 contains. 009820/1904