DE1568590B - Process for the preparation of straight-chain aliphatic and cycloaliphatic sulfonic acids - Google Patents

Description

1 2

According to German patent 735 096, the extraction with an aqueous sulfonic acid extract is

position of sulfonic acids is kept low by paraffin hydrocarbons.

substances by exposing a mixture of the coals There has now been a process for the production of

Hydrogen with sulfur dioxide and oxygen by means of straight-chain, aliphatic and cycloaliphatic

known photoactive rays. 5 sulfonic acids with 10 to 30 carbon atoms through

According to the German patent 903 815 it is known to convert the corresponding hydrocarbons

long-chain aliphatic sulfonic acids of paraffin and sulfur dioxide and oxygen under the action

hydrocarbons found by introducing sulfuric rays of high energy, which thereby

Dioxide and oxygen under the action of ozone is characterized by exposure to radiation for so long

to manufacture. According to the German patent 887 503 io, until the formation of sulfonic acid begins

the reaction also occurs with the addition of organic, after which the radiation switches off

Peroxides. What all these processes have in common is that three starting materials are passed on and the reaction

that in the implementation of long-chain hydrocarbon mixture continuously with a mixture of 15 to

substances the energy supply in the form of UV light, 50% sulfonic acids, 5 to 40% water, 20 to 60%

Ozone or peroxides must be done constantly. After 15 hydrocarbons and 3 to 10% sulfuric acid

F. Ansinger, “Chemistry and Technology of the Extracted.

Paraffinkohlenwasserstoffe ”, Berlin 1956, under- As high-energy radiation / radiation or a distinction is made between two groups of paraffin-carbon / 3 radiation with a dose rate between 10 ³ and hydrocarbons, one of which comprises hydrocarbons, 10" rad / hour. Corresponding / Radiation in which the reaction with sulfur dioxide and 20 can be obtained, for example, from ⁶⁰ Co sources of 50 to 10000 Ci of oxygen to form sulfonic acids, or from ¹³⁷ Cs sources from ozone or / 3 radiation from radionuclides such as Strontium-90 addition of peroxides; to be used. Likewise, the radiation from this group includes cyclohexane, methylcyclo- spent fuel elements from nuclear reactors or hexane and heptane. The other group, to The radiation from a nuclear reactor itself can be used, in particular the higher molecular weight paraffin carbons, including X-rays or high-energy electr tronen Hydrogen belong, need to react with from accelerators can to start the reaction sulfur dioxide and oxygen constantly one of the above can be used. X-rays and also energy-led measures. rich electrons have before / - rays and /? - ray-

Furthermore, from the German patent 1139 116 30 len from radionuclides the advantage that they are known, aliphatic and cycloaliphatic sulfone can be switched as soon as they are no longer required for the start of the acids by simultaneous conversion of saturated reaction,
unbranched aliphatic hydrocarbons with The irradiation time can be between 1 minute and 60 hours hydrogen with sulfur dioxide and oxygen below 35, depending on the 10 to 30 carbon atoms or cycloaliphatic carbon dose rate. At a dose rate of around 10 ³ rad / hour exposure to / rays. After that she is z. B. between 2 and 25 hours,
German Patent 1206 890 is also known. It is expedient that dark sulfonic acid-containing development takes place during the initial that the reaction is formed even with intermittent irradiation irradiation time. According to Canadian patent 697 085, heavy oil can be separated off and it is known from the reaction to remove η-hexane in a countermixture when irradiating.

was of sulfur dioxide and oxygen a self- The production of sulfone according to the invention

to trigger the sustaining sulfoxidation reaction. Acid can be used at temperatures between 0 and 80 ° C,

The η-hexane can start the reaction for a longer period of time, preferably between 10 and 40.degree

chain hydrocarbons e.g. B. Kerosene in proportions. Press between 0 and 50 atmospheres, in particular

are added, but 10% of the reaction - 45 cases above, are used, preferably

must not exceed the mixture. A pressure between 0 and 5 atm.

Mixture of short-chain and longer-chain sulphonic The gas mixture of sulfur dioxide and acidic acids receive. After the sulphonic material has been separated off, the acid is expediently acidified in a large excess from the reaction mixture with the help of sets, the volume of the per hour passing through water and alcohol, the unreacted 50 conducted gas mixture must be 10 to 1500 times that Exposing hydrocarbons for the purpose of a continuous volume of the hydrocarbons used Reaction conduct a special dry-wear can; preferably this is 100 bis Processed with dehydrating agents used 1,000 times the volume. The relationship before they are returned to the reaction vessel- sulfur dioxide to oxygen should according to the rules. 55 action equation 2: 1; be advantageous but

In all such processes, sulfone gas mixtures with a higher sulfur dioxide content are obtained acids with varying levels of disulfonic acids; used in a ratio between 3: 1 and 20: 1, especially when using / radiation is the particularly favorable results are achieved with The content of disulfonic acids is often so high that the mixtures are between 8: 1 and 14: 1. The gas detergent properties the mixture produced therefrom is expediently finely divided, e.g. B. Sodium sulfonates are impaired. with the help of a gassing ring, into the reaction

A process for the preparation of the mixture was also initiated.

long-chain sulfonic acids with a low content The extraction can be between 0 and 50 ° C, first disulfonic acids, the liquid reaction mixture preferably between 10 and 40 ° C made of long-chain paraffin carbons. It is particularly advantageous _{to choose the combined hydrocarbons, SO 2} and O _{2 to} continuously expose the extract so that it is exposed in the extract and the concentration of sulfonation vessel creates a separating layer between the extract and acids in the reaction vessel through a continuous protruding paraffin perceptible is.

Claims (1)

3 4 The composition of the extract depends on the products of disulfonic acids are so small that the the process conditions such as temperature, washing effect of the products are not impaired, concentration of sulfonic acid and pumping speed _R. . ₁ away. One works in such a way that in the extraction vessel example a mixture of 15 to 50% sulfonic acids, 5 to 5 in a reaction vessel with a capacity of 50 liters 40% water, 20 to 60% hydrocarbons and 401 of a mixture of straight-chain aliphatic 3 to 10% sulfuric acid is present. Preferred hydrocarbons with carbon numbers between an extract with a content of 20 to 40% 10 and 20 sulfur dioxide and oxygen in the ratio Sulphonic acids, 10 to 30% water, 25 to 45% nis 12: 1 at a rate of 6 m ³ per Hydrocarbons and 4 to 8% sulfuric acid. io hour initiated by means of a gassing ring. In This extract is then placed in a separator in the middle of the reaction vessel the at elevated temperature, preferably at 80 ⁶⁰ Co source, which the reaction mixture with a Up to 120 ° C largely freed from sulfuric acid, ^{irradiated dose rate of 2 · 10 5} rad / hour. the after which the resulting mixture, which is essentially the gas pressure in the vessel is 0.2 atü, the temperature borrowed from sulfonic acids and aliphatic carbons 15 15 ° C. The reaction mixture is constantly on the There is hydrogen, on sulfonic acids or on their ball 14 with the help of the pump 5 via the lines Salts such as sodium salts, potassium salts and ammonium 15 and 16 are pumped in a circle. The lines 18 and processed salts. 17 remain closed. During the early days of the In one embodiment of the method according to irradiation, the reaction mixture first becomes cloudy, according to the invention it is again dark brown in the diagram in the figure, and a dark one separates. Here, the straight-chain, aliphatic-specific heavy oil at the bottom of the reaction table and cycloaliphatic hydrocarbons are removed from the reaction mixture with 10 to 30 carbon atoms via line 2. In the further course of the irradiation, the supplied reaction vessel 1 brightens. The gaseous Re- the reaction mixture on; it is after 10 to action partners are light yellow on line 3 for 25 15 hours. After a further 2 hours, the sulfur dioxide and 4 for oxygen have blown a value of gassing ring into the reaction vessel 1 by means of a yield of oily sulfonic acid. 0.7 kg per hour is reached, after which the irradiation The gas mixture of sulfur dioxide and oxygen is turned off and the reaction mixture is passed through the reaction vessel with the aid of a further pump 8 in the circuit lines 18 and 17 with the aid of the pump 5. During the speed of 30 liters per hour in the initial irradiation time, a dark, tion vessel 6 is pumped. After a total of 17 Stunsulfonsäurehaltiges specifically heavy oil, which has reached the steady state of the system, ball 14 is deposited and withdrawn at 19, in which at the lower end of the extraction vessel 10 while the rest of the reaction mixture is about 1.5 liters per hour Mixture are withdrawn, lines 15 and 16 with the aid of the pump 5 around 35 which contains 36% sulfonic acids. This sulfonic acid is being pumped. The lines 18 and 17 are made up of 86% monosulfonic acids and are closed. When no more dark oil forms 14% from disulfonic acids. The sulfonic acid mixture and the sulfonic acid components in the reaction vessel then pass into the separator 11, where it reaches the desired value between 2 and 50% and remains at 90 ° C. for 2 hours. In doing so, the radiation is switched off and the 40-7 volume percent of a 45% strength aqueous sulfur reaction mixture is deposited with the pump 5 via the acid. This gives 0.54 kg of sulfone lines 18 and 17 in the extraction vessel 6 acids per hour. After 240 hours the re-sponsored. In the upper end 7 of the extraction vessel 6 action still unchanged in the course; then the water required for the extraction is terminated in one by interrupting the gas supply.
Amount supplied that a mixture of the 45 _p
Desired proportions of sulfonic acid, water, carbon fat claim:
Hydrogen and sulfuric acid are produced. This process for the production of straight-chain extract is continuously withdrawn at the lower end of the aliphatic and cycloaliphatic sulfone extraction vessel 10 and then acids with 10 to 30 carbon atoms are largely freed from sulfuric acid by reacting the corresponding hydrocarbons in a separator 11 at an elevated temperature. Substances with sulfur dioxide and oxygen under animal mixture is further processed at 13. The effect of high-energy rays, since the hydrocarbon is above the extract, is characterized by the fact that the sulfonic acid is removed from the top of the extraction vessel and the irradiation is carried out until the sulfonic acid is continuously formed via line 9 to reaction vessel 1, thereafter fed ierlich without further irradiation. the radiation switches off the three starting materials With the help of the method according to the invention, further feed and the reaction mixture nen continuously in particularly economical ierlich with a mixture of 15 to 50% Wise biodegradable sulfonic acids, sulfonic acids, 5 to 40% water, 20 to 60% will be presented. Particularly advantageous and at the same time 60 hydrocarbons and 3 to 10% sulfuric acid It is surprising that the contents of the process extracted. 1 sheet of drawings