DE735096C - Process for the production of sulphonic acids - Google Patents

Description

Process for the production of sulfonic acids It has been found that inan by equal early exposure to sulfur dioxide and Oxygen to saturated, ntchtaroniatisclie Hydrocarbons under light photoactive rays which apply the (iwn Iiohlenwasserstotten appropriate acids received. where one also uses `lie once initiated by irradiation -um- Continue the setting without further exposure can. As raw materials for the @ -or @ iegende @ -er- drive come in addition to the individual pure Hydrocarbons of the aliphatic mi (1 cycloaliphatic series. like I'rnpan. it-butane. Isobutane # n-hexane. nIf cptan. -1Ie thv l hpt.nt. n-Hexadclcan. Cvcloliexan. 11 @@ h @ "1C \" cl @ illelall etc., also the technically easy to @; itlglich, n Geneva niche such I @ ohlen #, vasserstolte in Ask how they oller in petroleum fractions synthetic, by fusing coal or by implementing IZolileilox_v (1 with Hydrogen - well known - experienced received: i # t- lichen Erzcu "itisseit preliminary. @werhnl: i @ i; @ uses nian for the present (le @@ ertahr, # n hohlenwasserstoftv. the ntö "liclist free of Olefin and oil are. eia (lens fabric groups already in: Ehr ges "in @ ren Mcligen (lie Can implement changes. @ 11an will be technical hydrocarbons zwerkm; il @ i ;; subject to appropriate cleaning. The disintegration of the IZ hydrocarbons with Sulfur dioxide and oxygen under light tw >> is how you do it. Bali nian for one »Mix the gases with lioino-ene as much as possible (1: n hydrocarbons ensures. application, of liquid hydrocarbon furnace 1; -r_w. Solutions of gaseous, liquid (tar solid I, hydrocarbons in suitable T, iistiit, -51171ttelIl. those with the applied oil, petroleum hydrogen completely or partially can be mixed to a limited extent. one leads (well-known -Mini names, such as Eiti- (liisen, a fine distribution of the reactive @ase here. The @@ achievement of sulfur se zti oxygen is not attached to the molar Quantities bound. z-% veclcniäßi- has a Proven t'brrschuG of sulfur dioxide. At Instead of oxygen one can also use air use, but here the l-in- setting under normal pressure accordingly cleiit lower partial pressure of the sulfur ciioxvcls ini gas dial slower. 11an came but also work under increased pressure; (This also applies to the Z @ erwen <Jun @ from reincin Satiers kills. The unisposition is made by photoactive Light in motion. \ voliet in some Cases which are initially caused by irradiation led unisposition into the dark without exposure keln l @ itet-l: iuft. _ Come as light duels, -: it expedient high-candle bulbs or mercury quartz lamps. In technical equipment, the light sources are arranged in front of correspondingly permeable stars in the reaction vessels or as immersion lamps centrally or radially in the reaction chambers. The heat that arises during exothermic use is advantageously dissipated by cooling, since otherwise the reaction temperature would rise too sharply. The disintegration rate is generally lower in the case of branched hydrocarbons than in the case of branched ones.

The sulphonic acids that arise during your present experience separate when lower hydrocarbons are used, for the most part turn out to be oils and can be obtained in raw form by separation in separating vessels. When using '#, the sulfonic acids of the higher hydrocarbons remain partially dissolved in them; they can then be extracted with solvents that are insoluble in coal - #.% - such as B. water or 1lethyl alcohol. separated «-earth. By concentrating the extracts the sulfonic acids are obtained in concentrated form. By neutralization z. B. init Alkalis and optionally separation of the unreacted hydrocarbons salts are obtained by known methods. In general, mainly salts are formed of llonosulphonic acids in a mixture of finite salts of disulphonic acids and alkali sulphates.

The substances obtainable according to your present process can be found technically versatile use, the higher molecular weight especially as capillary-active e'mittel.

Compared to the known process of converting hydrocarbons with sulfur dioxide and chlorine, optionally with exposure to sulfur, oxygen and chlorine-containing 1'erbindungen, essentially sulfochlorides, the present process offers the advantage that you get directly to the free sulfonic acids and that you can do without corrosive substances such as chlorine and hydrogen chloride can work. Examples i. In a narrow, tall, cylindrical Apparatus made of Jena glass, the one in the lower File with a glass frit to the .l? iiileituiig of Gases and in the upper ". th cooling coil and with a 11 ' reflux cooler is connected. will be ooo weight: share cyclohexane with a gas mixture behati (lelt, which is based on 2 liters of sulfur dioxide contains r mole of oxygen. The reaction vessel; eat is finitely loaded with a mercury quartz lamp radiates and the internal temperature through held at 15 to? 5 'for a long time. After a short time the contents of the apparatus become cloudy, and soon afterwards an iJ (begins to settle on the bottom, which multiplies rapidly.) All can continuously remove the precipitated O1 and refill it with fresh cyclohexane, without the conversion, which has already started, thereby If an hourly 1 gas mixture is introduced, about 65 g of oil per hour are obtained, which corresponds to the utilization of the applied (yes-ze from 8o to go °°.

The separated oil contains mainly Cvclolietansulfonsiiure and a little sulfuric acid: in moist air a hydrate of C @ 'cloliexan - tilfotisatirL! crystallizes from it. that can be obtained by suction in pure 1 # orin. To work up contributes nian the oil expediently in a volume of water, removed by blowing in steam cyclohexane, Sulfur dioxide and volatile decomposition products and then finitely neutralizes sodium hydroxide solution. The solution is evaporated to dryness. so inan receives a powder that is etlva qo °, '° contains cvclohexansulfonsaures -sodium in addition to io ° ,, ° sodium sulfate. By unicrystallizing the evc1ohexanesulphonic acid sodium is obtained in shiny flakes from water.

Gti similar results can be obtained if one looks at the conversions in violgl is or quartz apparatus carries out. Here comes the implementation, albeit slower, already started by irradiation with a high-candlestick incandescent lamp. -Man can produce cyclohexanesulfonic acid from cyclohexane, sulfur dioxide and `` Perform with pride in such a way that inan the unisposition, as described above, through Bringing irradiation in motion and switching off the light source after the beginning of the deposition of oil. The implementation continues in the dark without any disturbance, practically the same Yields as obtained with continuous irradiation.

2. If the cyclohexane is replaced by n-heptane in example r, the external picture of the dissolution is the same: here too, once the conversion has been initiated, it continues smoothly in the dark. By immersing it in water and treating it with steam, a solution is obtained which, after neutralization, finite sodium hydroxide solution and a (latnpfen, results in a semi-solid. L'rzetir, ni:. It consists of sodium salts of mainly heptannionic and some di: ulfonic acids with 13 to 10 ° sodium sulfate.

. 3. Replacing So obtained in Example r (las Cyclollexan (lurch 1letliylcycloliexan inan by (ler makeover on the Natriuni: Alze a semi-solid product in a mixture full deni about 75 to So ''', the Natriunisalze% -one lIetlivlcvclohexaninoliostilfonsä Uren. in addition to some disultonic acid with 25 bi: 20% sodium sulphate.

In an apparatus similar to that described in example i, the one with 800 parts by weight of carbon tetrachloride is filled, a gas mixture is passed every hour of 2o I n-butane, 10 1 sulfur dioxide and 3 1 oxygen and exposed to a Mercury vapor quartz glass. 'After a short time, the carbon tetrachloride becomes cloudy and separates out a colorless oil that is specifically lighter than the solvent is. 1Iai-1 receives about 16 parts by weight of oil per hour.

The upper oil layer is worked up as described in Example i and provides a mixture of about S; ° i, sodium salts of n-butanesulfonic acids and 13 °, lo sodium sulfate.

If isobutane is used instead of n-butane, the reaction proceeds somewhat slower, the resulting oil solidifies in moist air to form the crystalline substrate an isobutanesulfonic acid. After the work-up, a mixture of approximately full is obtained ; 7% p isobutanesulphonic acid sodium and 23% sodium sulphate.

If propane is used instead of n-butane, similar ones are obtained Results, the implementation is only slower here than with butane. Instead of carbon tetrachloride you can also use other suitable solvents, such as octylene chloride, with the same Apply success.

If in example i the cyclohexane is replaced by 3-llethyllieptane, so are the outward appearances of the implementation, which only proceeds much more slowly, very similar. ' After working up, a salt mixture from about 86 to is obtained SS ° r, sodium salts of 3-1 ethyl heptanesulfonic acids with 14 to 120/0 sodium sulfate.

6. If in example i the cyclohexane is replaced by a mixture which by hy drin tion of a full 2 = 0 to 32o ° boiling fraction of the by unisposition Obtained from carbon dioxide with hydrogen obtained hydrocarbon mixture is, and treated under irradiation with a mercury vapor lamp with a The mixture of sulfur dioxide and oxygen is observed to increase rapidly Yellowing of the hydrocarbon mixture with simultaneous oil separation. By Extraction with aqueous methyl alcohol gives a solution which, after removal of sulfur dioxide and the solvents used, neutralized and dried is steamed. "You get a gene table of sodium salts of sulfonic acids of the applied hydrocarbons with sodium sulphate.

Claims (1)

PATENT CLAIM Process for the production of sulfonic acids, thereby characterized that inan on saturated, non-aromatic hydrocarbons at the same time Sulfur dioxide and oxygen act under exposure to photoactive rays leaves and optionally the reaction initiated by irradiation in the dark continues.