PROCESS FOR THE EXTRACTION OF PARAFFINS FROM MIXTURES THEREOF WITH ALKANE-SULPHONIC ACIDS

Abstract: The invention relates to a process for the extraction of paraffins from mixtures obtained by the sulphoxidation of paraffins having a number of carbon atoms comprised within the range of from 12 to 18, which is characterized in that as the solvent CO₂ under supercritical conditions is used.

Description: The present invention relates to a process for the extraction of paraffins from mixtures thereof with alkane-sulphonic acids. More particularly, the present invention relates to a process for the extraction of paraffins from mixtures of said paraffins with alkane-sulphonic acids, sulphuric acid, slightly polar alcohols and water. The mixtures of alkane-sulphonic acids and paraffins are obtained in particular by the process of sulphoxidation of n-paraffins, e.g., according to German patent 910,165. The problems to be faced with the above said mixtures is that of the recovery of alkane-sulphonic acids or of their salts, and of paraffins, from sulphuric acid and the possible excess of SO₂ used in the sulphoxidation. As to SO₂, no particular problems exist, in as much as a distillation under a moderate vacuum, or a stripping with oxygen, which is recycled to the sulphoxidation reactor, is enough to completely separate it from the solution. For the separation of paraffins not converted into alkane-sulphonic acids, and of sulphuric acid, several processes have been suggested, one of which (European patent application 131,913) suggests isolating the alkane-sulphonic acids, or the alkane-sulphonates, from the mixtures obtained by sulphonating the paraffins, and subsequently separating sulphuric acid, by adding to the mixture as obtained by the sulphoxidation of n-paraffins, alcohols having a number of carbon atoms selected between 2 or 3, in such a way an upper phase, containing most of paraffins, being separated, and the mixture being then submitted to a separation of sulphuric acid by a weakly polar organic solvent immiscible, or sparingly miscible with water. The product containing the possibly salified alkane-­ sulphonic acids is heated to the purpose of separating the solvent and the residual paraffins, and is possibly whitened with hydrogen peroxide. The processed of the known art, that is disclosed in the above said European patent application included, suffer from the drawback that the separation of paraffins results very poor when the alcohol having a number of carbon atoms selected from 2 or 3 is used, so that the subsequent heating step must be carried out for a very long time, with consequent high energy consumption, and with the danger of deteriorating the alkane-sulphonic acids or alkane-sulphonates. It was surprisingly found that overcoming the drawbacks of the known art is possible by resorting to use of CO₂ in the supercritical state for the extraction of paraffins. The process according to the present invention comprises submitting the raw charge containing the alkane-sulphonic acids with a number of C atoms comprised within the range of from 12 to 18, one or more aliphatic alcohols having a solubility in water lower than 7% by weight, sulphuric acid, paraffins having a number of carbon atoms comprised within the range of from 12 to 18 and water, to an extraction by carbon dioxide under supercritical conditions, an extracted phase being separated which contains, besides CO₂, the paraffins and the present alcohol or alcohols, and a refined phase containing the alkane-sulphonic acids, sulphuric acid and water. Sulphuric acid is then neutralized or eliminated by known means, so that the alkane-sulphonic acids, or their salts, are recovered. As to the operating conditions under which the extraction step is carried out, they are the following: temperature comprised within the range of from 32°C to 80°C; the operating pressure may range from CO₂ critical pressure (73.8 bars) up to a value, depending on the operating temperature, such that the density of supercritical CO₂ is slightly lower than of the mixture being submitted to the extraction, in general of from 75 to 350 bars; carbon dioxide under supercritical conditions; the CO₂/SAS ratio being preferably comprised within the range of from 1/1 to 50/1 (SAS = secondary alkane-sulphonate or alkane-sulphonic acid). The aliphatic alcohols having a solubility in water lower than 7% can be linear, branched or cyclic, and have a number of carbon atoms comprised within the range of from 5 to 12, they being selected, in particular, from 1-­ pentanol, 1-hexanol, 1-heptanol, 1-octanol, 1-decanol, 1-­ dodecanol, 2-ethyl-1-butanol, 2-methy-1-pentanol, 2-­ ethyl-1-hexanol, 2,6-dimethyl-4-heptanol, 3-ethyl-1-­ hexanol, 2,7-dimethyl-octanol, 2-octanol, cyclohexanol, cyclooctanol and mixtures of these alcohols. As regards the separation of sulphuric acid, a separating agent can be used; preferably, the same aliphatic alcohols having a solubility in water less than 7%, as above mentioned, can be used. The process according to the present invention can be carried out as a continuous process or as a batch process, and is illustrated by the following examples in a non-limitative way. Example 1 The laboratory-size extraction equipment as schematically shown in Figure 1 was used. It consists of a refrigerating cycle for condensing CO₂ in heat exchanger (8). Liquid CO₂ (1) is pumped, by the membrane pump (2), to the pre-heater (3) and then to the extracting unit (4). The temperature of (3) and (4) is maintained constant, and at the same value, by circulating water coming from a thermostatic bath. Pressure in (4) is maintained constant at the desired value by means of the regulator (5) and of the actuation valve (6). CO₂, containing the products extracted from the raw material charged to (4), outflowing from (6), leaves the supercritical field in separation unit (7), wherein CO₂ evaporates and is condensed in (8), to be then sent back to the already described cycle, whilst the extracted phase remains inside the separation unit. Possible make-­ up CO₂ is fed through (9). The separation unit (7) is provided with two diametrically opposite glass windows, for the visual check of level. This latter is kept constant by acting on the temperature of water coming from a second thermostatic bath. Pressure in (7) is kept constant by means of a pressure switch, which controls the refrigerating cycle. Inside the extraction unit (4), a cylindrical vessel can be provided, which has both its cover and bottom plates made from porous sintered steel, and to which the extraction-undergoing raw product can be charged. In the preferred form, the extracting unit is packed with stainless steel bodies kept blocked by a demister. A second pump (10) is used to deliver the raw product to be submitted to the extraction, for the continuous operating mode; in this case, the refined product is discharged through valve (11). Inside the vessel of extraction unit (4), 126.1 g was charged of a raw mixture of (C₁₂-C₁₈)-paraffin-­ sulphonic acids (secondary alkane-sulphonic acids = SAS), containing, besides sulphonic and disulphonic acids: 1-hexanol = 17.06% by weight (C₁₂-C₁₈)-n-paraffins = 36.72% by weight H₂O = 11.22% by weight H₂SO₄ = 0.78% by weight and underwent the extraction by supercritical CO₂ at 40°C and under 150 bars for 1 hour (CO₂/raw SAS weight ratio = 14.5). At test end, the products contained in separation unit (7) (extracted phase) and in extraction unit (4) (refined phase) were respectively discharged through (12) and (11) and analyzed. The amount of extraction paraffin, relatively to that contained in charged raw SAS resulted to be 99.4%; that of 1-hexanol, of 91.9%. Example 2 The equipment as described in Example 1 was used. 125 g of a raw mixture of SAS, having the composition as indicated in Example 1, was submitted to extraction by supercritical CO₂ at 50°C and under 150 bars for 3 hours (CO₂/raw SAS weight ratio = 43.8). The analyses carried out on the extracted phase and on the refined phase at test end demonstrated that paraffin was extracted to an extent of 99.53%, based on paraffin contained in charged raw SAS, and 1-hexanol to an extent of 98.8%. Example 3 The equipment as described in Example 1 was used. 119.3 g of a raw mixture of paraffin-sulphonic acids, having the composition as indicated in Example 1, was submitted to extraction by supercritical CO₂ at 60°C and under 150 bars for 2 hours (CO₂/raw SAS weight ratio = 30.5). The analyses carried out on the extracted phase and on the refined phase at test end demonstrated that paraffin was extracted to an extent of 99.87%, based on paraffin contained in charged raw SAS, and 1-hexanol to an extent of 98.12%.

Claims: 1. Process for the extraction of paraffins from mixtures thereof with alkane-sulphonic acids, in particular from such mixtures as obtained by the sulphoxidation of paraffins having a number of carbon atoms comprised within the range of from 12 to 18, characterized in that the aqueous mixture containing the paraffins and the alkane-sulphonic acids and sulphuric acid in the presence of one or more aliphatic alcohols is submitted to an extraction by CO₂ under supercritical conditions, which extracts the paraffins. 2. Process according to claim 1, characterized in that the process is carried out at a temperature comprised within the range of from 32°C to 80°C. 3. Process according to claim 1, characterized in that the CO₂/SAS ratio is comprised within the range of from 1/1 to 50.1. 4. Process according to claim 1, characterized in that the process is carried out under a pressure of from 75 to 350 bars.

Inventors: FAGGIAN,LUCIO, MARCOTULLIO, ARMANDO, PICCHI, EMILIO, PLATONE, EDOARDO
Applicants: ENICHEM AUGUSTA S.P.A., ENIRICERCHE S.P.A.
Application year: 1987
Main classification: C07C303
IPC codes: C10G73, C07C9, C07C7, B01D11, C07C309, C07C1, C07C39, C07C303, C07C67, C07B63