US2121845A - Process for producing clear lightcolored, water-soluble sulphonation products of mineral oil - Google Patents

Description

Patented June 2 8 1938 PROCESS FOR PRODUCING CLEAR'LIGHT- COLORED, WATER-SOLUBLE SULPHONA-' TION PRODUCTS OF MINERAL OIL Erich'Arnold Wernicke, Hamburg, Germany No Drawing. Application January 9, 1934, Se-

rial No. 705,918. In .1933

This invention relates to a process for the pr duction of sulphonation products from sulphurbearing mineral oils, tar oils, and the like, i. e.

from oils containing about 2 per cent and more 5 of sulphur.

sulphonation products from mineral oils, tar oils, etc. are used for many purposes, as for instance for the preparation of. emulsions, for general technical purposes, or for the manufacture of pharmaceutical preparations and the like.

The products of this kind, obtained from sulphurbearing oils, have a special importance in this respect.

These products are usuallyof a very dark color and not clear, even in thin layers, because in their production the sulphuric acid exerts also a resinifying action due :to oxidation or condensation efiects, apart from the sulphonating action itself. The dark color of the sulphonation prod-- uct is disadvantageous for many purposes and the odor generally is regarded as disagreeable.

Various processes for refinement of oils to remove coloring impurities are known per se. In 1 the instant invention, however, the purpose is to remove the coloring ingredients without, at the same time, materially reducing the original sulphur content of the oils to be treated, whereas the prior art was directed also to the most complete removal of the sulphur, and. that was the principal scope or one of the purposes of the refinement. I A noteworthy difference over the refinement processes thus far known lies in the fact that'the materials in question cannot strictly be considered as hydrocarbon oils in view of their high sulphur content. A sulphur content, for instance, of 10% corresponds to a-content of sulphur compounds of approximately 50-60%, so that the experiences had with oils having less than 2% of sulphur, which can still be fairly classified as hydrocarbons, cannot simply be applied to the sulphur oils involved herein.

It must also be emphasized that usually the original color of the oil is not controlling. Thus,

' :5 a light-colored oil may, in the subsequentsulphonation, produce a dark resinous product. It is, therefore, an object to remove, by pre-refinement, all those oil substances which would cause a dark coloration of the final sulphonation product, retaining, nevertheless, as much as possible the original sulphur compounds.

The present invention solves this task in such a manner that the oils or their distillates, or singular fractions, are liberated, by a chemical 65 pre-refinement, from the ingredients that might Germany January 11,

5 Claims. (01. 196-40) cause a dark coloration of the end product in the sulphonation process. The main part of the sulphur compounds remains, however, in the oils,

and the oils are then carefully sulphonated under cooling or with partly concentrated sulphuric 5 acid, or with the use of a suitable diluent, whereupon the further process is carried out in-the usual manner. In the sulphonation procedure several of the indicated processes may be combined with each other.

- The ore-refinement can be carriedv out, for instance, with soda lye or with sulphuric acid,

the concentration of which has to be calculated from the character of the oil put into process,

so that on the one hand the resinifying substances will be removed as far as possible and, on the other hand, that no material degree of sulphonation or removal of sulphur compounds will take place. The pre-refinement can also be carried out with other known refining agents which may be used either alone or combined, depending on the chemical character of the oil, thus, for instance, with potash lye, aluminum chloride, phosphoric acid, fullers earth, bleaching clay, and

the like.

In the careful sulphonation process that part of the oil resulting from preceding sulphonations which cannot further be sulphonated or treated with sulphuric acid may serve as suitable diluent.

Depending on the thoroughness of the prerefinement and depending further on 'the'degree of care observed in the sulphonation process, after neutralizing the sulphonation mixture and separating the undissolved portions of the oil, transparent, clear water-soluble products of 35 light-yellow to brown color are obtained which do not generally impart their color to other substances when mixed with them, whereas without this treatment much darker, non-transparent," mostly black-brown products are obtained.

Under favorable circumstances many of the products of this process may be obtained more or less completely or practically odorles Following the first careful sulphonation this can be repeated several times with sulphuric acid of graduated increase in strength, so that each sulphonation process can, in a sense, be regarded as pre-refinement for the sulphonation with the g 4 next-following stronger acid. The acid concentration to be employed in the successive sulphonation steps is downwardly limited by the acid concentration used in the preceding step; there'is' no upward limit and, observing the neces-, sary care in other respects, the concentrations may be increased up to the stage of fuming sul- 55 desired consistency by adding water orby evaporation. The removal of sulphates can be carried out in any well known manner, either before or after the neutralization, for instance by dialysis or by extraction with solvents.

According to this invention sulphur-bearing petroleum or other oils, for instance from Italian mineral coal, Middle-German brown coal, South- German bituminous shale, orsimilar combinations or mixtures may be used with equal advantage for the manufacture of such sulphonation products. Analogous deposits of coal-like materials which are equally suitable for the process according to this invention on account of their sulphurcontent are found in all parts of the world. Practically it is, of course, preferable to.

begin with the distillates because the refinement is thereby simplified.

Example 1 As starting material a distilled Italian mineral coal-tar, having the following characteristics, is used: specific weight at 15 C. about 0.9; sulphur content 8.8%; boiling points about -250. 100 grams of this oil are pre-refined with soda lye of 39 B., sulphuric acid of 70% H2804 and fullers earth. The sulphur content after the prerefinement is 10.22%.

The refinedoil is now sulphonated with about 60 cc. sulphuric acid of 90% H2804 under stirring and cooling at 0 C. The sulphonation mixture is run into water, and sulpho-acid and oil are then neutralized with ammonia. After separating the oil, the product is evaporated to a water content of 41.24%. 10 grams are obtained of this product, which, in this condition, contains 6.84% of ammonium sulphate and 9.57% of sulphur. The organic substance .is 51.92% including 15.24% of sulphur. It has been calculated that the oil substance which has been sulphonated contains 11.01% of organic sulphur. The product is light-brown, transparent and clearly watersoluble. The reaction products of the oil and sulphuric acid obtained in the end product are true sulpho-acids and not esters because the latter would be split by the strong heating which takes place in the dilution of the sulphonation product with water and in the evaporation of the water from the neutralized product.

Example 2 As starting material a distilled Italian mineral coal-tar is used having the following character-,

istics: specific weight at 15 C. 0.890; sulphur content 7.0%; boiling analysis:

v Percent 101-200 54.3 200-269 531 grams of this oil are pre-refined with 35% soda lye, 85% phosphoric acid and fullers earth;

with ammonia. After separating the oil, the product is then evaporated to a water content of 42%. 69 grams of this product are obtained. In this condition it contains 11% of ammonium sill-- phate and 10.62% of sulphur. The organic substance therein is 47.%, including 16.92% of sulphur. It has been calculated that the oil' substance which has' been sulphonated contains 10.38% of organic sulphur. The product is light- -brown, transparent and clearly water-soluble.

Example 3.

As starting material a distilled Mid-German brown coal-gas-light oil is used having the fol-. lowing characteristics: specific weight at 15 C. 0.850; sulphur content 6.0%; boiling analysis:

. Percent 80 to 2.5 100 to 150 r 33 150 to 200 92 I 500 grams of this oil are-pre-refined with 50% potash lye and 50% sulphuric acid. The sulphur content of the oil after this pre-refinement still is 5.6%. The refined oil is now sulphonated with about 500 cc. sulphuric acid (pure concentrated) under stirring and cooling at about 0 .C. The sulphonation mixture is run into water and neutralized with ammonia. After removal of the unaffected part of the oil, having become separated by the dilution with water, the product is evap- Example 4 As starting material a distilled Tyrolean shale oil is used having the following characteristics:

specific weight at 15 C. 0.885; sulphur content 11.3% boiling analysis:

Percent 80 to 100 1.8 100 to 200 61.0 200 to 300 1 94.1

524 grams of this oil are pre-refined with waterfree aluminum chloride, 35% soda lye and fullers earth. The sulphur content of the oil after this pro-refinement is still 11%. The refined oil is now sulphonated with about 425 cc. sulphuric acid (pure concentrated) under stirring and cooling at about -'5 C. Thesulphonation mixture is run into water and sulpho-acid and oil are neutralized with ammonia. After removal of the unafiected part of the oil, having become separated by the dilution with water, the product is evaporated to a water content of 30.5%. i grams of this product are obtained. It contains in this condition 4.77% of ammonium sulphate and 14.80% of sulphur. The organic substance therein is 64.73%, including 21.07% of sulphur. It has been calculated that the sulphonated oil substance contains 17.53%, of organic sulphur. The

product is light-brown, transparent and clearly water-soluble.

' Example 5 As starting material a distilled Tyrolean shale oil is used refined with 35% soda'lye, 70% sullowing characteristics: specific weight at 15 C. 0.894; sulphur content 11.45%; boiling analysis:

Percent 130 to 200 '58 200 to 287 96.5

7.15 kg. of this oil are sulphonated with 16 1. sulphuric acid (technical 66 B.) under stirring at a temperature of about -8 C. The $111- phonation mixture is run into water and sulphoacid and oil are neutralized with ammonia. After removal of the unaffected part, having be-' come separated by the dilution with water, the product is evaporated to a water content of 24.25%. 1.83 kg. of this product are obtained. It contains in this condition 7.33% of ammonium sulphate and 14.87% of sulphur. The organic substance therein is 68.42%, including 19.13% of sulphur. The sulphonated oil substance contains 15.04% of organic sulphur. The product is light-brown, transparent and clearly watersoiuble.

463 grams of the oil, separated by the dilution of the sulphonation mixture with water, having a specific weight of 0.926 at 15 C., are diluted with an equal volume of petroleum and with 500 cc. of sulphuric acid (16 weight percent of 66 B. technical acid +84 weight percent of technical fuming acid with 18% of $03) under stirring at a temperature of about 15 C. The

sulphonation mixture is run into water and sulpho-acid and oil are neutralized with ammonia. After removal of the unaffected part of the oil, having become separated by the dilution with water, the product is evaporated to a water content of 50%.. 816 grams of this product are obtained which, in this condition, contain 10.95% of ammonium sulphate and 10.60% of sulphur. It has been calculated that the sulphonated oil substance contains 2.8% of organic sulphur. The product is light-brown, transparent and clearly water-soluble.

Obviously, the various steps of the process may be modified considerably with respect to the order and the number of steps and the specific materials used in the several methods exemplifying the refining and sulphonation steps, without departing from the spirit of the invention substantially as described and claimed, and it is understood that I do not desire to limit myself to the specific embodiments shown in the foregoing examples.

What I claim as new, and on which I pray the issuance of Letters Patent, is:-

1. A process for producing clear, light-colored,

water-soluble sulphonation products of mineral oils naturally containing more than two per cent of organically combined sulphur, without substantially impairing such natural organically combined sulphur content, which comprises selectively separating out of such oils the inherent resinifiable materials by treatment with a mineral acid of the group consisting of sulphuric acid and phosphoric acid, the concentration of said refining acid being adjusted substantially within the range of 50 to 70 percent for sul-' phuric acid, according to the quality of the oil treated; subsequently carefully sulphonating the treated oils at greatly reduced temperatures of C. and less with concentrated sulphuric acid; thereafter dissolving out the soluble portion of the sulphur-rich sulphonation products thus obtained in water and neutralizing the solution.

2. In a process for producing light colored water-soluble sulphonation products of mineral oils naturally containing more than two percent of organically combined sulphur, the steps which comprise selectively separating out of said oils the resinifiable materials without substantially impairing the organically combined sulphur content, by first treating the oil with sulphuric acid of non-sulphonating,concentration ranging from about 50 to 70% concentration, and subsequently treating the substantially de-resinified residue with higher concentrations of the acid to effect sulphonation.

3. A process for producing light colored, water-soluble sulphonation products of Tyrolean shale oil having a relatively high natural sul- .phur content of over 2%, which comprises the after dissolving the soluble portion of the sulphur-rich sulphonation products thus obtained in water and neutralizing the solution with ammonia.

4. A process for producing light-colored, clearly Water-soluble sulphonation products of Tyrolean shale oil having a'relatively high natural sulphur content of more than 2%, which comprises the steps of selectively separating out of said oils, before sulphonation, the inherent resinifiable materials without substantially impairing the natural organically combined sulphur content by treating the oil first with 35% soda lye, then with 70% sulphuric acid, and then with fullers earth; sulphonating the oil with 96% sulphuric acid at about -8 0., adding the sulphonation mixture to water and neutralizing the sulpho-acid and oil by treatment with ammonia; removing the unsulphonated oil which separates by dilution with the water, adding thereto an equal amount of new oil and about 10% more than an equal part of acid, stirring the mixture at about 15 C., running the sulphonation mixture into water, and neutralizing the su'lpho-acid and oil with ammonia.

5. A process for producing light-colored, wa-

naturally containing more than 2% of organically combined sulphur which comprises the steps of selectively separating out of said oils the in herent resinifiable materials without substantially impairing the natural organically combined sulphur by treating the oil first with 35% soda lye, then with 70% sulphuric acid, and then with fullers earth; sulphonating the treated oil with 96% sulphuric acid at about 8 C. thereafter dissolving the soluble portion of the sulphur-rich sulphonation products thus obtained in water and neutralizing the solution with ammonia.

ERICH ARNOLD WERNICKE.

-ter-soluble sulphonation products of mineral oils