US1949244A - Denatured alcohol and ester - Google Patents

Description

Patented Feb. 27, 1934 UNITED STTES ATENT OFFICE.

DENATURED ALCOHOL AND ESTER William N. Davis and John T.

Rutherford,

No Drawing. Application August 8, 1932 Serial No. 628,003

9 Claims.

This invention relates to the production of denatured organic liquids, such as alcohols and esters.

In the co-pending application of John T.

Rutherford, Serial No. 628,004, filed August 8,

1932, covering Sulphur dioxide extracts of petroleum and processes of securing the same, there is described the production of certain new products from petroleum secured by subjecting petroleum oil to a double extraction process with sulphur dioxide. We have discovered that the sulphur dioxide extracts of petroleum, both those described in said co-pending application and others resulting from a single extraction, may be used with advantage in the denaturing of organic liquids, such as alcohols and esters.

The extracts of petroleum derived by treating petroleum with sulphur dioxide contain unsaturated, aromatic, and sulphur containing bodies in greater amounts than are normally present in petroleum oil. It has been discovered that these aromatic, unsaturated and sulphur bearing oils are of value in denaturing organic liquids, such as alcohols. The extracts of petroleum obtained by treating petroleum with sulphur dioxide contain a wide range of boiling points and, therefore, can not be removed from organic liquids, such as ordinary alcohol, by normal processes 'of distillation and rectification. Petroleum oil generally is not sufficiently miscible with alcohol, especially in dilute form, to be fully satisfactory as a denaturant. It has been found, however, that these sulphur dioxide extracts of petroleum are much more miscible with alcohol both in concentrated and relatively dilute form. The sulphur dioxide extracts have also a distinctive odor and a disagreeable taste in excess of that of petroleum oils generally, but preserve approximately the same non-toxic properties. These points render sulphur dioxide extracts more suitable than regular petroleum oils for use as alcohol denaturants or as denaturants of other organic liquids.

It is a general object of the present invention, therefore, to provide an organic liquid denatured through the use of a sulphur dioxide extract of petroleum.

It is further found that sulphur dioxide extracts of petroleum are useful in denaturing alcohols as solvents or diluents for other denaturants. Thus, in denaturing alcohols with the acid oils derived from the sulphuric acid sludges of petroleum, as described in the co-pending application of William H. Hampton, Serial No. 508,369, filed January 12, 1931, it is frequently desired to add a diluent. We have discovered that sulphur dioxide extracts of petroleum may be used asa diluent and solvent for these acid oils in connection with their use as organic liquid denaturants.

The present invention, together with various objects and advantages thereof will best be understood from a description of a preferred form or forms of products embodying the invention. For this purpose, there is hereafter described a preferred form of denatured alcohol and process of producing the same.

In one example of the invention, a crude pressure naphtha obtained from the pyrogenetic cracking of California fuel oil was first topped or reduced to a 200 F. initial boiling point. This topped pressure naphtha was treated with twice its volume of liquid sulphur dioxide, according to the ordinary Edeleanu method. The topped naphtha before treatment had the following characteristics:

Gravity A. P. I 47.3 Initial boiling point 208 F. 20% 250 F. 50% 280 F. 30 90% 386 F. Final boiling point 506 F. Per cent sulphur .73 C/H ratio 85.l0/l3.27 Miscibility with an equal volume of 95% ethyl alcohol Complete above 87 F.

After contact of such topped crude pressure naphtha with'sulphur dioxide, the hydrocarbon and liquid sulphur dioxide layers are separated. The liquid sulphur dioxide layer was then heated 90 for evaporation of its sulphur dioxide content, and there was secured as an extracted product an oil equal to 68.5% of the original naphtha treated.

This extract had the following properties:

' It will be seen that the extracted product be-' cause of its greater alcohol solubility and the concentration of aromatic, unsaturated and sulphur compounds is an excellent material for use in denaturing alcohols and may be added for that 110 purpose to alcohol in amounts up to 5%. It is difficult or impossible to separate by distillation, and when added to 95% alcohol in 1 ,5 percentage,

a denaturant for alcohol may also be used for denaturing other organic liquids, such; for example, as ethyl esters, in which case it may be used in .amounts as low as one-eighth of 1%, by volume.

It also may be used in combination with other denaturing materials for organic liquids. For example, the acid oils derived by hydrolysis of acid sludge resulting-from the sulphuric acid treatment of petroleum which are in themselves excellent denaturing materials.

For example, by treating gasoline or kerosene distillates with concentrated sulphuric acids a sulphuric acid sludge is formed, which when hydrolyzed in a retort under temperature and pressure, for example 290 F. and 20 lbs. pressure, will yield an acid in one layer and an acid oil or tail as an upper layer. This acid oil or tail, preferably re-distilled to give av fraction of desired range of boiling points, preferably boiling between say 100 F. and 450 F., although in certain cases higher and lower boiling points may be ineluded, has been found to be a most effective denaturant due principally to the relatively high content of sulphur bodies which are in the neighborhood of 5 to 10%. It is frequently desirable with these denaturants derived from acid sludge to use a diluent. When ordinary petroleum oil is employed as a diluent, turbidity appears upon addition of water when the strength of the alcohol is reduced to 15%.

By employing the sulphur dioxide extracts of petroleum, it is found that no turbidity appears in the denatured alcohol until the strength of the alcohol is reduced to about While the aforementioned product derived.

from extracting a light petroleum oil once with sulphur dioxide is an excellent denaturant, either alone or in combination with other denaturants, it has been discovered that a denaturant of still superior properties may be derived by first subjecting the extract to further treatment before it is used as a denaturant.

For this purpose, the extract thus obtained may be blended with an equal proportion of a refined oil. The refined oil is of a different range of boiling points than the extract. The mixed refined oil and sulphur dioxide extract is then treated with twice its volume of liquid sulphur dioxide. Upon settling, there is secured a separation of hydrocarbon and liquid sulphur dioxide layers. The liquid sulphur dioxidelayer is separated from the hydrocarbon and treated for the removal of the sulphur dioxide, thereby producing an extracted product of petroleum. When this extracted product is re-distilled to secure substantially the same boiling point range as the original pressure naphtha, ,a yield of 37.6%of extracted and re-distilled product is obtained, which'upon neutralizing possess the following properties:

Gravity A. P. I 36. 3

Initial boiling point 257 F.

20% 299 F. 50% 366 F. 90% 403 F.

Final boiling point 447 F. Per cent sulphur 1. 93 C/H ratio 87. 1/11. 9 Miscibility with an equal portion of 95% ethyl alcohol Complete above 58 F. A product obtained by this double extraction contains a further degree of concentration of unsaturates and aromatics. It has greater alcohol solubility, and when used as a denaturant of alcohols the alcohol will stand a greater water dilution before turbidity appears.

In addition to the use of the extracts obtained by these double extraction processes described, the extract maybe subject to one or more additional extractions with sulphur dioxide-in a likemanner to that described in connection with the second extraction. The alcohol solubility of the prodnot and the concentration of aromatic, unsaturated and sulphur compounds will correspondingly increase andthe value of the product as a denaturant for alcohols or other organic liquids will also increase.

It is not necessary in producing the sulphur di oxide extract to be used in the denatured alcohol that one start with a naphtha or gasoline cut of petroleum, as certain kerosene distillates may also be employed and yield extracted oils of value as a denaturant.

While the particular denatured organic liquids herein described and the process of producing the same are well adapted to carry out the objects of the present invention, it is to be understood that various modifications and changes may be made without departing from the principle of the invention, as set forth in the appended claims.

1. A denatured alcohol or ester containing the extracted oils derived by the sulphur dioxide extraction treatment of petroleum oils, said oils containing organic sulphur bodies and a relatively large amount of unsaturated and aromatic constituents.

2. A denatured alcohol containing hydrocarbon oil as a denaturant containing a high carbon to hydrogen ratio and consisting largely of unsaturated and aromatic constituents, said denaturant being the extracted oil derived from the extraction of petroleum oil with sulphur dioxide.

3. A denatured alcohol or ester containing as a denaturant an extract ofpetroleum oil containing a high carbon to hydrogen ratio and consisting largely of unsaturated and aromatic constituents, said extract being derived from ex- 1 stituents, said extract being derived from extracting petroleum oil with sulphur dioxide, the petroleum oil extracted havinga low range of boiling points.

5. A denatured alcohol comprising as a denaturant the extracted unsaturated and aromatic oils derived from a sulphur dioxide treatment of kerosene or gasoline fractions of petroleum, said denaturantv oils containing organic sulphur bodies and having a boiling point range such that they cannot be removed from alcohol by ordinary distillation.

6. A denatured alcohol containing as a denaturant the extracted oils derived from the sulphur dioxide treatment of kerosene or gasoline fractions of petroleum, said denaturant oils containing large percentages of unsaturated and aromatic bodies and sulphur bodies, said denaturant oils having a. boiling point range such that they can not be removed from alcohol by distillation,

said denaturant oils also being inseparable from alcohol by refrigeration and filtering agents. h 7. A denatured alcohol including as a denaturant the extracted oils derived from the extraction with sulphur dioxide of the extracted petroleum oils which are derived fromextraction of petroleum with sulphur dioxide.-

8. A denatured organic liquid containing as a denaturant the extracted oils derived from a process of extracting petroleum oil with sulphur dioxide, the petroleum oil being the extracted oil resulting from a previous process of extracting a petroleum oil with sulphur dioxide.

CERTIFICATE Patent No. l, 649, 244.

WILLIAM N.

9. A denatured alcohol or ester including as a denaturant the extracted oils derived from a process in which petroleum oil is first extracted with sulphur dioxide, and the extracted fraction is thereafter again extracted from sulphur dioxide, the denaturant oils being the extracted prodnot of the second extraction.

WILLIAM N. DAVIS. JOHN T. RUTHERFORD.

or coRinzc'tioN.

February 27, 1934.

DAVIS, ET AL.

It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows:

Page 2, line 33, for

"15%" read and that the said Letters Patent should be read with this correction therein that the same may conform to the record of the case in the Patent Office.

Signed and seaied this 15th day of May, A. D. 1934.

(Seal) Bryan M. Battey Acting Commissioner of Patents.