Patented Dec. 3, 1940 I UNITED STATES 7 I 2,22a,79o or y DENATURED aLconoL comosr'rron Paul Mahler, New York, N. Y, and can Haner,
Moylan, Pa., assignors to Publicker, Inc., Philadelphia, Pa., a corporation of Delaware No Drawing.
Application October 15, 1937, Serial No. 169,256
7Claims. ((1202-77) g The present invention relates to certain-new and'u'seiul denatured alcohol compositions and it relates more particularly to denatured alcohol compositions which will be more resistant to commercially feasible clean-up" least in part, suflicient to impart to the resultantalcohol a characteristic taste and/or odor sumcient to make it unfit for beverage purposes.
Denaturants belonging to certain separate organic groups have been found to have certain inherent weaknesses whenused by themselves, which may react uniavorablyto their individual use.
eflect of a given amount or proportion of any member ot-one class orgroup, isjgreater when associated with one or more members of another class or group of compounds than'when it is used by itself. Thus,.in the case of certain aldeh'ydes, a rather pungent odor is imparted which may at times be objectionable and furthermore the residual odor on evaporation lasts longer than might be desired for certain uses. In the case of the nitriles, larger quantities impart a somewhat disagreeable odor to the alcohol which may be objectionable for some commercial uses. Ketones in general impart an aromatic odor and taste to the rectified alcohol which isnot as strong a protection against its illicit use than if the taste were objectionable. These weaknesses can be overcome byv the herein disclosed combination of. two or more materials, 'each' of which possesses distinctive denaturant qualities that in combination greatly reduces the objectionable features of the individual materials. y
We have found, according to the present invention, that by combiningmembers of dlii'erent chemical groups or or different chemical families,
' as for instance, an aldehyde and a saturated 'ketone-such as methyl isobutyl ketone, and an I unsaturated ketone such as mesityl oxide, and a nitrile produces a composition, when combined with ethyl alcohol, which will possess advantages not possessed by a composition containing ethyl alcohol and only one of these other compounds. Whereas each of the materials or compounds proceduresg than any one compound or compounds belong Moreover, we have found that the denaturant used in the denatu ring mixture is a good 'de-. naturant when employed in the proportion of- PATENT; oFliters} from one totwo parts'to one hundred parts of 1 alcohol, it does not necessarily follow that the same denaturant when used in the proportion found in the, mixture would either adequately protect the alcohol or give it the desired char acteristics 'Io r commercial uses. However, the combination of the compounds as found in the composition is an effective denaturant. To'illustrate: a denaturantcomposition consisting or five parts butyraldehyde, sixty-three partsv methyl .isobutyl' ketone and thirty-two parts, mesityl oxide is very efle'ctive as a denaturant when used in the proportion or two parts to onehund'red parts of alcohol. However, an alcohol denatured with 5" part of the aldehyde alone (the actual amount of aldehyde in the denaturlngcompositionl would be ineffective. An alcohol denatured with 1.26 parts methyl risobutyl ketone alone would impart'a very pleasant odor and taste 'to the recovered spirit and an. alcohol denatured with 0.64 part of mesityl oxide alone might not give a properly denatured alcohol. However, the
combination of the three materials used in the above proportions produces an alcohol which appears to be better denatured than any heretofore obtained.
It is believed, and experiments seem to verify this belief, that an excess denaturant produces no beneficial results. This is sobecause after. the various physical clean-up" treatments, the only efiective quantity'ofthe materials is that which remains in the diluted alcohol solution, the rest having been thrown out and removed by the solvents. Therefore, thereis nothing to be gained by increasing the amount oi the denaturant above the quantity which will remain in solution. This has been verified in several in- The denaturing efiect or. a mixture containing two or more components appears to be effected 1 by the relative proportions of these components in thedenatured alcohol composition. Thus, a mixture made up of 50%. butyraldehyde, 12 95 What the minimethyl isobutyl ketone, and it'l mesityl oxide is not nearly as effective as one containing 5%,
63%, and 32%, respectively, of these components, a
even though two parts of both denaturing mixtures are used (in relation to one hundred parts of alcohol). We believe this'behavior to be-due to the materials remaining in the aqueous solution distilling as an azeotrope. However, it is not unlikely that changing the proportions oi these components may also affect their respective solubilities in the aqueous alcohol solution. Either or both of these effects may be responsible for the peculiar change in the denaturation of mixtures composed of the same materials but of different proportions.
There is another class of denaturants which may be varyingly affected by the type of chemical treatment employed in the bootleg clean-up." As an example, allyl cyanide, while in itself a very oflective denaturant, may be changed very appreciably by the type of chemical treatment to which it is subjected. The most pronounced change is produced when permanganate is used as an oxidant. In this case, the characteristic offensive taste of the cyanide or nitrile is eliminated and instead of it,-one can unmistakably notice the presence of the inorganic cyanide. Other oxidizing agents appear to have similar effects but to nowhere near the same extent as permanganate. It is believed that materials belonging to the saturated aldehydes or ketones are not aii'ected by these treatments but unsaturated materials may very likely undergo such a change.
A further advantage is gained by the hereindisclosed combination of denaturants, in that such combination makes the possible cleaningup" of such a denatured alcohol composition, by any series of chemical or physical means, very much more difllcult than if the alcohol were denatured with any single compound or compounds belonging to this same group.
In combining individual denaturing compounds, the resultant alcohol solution (before the final fractional distillation) will contain a mixture of the desired azeotropic distillation characteristics or several azetropes. By this combination, one may obtain a'recovered alcohol far 40 more protected than if it had been denatured originally with a quantity of anyone of the several components equal to the proportionate amount found in the combined mixture.
Thus, we have found that two parts of the fol- 45 lowing denaturant mixtures when added to-one hundred parts of ethyl alcohol, of the usual commercial concentration, will resist any of the commercial feasible cleaning-up processes:
Example No.1.33 each of isovaleraldehyde, pinacolone and allyl cyanide Example No. 2.-50% 'isovaleraldehyde 37 /2% mesityl oxide 12 methyl isobutyl ketone Example No. 3.-'70% pinacolone v methyl isobutyl ketone 10% mesityl oxide 5% isovaleraldehyde It will be noted thatthe compounds of each 0 composition belong to diiferent chemical families, as for instance, an aldehyde on one hand;- a saturated ketone on the other hand, as for instance, methyl isobutyl ketone, an unsaturated ketone, like mesityl oxide;a nitrile like allyl cyanide, ethyl cyanide, iso and normal butyl cyanide and iso and normal amyl cyanide, and an aldehyde like isovaleraldehyde. In place of the valeraldehyde, we may utilize propionaldehyde, butyraldehyde, normal valeraldehyde, or an unsaturated aldehyde such as crotonaldehyde.
Similar equivalents for the saturated and unsaturated ketones may be used.
hereby claimed as new and desired to be secured by Letters Patent, is:
'1. A denatured alcohol composition including ethyl alcohol and small proportions of a generally pure aliphatic aldehyde having from three to six carbon atoms and generally pure mesityl oxide.
2. A denatured alcohol composition including ethyl alcohol and small proportions of a generally pure aliphatic aldehyde having from three to six carbon atoms and a generally pure nitrile having from three to six carbon atoms and a generally pure ketone.
3. A denatured alcohol composition including ethyl alcohol, and generally pure butyraldehyde, methyl isobutyl ketone, and mesityl oxide;the combined denaturant compounds being in the proportion of more or less approximately one to two parts, by volume, to one hundred parts of ethyl alcohol of commercialconcentration.
4. A denatured alcohol composition including ethyl alcohol, and generally pure butyraldehyde, mesityl oxide and methyl isobutyl ketone;the combined denaturant compounds being in the proportion of more or less approximately one to two parts, by volume, to one hundred parts of ethyl alcohol of commercial concentration.
5. A denatured alcohol composition including ethyl alcohol, and generally pure pinacolone, methyl isobutyl ketone, mesityl oxide and butyraldehyde;the combined denaturant compounds being in the proportion of more or less approximately one to two parts, by volume, to one hundred parts of ethyl alcohol of commercial concentration.
6. A denatured alcohol composition including ethyl alcohol, and generally pure butyraldehyde, mesityl oxide and methyl isobutyl ketone;-the combined denaturant compounds being in the proportion of more or less approximately one to two parts, by volume, to one hundred parts of ethyl alcohol of commercial concentration, and the denaturant compounds being in the ratio to each other of more or less approximately 50% of butyraldehyde, more or less approximately 37 /2 of mesityl oxide, and more or less approximately 12 /2 of methyl isobutyl ketone (all by volume).
7. A denatured alcohol composition including ethyl alcohol, and generally pure pinacolone, methyl isobutyl ketone, mesityl oxide and butyraldehyde; the combined denaturant compounds being in the proportion of more or less approximately one to two parts, by volume, to one hundred parts of ethyl alcohol of commercial concentration, and the denaturant compounds being in the ratio to each other of more or less approximately 70% pinacolone, more or less approximately 15% methyl isobutyl ketone, more or less approximately 10% mesityl oxide, and more or less approximately 5% butyraldehyde (all by volume).
PAUL MABLER. CARL HANER