US2017391A - Insecticidal and fungicidal composition - Google Patents

Description

Patented a. is, 1935 oomosrrron Arthur George Vale Berry, Pifinte-a-Pierre,

Trinidad, British West Indies, assignor to Trinidad Leaseholds, Limited, London, England N o Drawing. Application December 22, 1933, Serial No. 703,666. In Great Britain November 13Claims. (Cl. 167-22) This invention relates to compositions adapted to be used as insecticides and fungicides and otherwise for agricultural and horticultural purposes.

The invention consists, broadly, in a composi-, tion containing phenolic compounds and/or mercaptans derived from alkaline wash liquors which have been employed in the refining of crude hydrocarbon oils of a character yielding products suitable for use as fuels in internal combustion engines which expression is used herein as a generic expression meaning petroleum oils, shale oils, peat. oils, lignite oils and theJike and'particularly cracked petroleum oils by acidification of such. wash liquors and alkaline metal. polysulphides in association with agents adapted to promote the emulsification of the phenolic compounds and/or mercaptans in water.-

Normally, in accordance with the invention, the compositions will contain salts of naphthenic acids which may function as emulsifying agents and optionally also other bodies,-for instance, soaps adapted to function in the like capacity.

The invention, further, consists in the process of producing compositions adapted for the purposes above indicated which comprises dissolving free or elemental sulphur in the product obtained by acidifying the alkali wash liquors which have been employed in the refining of hydrocarbons, separating the oily layer containing, the acidic bodies from the aqueous layer and treating the oily layer, if necessary, with a weak alkali in order to convert the naphthenic acids into their corresponding salts and dissolving therein free or elemental sulphur. r

The salts of naphthenic acids present in the composition will function as an emulsifying agent but additional emulsifying agents, for instance,

soaps of fatty or resin acids may be incorporated in the composition.

The alkaline wash liquors employed in carrying the invention into eflfect obtained in the refining of hydrocarbons may be such as are derived from the treatment of the hydrocarbons with aqueous solutions of alkali, for instance, caustic soda alone or similar aqueous solutions in which litharge has been dissolved.

when the spent alkaline wash liquors are acidifled by a strong acidsuch as sulphuric acid or hydrochloric acid the oily material separated will contain naphthenic acids as such. If, however,

the spent wash liquors are treated with weaker acids. such, for example, as. carbon dioxide or sulphuretted hydrogen, the salts of the naphthenic acids will not be decomposed to mappreciable extent but the other acidic bodies,

namely, the phenols and/or mercaptans will be liberated and will separate-as a more or less oleaginous product. containing a substantial amount of the salts of naphthenic acids. 5

Where. the spent wash liquors are acidified by strong acids, for example sulphuric acid, the oily material separating will, as stated, contain 'naphthenic acidsin the .free-stateand the ofls separating maybe washed with, for instance, a 9 small proportion of water tolremove inorganic salts and free sulphuric acid and, thereafter, neutralized with an excessof a solution of a weakalkali such as, for example, sodium carbonate in order toconvert the naphthenic acids into their corresponding salts or soaps.

.As these salts or soaps functionas emulsifying agents they will promote the eniul'sification of those organic acidic compounds's ich as phenolic compounds and/or mercaptans which were present in the oily material and whichuemain substantially assuch after. the addition of the solution of weak alkali, for example, sodium car-. bonate.

At this point it is to be remarked that when the procedure above described is applied to the treatment of spent wash liquors obtained by treating hydrocarbon material with solutions of alkaliin which litharge has bee'ndissolved, the acidic organic oil will. be substantially free from mercaptans and like sulphur compounds.

. The oily material obtained in the manner above described is allowed to settle whereby the aqueous liquid in excess of that capable of being held in the form of anemulsion with the phenolic bodies I or mercaptans. present will separate out and removed. The residual oily material left is a clear homogenous productwhich, however contains a considerable proportion and in some cases up to 50 per cent. of aqueous material which does-. not separate even on prolonged standing.

In the material constituting the upper layer and which consists essentially or phenolic compounds and/or merc'aptans with naphthenic acid salts, water and a proportion of an. alkali, a proportion of free or elemental sulphur is dissolved, the solution thereof being promoted by agitation.

Optionally, also heating to a temperature not exceeding 50 to C. to promote the solu on of the sulphur may be resorted to. I,

The product obtained when the required amountv of sulphur has been dissolved, tends "to deposit an aqueous layer varying in amount ac-sg cording to the proportion of naphthenic acid present in the form of itssalts.

The product, as a whole, may be used in any of the capacities or for any of the purposes above indicated on dilution with water to the desired concentration. If, however, the product separates too readily from' water or if, for instance, the proportion of the aqueous layer separating out is considered to be excessive a further quantity of a suitable emulsifying agent may be added to prevent such separation and to enable on dilution a suitable emulsion adapted to be used as a spraying fluid to be obtained. 3

Where the spent alkaline wash liquors are treated with weaker acids such, for instance, as .carbon dioxide which may be used in the form of flue gases, the naphthenic acids will be present in the material initially separated in the form of water-soluble soaps, while the other acidic organic compounds such as the phenolic compounds and/or mercaptans. will be present in the free state. The product separating in this case corresponds more or less with the product obtained in the manner previously described after treatment thereof with weak alkalies, that is to-say, a

considerable proportion of aqueous material will be retained in the oily layer, the excess being in an emulsified form and separating out as a bottom layer on standing.

The aqueous material so separating is a solution of salts of the alkali originally present in the wash liquor with the acids used for precipitation and will consist, for example, of sodium carbonate and sodium bicarbonate and is removed from the undissolved supernatant liquid in which there is then dissolved free or elemental I sulphur in a manner generally as described above. If neces sary, in this case also additional emulsifying agent may be added to homogenize to some extent the layer of the aqueous material and the upper oily layer which tends to separate when the sulphur has been dissolved.-

Furthermore, additional emulsifying agent may be added to prevent separation of oil when the product is diluted with water to concentrations in which it may be employed'as a spraying fluid.

The final product obtained by either of the pro-- cedures described above is a concentrated emulsion or solution of organic acidic compounds, naphthenic acid salts, alkali metal polysulphides and water, together, in some cases with additional emulsify agent.

The additional emulsifying agent may be a further .quantity of alkali metal salts of naphthenic acids, for instance the sodium salts thereof, or soaps containing the fatty acids derived.

from animal or vegetable oils or fats. In many cases, however, it is not essential to produce a product which forms a very perfect emulsion, in fact, in practice it has been found that a small percentage of separated aqueous solution consisting substantially of a solution of sodium polysulphides is an advantage, in that the fungicidal value of the product is thereby improved.

The quantity of emulsifying agent added, therefore, is not necessarily that required to produce a perfectly homogenous product on dilution.

The concentration of phenolic bodies and/or mercaptans in the final product may be varied. In many cases it is found desirable in order to obtain products of increased toxicity toadd an additional proportion of such phenolic bodies and/or mercaptans obtained by treating the wash liquors with acid to the products obtained as above described as it appears that the phenolic bodies or mercaptans are themselves more toxic to insects and other pests or certain: of them than the same product after dissolving sulphur in it.

Compositions in accordance with the invention Q may also beformed from the phenolic and sulphur 5 function as, emulsifying agents, must be mixed with a proportion of the salts of such acids alone or in association with other emulsifying agents and the'mixture thereafter treated in order to cause free or elemental sulphur to become dissolved in the mixture.

Altematively, proportions of the phenolic or sulphur-containing bodies obtained in accordance with the procedure described in the said specification may be added to compositions produced in the manner indicated in the preceding examples.

Generally it may be stated that an'increase in the proportion of phenolic-bodies derived .from the alkaline wash liquors in the final product is desirable for the reason that such phenolic bodies are extremely toxic to insects and they, furthermore, operate to reduce the tendency of the polysulphides to separate with the result that on dilution of the compositions with water emulsions are obtained having a better colour and appearance than are obtainable when similar composi- 0 tions containing a lower proportion of phenolic bodies are diluted.

Having now described my invention, what I claim as new and desire to secure by Letters Patent is:--

l. The process of producing compositions adapted to beiused as insecticides and fungicides and otherwise for agricultural and horticultural purposes which comprises dissolving free sulphur in the product obtained by acidifying alkali wash 4' liquors which have been employed in the refining of crude hydrocarbon oils of a character yielding products suitable for use as fuels in internal combustion engines, separating the oily layer containing the acidic bodies from the aqueous layer and treating the oily layer, if necessary, with a weak alkali in order to convert the naphthenic acids into their corresponding salts. 1

2. The process of producing compositions adapted to be used as insecticides and fungicides and otherwise for agricultural and horticultural purposes which comprises dissolving free sulphur in the product obtained by acidifying the alkali wash liquors which have been employed in the I refining of crude hydrocarbon oils ofacharacter 55 yielding products suitable for,use as fuelsvin internal combustion engines, separating the oily layer containing the acidic bodies from the aqueous layer and treating the oily layer, if necessary, with a weak alkali in order to convert the naphthenic acids'into their corresponding salts adding further emulsifying agents and dissolving therein free sulphur. v

3. The process of producing compositions adapted to be used as insecticides and fungicides and otherwise for agricultural and horticultural purposes which comprises acidifying the alkali wash liquors. which have been employed in the refining of crude hydrocarbon oils of acharacter yielding products suitable for use as fuels in inwith a weak alkali in order to convert the naph- .f

4. The process of producing compositions adapted to be used as insecticides and fungicides and otherwise for agricultural and horticultural purposes which comprises-acidifying the alkali wash liquors which have been employed in the refining of crude hydrocarbon oils of a character yielding products suitable for use as fuels in internal combustion engines, separating the oily layer containing the acidic bodies from the aqueous layer and treating the oily layer, if necessary, with a weak alkali in order to convert the naphthenic acids into their corresponding salts adding a proportion of acidic organic compounds consisting of phenolic bodies and dissolving therein free sulphur.

5. The process of producing compositions adapted to be used as insecticides and fungicides and otherwise for agricultural and horticultural purposes which comprises acidifying the alkali wash liquors which have been employed in the refining of crude hydrocarbon oils of a character yielding products suitable for use as fuels in internal combustion engines, separating the oily layer containing the acidic bodies from the aqueous layer and treating the oily layer, if necessary, with a weak alkali in order to convert the nap'thenic acids into their corresponding salts adding a proportion af acidic organic compounds consisting of phenolic bodies and mercaptans and dissolving therein free sulphur.

6. The process of producing compositions adapted to be used as insecticides and fungicides and otherwise for agricultural and horticultural purposes which comprises acidifying the alkali wash liquors which have been employed in the refining of crude hydrocarbon oils of a character yielding products suitable for use as fuels in in- .ternal combustion "engines, separating the oily layer containing the acidic bodies from the aqueous layer and treating the oily layer, if necessary, with aweak alkali in order to convert the naphthenicacids into their corresponding salts adding a further proportion of acidic organic compounds consisting of phenolic bodies, mercaptans and salts of naphthenic acids and dissolving therein free sulphur.

7. The process of producing compositions adapted to be used as insecticides and fungicides and otherwise for agricultural and horticultural purposes which comprises acidifyingthe alkali wash liquors which have been employed in the refining of petroluem oils, separating the oily layer containing the acidic bodies from ithe aqueous layer and dissolving therein free sulphur.

8. The process of producing compositions adapted to be used as insecticides and fungicides and otherwise for agricultural and horticultural purposes which comprises dissolving free sulphur inthe product obtained by acidifying the alkali wash liquors which have been employed in the refining of petroleum oils, separating the oily layer containing the acidic bodies from. the aqueous layer and treating the oily layer, if necessary, with a weak alkali in order to convert the naphthenic acids into their correspondling salts adding further emulsifying agents.

9. The process of producing compositions adapted to be used as insecticides and fungicides and otherwise for agricultural and horticultural purposes which comprises acidifying the alkali wash liquors which have been employed in the refining of petroleum oils, separating the oily layer containing the acidic bodies from the aqueous layer and treating the oily layer, if necessary, with a weak alkali in order to convert the naphthenic acids into their corresponding salts adding a soap and dissolving therein free sulphur.

10. The process of producing compositions adapted to be used as insecticides and fungicides and otherwise for agricultural and horticultural purposes which comprises acidifying the alkali wash liquors which have been employed in the refining of petroleum oils, separating the oily layer containing the acidic bodies from the aqueous layer and treating the oily layer, if necessary, with a weak alkali in order to convert the naphthenic acids into their corresponding salts adding a proportion of acidic organic compounds consisting of phenolic bodies and dissolving therein free sulphur.

11..I'he process of producing compositions adapted to be used as insecticides and fungicides and otherwise for agricultural and horticultural purposes which comprises dissolving free sulphur in the product obtained by acidifying the alkali Wash liquors which have been employed in the refining of petroleum oils, separating the oily layer containing the acidic bodies from the aqueous layer and treating the oily layer, if necessary, with a weak alkali in order to convert the naphthenic acids into their corresponding salts adding a proportion of acidic organic compounds consisting of phenolic bodies and mercaptans.

12. The process of producing compositions adapted to be used as insecticides and fungicides and otherwise for agricultural and horticultural purposes which comprises dissolving free sulphur in the product obtained by acidifying the alkali wash liquors which have been employed in the refining of petroleum oils, separating the oily layer containing the acidic bodies from the aqueous layer and treating the oily layer, if necessary, with a'weak alkali in order to convert the naphthenic acids into their corresponding salts adding a proportion of acidic organic compounds consisting of phenolic bodies, mercaptans and salts of naphthenic acids.

13. The process of producing compositions adapted to be used as insecticides and fungicides and otherwise for agricultural and horticultural purposes which comprises dissolving free sulphur in the product obtained by acidifying the alkali wash liquors whichv have been employed in the refining of cracked petroleum oils, separating the oily layer containing the acidic bodies from the ,aqueous layer and treating the oily layer, if necessary, with a weak alkali in order to convert the naphthenic acids into their corresponding salts.