Simultaneously with the work in the field of synthetic acids BN Tobacco studied natural naphthenic acids – their compounds, properties and the possibility of their rational use. The ratio of naphthenic acids to different oxidants was studied. It has been shown that in known cases naphthenic acids during oxidation form polynaphthenic acids, which in their properties are similar to “hydroxy acids” obtained during the oxidation of petroleum hydrocarbons by air. The mechanism of oxidative condensation was discovered and it was stated for the first time that “polynaphthenic” acids are oxidation products of naphthenic acids.
At about the same time, on the basis of observations of the oxidation of petroleum hydrocarbons, the position was expressed about the formation of natural naphthenic acids by slow oxidation of hydrocarbons by air. This possibility was further confirmed by a study of the crust formed on sodium metal, which contained a large number of “polynaphthenic” acids and fewer liquid soluble in gasoline naphthenic acids. A separate study performed by BN Tyutyunnikov and his colleagues were able to establish that in the acids of solar oil of Baku oil and soap oil of Maikop oil, the carboxyl group is at the end of the side chain. At the same time, the effect of nitric acid and aluminum nitrate on naphthenic acids was studied, and the formation of nitro compounds was shown.
In this regard, an attempt has been made to use this fact to prove the presence of naphthenic acids in a mixture with fatty acids that do not give such compounds.The same group of works includes the study of the possibility of using naphthenic acids as raw materials for the manufacture of fact and the detection of the presence of strong dehydrogenation of them (acids) under the influence of sulfur with the formation of carbon powder. For the analysis of soap, in the manufacture of a number of varieties of which naphthenic acids were readily used, the laboratory developed a method for their qualitative and quantitative determination in a mixture with fatty and resin acids. A method based on their saturation and some properties of their copper salts has been developed for the qualitative determination of naphthenic acids.
The use of naphthenic acids for some technical purposes has been successful. For example, on the basis of sodium soap of naphthenic acids B.N. Tyutyunnikov and his staff developed a special anti-emergency lubricant in the mid-1930s to prevent the “burning” of car axles, which was used with great success on a number of Union railways. Good results of naphthenic acid soap were given when used as a temporary binder in the manufacture of some special ceramic materials.
The study of employees of the Department of Fat Technology was the study of drying of fatty oils and drying oils. It is possible to specify an estimation of the newest methods of definition of purity of vegetable drying oils. B.N. Tyutyunnikov studied the process of cracking oil paints in the wet state. Professor Eibner’s explanation of this phenomenon due to the formation of volatile oxidation products was shown to be incorrect.
A colloid-chemical explanation of the process associated with the change in oil volume during oxidation and coagulation of the colloidal solution was given. This work in 1935 was awarded the prize. F.E. Dzerzhinsky. A substitute for Chinese tung oil was invented. The latter was prepared from castor oil by cleavage of water from it in the presence of a complex catalyst that prevents polymerization. The acylglycerols of the linoleic acid isomer, which has conjugated double bonds, are formed.
Special work has revealed the full suitability of this product for painting the underwater part of ships. In the field of fat hydrogenation investigated B.N. Tyutyunnikov order and characteristics of the main and adverse reactions occurring in the autoclave, the composition of the catalysts and some technical issues. From works in the same area it is necessary to note research, the order of change of structure of acids of sunflower oil in the conditions of factory hydrogenation that showed failure of the theory of formation (at hydrogenation) of so-called isooleic acids.
A study conducted in the early 1930s showed the possibility of converting oleic acid to a solid isomer under the influence of heating in an atmosphere of carbon dioxide and in the presence of nickel. Extremely severe corrosion of autoclaves was observed at the Slavic Hydrogenation Plant. Investigations of the causes of corrosion led to the finding of the formation in the autoclave of formic and acetic acids, and their corresponding aldehydes and methyl alcohol.
The study of this process in the laboratory (B.N. Tyutyunnikov, A.S. Chernichkina, 1935) showed that the source of the formation of these substances is acrolein, which under the action of moisture gives the above aldehydes, from which acids are formed by the Cannitsaro reaction. The study (B.N. Tyutyunnikov and I.I. Sorokin, 1936) of the regime of purification of circulating hydrogen at the same plant made it possible to draw a conclusion about the rational construction of an appropriate treatment system, and also noted the restoration of autoclaves not only carbon monoxide to methane, but also carbon dioxide, as well as the formation of a number of volatile products. Much attention was paid to the study of fat hydrogenation catalysts.
Thus, in particular, B.N. Tyutyunnikov developed a special catalyst, activated sulfur nickel, which in hydrogenation under pressure converts glycerides of linoleic acid only into oleic glycerides and thus allows the production of artificial olive oil from more unsaturated oils. A team of laboratory staff took part in the transition of the Slavic Hydrogenation Plant to work with an ant-nickel salt catalyst. A method of hydrogenation of phenol has been developed and a rather favorable effect of the hexalin obtained on the detergency of soap solutions has been shown. The composition of various oils of domestic origin that have technical significance or represent greater prospects for use was studied.
Of particular interest was the study of milk thistle oil, which found that its “poisonous” properties are due to the presence of a substance similar to croton resin. Continuation of the study showed the presence of another crystalline, waxy substance in the oil. A method of refining milk thistle oil was developed to remove the specified toxic substance from it. Much attention was paid to theoretical and practical issues of soap making. The main areas of work were to clarify the conditions for obtaining soap with maximum consumer value and to summarize the scientific and theoretical basis for the production and consumption of detergents. From them it is possible to note the following: emulsifying ability of various soap solutions in various temperature conditions and influence of impurity on it.
Next, the ability of soap solutions to wash away oily contaminants was studied in the designed device. These works have led to the conclusion that it is impossible to characterize the value of the detergency of the soap solution by one value of their surface tension, as some researchers have often suggested. At the same time, these studies have shown that the ability to wash oil in naphthenic and especially rosin soaps is negligible. Given the great importance given by the consumer and soap makers to the value of the foaming ability of soap solutions, as an indicator of the value of soap, a study of this ability was performed in a specially designed device. The study yielded a number of interesting observations: it showed the low foaming ability of rosin soaps and the ability of baking soda to increase it in rosin and reduce it in fatty soaps. B.N. Tyutyunnikov, Н.А. Kasyanova, A.A. Hirschman et al., 1930-37 the composition and structure of soap solutions were studied. This is an extremely important issue, as the structural ingredients of the latter must determine the relevant properties of soap solutions that underlie their detergency. Until recently, the scientific literature was dominated by the idea of a relatively small degree of hydrolysis in soap solutions, based on the work of McBen and his colleagues.