Methods of the combusting and processing of Israeli oil shale (higher heating value 1150 kcal/kg, oil yield 5-6 %), and shale oil (sulphur content 5-7 %) are described. Oil shale is the only source of energy and only organic natural resource in Israel. Its reserves are of about 12 billion tons.
Methods of ichthyol production from the Israeli shale oil are investigated. Ichthyol (ichthammol) is an anti-inflammation and analgesic remedy, used for curing skin diseases.The scheme developed includes the following steps: purification of the oil fraction; sulfonation ofthe fraction; neutralization of the sulfonic acids by ammonium hydroxide; purification of the crude ichthyol. The ichthyolyield is 170--250 % of the initialfraction (75-120 %of the total oil). The ichthyol obtained meets requirements of the British Pharmacopoeia. Simplicity of the synthesis, high yield, and high price for ichthyol make its production economically favourable.Ichthyol (it is also called ichthammol, etc.) is an anti-inflammation and analgesic remedy, obtained from shale oils. It is applied for curing skin diseases such as eczema, ulcers, furuncles, etc. It is used in creams, ointments, bandages, and lotions, often with zinc oxide. Different remedies of ichthyol type are used now in Germany, Spain,
A plasticizer obtained from high-sulfur shale oil (S content 6.5 %) was investigated as an additive for тфег compounds in quantities of 15 and 30 % on medium-high acrylonitrile -butadiene rubber, in comparison with dioctyl phtalate (DOP). The chemical composition of the shale oil additive was studied by chemical and spectral methods. The shale oil additive consisted mainly of compounds Cl4~Cyy. About 40 % of the total product consisted of sulfur compounds, mainly heavy derivatives of thiophene. The shale oil additive contained 45 % polar aromatic and hetero-element components. As opposed to DOP, the shale oil plasticizer does not contain ester groups.However, high content of sulfur compounds and polar components result in chemical interaction and a satisfactory compatibility of the additive with rubber. Rubber compounds containing shale ой had a lower hardness, tensile strength and tear resistance, as compared to compounds containing DOP. Regarding flexibility, resistance to low temperature, swelling in oil, fuel and water, both rubber compounds had similar properties at 15 % plasticizers. The properties of rubber compound containing 15 % shale oil are promising.
Some problems of the cryoscopic method of the average molecular mass determination of shale oils were studied and a modification of the method is proposed. Diphenyl ether, diphenylmethane, dioxane, and benzene were compared as cryoscopic solvents. The presence of molecular complexes in the shale oil hampers an accurate determination of its molecular mass by cryoscopic methods.Diphenyl ether is recommended as a solvent for the cryoscopic determination of the molecular mass of the shale oils and their components. It yields more accurate results, as compared to other suitable solvents; besides, it is not hygroscopic, less toxicant, has a low vapor pressure and makes measurements at ambient temperature possible.Diphenylmethane is suitable for the determination of the molecular mass of the hydrocarbons, but cannot be applied to polar compounds.Cryoscopic methods are usually used for the determination of the molecular mass of the shale oils. All the modifications of the cryoscopic methods are based on the measurement of the depression of the solvent freezing point that arises as a result of the sample addition to the solvent. The application of cryoscopic methods is advantageous ifthe samples tobe measured are mixtures of volatile and nonvolatile components, or are unstable, or reactive. These methods are well developed and are applied to shale oils for many years. Nevertheless, some methodical problems may occur. Shale oils are complicated mixtures of compounds having a different chemical naturehydrocarbons of the various types, compounds of oxygen, nitrogen, sulfur, etc. The molecular mass of these compounds may not always be determined by means of the same solvent with the required accuracy.In most cases benzene, and sometimes dioxane, are used as solvents for the molecular mass determination of shale oil products. However, these solvents, especially benzene, have serious disadvantages. -Benzene forms so called solid solutions with phenols, thiophenes, pyridine, some naphthenes, and paraffins [l-3].This results ш ап increase of molecular mass during the measurements. Polar compounds, such as phenols, carboxylic acids, nitrogen compounds, when measured in benzene, also show molecular masses that are too high due to the molecular selfassociation. Benzene and dioxane are toxicant and have a high vapors pressure at ambient temperature. As dioxane gives solutions with water, this solvent must be dried carefully. Freezing points of benzene and dioxane are not convenient for the measurement at the ambient temperatures. |For these reasons we propose that solvents such as diphenylmethane and diphenyl ether will be much more suitable for measuring the molecular mass of the shale oils. These solvents have higher freezing points, as compared to benzene and dioxane, which makes measurements at ambient temperature possible. The cryoscopic constants of these solvents are high enough; this provides for a high
The composition and properties of heavy residues of Israeli shale oil (S content 6.8 %) were investigated as a source for bitumens. Both principal methods of asphalt productionvacuum distillation and oxidizing with airwere studied. Straight-run bitumen had satisfactory characteristics. As to oxidized bitumen, the values of its penetration, ductility and softening point were also satisfactory. The drawback of shale oil bitumens is their high viscosity after the thin film oven test, which means their high sensitivity to aging. The shale oil composition changes significantly as a result of distillation and oxidation. The content of asphaltenes sharply increases: from 3.5 to 20-22 % in straight-run bitumen and to 30 % in oxidized bitumen. It is explained by the reactions of condensation and polymerization of the most unstable polar components during heating and oxidation. Unlike petroleum, shale oil is a product ofpyrogenic origin, i.e., it is formed as a result of thermal decomposition of large molecules of kerogen and a part of this cracked material consists of unstable fragments of these molecules, which have a tendency to polymerization. The C/H ratio and nitrogen content increase significantly т the order "saturated hydrocarbonsnaphthenoaromaticsaromaticsasphaltenes".
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