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The exhaustion of petroleum reserves has given impetus to the search for new sources of hydrocarbon raw materials. One such source is heavy crudes, which contain large amounts of high-molecular-weight hydrocarbons and other compounds. Minimum processing of these crudes will yield finished products -- paving asphalts [I]. This establishes a foundation for organizing production of hlgh-quality materials of construction without major expenditures, close to the raw material production site, where shortages have been felt up to now. Here we are reporting on a study of the liquid-phase oxidation of heavy crudes and the features of regulation of commercial properties of the final products -- asphalt. As the starting material we used a crude from the Karazhanbas field with the following physicochemical characteristics: density at 20~ 941 kg/m3; viscosity at 50~ 0.14 Pa.sec; solid point+22~ yield of cuts below 350~ 15.6% by weight; content of paraffinic hydrocarbons 2% by weight, resins 21% by weight, asphaltenes 6% by weight. It will be noted that this crude has a high viscosity and high density and contains very little light products in comparison with conventional etudes. The commercial properties of the asphalts obtained by oxidation were regulated by adding asphalt-resin and wax deposits (AKWD) to the crude. These deposits accumulate on the surface of oil-well tubing and discharge lines; they are waste materials in petroleum production and are disposed of by dumping. The ARWD used in the present work had the following physicochemical characteristics: density at 20~ 989 kg/m s, dropping point 85~ content of asphaltenes 2.5% by weight, solid contaminants~.< 11.2% by weight. The liquid-phase oxidation was performed in a laboratory unit by a conventional method [2] under the following conditions: total charge 130 g, oxidation time 30 min, temperature 270~ air input 1 liter/min. The influence of the usual factors affecting asphalt quality was no different from that established in [3]~ Specific values were selected for the oxidation parameters on the basis of the significance of changes in quality index of the final product. The present work has been aimed at control of the physlcochemical properties of oxidized asphalt by varying the dimensions of the complex structural units (CSUs) of this petroleum disperse system (PDS), on the basis of the theory of regulated phase transitions [4, 5]; a further aim was to establish the conditions of oxidation under which the dimensions of the CSUs of the petroleum system will be optimal. In Fig. 1 we show the effects of varying the crude oil/ARWD ratio in the mixture on certain physicochemical properties of the starting material and the final asphalt. In view of the nonmonotonic character of the dependence of the R&B softening point of the oxidation feed (which expresses indirectly a measure of intermolecular interaction) on the content of AKWD in the feed, we can assume tentatively that there will be an analogous change in the properties of the processed products. And in fact, after oxidation of the blends of crude with ARWD, we found a complex effect of the ARWD on the asphalt quality. As was expected, with ARWDcontents of 30-50% by weight, the change in asphalt properties was nonmonotonic (see Fig. i). The ARWD is a complex mixture of hlgh-molecular-weight paraffinic--naphthenic and aromatic hydrocarbons, resins, and asphaltenes. This mae=rial has a rather high structural--mechanical strength as a consequence of significant int~rmolecular interaction, expressed as a relatively high dropping point. Consequently, an increase in the content of these deposits in the oxidation feed should increase the strength properties of both the original PDS and the asphalt. Institute of Chemistry of Petroleum and Natural Salts, Academy of Sciences of the Kazakh SSR (Mangyshlak Laboratory). Translated from Khlmiya i Tekhnologiya Topliv i Masel, No. 7, pp. 10-11, July, 1987.



9 1988 Plenum Publishing Corporation

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ARWD content, xdt.% Fig. 1

ARWD content, wt. % Fig. 2

Fig. i. Softening point (dashed curve) of oxidation feed and needle penetration (continuous curve) of asphalt product as functions of content of ARWD in feed. Fig. 2. Influence of ARWD content in feed on increase and softening point of asphalt in comparison with softening point of feed (continuous curve) and on radius of particles in asphalt. Dispersity of asphalts was determined by procedure given in [7], in a 1% solution of heptane-toluene solvent (3:1 by volume). However, the decrease in softening point of the feed and the simultaneous increase in penetration of the asphalt with contents of ARWD in the feed amounting to 30-50% by weight is evidence of the reverse. This is readily explained on the assumption of an extremal change in the dimensions of the CSU at these contents of ARWD, owing to a decrease in the ratio of specific volume energies of the dispersion medium and disperse phase [6] when the ratio of PDS components is changed. The relationships shown in Fig. 2 support this hypothesis. The the most susceptible to the action of external factors in oxidation, from this material contains CSUs with a minimum size. Consequently, for an optimum in the liquid-phase oxidation of heavy crude from the content of about 40% ARWD by weight. system with 40% ARWD is and the asphalt prepared one of the conditions Karazhanbas field is a

Thus, in the liquid-phase oxidation of heavy Karazhanbas crude, it is possible to control the asphalt properties by changing the CSU dimensions in order to obtain the required structural-mechanical properties. One method fpr accomplishing such control is the introduction of ARWD into the feed. This approach makes it possible not only to obtain valuable materials of construction, but also to solve successfully certain ecological problems in petroleum production and processing. LITERATURE CITED i. 2. 3. 4. 5. 6. 7. N. K. Nadirov, A. E. Braun, M. S. Trokhimenko, et al., Petroleum Bituminous Rocks of Kazakhstan: Problems and Prospects [in Russian], Nauka, Alma-Ata (1985). R. B. Gun, Petroleum Asphalts [in Russian], Khimiya, Moscow (1973). I. B. Grudnikov, Production of Petroleum Asphalts [in Russian], Khimiya, Moscow (1983). Z. I. Syunyaev, Khim. Tekhnol. Topl. Masel, No. 6, 2-5 (1985). Z. I. Syunyaev, Khim. Tekhnol. Topl. Masel, No. 8, 5-7 (1986). R. Z. Syunyaev and O. G. Safiev, Izv. Vyssh. Uchebn. Zaved., Neff' Gaz, No. 2, 50-54 (1984). I. Ya. Slonim, Opt. Spektrosk., ~, No. i, 98-108 (1960).