\[ \begin{array}{c} \mathrm{C_6H_5I[OCOCH(NHCOCH_3)C_2H_5]_2} \\[-2mm] \begin{array}{rcl} & \xrightarrow[\ ]{\mathrm{H,\ H_2O}} & \mathrm{C_6H_5I + 2HOCOCH(NHCOCH_3)C_2H_5} \\ && \mathrm{III} \\[-1mm] & \longrightarrow & \mathrm{C_6H_5I + 2\,OCOCH(NHCOCH_3)C_2H_5^{\bullet}} \\ && \mathrm{IV}\qquad\qquad\mathrm{V} \\[-1mm] && \downarrow \\[-1mm] && \mathrm{2CO_2 + [CH(NHCOCH_3)C_2H_5]_2} \\ && \mathrm{VI} \end{array} \\[2mm] \downarrow \\[-1mm] \mathrm{C_6H_5I^{+}OCOCH(NHCOCH_3)C_2H_5} \;+\; \mathrm{^{-}OCOCH(NHCOCH_3)C_2H_5} \;\longrightarrow \\[-1mm] \mathrm{VII}\qquad\qquad\qquad\qquad\mathrm{VIII} \\[2mm] \longrightarrow\; \mathrm{C_6H_5OCOCH(NHCOCH_3)C_2H_5} \;+\; \mathrm{IOCOCH(NHCOCH_3)C_2H_5} \\[-1mm] \mathrm{IX}\qquad\qquad\qquad\qquad\mathrm{X} \\[-1mm] \qquad\qquad\qquad\qquad\downarrow \\[-1mm] \qquad\qquad\qquad \mathrm{CO_2 + ICH(NHCOCH_3)C_2H_5} \\[-1mm] \qquad\qquad\qquad\mathrm{XI} \end{array} \]

A \(0.01\)-mole sample of the butyrate was heated in a nitrogen stream in a Würtz flask for 4 minutes at \(100^\circ\). The liquid decomposition products, after condensation of their vapors in a condenser, were collected in a receiver; the gaseous products (carbon dioxide) were absorbed with a potassium hydroxide solution in Drechsel bottles. In the transformation products, iodobenzene, acetylaminobutyric acid, iodoacylamine (XI), and phenol—detected after hydrolysis of the decomposition products—were found. The latter apparently arose from phenylacylaminobutyrate (IX). Per mole of butyrate, \(0.4\) mole of carbon dioxide is evolved. The study of the thermal transformation reaction is continuing.

References

1. Dictionary of Organic Compounds, vol. I, 564, 1949.
2. K. H. Pausaker, J. Chem. Soc., 1989 (1953).
3. J. F. Shazetkin, H. Saltzman, Anal. Chem., 35, 1428 (1963).
4. R. Bell, K. F. Morgan, J. Chem. Soc., 1209 (1960).

PYROLYSIS OF THE GASOLINE FRACTION OF THE NORTH-SILGINSKY GAS CONDENSATE

M. D. Medvedev, S. I. Smolyaninov, A. V. Kravtsov, L. S. Blinova

In Tomsk Oblast, six deposits of the gas-condensate type have been discovered. The reservoir gas of these deposits contains a significant quantity of liquid hydrocarbons—gas condensate.

Studies carried out by the Department of Chemical Technology of Fuels of the Tomsk Polytechnic Institute /1/ make it possible to judge the straight-run gas-condensate gasolines from fields of the Tomsk region as a favorable feedstock for the pyrolysis process aimed at obtaining monomers.

In the present work, the pyrolysis process of the gasoline fraction (initial boiling point–180°C) of gas condensate from the North-Silginsky field was studied in order to establish the optimal parameters of the “ethylene” regime and to refine the yield and composition of gaseous and liquid products.

The studies were carried out in a unit with a flow-type reactor. The fraction was obtained by atmospheric distillation of gas condensate on an ARN-2 apparatus and has the following physicochemical characteristics:

Boiling range — initial boiling point–180°C.
Yield — 60.8%.
Average molecular weight — 96.
Density — 0.7160 g/cm³.
Refractive index — 1.400.

Content of paraffinic hydrocarbons — 75 wt.%.
Content of naphthenic hydrocarbons — 19 wt.%.
Content of aromatic hydrocarbons — 6 wt.%.

It follows from these data that the gasoline fraction of the gas condensate has a methane character, is distinguished by a low content of aromatic hydrocarbons, and contains no organosulfur compounds.

In carrying out the search for the “ethylene” regime, a simplex method for planning extremal experiments /2/ was used; with its aid a series of experiments was conducted and the optimal parameters of the pyrolysis process were found:

Temperature at the reactor outlet — 785°C.
Feed rate — 1.8 h⁻¹.
Dilution with steam — 55 wt.%.

Under these conditions, the ethylene yield reached 33.2 wt.% based on the original feedstock.

The table shows the material balance of pyrolysis of gasoline from the North-Silginsky gas condensate under the optimal regime.

Table 1.

Material balance of pyrolysis in the “ethylene”
regime

Mathematical processing of the results showed that the response surface /3/ has significant curvature, and this confirms that the optimum region has been found correctly and that the parameters correspond to the “ethylene” regime. In this regime the total yield of monoolefins in the pyrolysis gas was 46,2 wt. % based on the initial gasoline. A significant yield of carbon oxides is observed—4,8%. This can be explained by the fact that, under these conditions, reactions occur involving the interaction of water vapor with hydrocarbons and with carbon-

deposited on the walls of the reactor. In the “ethylene” regime, the yield of propylene is insignificant and amounts to 8.3 wt.%.

The studies carried out showed that straight-run gasoline from the gas condensate of the North-Silginsky field of Tomsk Oblast can be used as a feedstock for the process of homogeneous pyrolysis in order to obtain monoolefins.

Literature

1. “Investigation of gas condensates from fields of Tomsk Oblast as feedstock for microbiological synthesis.” Polytechnic Institute, report on topic III/69, Tomsk, 1971.

2. V. V. Nalimov, N. A. Chernova. Statistical Methods for Planning Extreme Experiments. Moscow, “Nauka,” 1965.

3. L. Z. Rumshinsky. Mathematical Processing of Experimental Results. Moscow, “Nauka,” 1971.

HETEROGENEOUS PYROLYSIS OF STRAIGHT-RUN GASOLINE

S. I. Smolyaninov, M. D. Medvedev, A. V. Kravtsov, L. P. Yarosh

The growing demand for gaseous unsaturated hydrocarbons requires investigation of processes for producing olefins that make it possible to increase the capacity of units, reduce production costs, and consequently obtain cheaper target products.

In the present work, the process of heterogeneous pyrolysis of straight-run gasoline from Samotlor-field crude oil was investigated. As the catalyst, a specially prepared standard iron oxide of the “chda” grade was used, with Fe content of 69.8–70.1. The gasoline was obtained by atmospheric distillation on an ARN-2 and has the following physicochemical characteristics:

Boiling range — initial boiling point–180°C.
Yield — 23.8%.
Molecular weight — 114.
Density — 0.7419 g/ml.
Refractive index — 1.420.

Group composition:

Paraffinic hydrocarbons — 64.5 wt.%.
Naphthenic hydrocarbons — 25.7 wt.%.
Aromatic hydrocarbons — 9.8 wt.%.