Study of the Influence of Macrokinetic Factors on the Synthesis of Organic Compounds from Carbon Monoxide and Water Vapor
Abstract Generated abstract
This study examines macrokinetic factors affecting the synthesis of organic compounds from carbon monoxide and water vapor over an iron, copper catalyst at atmospheric pressure and at 10 atm. Experiments in the range 473 to 523 K varied the linear feed rate of reactants and assessed its effect on carbon monoxide conversion and hydrocarbon formation rate. The authors propose a simplified kinetic expression valid up to an overall carbon monoxide conversion of 0.7, estimate apparent and true activation energies, and show that reaction order changes with gas flow velocity. The results indicate that, under the investigated conditions, the process occurs in an external transition region at atmospheric pressure and in an internal diffusion region at medium pressure.
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PROCEEDINGS
of the Tomsk Order of the October Revolution and Order of the Red Banner of Labor
S. M. Kirov Polytechnic Institute
Volume 257 1973
INVESTIGATION OF THE INFLUENCE OF MACROKINETIC FACTORS ON THE SYNTHESIS OF ORGANIC COMPOUNDS FROM CARBON MONOXIDE AND WATER VAPOR
V. M. Mironov, A. V. Kravtsov, S. I. Smolyaninov, I. V. Goncharov
The synthesis of organic compounds from carbon monoxide and water vapor, discovered by G. Kölbel and F. Engelhardt, proceeds according to the overall equation [1, 2, 3]
\[ 3CO + H_2O = (-CH_2-) + 2CO_2 + 58.4 \frac{\text{kcal}}{\text{mol}} \]
We have for the first time investigated the macrokinetics of this process on an iron–copper catalyst at atmospheric and medium (10 atm) pressures in the temperature range 473–523°K, and have shown the influence, under these conditions, of changes in the linear feed rate of the reactants (from 0.059 to 1.475 cm/sec) both on the degree of conversion of carbon monoxide and on the rate of hydrocarbon formation.
A simplified kinetic equation is proposed for the process of formation of organic compounds from carbon monoxide and water vapor, which is applicable up to an overall degree of conversion of carbon monoxide of 0.7:
\[ r_y = K_y \cdot \alpha^{n_2} \cdot (1 - Y_c)^{n_1+n_2} \]
where
\(r_y\) is the observed rate of hydrocarbon formation;
\(K_y\) is the effective rate constant;
\(Y_c\) is the overall degree of conversion of carbon monoxide;
\(n_1\) and \(n_2\) are the reaction orders with respect to carbon monoxide and water vapor;
\(\alpha\) is the current ratio of the degree of conversion of water vapor to the degree of conversion of carbon monoxide.
The apparent activation energies of the process, determined from the temperature dependence of the effective rate constant, are 16 kcal/mol for synthesis at atmospheric pressure and 17.5 kcal/mol for synthesis at medium pressure. A sharp increase in the values of this quantity occurs at the fictitious linear velocity
\[ W_{\varphi} = \]
1.745 cm/sec in the temperature range 503–523°K, when it reaches 29 kcal/mol.
The true activation energy of the reaction was 32 kcal/mol.
The overall reaction order also depends on the fictitious linear velocity of the gas flow and increases from first to second as \(W_{\varphi}\) increases from 0.059 to 1.475 cm/sec.
Overall, the results of the work suggest that the formation of organic compounds in the process studied proceeds, at atmospheric pressure, in the external transition region, and at medium pressure—in the region of internal diffusion.
References
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H. Kölbel, F. Engelgardt, Erdöl und Kohle, 2, 520, 1949; 3, 529, 1950; 5, 1, 1952; 9, 225, 1956.
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N. V. Lavrov, A. M. Mosin, I. F. Bogdanov. Zh. khim. zh., 62, 1960.
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S. I. Smolyaninov, V. M. Mironov, A. V. Kravtsov. Khimiya i tekhnologiya topliva i masel, 8, 12, 1962.