The formation of heavy hydrocarbons, commonly called "green oil," has an important role in the deactivation of acetylene hydrogenation catalysts used in ethylene manufacturing plants. Using a tapered-element oscillating microbalance coupled with online gas chromatography, we measured the rate of green oil formation, acetylene conversion, and selectivities for ethylene, ethane, 1,3-butadiene, 1-butene, cis- and trans-2-butenes, and 1-hexene simultaneously over a wide range of conditions. The system allowed the comparison of activity, selectivity, and rate of green oil formation for a variety of catalysts under diverse conditions (e.g., pressure, temperature, carbon monoxide concentration, gas hourly space velocity, and H_2/C_2H_2 ratio). Using these data, we developed a deactivation rate law for acetylene hydrogenation that incorporated green oil formation kinetics.
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