KINETICS OF THE GAS-SLURRY METHANOL-HIGHER ALCOHOL SYNTHESIS FROM CO/CO2/H-2 OVER A CS-CU/ZNO/AL2O3 CATALYST, INCLUDING SIMULTANEOUS FORMATION OF METHYL-ESTERS AND HYDROCARBONS

First kinetic results are presented for the gas-slurry methanol-higher alcohol synthesis from CO/CO2/H-2 (syngas) over a CU0.44Zn0.43Al0.12Cs0.031 catalyst (particle size: 50-75 mu m), slurried in n-octacosane. Experimental conditions varied as follows: pressure = 20-80 bar, temperature = 473-573 K, H-2/CO ratio in the feed = 0.53-3.38, mole fraction CO2 in the feed = 0.026-0.037 and space velocity = 0.065 X 10(-3)-1.395 X 10(-3) Nm(3) s(-1) kg(cat)(-1). Methanol was the major product. Further, higher 1-alcohols, 2-methyl-1-alcohols, methyl esters, n-paraffins, CO2 and H2O were formed. In contrast to observations in a gas-solid system, formation of 2-methyl-n-paraffins was negligible. From the same model, proposed earlier for the gas-solid systems B.B. Breeman et al., Chem. Eng. Sci., 49, 24A (1995), the product distributions of the alcohols, the paraffins and the methyl esters could be predicted with average relative deviations of 5.9%, 7.8% and 1.6%, respectively. The presence of n-octacosane as a slurry liquid appeared to affect substantially both the product distributions and the values of the model parameters relative to the corresponding gas-solid system.