ChemInform Abstract: Higher Alcohol and Oxygenate Synthesis Over Cesium‐Doped Cu/ZnO Catalysts

Abstract

Abstract The synthesis of higher (C+2) alcohols and esters has been studied over cesium-doped Cu ZnO catalysts. Under higher alcohol synthesis conditions, e.g., 583 K, 7.6 MPa, and gas hourly space velocity = 3260 liters (STP)/kg cat/hr with a H 2 CO = 0.45 synthesis gas, the presence of cesium promoted the formation of higher oxygenates, especially 2-methyl-1-propanol. The yields of products passed through distinct maxima at cesium nominal concentrations of 0.3–0.5%. These nominal concentrations generated optimum surface cesium concentrations of 15–25%. Under the reaction conditions employed, the principal role of cesium was to increase the ethanol synthesis rate and to provide an even greater enhancement in the rate of ethanol conversion to 1-propanol and subsequently to higher alcohols. To obtain insight into the mechanism of the carbon chain growth, e.g., C1 → C2, C2 → C3, and linear versus branched carbon chain growth, a 13C-NMR study of the C2C4 products formed over Cu ZnO and 0.4 mol% Cs/Cu/ZnO catalysts was performed. Separate injections into the CO H 2 synthesis gas of methanol and ethanol with natural-abundance 13C and enriched by 13C in specific positions showed that (i) lower alcohols were incorporated into the synthesis to form higher alcohols; (ii) carbon chain growth occurred in a stepwise manner dominated by the addition of oxygenated C1 intermediates at the β carbons of the oxygenated Cn (n ≥ 2) intermediates but also proceeding via linear addition Cn + C1 (n ≥ 1); and (iii) the presence of cesium had a dramatic effect on the reaction mechanism and promoted greatly the synthesis rates. The mechanistic effects of the alkali dopant were most pronounced in the C2 → C3 step. Over the Cu ZnO catalyst, injection of ethanol produced 1-propanol via linear chain growth, i.e., CH 3 13 CH 2 OH + CO H 2 → CH 3 13 CH 2 CH 2 OH . The presence of Cs effected a mechanistic switch and promoted β-carbon addition, CH 3 13 CH 2 OH + CO H 2 → 13 CH 3 CH 2 CH 2 OH . The position of the 13C label in the CH3 group of propanol provides evidence for retention of oxygen associated with the C1 intermediate, formed from CO H 2 , and loss of oxygen associated with the 13CH2OH group of ethanol. Mechanistically, such a retention is favored by a β-ketoalkoxide intermediate that is bonded to the cesium centers via its anionic oxygen. This unique mechanism is termed herein as aldol coupling with oxygen retention reversal and is specific to the presence of the cesium salt dopant. Higher alcohol synthetic steps C2 + C2 and Cn + Cm (n ≥ 3, m = 1, 2, 3) were also analyzed. Both oxygen retention reversal and normal oxygen retention were observed in coupling reactions leading to the higher-molecular-weight products (m + n > 3), and this observation is attributed to steric effects favoring the cis conformation of the β-alkoxide followed by rejection of either of its two oxygens.