Impact of KMnO4 on CZA/13X Catalysts for Direct LPG Synthesis
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Abstract
The direct synthesis of liquefied petroleum gas (LPG) from synthesis gas represents a promising sustainable pathway for alternative fuel production. This study investigates the catalytic performance of copper-zinc-aluminum oxide catalysts (CuO-ZnO-Al2O3; CZA) with molar ratio 2:2:1, prepared via a co-precipitation method and physically mixed with zeolite 13X. The modification using KMnO4 was specifically explored to evaluate its potential in tuning zeolite acidity through alkali (K) promotion and enhancing metal dispersion via manganese (Mn) redox effects. Three catalyst systems were evaluated: CZA/13X, CZA/10%KMnO4-13X, and CZA/20%KMnO4-13X, where potassium permanganate was impregnated onto zeolite 13X at concentrations of 10% and 20% w/v respectively. Catalytic performance was assessed using a fixed-bed reactor at 350°C, 40 bar, with H2:CO ratio of 2:1 for 4 h. Gas chromatography analysis revealed that unmodified CZA/13X exhibited the highest catalytic activity with a CO conversion of 87.64%, LPG selectivity of 38.16%, and LPG yield of 33.47%, In comparison, the KMnO4-modified systems showed decreased performance, with CO conversions of 86.83% and 83.14% for the 10% and 20% loading, respectively. These results suggest that the excessive blockage of zeolite acid sites by potassium and manganese species outweighs any potential benefits from redox or basic promotion, thereby hindering the methanol-to-hydrocarbon dehydration step. These findings highlight the critical balance of the metal-acid functions and indicate that while KMnO4 modification was expected to tune selectivity, it proved counterproductive under the studied conditions due to the suppression of key active sites.
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