Synthesis of Oxygenated Hydrocarbons from Ethanol over Sulfided KCoMo-Based Catalysts: Influence of Novel Fiber- and Powder-Activated Carbon Supports

Abstract

Ethanol has become a viable feedstock for basic organic synthesis. The catalytic conversion of ethanol provides access to such chemicals as diethyl ether, ethyl acetate, and acetaldehyde. Carbonaceous materials are extensively studied as supports for heterogeneous catalysts due to their chemical and thermal stability, high surface area, and tunable texture. In this paper, ethanol conversion over K10Co3.7Mo12S-catalysts supported on novel activated carbon (AC) materials (i.e., novel powder-AC (DAS and YPK-1), fiber non-woven AC material (AHM), and fabric active sorption (TCA)) was investigated. The catalysts were prepared by the incipient wetness co-impregnation method followed by sulfidation. The catalysts were characterized by employing N2 adsorption–desorption measurements, TEM, SEM/EDX, UV–Vis spectroscopy, and XRF. Catalytic performance was assessed in a fixed-bed down-flow reactor operating at 320 °C, 2.5 MPa, and with continuous ethanol feeding in an He atmosphere. Activity is highly dependent on the support type and catalyst’s textural properties. The activity of the fiber-supported catalysts was found to be greater than the powder-supported catalysts. Ethanol conversion at T = 320 °C, P = 2.5 MPa, and GHSV = 760 L h−1 kgcat−1 increased as follows: (38.7%) KCoMoS2/YPK-1 < (49.5%) KCoMoS2/DAS < (58.2%) KCoMoS2/TCA < (67.1%) KCoMoS2/AHM. Catalysts supported by powder-AC enhanced the formation of MoS2-crystallites, whereas the high acidity of fiber-AC seemed to inhibit the formation of MoS2-crystallites. Simultaneously, a high surface area and a microporous catalytic structure enhance the formation of oxygenates from hydrocarbons. The dehydration and dehydrogenation reactions, which led to the creation of ethene and acetaldehyde, were shown to require a highly acidic catalyst, while the synthesis of ethyl acetate and higher alcohols required a less acidic catalyst.