The bulk of the products that were synthesized from Fischer–Tropsch synthesis (FTS) is a wide range (C1–C70+) of hydrocarbons, primarily straight-chained paraffins. Additional hydrocarbon products, which can also be a majority, are linear olefins, specifically: 1-olefin, trans-2-olefin, and cis-2-olefin. Minor hydrocarbon products can include isomerized hydrocarbons, predominantly methyl-branched paraffin, cyclic hydrocarbons mainly derived from high-temperature FTS and internal olefins. Combined, these products provide 80–95% of the total products (excluding CO2) generated from syngas. A vast number of different oxygenated species, such as aldehydes, ketones, acids, and alcohols, are also embedded in this product range. These materials can be used to probe the FTS mechanism or to produce alternative chemicals. The purpose of this article is to compare the product selectivity over several FTS catalysts. Discussions center on typical product selectivity of commonly used catalysts, as well as some uncommon formulations that display selectivity anomalies. Reaction tests were conducted while using an isothermal continuously stirred tank reactor. Carbon mole percentages of CO that are converted to specific materials for Co, Fe, and Ru catalysts vary, but they depend on support type (especially with cobalt and ruthenium) and promoters (especially with iron). All three active metals produced linear alcohols as the major oxygenated product. In addition, only iron produced significant selectivities to acids, aldehydes, and ketones. Iron catalysts consistently produced the most isomerized products of the catalysts that were tested. Not only does product selectivity provide a fingerprint of the catalyst formulation, but it also points to a viable proposed mechanistic route.
This focused review article underscores how metal reduction promoters can impact deactivation phenomena associated with cobalt Fischer-Tropsch synthesis catalysts. Promoters can exacerbate sintering if the additional cobalt metal clusters, formed as a result of the promoting effect, are in close proximity at the nanoscale to other cobalt particles on the surface. Recent efforts have shown that when promoters are used to facilitate the reduction of small crystallites with the aim of increasing surface Co0 site densities (e.g., in research catalysts), ultra-small crystallites (e.g., <2–4.4 nm) formed are more susceptible to oxidation at high conversion relative to larger ones. The choice of promoter is important, as certain metals (e.g., Au) that promote cobalt oxide reduction can separate from cobalt during oxidation-reduction (regeneration) cycles. Finally, some elements have been identified to promote reduction but either poison the surface of Co0 (e.g., Cu), or produce excessive light gas selectivity (e.g., Cu and Pd, or Au at high loading). Computational studies indicate that certain promoters may inhibit polymeric C formation by hindering C-C coupling.
28 January 2014 in Industrial & Engineering Chemistry Research