Page 201

Methanol homologation to produce higher alcohols has also been invoked in the synthesis of higher alcohols from CO/CO2/H2 over alkalipromoted Cu/ZnO and Zn/Cr catalysts [102104]. In both cases the reaction is carried out at high pressure (>7.5 MPa) and high
temperatures (250325C for the Cu/ZnO catalyst and 300400C for the Zn/Cr catalyst). The product obtained from this synthesis is a
complex mixture of alcohols, aldehydes, esters, and hydrocarbons, the relative amounts of each being very dependent on the catalyst and
the operating conditions [102104]. The product alcohols are primarily 2-methyl branched and linear alcohols. Various investigators have
shown that addition of alkali metal salts, such as K2CO3 and CsOH, increases the selectivity to the higher alcohols, as does operation with
low ratio synthesis gas (H2/CO < 1) [102106]. This technology offers a route to an oxygenate mix suitable for blending with gasolines, and
commercial processes have been proposed [107,108].
Based on mechanistic and kinetic studies of the higher alcohol synthesis from synthesis gas, it has been shown that the ethanol in the mixedoxygenate product is produced from intermediates derived from methanol, not CO [103,109]. Kinetic models of the synthesis have been
developed that are able to explain the observed product distribution [110,111]. These models are based on a detailed understanding of the
reaction mechanism in which two types of reactions dominate: aldol condensation, which yields primarily 2-methyl branched alcohols, and
C1 coupling reactions, which yield linear alcohols [106,111]. Estimates of the parameters of the kinetic models that quantitatively describe
the oxygenate product distributions suggest that the rate of ethanol formation is about an order of magnitude lower than the rate of
production of branched alcohols [111,112]. On the Cs/Cu/Zn catalysts, this results in a minimum in yield of ethanol compared with the
yields of methanol, 1-propanol, and 2-methyl-1 propanol. Although methanol conversion to ethanol has been confirmed as part of the higher
alcohol synthesis from synthesis gas, this synthesis does not offer a plausible route for the conversion of methanol to ethanol. Under the
reaction conditions methanol rapidly decomposes, even at a pressure of 0.1 MPa [113], to yield an equilibrium mix of methanol, CO, and
H2. Furthermore, as shown by the data in Table 7, the yield of ethanol remains low even with methanol in the feed.
Higher alcohol formation from synthesis gas is also known to occur over MoS2-based catalysts. The alcohol product distribution is quite
different from the modified methanol synthesis catalysts and consists primarily of linear alcohols [114]. In particular, the product
distribution with Cs/Co/MoS2 catalysts has a maximum in the yield of ethanol [115]. A modification of this synthesis in which higher
alcohols formed from methanol and synthesis gas has been claimed by Quarderer et al. [116]. As K2CO3-promoted CoS/MoS2 catalyst,
operated at