Butanol chemical conversion

Immobilisation of an Acetobacter aceti strain in calcium alginate resulted in improvement of the operational stability, substrate tolerance and specific activity of the cells and 23 g phenylacetic acid was produced within 9 days of fed-batch cultivation in an airlift bioreactor [133]. Lyophilised mycelia of Aspergillus oryzae and Rhizopus oryzae have been shown to efficiently catalyse ester formation with phenylacetic acid and phenylpropanoic acid and different short-chain alkanols in organic solvent media owing to their carboxylesterase activities [134, 135] (Scheme 23.8). For instance, in n-heptane with 35 mM acid and 70 mM alcohol, the formation of ethyl acetate and propylphenyl acetate was less effective (60 and 65% conversion yield) than if alcohols with increased chain lengths were used (1-butanol 85%, 3-methyl-l-butanol 86%, 1-pentanol 91%, 1-hexanol 100%). This effect was explained by a higher chemical affinity of the longer-chain alcohols, which are more hydrophobic, to the solvent. 

Al3+-exchanged synthetic hectorite is a good catalyst for these conversions, and the 13C NMR spectrum obtained in the interlamellar, proton-catalyzed addition of water to 2-methylpropene is indistinguishable (Fig. 79) from that of f-butanol. Doubtless studies of this kind, where natural-abundance, 3C NMR signals are used to probe the chemical identity and motional freedom of reactant and product species situated in the interlamellar spaces of clays or pillared clays (see below), will become increasingly popular. Using l3C NMR linewidths and spin-lattice relaxation studies, Matsumoto et al. (466) have succeeded in discriminating between the internal and external surfaces of pillared montmorillonites. 

Commodity Chemicals acetic acid, acetone, butanol, ethanol, many other products from biomass conversion processes. 

Although a feedstock, or a particular feedstock source, is initially taken up because it is produced in excess or is even a waste product, its success can result in the need to manufacture it specially for that process, thereby losing the rationale for its original adoption. One can see this progression at work with coal-tar (in particular phenol ) and synthetic dyes, with coke-based ammonia and the Solvay process, with calcium carbide and acetylene-based chemicals, and, more recently, with refinery gases and petrochemicals. Conversely, butanol became such a major by-product of butadiene production that I.G. could only sell a quarter of it by 1943. ... 

A total of almost 250 ISPR projects in microbial whole cell biotechnology are listed in Table 2. Over one third of these projects have dealt with the production of organic solvents such as ethanol, butanol, acetone or propanol (90 projects). Ethanol (70% of all the solvents) has been by far the most important microbial product for which different ISPR techniques have been applied. The second most important class of products involved in ISPR projects have been organic acids such as lactic, acetic, butyric, or propionic acid (54 projects). Most of effort in this product class has focused on lactic acid (55% of all organic acids). Important ISPR activities have also been reported for the microbial production of various aromas and fine chemicals (30 projects in each product category). A considerable amount of ISPR approaches have been shown in steroid conversions (17 projects) and the production of secondary metaboHtes and various enzymes (13 projects in each product category). 

Hanika et al. (2003) investigated the esterification of acetic acid and butanol in a trickle bed reactor, packed with a strong acid ion- exchange resin (Purolite 151) at 343 K - 393 K. Experimental data illustrate the benefit of simultaneous esterification and partial evaporation of the reaction products in the multi-functional trickle bed reactor. In case of total wetting of the catalyst bed, contact of vaporized products (ester and water) with catalyst was naturally limited and thus, the backward reaction i.e. ester hydrolysis was suppressed. This phenomenon shifted the chemical equilibrium conversion to high values. Saletan (1952) obtained quantitative reaction rate data for the formation of ethyl acetate from ethanol and acetic acid in fixed beds of cation exchange resin catalyst. The complex interaction of diffusion and reaction kinetics within the resin, which determine over-all esterification rate, has been resolved mathematically. 

Researchers at MSU have also demonstrated the proof of concept that syngas can be converted to chemicals, such as ethylene, alcohols, and hydrocarbons using a combination of commercial and proprietary catalysts and reactor design (Liu et al., 2009). They showed that the enhanced conversions of higher alcohols (e.g. ethanol, propanol, and butanol) to hydrocarbon (30-40% by mass) at pressures to 70 bar compared to that observed for methanol conversion at (1-2% by mass). The analyses of hydrocarbon products showed an octane number of 80-90 with API gravities of 50-55. 

A (Chang et al., 2010). Butanol can also be converted to butyric acid using transition metal-catalyzed oxidation witii more than a 99% product yield (route B Wang et al., 2007). However, this conversion is not as interesting, as butanol is a more important C4 platform chemical as compared to others due to its potential to replace gasoline. All of the routes of conversion of butyric acid are shown in Fig. 7.1. 

Short chain primary alcohols such as methanol, ethanol, and butanol are widely employed in FAAE production. Secondary alcohols include isopropanol and 2-butanol for industrial production. Methanol and ethanol are used because of their availability and low cost. Ethanol is less toxic but yields a lower conversion efficiency than methanol. Alcohol requirements are based on the type of lipase or chemical catalyst and reactor used for the process. Glycerol obtained... 

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