Fermentation ethanol synthesis

For acetogens, such as the ones identified for producer gas fermentation, ethanol synthesis is reported to follow the Wood-Ljungdahl pathway. The overall stoichiometry for the formation of ethanol (C2H5OH) from CO, CO2, and H2 is... 

The situation with regard to ethanol is much clearer there is long industrial experience in the manufacture of ethanol from wood, by fermentation of the sugars in the waste effluents of pulp mills, or of the sugars made by wood hydrolysis ( ). In the years following World War II, wood hydrolysis plants have been unable to compete economically with petroleum-based ethanol synthesis, mainly by hydration of ethylene, and they have been shut down in most countries. However, in the Soviet Union, we understand, there are still about 30 wood hydrolysis plants in operation (10). Many of these are used for fodder yeast production (11) but the wood sugars are also available for ethanol production. 

When plants experience anoxic conditions there is a shift in carbohydrate metabolism from an oxidative to a fermentative pathway (Fig. 1). In the absence of oxygen, ATP is generated not by the Krebs cycle but by alcoholic fermentation, i.e. glycolysis and ethanol synthesis. 

We have been studying the anaerobic response in cotton, a crop which experiences a reduction in growth rate during irrigation or waterlogging. Cotton shows a level of anaerobically inducible ADH activity comparable with that of maize, a plant which is relatively resistant to anoxia (A. Millar, unpublished data T.L. Setter, unpublished data). However, in cotton the level of the enzyme catalysing the preceding step in the fermentation pathway, PDC, is relatively low and this may lead to low rates of ethanol synthesis and hence low tolerance to anoxia. 

The processes for manufacturing methanol by synthesis gas reduction and ethanol by ethylene hydration and fermentation are very dissimilar and contribute to their cost differentials. The embedded raw-material cost per unit volume of alcohol has been a major cost factor. For example, assuming feedstock costs for the manufacture of methanol, synthetic ethanol, and fermentation ethanol are natural gas at 3.32/GJ ( 3.50/10 Btu), ethylene at 0.485/kg ( 0.22/lb), and corn at 0.098/kg ( 2.50/bu), respectively, the corresponding cost of the feedstock at an overall yield of 60% or 100% of the theoretical alcohol yields can be estimated as shown in Table 11.12. In nominal dollars, these feedstock costs are realistic for the mid-1990s and, with the exception of corn, have held up reasonably well for several years. The selling prices of the alcohols correlate with the embedded feedstock costs. This simple analysis ignores the value of by-products, processing differences, and the economies of scale, but it emphasizes one of the major reasons why the cost of methanol is low relative to the cost of synthetic and fermentation ethanol. The embedded feedstock cost has always been low for methanol because of the low cost of natural gas. The data in Table 11.12 also indicate that fermentation ethanol for fuel applications was quite competitive with synthetic ethanol when the data in this table were tabulated in contrast to the market years ago when synthetic ethanol had lower market prices than fermentation ethanol. Other factors also... 

When perfected, synthesis-gas-to-ethanol technology can be expected to have a large impact on fermentation ethanol markets. It is likely that thermochemical ethanol would then be manufactured at production costs in the same range as methanol from synthesis gas, which can be produced by gasification of virtually any fossil or biomass feedstock. Applying the advances that have been made for conversion of lignocellulosic feedstocks via enzymatically catalyzed options, it has been estimated that the production cost of fermentation ethanol... 

Another potentially adverse impact on fermentation ethanol markets is presented by the options available for the manufacture of mixed alcohols from synthesis gas. Sufficient experimental data have been accumulated to show how the alcohol yields and distributions can be manipulated and what catalysts and conditions are effective. Some of these data have established the utility of mixed alcohols as motor fuels and motor fuel components. 

Ethanol is the only renewable liquid fuel made in commercial quantities and supplies about 1% of the gasoline type transport fuels used in the USA. Approximately 95% of the commercial production of ethanol in the USA is currently by direct fermentation of com-sourced carbohydrates. However, fermentation of synthesis gas has the advantage over direct fermentation of sugars from cellulose and the hemicelluloses in that all wood components, including lignin and bark, are suitable feedstocks. 

One of the most convincing arguments against the further development of fermentation ethanol plants is the advent of synthetic ethanol. As far back as 1921 plants were erected in Germany for the synthesis of ethanol from hydrocarbons but were not at that time very successful. Processes for the production of the synthetic product have been developed in Europe to a commercial scale while at least two American chemical companies have carried the process beyond the experimental stage. A pennit was recently granted by the Commissioner of Prohibition to conduct an experi-... 

The synthesis of ethylene by the dehydration of fermentation ethanol was formerly practised in the industrial countries before the development of steam cracking. This... 

Samain E, Albagnac G, Dubourguier HC and Touzel JP (1982) Characterization of a new propionic acid bacterium that ferments ethanol and displays a growth factor-dependent association with Gram-negative homoacetogen. FEMS Microbiol Lett 15 69-74 Samoilov PM, Baranova NA, Vorobjeva LI and Fedulova IE (1968) Influence of carbon source on the secretion of amino acids and protein synthesis by Mycobacterium luteum. Mikrobiologiya 37 264-268... 

Industrial ethyl alcohol can be produced synthetically from ethylene [74-85-17, as a by-product of certain industrial operations, or by the fermentation of sugar, starch, or cellulose. The synthetic route suppHes most of the industrial market in the United States. The first synthesis of ethanol from ethylene occurred in 1828 in Michael Faraday s lab in Cambridge (40). 

Other Methods of Preparation. In addition to the direct hydration process, the sulfuric acid process, and fermentation routes to manufacture ethanol, several other processes have been suggested. These include the hydration of ethylene by dilute acids, the hydrolysis of ethyl esters other than sulfates, the hydrogenation of acetaldehyde, and the use of synthesis gas. None of these methods has been successfilUy implemented on a commercial scale, but the route from synthesis gas has received a great deal of attention since the 1974 oil embargo. 

Synthesis Ga.s, Since petroleum prices rose abmpdy in 1974, the production of ethanol from synthesis gas, a mixture of carbon monoxide and hydrogen, has received considerable attention. The use of synthesis gas as a base raw material has the same drawback as fermentation technology low yields limited by stoichiometry. 

The first use of butadiene to make synthetic rubber was demonstrated in Russia in 1910 by S.V. Lebchev, who also developed a synthesis of butadiene from ethanol obtained by fermentation. 

A chemical reactor is an apparatus of any geometric configuration in which a chemical reaction takes place. Depending on the mode of operation, process conditions, and properties of the reaction mixture, reactors can differ from each other significantly. An apparatus for the continuous catalytic synthesis of ammonia from hydrogen and nitrogen, operated at 720 K and 300 bar is completely different from a batch fermenter for the manufacture of ethanol from starch operated at 300 K and 1 bar. The mode of operation, process conditions, and physicochemical properties of the reaction mixture will be decisive in the selection of the shape and size of the reactor. 

Once the product specifications have been fixed, some decisions need to be made regarding the reaction path. There are sometimes different paths to the same product. For example, suppose ethanol is to be manufactured. Ethylene could be used as a raw material and reacted with water to produce ethanol. An alternative would be to start with methanol as a raw material and react it with synthesis gas (a mixture of carbon monoxide and hydrogen) to produce the same product. These two paths employ chemical reactor technology. A third path could employ a biochemical reaction (or fermentation) that exploits the metabolic processes of microorganisms in a biochemical reactor. Ethanol could therefore also be manufactured by fermentation of a carbohydrate. 

Second-generation biofuel technologies make use of a much wider range of biomass feedstock (e.g., forest residues, biomass waste, wood, woodchips, grasses and short rotation crops, etc.) for the production of ethanol biofuels based on the fermentation of lignocellulosic material, while other routes include thermo-chemical processes such as biomass gasification followed by a transformation from gas to liquid (e.g., synthesis) to obtain synthetic fuels similar to diesel. The conversion processes for these routes have been available for decades, but none of them have yet reached a high scale commercial level. 

Conversion of lignocellulose into transportation fuels via pyrolysis and subsequent oil upgrading [72], via gasification and subsequent Fischer-Tropsch or methanol synthesis [3], via hydrolysis and subsequent fermentation to ethanol or subsequent conversion into ethyl levulinate [45, 46, 73]. 

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