Ethanol-water separation processes

A general scheme of the extractive alcoholic fermentation proposed by Silva et al. (3) is shown in Fig. 1. The process consists of four interlinked units the fermentor (ethanol production unit), the centrifuge (cell separation unit), the cell treatment unit, and the vacuum flash vessel (ethanol-water separation unit). A detailed description of the process and mathematical model can be found in ref. 5. 

ETBE is recovered as the bottoms product of the distillation unit. The ethanol-rich C4 distillate is sent to the ethanol recovery section. Water is used to extract excess ethanol and recycle it back to process. At the top of the ethanol/water separation column, an ethanol/water azeotrope is recycled to the reactor section. The isobutene-depleted C4 stream may be sent to a raffinate stripper or to a molsieve-based unit to remove oxygenates such as DEE, ETBE, ethanol and tert-butanol. 

Axial flow pumps, 134, 136, 140 applicafion range, 150 Azeotrope separation, 387,388,420-426 Azeotropic distillation, 420-426 acetonitrile/water separation, 422 commercial examples, 421-424 design method, 424 ethanol/water/benzene process, 424 n-heptane/toluene/MEK process, 424 vapor-liquid equilibrium data, 421, 423, 425,426... 

Ethanol produced by fermentation is conventionally dehydrated by distillation, an inefficient process that consumes energy equivalent to a large fraction of the energy content of the product ethanol.(X) Reverse osmosis (RO) has been considered before for ethanol-water separation because of its inherent energy efficiency. However, a difficulty encountered in using RO is the high osmotic pressures associated with concentrated ethanol solutions. For example, the osmotic pressure of a 15-volX ethanol solution is about 960 psi, and that of a 50-volX solution is about 3700 psi.(2,) Because most... 

When the ethanol is not blended but used as such as fuel, hydrous ethanol (e.g. 95%) can be applied. In a cascade-type continuous set-up [27] a partial evaporation of the fermentation liquid was carried out and the ethanol-water mixture was passed over a H-ZSM5 zeolite (350 °C, 1 atm). As in the MTG (methanol to gasoline) [28, 29] process a mixture of alkanes (mainly C3-C5) and aromatics (mainly toluene, xylenes and C<)-compounds) was obtained. In this approach the ethanol-water separation is avoided the hydrocarbons and water are non-miscible and separate by gravity. Though its octane number is good there is no future in MTG-gasoline because of the trend to lower the aromatics content. 

For the ethanol-water separation, the requirement of thorough removal of ethanol from the recycled CO2 represents a technical challenge that increases the complexity and cost of the process relative to the simplified diagram shown in figure 8.10. The reasons for the increased complexity are explained below. Figure 8.13 illustrates the ethanol extraction process in the instance where the recycled CO2 has an ethanol concentration of 0.1 wt%. At the raffinate section of the extractor the ethanol concentration in the water-rich phase is now dictated by considerations of equilibrium and by the value of the distribution coefficient. The limitation attributed to equilibrium is indicated by the... 

Figure 2.11 Comparison of the primary energy usage for ethanol/water separation using traditionai distillation/adsorption process (Fig. 2.9) and hybrid membrane-assisted vapor stripping (MAVS Fig. 2.10) process. Minimum energy (from minimum work calculation) shown as reference. Assumptions 37% and 85% efficient conversion of primary energy to electrical energy and thermal energy, respectively, 0.02 wt% ethanol in stripping column bottoms, and 99.5 wt% ethanol product (0.5 wt% water).

Vane LM, Alvarez FR, Huang Y, Baker RW. Experimental validation of hybrid distiUation-vapor permeation process for energy efficient ethanol-water separation. J Chem Tech Biotechnol 2010 85 502-11. 

In the same extractive distillation category, recent research developments have shown that it is possible to use nonvolatile hyperbranched polymers or ionic liquid as entrainers in the extractive distillation process. An example in the literature (Seiler et al." ) is for ethanol-water separation using hyperbranched polyglycerol or ionic liquid like [EMIM] [BF4] as entrai-ner. Because the entrainer is nonvolatile, the recovery of entrainer is much easier than saline extractive distillation. 

Many papers point out the economic advantages of pervaporation over conventional processes. A quantitative economic comparison between azeotropic distillation and hybrid column-pervaporation is presented by Guerreri," whose results show higher capital cost but much lower energy cost for the ethanol-water separation. A review of industrial applications of pervaporation, coupled with either distillation columns or chemical reactors, is... 

Pervaporation is a relatively new process with elements in common with reverse osmosis and gas separation. In pervaporation, a liquid mixture contacts one side of a membrane, and the permeate is removed as a vapor from the other. Currendy, the only industrial application of pervaporation is the dehydration of organic solvents, in particular, the dehydration of 90—95% ethanol solutions, a difficult separation problem because an ethanol—water azeotrope forms at 95% ethanol. However, pervaporation processes are also being developed for the removal of dissolved organics from water and the separation of organic solvent mixtures. These applications are likely to become commercial after the year 2000. 

Pervaporation. Pervaporation differs from the other membrane processes described so far in that the phase-state on one side of the membrane is different from that on the other side. The term pervaporation is a combination of the words permselective and evaporation. The feed to the membrane module is a mixture (e.g. ethanol-water mixture) at a pressure high enough to maintain it in the liquid phase. The liquid mixture is contacted with a dense membrane. The other side of the membrane is maintained at a pressure at or below the dew point of the permeate, thus maintaining it in the vapor phase. The permeate side is often held under vacuum conditions. Pervaporation is potentially useful when separating mixtures that form azeotropes (e.g. ethanol-water mixture). One of the ways to change the vapor-liquid equilibrium to overcome azeotropic behavior is to place a membrane between the vapor and liquid phases. Temperatures are restricted to below 100°C, and as with other liquid membrane processes, feed pretreatment and membrane cleaning are necessary. 

The catalytic esterification of ethanol and acetic acid to ethyl acetate and water has been taken as a representative example to emphasize the potential advantages of the application of membrane technology compared with conventional distillation [48], see Fig. 13.6. From the McCabe-Thiele diagram for the separation of ethanol-water mixtures it follows that pervaporation can reach high water selectivities at the azeotropic point in contrast to the distillation process. Considering the economic evaluation of membrane-assisted esterifications compared with the conventional distillation technique, a decrease of 75% in energy input and 50% lower investment and operation costs can be calculated. The characteristics of the membrane and the module design mainly determine the investment costs of membrane processes, whereas the operational costs are influenced by the hfetime of the membranes. 

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