ISSN 0040 5795, Theoretical Foundations of Chemical Engineering, 2010, Vol. 44, No. 4, pp. 545556.

Pleiades Publishing, Ltd., 2010. Original Russian Text A.K. Frolkova, V.M. Raeva, 2009, published in Khimicheskaya Tekhnologiya, 2009, Vol. 10, No. 8, pp. 469482.

ORGANIC TECHNOLOGIES

Bioethanol Dehydration: State of the Art

A. K. Frolkova and V. M. Raeva
Moscow State Academy of Fine Chemical Technology, pr. Vernadskogo 86, Moscow, 119571 Russia e mail: frolkova@mitht.ru, raeva@www.com.ru
Received February 24, 2009

AbstractThis article is a survey of the present day methods of dehydration of ethanol resulting from fer mentation processes. The existing separation techniques for waterethanol mixtures of various compositions are compared, and the conditions under which each particular technique is preferable are formulated. Key words: bioethanol dehydration, dehydrated ethanol, waterethanol mixtures, azeotropes, distillation, hybrid process. DOI: 10.1134/S0040579510040342

Bioethanol is considered to be the most promising fuel of the future since it is obtained from renewable sources, namely, biomass and is environmentally friendly. Ethanol raises the octane number of gasoline, is an antiknock agent, and can replace existing gaso line additives. In the United States, the fuel containing 10 wt % ethanol is becoming increasingly popular because of the recent limitations imposed on the con centration of ethers in the fuel, including methyl tert butyl ether, a detrimental oxygenate. Fuel composi tions containing at least 10 wt % ethanol need no anti freeze in the cold season. The introduction of ethanol not only saves gasoline (fuel derived from nonrenew able natural sources) by replacing it, but also markedly raises the extent of combustion of the fuel, thereby reducing the carbon monoxide level in the exhaust. Ethanol enhances the efficiency of the engine and is an excellent engine cleaning agent [1, 2]. The data listed in Table 1 characterize ethanol pro duction in some countries. Note that 73% of the world ethanol output is fuel ethanol. The fuel ethanol is mainly bioethanol obtained via enzymatic processes [3, 4]. National bioethanol programs in various coun tries take into consideration not only their own demand for fuel ethanol, but also social and environ mental aspects, such as mitigation of climatic conse quences and energetic security enhancement [5, 6]. Because of the high price of petroleum and the poor choice of alternative motor fuels, Brazil, some EU countries, India, and China actively develop their liq uid bioethanol production. Note that, in many countries, the government pro vides strong support for biofuel programs in order to make this branch of industry competitive. This support includes tax credits and regulations making use of bio fuel obligatory. EU and US manufacturers receive additional support as high ethanol import tariffs. According to some estimates, a protective biofuel pol

icy could ensure a fivefold increase in the proportion of biofuel used in the world transport, specifically from 1% today to 6% in 2020. The world bioethanol output in 2007 was 49.6 billion liters. The total annual average bioethanol output growth rate in the world in 2002 2007 was 19%. The world leaders in bioethanol pro duction are the United States and Brazil (Table 2). Their contribution to the world bioethanol output is 87.9%. EU countries, China, Canada, Thailand, India, and Australia are stepping up their ethanol out
Table 1. Ethanol production in the world [3, 7] Annual ethanol output, mil. l/yr Country 2003 United States Brazil China India France Germany Russia Canada Spain South Africa Thailand England Ukraine Columbia Poland Saudi Arabia Italy 10900 14428 3400 190 817 280 745 204 304 404 250 410 284 350 240 2004 13950 15338 3650 2000 830 270 766 245 420 409 280 400 290 340 210 2005 16139 15999 3800 1669 908 431 749 231 352 390 299 348 246 270 220 121 151 2006 18376 16998 3 849 1900 950 765 647 579 462 386 352 280 269 269 250 200 162

545

546 Table 2. Bioethanol production in 2007 Country United States Brazil EU*** China
Notes:

FROLKOVA, RAEVA

Amount, bil. l 24.6 19 2.2 1.8

Annual average output growth rate*, % 25 8.6 35.1 124.2**

Contribution to the world output, % 49.6 38.3 4.4 3.7

* In 20022007. ** In 20032007. *** Thirty two manufacturers.

put. New bioethanol facilities have been put into oper ation in Columbia, Central America, Turkey, Paki stan, Peru, Argentine, and Paraguay [8]. Evidently, the steady growth of the world consump tion of bioethanol has stimulated research aimed at improving and optimizing all bioethanol production stages. This survey of the scientific and technical liter ature is limited to the dehydration of ethanol resulting from enzymatic processes. At present, absolute etha nol containing 99.5 wt % alcohol or more is in greatest demand in fuel applications. The presence of water in the fuel is undesired because of the formation of sepa rating mixtures with hydrocarbons. The separation strategy for systems of various com positions into products with preset quality is dictated by the existence of azeotropy in the ethanolwater system. This strategy involves methods of separation of azeotropic mixtures (azeotropic, heteroazeotropic, extractive, and salt effect distillation techniques; dis tillation combined with phase separation; pressure swing distillation; etc.), which are aimed at circum venting thermodynamic limitations and are based on the principle of concentration field redistribution between distillation regions [9, 10]. In the foreign lit erature, these techniques are considered as separate engineering solutions. The purpose of this survey of data published in the latest decade is to compare approaches to the dehydra tion of fermentative and synthetic ethanol and to find the conditions under which each particular dehydra tion technique is preferable. Significant points here are the process capacity and the stock composition. For example, extraction, pervaporation, and molecu lar sieve adsorption are not usually employed in large scale ethanol dehydration. At the same time, these techniques are successfully used in the continuous separation of small amounts of waterethanol mix tures. Below, these techniques will be considered in greater detail. PERVAPORATION The separation efficiency in pervaporation is manly determined by the properties of the membranes and

process conditions. Here, the physicochemical prop erties of the components being separated and those of the mixture are of much lower significance than in the case of distillation. This allows azeotropic mixtures to be separated. In pervaporation, the mixture to be sep arated does not need to be brought to boiling and it is, therefore, possible to utilize low grade heat. As dis tinct from distillation, which needs multiple evapora tions of the entire mixture, pervaporation consumes energy only for permeate evaporation. Pervaporation generally does not require any extra reagents. Azeotro pic and extractive distillation, extraction, and other methods employing extra chemicals (separation or extracting agents) need subsequent recovery of these chemicals, which complicates the separation technol ogy. The operational advantages of membrane units are obvious. Their modular design allows their capacity to be varied by simply adding or cutting off membrane modules and makes easier their maintenance. The specific surface area of a membrane (phase contact area) in a membrane unit is several times larger than the same parameter in any tray or packed distillation column. Accordingly, membrane modules are much smaller [11, 12]. All of the above facts are undoubtedly of great sig nificance. However, the optimality of a given technol ogy is governed by its cost. We compared the operating expenses of ethanol dehydration to 99.8 wt % by per meation, pervaporation, distillation, and adsorption for a fixed production rate of 30 t/day, which were found to be $15.75, $12.616.6, $31.9545.65, and $36.6 per ton, respectively [13]. In addition, we think that there is a plant equip ment standardization problem. A distillation tray of a particular type can be used in the separation of various mixtures. The decisive criteria in the selection of a tray are its efficiency and some performance parameters. For example, perforated trays should not be used for polymerizable substances, because temperature dis turbances can cause their failure. By contrast, the performance of a membrane in separation of various mixtures depends on its chemical nature. In pervaporation, it depends on the water con tent of the initial ethanolwater mixture whether hydrophilic membranes should be used to separate water or hydrophobic membranes should be employed to separate ethanol [8, 14]. It is theoretically possible to organize consecutive separation of solutions con taining different ethanol concentrations on mem branes of different natures. However, the separation capacity of moist membranes is insufficient for com mercial scale basic organic synthesis. Raising the number of membranes modules shortens the pervapo ration time and thus reduces energy consumption, but it increases the depreciation cost of the membranes. This is a restrictive factor in the replacement of distil lation with pervaporation in large scale separation technologies. In order to promote the commercializa
No. 4 2010

JOURNAL OF CTHEORETICAL FOUNDATIONS OF CHEMICAL ENGINEERING Vol. 44

BIOETHANOL DEHYDRATION: STATE OF THE ART Table 3. Comparison of methods of ethanol dehydration from 94 to 99.9 vol % [12] Cost Expense item permeation pervaporation Steam Electricity Cooling water Replacement of membranes Entrainer Replacement of molecular sieves Total cost 20.0 2.0 9.5 31.5 6.4 8.8 2.0 15.3 32.5 heteroazeotropic distillation with cyclohexane 60.0 4.0 7.5 4.8 76.3

547

adsorption on molecular sieves 40.0 2.6 5.0 25.0 72.6

Note: Costs are in DM/t as of the year 1991.

tion of the pervaporation separation of waterethanol mixtures, it is necessary to continue search for mem branes and membrane materials meeting the specific requirements of this separation problem and to study the main factors in their separation efficiency, such as the feed composition, process temperature, and per meate pressure [15, 16]. In 2000, Sulzer Chemtech Membrantechnik AG (Germany) installed ethanol dehydration membrane modules with 500150000 l/day capacity at 24 plants [12]. Table 3 presents a comparison between the costs of ethanol dehydration from 94 to 99.9 vol % by differ ent methods. Evidently, the membrane separation methods are highly competitive. However, these data leave aside the costs of ethanol solution preconcentra tion to a near azeotropic composition. ADSORPTION Two water adsorption techniques are used in the separation of waterethanol mixturesliquid phase and vapor phase adsorption. Adsorbents employed in the liquid phase process are type A zeolites, cellulose based materials, etc. Vapor phase water adsorption widely relies on inorganic adsorbents, such s zeolite molecular sieves (3A and 4A), lithium chloride, and silica gel. Sub stances of biological origin are considered only as poten tial adsorbents for this application [17]. Molecular sieves with a small pore size adsorb water molecules well, so they are most efficient in water removal from solutions with low water content. There is an ethanol dehydration method in which the waterethanol solution is concentrated by distillation, the product is then dehydrated using molecular sieves, and the adsorbent is regenerated by desorption [18]. A drawback of this method is the large amount of liquid forming at the molecular sieve regeneration stage. Carrying out this process in the vapor phase excludes the wetting of the molecular sieves in adsorption and their drying in desorption, thus reducing heat and energy consumption [18].

Ethanol dehydration over synthetic molecular sieves offers some technological advantages, such as a simple process design, a long service life of up to 5 years, ease of regeneration, and high economic effi ciency. The latter is due to the high adsorption capac ity and the considerable water diffusion rate. However, as compared to pervaporation, water adsorption is now attracting much less attention. Researchers cur rent efforts are being focused on experimental deter mination of the capacity of various zeolites for sepa rating ethanolwater mixtures and on simulation of adsorption in particular systems [19, 20]. Carbon is another efficient water adsorbent. It can dehydrate waterethanol vapor mixtures containing 1.650.9% water. Carrying out the process in an adia batic carbon adsorber demonstrated that the adsor bent is stable over 85 adsorptiondesorption cycles using hot air or nitrogen (80120C). However, as in the case of pervaporation, integration of different methods is appropriate here: dilute ethanol should be concentrated to a near azeotropic composition by dis tillation, and the product should be further dehydrated by adsorption [21]. The present day commercial scale process named Pressure Swing Adsorption (PSA) is conducted in an adsorberdesorber complex. Adsorption is carried out on zeolites at an elevated pressure of 379.2 kPa and a temperature of 440 K. The feed, which contains 92 wt % ethanol, is introduced into the top section of the column at a rate of 10410 kg/h. The ethanol con centration in the product stream is above 99.5 wt %. The regeneration of the adsorbent includes the follow ing steps: reducing the pressure to 13.8 kPa, which causes partial water desorption; water desorption at 3.8 kPa; removal of residual water with part of the vaporous product stream (99.5 wt % ethanol); and raising the pressure to 379.2 kPa. The duration of a cycle is 345 s. Unlike conven tional adsorption, the PSA processes does not use hot nitrogen or air in regeneration [22].
No. 4 2010

THEORETICAL FOUNDATIONS OF CHEMICAL ENGINEERING Vol. 44

548

FROLKOVA, RAEVA

EXTRACTION The solvents used in the liquidliquid extraction of ethanol from dilute aqueous fermentation solutions must meet not only standard requirements, including low solubility in the aqueous phase, short separation time, chemical inertness, and environmental friendli ness, but also a number of specific requirements. For example, if the aqueous phase is returned to the fer menter, the extracting agent should be both nontoxic and innutritious to microorganisms [23]. It is pertinent to use extraction for aqueous solu tions containing 25 wt % ethanol. The dilute solu tion is sometimes concentrated to an ethanol content of 1030 wt %. Extraction with paraffin oil is con ducted at 105C, and the extract is then cooled to 30C. The resulting ethanolic phase contains 4 5 wt % light hydrocarbons and can be added directly to a fuel [22]. Obviously, this technology does not include ethanol dehydration. A new process was suggested for ethanol isolation from fermentation broths. In this process, the extract ing agent is completely soluble above the upper critical solution temperature (UCST) and is partially soluble at lower temperatures (in the two phase region at 60 100C). The hot solvent, which is hexadecane, is brought into contact with the waterethanol mixture at 115C (15 above UCST) to extract ethanol. The ethanolsolvent mixture is then cooled to 30C in a separator, and the solvent is returned to the extractor. According to experimental data, this separation pro cess affords ethanol containing <1% water [24]. Separation of waterethanol mixtures with super critical CO2 has not been commercialized in the basic organic synthesis industry. However, this extractant is used in the pharmaceutical industry. Supercritical CO2 has a comparatively low critical point (7.38 MPa, 304.25 K) and is inexpensive. Furthermore, it is envi ronmentally friendly [25]. Carbon dioxide is easy to recover: it is readily separable from ethanol in a distil lation column under elevated pressure. Since the CO2ethanolwater mixture is zeotropic at 333.2 K and 10 MPa, it can be separated by conventional dis tillation as well [26, 27]. Budich and Brunner [28] compared the amounts of energy required for obtain ing anhydrous ethanol (kJ/l) by various methods: pres sure swing, 4730; heteroazeotropic distillation with pentane, 8100; extraction with supercritical CO2, 2500. The potential of supercritical carbon dioxide for separation of aqueous ethanol solutions is now being investigated. In particular, the following factors in batch extraction are discussed: reflux ratio, ethanol concentration in the initial solution, and extraction conditions and time. There have been studies on the separation of dilute fermentation solutions of ethanol (0.11.7 wt %) with supercritical carbon dioxide. It was demonstrated that raising the pressure, tempera

ture, and ethanol concentration in the initial solution is favorable for extraction [22, 28, 29]. Since the aqueous solutions resulting from fermen tation are dilute (415% ethanol, according to differ ent sources), they can be directly separated by extrac tion, pervaporation, or pervaporation or preconcen trated to a near azeotropic composition by distillation [21, 25, 29]. As was noted above, the present day approach to separation of azeotropic mixtures is based on concen tration field redistribution between separation regions. The basic elements of this azeotropic separation tech nology include separation complexes (sets of appara tuses coupled by feedforwards and feedbacks) each executing its particular function. In recent years, there have been extensive theoretical studies of the opera tion of these complexes [9, 10]. We will dwell on con tinuous dehydration processes for the azeotropic eth anolwater system that are based on the principle of concentration field redistribution between separation regions and have been commercialized in the basic organic synthesis industry. PRESSURE SWING DISTILLATION If the composition of the binary azeotrope changes as the external conditions (temperature, pressure) are varied, it is possible to separate the mixture in a com plex of distillation columns operating at different pres sures. Ethanol dehydration by this method was sug gested by Lvov [30] as early as 1960. At present, this method is used in the dehydration of ethanol resulting from fermentation [31]. An efficient way of isolating ethanol from the fermentation solution is by pervapo ration, which affords an ethanol concentration of up to 40 mol %, followed by distillation under varying pressure (pressure swing distillation). In this tech nique, utilizing the heat of the streams coupling the columns can reduce the operating expenses for etha nol production by 44% [32]. Figure 1 shows the typical distillation flowsheet for the ethanol (1)water (2) mixture with the composi tion XF. The appropriateness of this flowsheet is gov erned by the value of the azeotropic shift x = x' x'' (change in the azeotrope composition) caused by a change in pressure from P1 to P2. The maximum x value in the technologically acceptable pressure range minimizes the recycle rate and reduces the energy required for separation [33]. EXTRACTIVE DISTILLATION In the case of extractive distillation, the principle of concentration field redistribution between continuous distillation regions means directed transformation of the phase diagram of the initial system in the presence of an appropriate separating agent selectively changing the relative volatility of the components. With an appropriate high boiling separating agent, this separa
No. 4 2010

JOURNAL OF CTHEORETICAL FOUNDATIONS OF CHEMICAL ENGINEERING Vol. 44

BIOETHANOL DEHYDRATION: STATE OF THE ART

549 (b) x I xF x'

, ,

tion method is the least energy intensive because the separation agent almost does not evaporate. The binary azeotropic mixture ethanolwater with the ini tial composition xF is separated using the standard uni form complex consisting of two columns (Fig. 2), namely, an extractive distillation column (I) and a simple distillation column recovering the separation agent (II) [34]. Here, the separation agent can be a compound forming homogeneous mixtures with the azeotrope components, such as ethylene glycol, glyc erol, 1,3 diaminopentane, diethylenetriamine, and hexachlorobutadiene. General requirements and conventional selection methods for separation agents were described by Kogan [35]. The present day approaches to agent selection and to prediction of separation results need a deeper insight into the nonlocal properties of the dia grams of extractive systems, including the mutual arrangement of particular manifolds in the concentra tion simplex: univolatility lines, pseudoideal mani folds, Bancroft isothermisobar lines, and isotherm isobar lines of the inversion of partial molar heats of evaporation [36]. A comparatively new method that has not been widely commercialized in the industrial separation of waterethanol mixtures is extractive distillation in a single column using ethylene glycol as the separation agent [3740]. This technology is promising for batch distillation of small amounts of mixtures in the phar maceutical and fine chemical industries. Brito et al. [37] considered ethanol dehydration in the presence of ethylene glycol in one column having 20 trays (count ing from the column bottom). The initial solution (85 mol % ethanol) is fed to the 12th tray, and almost pure water (99.27 mol %) is drawn from the 6th tray. The distillate contains 99.71 mol % ethanol and some impurities. The bottom product is pure ethylene glycol (99.98 mol %), which is returned to the column top. The column can be fitted with a second reboiler [38]. The classical extractive distillation design ensures the same product quality and ethylene glycol purity, but it involves two columns (Fig. 2). The first is the ethanol separation column. It has 20 trays, with the feed intro duced at the 12th tray and ethylene glycol entered at the top. The second is the water separation column, which again has 20 trays, with the feed entered at the 6th tray. This separation design is more energy and capital intensive. Bioethanol dehydration technologies employ not only conventional separation agents, but also dissolved salts, mixtures of liquid separation agents and salts, ionic liquids, and highly branched polymers [17, 41]. Researchers are expressing increasing interest in ionic liquids. By way of example, we will present the total numbers of recent publications dealing with ionic liquids in two well known journals: The Journal of Chemical Engineering Data, over 120 articles from 2000 till now; Fluid Phase Equilibria, over 110 articles from 2004 till now. In separation technologies, ionic

y1 P1 P2

(a)

II

xF

x' x'' x

X1

Fig. 1. Pressure swing distillation of the azeotropic mix ture ethanol (1)water (2): (a) liquidvapor equilibrium diagram; (b) distillation flowsheet involving (I) a column operating at the pressure P1 and (II) a column operating at the pressure P2.

liquids can replace many toxic and hazardous volatile compounds that are used today as separation agents. As distinct from most conventional solvents, which are molecular compounds, ionic liquids are salts with a low melting point. They are liquid in a wide tempera ture range and are inert toward air and water. In addi tion, the have a low vapor pressure and do not contam inate the environment. Most studies have so far been focused on the effects of ionic liquids on the phase equilibrium in waterethanol mixtures of various compositions [4249] and on the applicability of model equations to phase equilibria in systems involv ing ionic liquids [50]. A variant (limiting case) of extractive distillation is salt effect distillation. The separation agent in this technique is a salt solution that is mainly miscible with one of the mixture components, reducing its relative volatility. The dissociation of the salt is accompanied by the solvation of the ions of the less volatile compo nent (water). Salt effect distillation is a suitable method for mixtures n which comparatively small amounts of a salt can markedly raise the relative vola tility of a component.
1 2

xF I 23 3 II

Fig. 2. Extractive distillation of the ethanol (1)water (2) mixture with a high boiling separation agent (3) in two dis tillation columns (I, II). No. 4 2010

THEORETICAL FOUNDATIONS OF CHEMICAL ENGINEERING Vol. 44

550 y 1.0 1 2 0.5

FROLKOVA, RAEVA

solutions [5155]. Figure 3 shows a phase diagram illustrating the effect of a salt on the vaporliquid equilibrium in the ethanolwater system. One of the unsolved problems of phase equilibrium simulation and salt effect distillation design, including in ethanol dehydration, is that of taking into account the effects of the salt on the enthalpy of liquid flows in the column and on the isobaric heat capacities [51, 55]. There has been a historical survey of the commer cialization of this method in industry (HIAG process). In 19301950, about 100 plants using this technology was built in Europe, and their total capacity was up to 43000 t/yr. The last plant of this type was put into operation in 1965 in Brazil. This ethanol dehydration technology employs a mixture of sodium and potas sium acetates, which are introduced into the hot reflux of the distillation column. Dilute ethanol solutions (<10 wt % ethanol) to be dehydrated should generally be preconcentrated [51]. However, there has been only a single work [55] in which two salt effect distillation processes (using potassium acetate) are suggested and completely cal culated for dilute and concentrated aqueous solutions (Figs. 4, 5, respectively). In the former case, dilute ethanol is fed into extractive distillation column 1. The salt recovery stage consists of evaporation followed by drying with hot air in unit 3. The later design includes preconcentrating distillation column 1, extractive dis tillation column 2, and drying unit 3. For these designs, it is possible to compare the operation param eters of the extractive distillation column (Table 4) and energy consumptions at particular stages pf the pro cess (Table 5). The total energy consumption is higher for the dehydration of dilute ethanol. There are energy consumption data (MJ/(kg etha nol)) for ethanol dehydration by extractive or azeotro pic distillation with the following separation agents [55]: ethylene glycol,
Air 3

0 0.5 x1

Fig. 3. Qualitative vaporliquid equilibrium diagram of the ethanol (1)water (2) system at atmospheric pressure in the absence of a salt (dashed line) and in the presence of a salt (solid line).

Ethanol KAc Feed Vapor 1 1 2 Vapor Condensate

Fig. 4. Salt effect distillation of dilute aqueous ethanol solutions [55]: (1) extractive distillation column, (2) evap oration unit, and (3) drying unit.

Air r 2 r 2 Air 3

KAc

Ethanol KAc Feed 1 2

Water

Air

KAc

34.06; diethyl ether, 13.59; benzene, 12.15; pen tane, 10.87. The above process involving ethanol pre concentration is characterized by the lowest energy consumption of 9.27 MJ/kg. This technology is being improved by seeking new separation agents, optimiz ing heat flows, introducing an extra distillation col umn for concentrating the solution (with a heat pump and optimal side recycle), and using an evaporator for concentrating and drying the salt [53, 54]. The separation efficiency can also be enhanced by combining separation agents. Unlike salt effect distil lation, this technology does not need salt recovery (Figs. 4, 5). It is possible to carry out extractivesalt distillation [56, 57]. Table 6 lists column operation parameters for extractive distillation with ethylene gly col and calcium chloride (CaCl2 concentration of 0.075 g/(ml ethylene glycol)).
No. 4 2010

Fig. 5. Salt effect distillation of concentrated aqueous eth anol solutions [55]: (1) distillation column, (2) extractive distillation column, and (3) drying unit.

Various salts, including sodium nitrate, lithium chloride, sodium chloride, potassium chloride, cal cium chloride, potassium iodide, and potassium ace tate, were suggested for separation of aqueous ethanol

JOURNAL OF CTHEORETICAL FOUNDATIONS OF CHEMICAL ENGINEERING Vol. 44

BIOETHANOL DEHYDRATION: STATE OF THE ART

551

AZEOTROPIC DISTILLATION In azeotropic distillation, a substance forming homogeneous azeotropes with the components of the initial mixture is introduced into the column. The sep aration of the new azeotropic mixture requires a spe cial purpose technique to be used. It is commonly thought that azeotropic distillation in most cases is less economic in terms of energy because the azeotrope forming agent undergoes multiple evaporations. Homo azeotropic distillation is considered to be appropriate when the mixture of the azeotrope forming agent with one of the components is usable without being separated. For the dehydration of ethanolwater mixtures, he only separation agent of this kind is ethylenediamine. It forms a homogeneous, maximum boiling azeotrope with water and is unstable without water [34]. HETEROAZEOTROPIC DISTILLATION Heteroazeotropic distillation is the azeotropic dis tillation technique in which the liquid is separated deliberately into two phases by introducing a het eroazeotrope forming agent into the system. A classi cal example of heteroazeotropic distillation is ethanol dehydration with benzene [30]. In this process, ben zene (3), which has limited solubility in water, is added to the azeotropic ethanol (1)water (2) mixture (Fig. 6a). In the steady state operation of the separa tion complex, the role of the heteroazeotrope forming agent is played by the organic (benzene) layer. Other separation agents are possible here, including dichlo roethane, isobutyl alcohol, butyl acetate, propyl ace tate, diethyl ether, diisopropyl ether, cyclohexane, 2,2,4 trimethylpentane, toluene, n pentane, cyclo pentane, methylcyclopentane, n hexane, 2 methyl pentane, hex 1 ene, 2,2 dimethylpentane, and 2,2,3 trimethylbutane [22, 35, 58, 59]. Since the fermentation of vegetable feedstocks, biowaste, polysaccharides, sugar, treacle, and other biomaterials yields dilute aqueous ethanol solutions, it is appropriate to carry out conventional distillation to obtain a near azeotropic composition prior to het eroazeotropic distillation (Fig. 6b). ADSORPTIONDISTILLATION COMPLEXES Ethanol can be dehydrated by combining distilla tion and adsorption. The original scheme of the pres sure swing adsorption process is presented in Fig. 7. The initial mixture is fed into the vaporizer and is then directed to a standard adsorption section consisting of adsorber I and desorber II. Adsorption column I is operated at a higher pressure than desorption column II. The desorption agent is dehydrated ethanol (part of the product stream). After a certain time, the pressure in the columns is changed so that the adsorber becomes the desorber and vice versa. The adsorption product, which is dehydrated etha nol, leaves adsorber I as a vapor. The heat of this

Table 4. Comparison between salt effect distillation columns using potassium acetate [55] Parameter values Distillation column parameters Feed flow rate, mol/s Feed composition, mol % ethanol Feed temperature, K Number of trays Feed tray number Minimum/working reflux ratio Salt flow rate, mol/s Reboiler power, W dilute ethanol concentrated as the feed ethanol as the feed 555.5 2.4 303.15 37 18 2.1/2.5 3.74 4.85 106 22.22 60 353.45 35 5 1.0/1.2 1.80 3.07 105

Note: Distillate composition: 98.9 mol % ethanol; distillate flow rate: 13.5 mol/s.

Table 5. Energy consumption in salt effect distillation pro cesses [55] Energy consumption at particular process stages, W Apparatus dilute ethanol concentrated as the feed ethanol as the feed Extractive distillation column Preconcentration column Evaporation unit Drying unit Total energy consumption 4.85 106 2.16 107 4.53 106 3.1 107 3.07 105 4.84 106 5.55 106 10.7 106

stream is used to heat the bottom section of the initial mixture distillation column. The ethanol pure frac tion from desorber II provides the feed for the distilla tion column. The distillate from this column, which has a near azeotropic composition, is returned to the
(a) 3 xF xF 1 2 2 1 2 (b) 3

Fig. 6. Dehydration of ethanol (1)water (2) mixtures by heteroazeotropic distillation: (a) structure of the separa tion complex; (b) design involving a preconcentration stage [22]. No. 4 2010

THEORETICAL FOUNDATIONS OF CHEMICAL ENGINEERING Vol. 44

552

FROLKOVA, RAEVA

Table 6. Column operation parameters for extractivesalt dis tillation with ethylene glycol and calcium chloride [57] Parameter values for the columns Operation parameter Feed flow rate, kmol/h Extracting agent flow rate, kmol/h Distillate flow rate, kmol/h Feed temperature, K Extracting agent tem perature, K Reflux ratio Number of theoretical trays Feed tray number Pressure, atm Energy consumption, kJ/(kg ethanol) Extractive distil lation column 100 30 88.864 351.33 353.15 0.35 18 12 1 1204 Extracting agent recovery column 44 13.70 394.13 0.25 11 6 0.2 221

vaporizer. The bottom product contains only traces of ethanol. PERVAPORATIONDISTILLATION COMPLEXES An analysis of the literature demonstrated that the development and commercialization of hybrid pro cesses combining distillation and membrane separa tion is among the priority areas today. Waterethanol mixtures are usually separated by pervaporation or

permeation. In both processes, the initial mixture (liq uid in pervaporation and vapor in permeation) is sep arated by means of partial evaporation through a selec tive nonporous membrane and the permeate is in the vapor state. The retentate is a liquid in pervaporation and a vapor in permeation. A large number of hybrid ethanol dehydration schemes with different orders of mass transfer pro cesses for various feedstock compositions (distillation + pervaporation, pervaporation + distillation, distilla tion + pervaporation + distillation) have already been commercialized [58, 61]. The conceptual scheme of the hybrid separation process is presented in Fig. 8. This scheme includes distillation column 1 for con centrating the ethanolwater mixture and pervapora tion unit 2 for obtaining pure ethanol [62, 63]. The dilute aqueous ethanol solutions resulting from fer mentation are usually subjected to preconcentration. Several pervaporation modules are employed in some cases (Table 7), and this allows very dilute ethanol solutions to be dehydrated [58]. Here, the bottoms of the distillation column are almost pure water. Another possible ethanol dehydration scheme includes two distillation columns (1, 2) and one per vaporation module (3) (Fig. 9). This variant is intended for water rich feedstocks. The diagrams of distillation and evaporation through the membrane illustrate the principle of concentration field redistri bution between separation regions. The performance of all of the above hybrid schemes can be optimized by increasing the surface area of the membrane, by improving its geometry, by reducing the reflux ratio of the distillation column, and by optimizing the recycle stream (changing from partial to total recycle) [62, 64, 65]. The development of the physicochemical founda tions of mass transfer processes has improved conven
Retentate

Vapour superheater

Condencer

Condencer Distillate (~95%)

Distillate 2 3 6

Evaporizer

Col. I

Col. II

Ethanol (~70%)

Rectifying column

Feed 1 Permeate 4

Dehydrated ethanol

Feed (~92%) Dehydrated ethanol (~99.6%)

Dehydrated ethanol (vapour)

Heat exchanger

Condencer

Bottom product (water)

Water
Fig. 8. Distillationmembrane complex for separation of ethanol (1)water (2) mixtures: (1) distillation column, (2) membrane unit, and (36) heat exchangers. No. 4 2010

Fig. 7. Ethanol dehydration via pressure swing adsorption and distillation [60]: (I) adsorber and (II) desorber.

JOURNAL OF CTHEORETICAL FOUNDATIONS OF CHEMICAL ENGINEERING Vol. 44

BIOETHANOL DEHYDRATION: STATE OF THE ART Table 7. Outcomes of separation processes combining distillation and pervaporation Ethanol concentration Separation data Feed composition composition of the perme for distillation distillate composition number of modules ethanol quality ate from the last module 43 wt % 4 mol % 812 vol % 82 wt % 60 mol % 94 vol % 1 2 3 99.9 wt % 99.5 wt % >99.9 vol % Not indicated 4050 mol % 1220 vol %

553

Reference

[62], [63] [58] [11]

tional separation technologies and has given birth to radically new ones. For example, waterethanol mix tures have been separated by the action of pulsed cav itation and the use of electric fields and ion exchange sorption for this purpose is discussed. Electrohydrodynamic distillation columns have recently been suggested for recovery of comparatively small amounts of solvents (up to 5000 t per year) in the electronic industry. Mass transfer in these apparatuses is intensified and controlled by means of an electric field in the liquid spraying regime. The water content of recovered ethanol should not exceed 12 vol %. An electrohydrodynamic distillation apparatus with a 1 m long contact zone ensures, in a wide range of reflux ratios, an ethanol concentration of >92 vol % in the recovered solvent and a residual ethanol concen tration of below 1 vol % in the bottoms [66]. The introduction of a molecular sieve into the sep aration system produces an effect on the liquidvapor equilibrium in the ethanolwater system: pure ethanol was obtained from a 40% ethanol solution [67]. It is likely that distillation and adsorption can be combined in one apparatus. A separation technology combining adsorption o molecular sieves, pervaporation, and dis tillation has been suggested for ethanolwater mix tures [1]. Another tendency in present day bioethanol pro duction technologies is toward combining a chemical reaction and a separating mass transfer process in one apparatus. Fermentation has been combined with dis tillation [68] and with membrane separation [6972]. It is claimed that fermentation followed by vacuum membrane distillation is economically attractive. A hydrophobic and a hydrophilic membrane are used, respectively, to remove ethanol and water from the reaction system, and the water is returned to the fer menter [17]. The comparative analyses of various ethanol dehy dration methods have mostly been qualitative and have been limited to ascertaining that distillation is an energy intensive process and to emphasizing the advantages of the method developed by a particular author. The most significant advantages and draw backs of particular ethanol dehydration technologies were discussed by Moura and Medeiros [73]. Adsorp tion on molecular sieves is attractive for its low energy

demand for separation, operational stability, and high productivity (the last statement seems questionable to us). The main flaw of this technology is the high cost of the equipment. Extractive distillation with ethylene glycol is notable for its high productivity and control reliability. Its obvious disadvantage is high operating expenses. This is also true for heteroazeotropic distil lation with cyclohexane. The advantage offered by vapor permeation is low energy consumption, and its drawbacks are the high cost of the equipment and the risk of innovationthis process has not been widely commercialized as yet. Unfortunately, we did not find economic assess ments that would allow a correct comparison of etha nol dehydration methods as was done for isopropanol dehydration [74]. Even energy demands cannot be compared in most cases. The choice of bioethanol dehydration method depends primarily on the capacity of the fermentation unit. For small amounts of bioethanol, it is appropri ate to use batch extractive distillation, pervaporation, or adsorption. Kaminski et al. [1] compared the eco nomic efficiencies of distillation and pervaporation in ethanol dehydration to a concentration of 99.5 wt %. For a production rate of 100 l/day, azeotropic distilla tion with cyclohexane and adsorption are more costly than pervaporation by a factor of 2 and 1.5, respec tively. For production rates higher than 100 l/h, the
(a) y1
Concentrate 3

(b)
x1 = 0.85

I II 0

F0 x1 = 0.04 1 Permeate Water Ethanol x1 = 0.095 2

x Az x1

Fig. 9. (a) Diagrams of (I) distillation and (II) evaporation through the membrane. (b) Separation complex for etha nol (1)water (2) mixtures resulting from fermentation: (1, 2) distillation columns and (3) membrane module. No. 4 2010

THEORETICAL FOUNDATIONS OF CHEMICAL ENGINEERING Vol. 44

554

FROLKOVA, RAEVA 12. Kujawski, W., Application of Pervaporation and Vapor Permeation in Environmental Protection, Pol. J. Envi ron. Stud., 2000, vol. 9, no. 1, pp. 1326. 13. Wee, S.L., Tye, C.T., and Bhatia, S., Membrane Sepa ration ProcessPervaporation through Zeolite Mem brane, Sep. Purif. Technol., 2008, vol. 63, no. 3, pp. 500516. 14. Namboodiri, V.V. and Vane, L.M., High Permeability Membranes for the Dehydration of Low Water Content Ethanol by Pervaporation, J. Membr. Sci., 2007, vol. 306, nos. 12, pp. 209215. 15. Banat, F., Abu, Al RabF., and Bani Melhem, K., Desalination by Vacuum Membrane Distillation: Sen sitivity Analysis, Sep. Purif. Technol., 2003, vol. 33, no. 1, pp. 7587. 16. Furukawa, S., Goda, K., Zhang, Yi., and Nitta, T., Molecular Simulation Study on Adsorption and Diffu sion Behavior of Ethanol/Water Molecules in NaA Zeolite Crystal, J. Chem. Eng. Jpn., 2004, vol. 37, no. 1, pp. 6774. 17. Huang, H.J., Ramaswamy, S., Tschirner, W., and Ramarao, B.V., A Review of Separation Technologies in Current and Future Biorefineries, Sep. Purif. Tech nol., 2008, vol. 62, no. 1, pp. 121. 18. Makarov, V.V. Petrykin, A.A., Skvortsov, E.A., et al., RF Patent 2?265?473, Byull. Izobret., 2005, no. 34. 19. Lu, L., Shao, Q., and Huang, LuX., Simulation of Adsorption and Separation of EthanolWater Mixtures with Zeolite and Carbon Nanotube, Fluid Phase Equilib., 2007, vol. 261, nos. 12, pp. 191198. 20. Ladisch, M.R., Voloch, M., Hong, J., et al., Cornmeal Adsorber for Dehydrating Ethanol Vapors, Ind. Eng. Chem. Proc. Des. Dev., 1983, vol. 23, pp. 437445. 21. Simo, M., Brown, C.J., and Hlavacek, V., Simulation of Pressure Swing Adsorption in Fuel Ethanol Produc tion Process, Comput. Chem. Eng., 2008, vol. 32, no. 7, pp. 16351649. 22. Pucci, A., Phase Equilibria of Alkanol/Alkane Mix tures in New Oil and Gas Process Development, Pure Appl. Chem., 1989, vol. 61, no. 8, pp. 13631372. 23. Offemanm, R.D., Stephenson, S.K., Franqui, P., and Cline, J.L., Extraction of Ethanol with Higher Alcohol Solvents and Their Toxicity to Yeast, Sep. Purif. Tech nol., 2008, vol. 63, no. 2, pp. 444451. 24. www.ethanolindia.net/molecular_sieves.html,vasatwiki. icri sat. org/index.php/Grain_alcohol#Purification 25. Rodrigues, M.A., Almeida, J., Li, J., Matos, H.A., and De Azevendo, E.G., Efficiency of Water Removal from Water/Ethanol Mixtures Using Supercritical Carbon Dioxide, Braz. J. Chem. Eng., 2006, vol. 23, no. 2, pp. 205212. 26. Knez, Z., Skerget, M., Ilic, L., and Liitge, C., Vapor Liquid Equilibrium of CO2Organic Binary Solvent Systems (Ethanol, Tetrahydrofuran, ortho Xylene, meta Xylene, para Xylene), J. Supercrit. Fluids, 2008, vol. 43, no. 3, pp. 383389. 27. Giivenc, A., Mehmetoglu, U., and Calimi, A., Super critical Extraction of Ethanol, Turk. J. Chem., 1999, vol. 33, pp. 285291. 28. Budich, M. and Brunner, G., Supercritical Fluid Extraction of Ethanol from Aqueous Solutions, J. Supercrit. Fluids, 2003, vol. 25, no. 1, pp. 4555.
No. 4 2010

cost of pervaporation depends linearly on the produc tion rate. Pervaporation is economically efficient at water concentrations below 10 wt %. The residual water con centration in ethanol in this case is 1100 ppm. Distilla tion is preferable at production rates of above 5000 l/h. Thus, the present day approach to ethanol dehy dration reliw on combining different mass transfer processes. Dilute solutes containing 112 wt % etha nol should be preconcentrated by distillation to a near azeotropic composition. This should be followed by using inhomogeneous separation techniques involving salt effect distillation, heteroazeotropic dis tillation, and distillationpervaporation and adsorp tiondistillation complexes [22, 55, 58]. REFERENCES
1. Kaminski, W., Marszalek, J., and Ciolkowska, A., Renewable Energy SourceDehydrated Ethanol, Chem. Eng. J., 2008, vol. 135, no. 1, pp. 95102. 2. Tsarev, A.V., Balabin, R.M., Karpov, S.A., and Syun yaev, R.Z., Optimization of the Performance and Envi ronmental Properties of EthanolGasoline Fuels Using Microwave Treatment, Alternat. Energet. Ekol., 2007, vol. 52, no. 8, pp. 6974. 3. Sanches, O.J. and Cardona, C.A., Trends in Biotech nological Production of Fuel Ethanol from Different Feedstocks, Bioresour. Technol., 2008, vol. 99, no. 13, pp. 52705295. 4. Cardona, C.A. and Sanches, O.J., Fuel Ethanol Pro duction: Process Design Trends and Integration Opportunities, Bioresour. Technol., 2007, vol. 98, no. 2, pp. 24152457. 5. Wasewar, K.L. and Pangarkar, V.G., Intensification of Recovery of Ethanol from Fermentation Broth Using Pervaporation: Economical Evaluation, Chem. Bio chem. Eng. Q., 2006, vol. 20, no. 2, pp. 135145. 6. Blackburn, W.J. and Teague, J.M., Coordinating Cali fornias Efforts to Promote Waste to Alcohol Produc tion, Appl. Biochem. Biotechnol., 1998, vol. 70 72, pp. 821841. 7. Karpov, S.A., Current Aspects of Fuel Ethanol Produc tion in Russia and Abroad, Chem. Technol. Fuels Oils, 2008, vol. 44, no. 1, pp. 14. 8. www.abercade.ru/research/analysis/425.html, www.e vid.ru/index m 192 p 63 article 17596.htm 9. Serafimov, L.A. and Frolkova, A.K., Fundamental Principle of Concentration Field Redistribution between Separation Regions as a Basis for the Design of Technological Systems, Teor. Osn. Khim. Tekhnol., 1997, vol. 31, no. 2, pp. 193201 [Theor. Found. Chem. Eng. (Engl. Transl.), vol. 31, no. 2, pp. 159166]. 10. Frolkova, A.K., Theoretical Foundations of Multicom ponent Multiphase Separation Using Functional Com plexes, Doctoral (Eng.) Dissertation, Moscow: Moscow Inst. of Fine Chemical Technology, 2000. 11. Polyakov, A.M., Some Aspects of the Pervaporation Separation of Liquid Mixtures, Krit. Tekhnol. Membr., 2004, vol. 24, no. 4, pp. 2944.

JOURNAL OF CTHEORETICAL FOUNDATIONS OF CHEMICAL ENGINEERING Vol. 44

BIOETHANOL DEHYDRATION: STATE OF THE ART 29. Schacht, C., Zetzl, C., and Brunner, G., From Plant Materials to Ethanol by Means of Supercritical Fluid Technology, J. Supercrit. Fluids, 2008, vol. 46, no. 3, pp. 299321. 30. Lvov, S.V., Nekotorye voprosy rektifikatsii binarnykh i mnogokomponentnykh smesei (Topics in the Distillation of Binary and Multicomponent Mixtures), Moscow: Akad. Nauk SSSR, 1960. 31. Najmul Arifeen, Ruohang Wang Ioannis, Kookos, K., et al., Process Design and Optimization of Novel Wheat Based Continuous Bioethanol Production Sys tem, Biotechnol. Prog., 2007, vol. 23, no. 6, pp. 1394 1403. 32. www.chemsite.ru/abstract_25040.htm 33. Serafimov, L.A., Separation of Azeotropic Mixtures, in Azeotropiya i poliazetropiya (Azeotropy and Polyzeot ropy), Sventoslavskii, V.V,, Ed., Moscow: Khimiya, 1968, ch. XXI, pp. 13941403. 34. Timofeev, V.S. and Serafimov, L.A., Printsipy tekh nologii osnovnogo organicheskogo i neftekhimicheskogo sinteza (Principles of Basic Organic and Petrochemical Synthesis Technology), Moscow: Vysshaya Shkola, 2003. 35. Kogan, V.B., Azeotropnaya i ekstraktivnaya rekti fikatsiya (Azeotropic and Extractive Distillation), Len ingrad: Khimiya, 1971. 36. Serafimov, L.A., Frolkova, A.K., and Bushina, D.I., Extractive Distillation of Binary Azeotropic Mixtures, Teor. Osn. Khim. Tekhnol., 2008, vol. 42, no. 5, pp. 521 530 [Theor. Found. Chem. Eng. (Engl. Transl.), vol. 42, no. 5, pp. 507516]. 37. Brito, R.R., Maciel, M.R.W., and Meirelles, A.A., New Extractive Distillation Configuration for Separating Binary Azeotropic Mixtures, The First European Con gress on Chemical Engineering, Florence, Italy, 1997, vol. 2, pp. 13331336. 38. Hua Chao, Li Xingang, Xu Shimin, and Bai Peng, Design and Operation of Batch Extractive Distillation with Two Reboilers, Chin. J. Chem. Eng., 2007, vol. 15, no. 2, pp. 286290. 39. Kotai, B., Lang, P., and Modla, G., Batch Extractive Distillation As Hybrid Process: Separation of Mini mum Boiling Azeotropes, Chem. Eng. Sci., 2007, vol. 2. 40. Anokhina, E., Grigorieva, A., and Timoshenko, A., Ethanol Dehydration in the Complex Column with Refining Side Section, Proc. 35th Int. Conf. of Slovak Society of Chemical Engineering, Tatranske Matliare, Slovakia, 2008, p. 171. 41. Seiler, M., Kohler, D., and Arlt, W., Hyperbranched Polymers: New Selective Solvents for Extractive Distil lation and Solvent Extraction, Sep. Purif. Technol., 2003, vol. 30, no. 2, pp. 179197. 42. Zhao Jin, Dong Cong Cong, Li Chun Xi, et al., Iso baric VaporLiquid Equilibria for EthanolWater Sys tem Containing Different Ionic Liquids at Atmospheric Pressure, Fluid Phase Equilib., 2006, vol. 242, no. 2, pp. 147153. 43. Jiang Xiao Chuan, Wang Jun Feng, Li Chun Xi, et al., Vapor Pressure Measurement for Binary and Ternary Systems Containing Methanol, Ethanol and Ionic Liq uid 1 Ethyl 3 Ethylimidazolium Diethylphosphate, J. Chem. Thermodyn., 2007, vol. 39, no. 6, pp. 841846.

555

44. Calvar, N., Gonzalez, B., Gomez, E., and Dominguez, A., Study of the Behaviour of the Azeotropic Mixture Etha nolWater with Imidazolium Based Ionic Liquids, Fluid Phase Equilib., 2007, vol. 259, no. 1, pp. 5156. 45. Wang Jun Feng, Li Chun Xi, Wang Zi Hao, et al., Vapor Pressure Measurement for Water, Methanol, Ethanol, and Their Binary Mixtures in the Presence of an Ionic Liquid 1 Ethyl 3 Methylimidazolium Dime thylphosphate, Fluid Phase Equilib., 2007, vol. 255, no. 2, pp. 186192. 46. Jin Zhao, Xiao Chuan Jiang, Chun Xi Li, and Zi Hao Wang, Vapor Pressure Measurement for Binary and Ternary Systems Containing a Phosphoric Ionic Liq uid, Fluid Phase Equilib., 2006, vol. 247, nos. 12, pp. 190198. 47. Ge Yun, Zhang Lianzhong, Yuan Xingcai, et al., Selec tion of Ionic Liquids as Entrainers for Separation of (Water + Ethanol), J. Chem. Thermodyn., 2008, vol. 40, no. 8, pp. 12481252. 48. Jun Feng Wang, Chun Xi Li, and Zi Hao Wang, Mea surement and Prediction of Vapor Pressure of Binary and Ternary Systems Containing 1 Ethyl 3 Methylim idazolium Ethyl Sulfate, J. Chem. Eng. Data, 2007, vol. 52, no. 4, pp. 13071312. 49. Calvar, N., Gonzalez, B., Gomez, E., and Dominguez, A., Vapor Liquid Equilibria for Ternary System Etha nol + Water + 1 Ethyl 3 Methylimidazolium Ethyl Sulfate and Corresponding Binary Systems Containing the Ionic Liquids at 101.3 kPa, J. Chem. Eng. Data, 2008, vol. 53, no. 3, pp. 820825. 50. Simoni, L.D., Lin, Y., Brennecke, J.F., and Stadtherr, M.A., Modeling LiquidLiquid Equilibrium of Ionic Liquid Systems with NRTL, Electrolyte NRTL, and UNIQUAC, Ind. Eng. Chem. Res., 2008, vol. 47, no. 1, pp. 256272. 51. Torres, J.L., Grenhlein, H.E., and Lynd, L.R., Com puter Simulation of the Dartmouth Process for Separa tion of Dilute Ethanol/Water Mixtures, Appl. Biochem. Biotechnol., 1989, vol. 20/21, pp. 621633. 52. Pinto, R.T.P., Wolf Maciel, M.R., and Lintome, L., Saline Extractive Distillation Process for Ethanol Puri fication, Comput. Chem. Eng., 2000, vol. 24, no. 2, pp. 16891694. 53. Ligero, E.L. and Ravagnani, T.M.K., Simulation of Salt Extractive Distillation with Spray Dryer Salt Recovery for Anhydrous Ethanol Production, J. Chem. Eng. Jpn., 2002, vol. 35, no. 6, pp. 557563. 54. Llano Restrepo, M. and Aguilar Arias, J., Modeling and Simulation of Saline Extractive Distillation Col umns for the Production of Absolute Ethanol, Comput. Chem. Eng., 2003, vol. 27, no. 4, pp. 527549. 55. Ligero, E.L. and Ravagnani, T.M.K., Dehydration of Ethanol with Salt Extractive DistillationA Compar ative Analysis between Processes with Salt Recovery, Chem. Eng. Process., 2003, vol. 42, no. 7, pp. 543552. 56. Zhigang Lei, Hongyou Wang, Rongqi Zhou, and Zhanting Duan, Influence of Salt Added to Solvent on Extractive Distillation, Chem. Eng. J., 2002, vol. 87, no. 2, pp. 149156. 57. Gil, I.D., Uyazan, A.M., Aguilar, J.L., et al., Separa tion of Ethanol and Water by Extractive Distillation with Salt and Solvent As Entrainer: Process Simula
No. 4 2010

THEORETICAL FOUNDATIONS OF CHEMICAL ENGINEERING Vol. 44

556

FROLKOVA, RAEVA tion, Braz. J. Chem. Eng., 2008, vol. 25, no. 1, pp. 207 215. Hilmen, E. K., Separation of Azeotropic Mixtures: Tools for Analysis and Studies on Batch Distillation Operation, Thesis Submitted for the Degree of Dr. Eng., Norwegian University of Science and Technology, Department of Chemical Engineering, 2001. Vasconcelos, C.J.G. and Wolf Maciel, M.R., Dynamic and Control of High Purity Heterogeneous Azeotropic Distillation Process, Comput. Aided Chem. Eng., 2000, vol. 8, pp. 217222. Zielinski, L., Bioethanol Dehydration in Pressure Swing Adsorption Proces, www.msuil.ru/unesco. forum.doc1/17doc Koczka, K., Mizsey, P., and Fonyo, Z., Rigorous Mod elling and Optimization of Hybrid Separation Pro cesses Based on Pervaporation, Central Eur. J. Chem., 2007, vol. 5, no. 4, pp. 11241147. Kafarov, V.V., Gordeev, L.S., and Glebov, M.B., Sepa ration of Azeotropic Mixtures in Membrane Rectifica tion Processes, Teor. Osn. Khim. Tekhnol., 1996, vol. 30, no. 2, pp. 180187 [Theor. Found. Chem. Eng. (Engl. Transl.), vol. 30, no. 2, pp. 160167]. Olujic, Z., Perez, P., De Bruijn, F.T., et al., Augmenting Distillation by Membranes: Developments and Pros pects, Chem. Biochem. Eng. Q, 2006, vol. 20, no. 3, pp. 301318. Szitkai, Z., Lelkes, Z., Rev, E., and Fonyo, Z., Optimi zation of Hybrid Ethanol Dehydration Systems, Chem. Eng. Process., 2002, vol. 41, no. 7, pp. 631646. Del Pozo Gomez, M.T., Klein, A., Repke, J. U., and Wozny, G., A New Energy Integrated Pervaporation Distillation Approach, Desalination, 2008, vol. 224, nos. 13, pp. 2833. Bologa, M.K. and Maksimuk, E.P., Recovery of Pro cess Liquids in an Electric Field, Int. Conf. Fizikar 2005, Baku, 2005, no. 114, p. 430. 67. Banat Fawzi, A., Abu Al Rub Fahmi, A., and Simandl Jana, Analysis of VaporLiquid Equilibrium of Etha nolWater System via Headspace Gas Chromatogra phy: Effect of Molecular Sieves, Sep. Purif. Technol., 2000, vol. 18, no. 2, pp. 111118. 68. Ohashi, R., Kamoshita, Y., Kishimoto, M., and Suzuki, T., Continuous Production and Separation of Ethanol without Effluence of Waste Water Using a Dis tiller Integrated SCMReactor System, J. Ferment. Bioeng., 1998, vol. 86, no. 2, pp. 220225. 69. Kaseno, A., Miyazawa, I., and Kokugan, T., Effect of Product Removal by a Pervaporation on Ethanol Fer mentation, J. Ferment. Bioeng., 1998, vol. 86, no. 5, pp. 488493. 70. Calibo, R.L., Matsumura, M., and Kataoka, H., Con tinuous Ethanol Fermentation of Concentrated Sugar Solutions Coupled with Membrane Distillation Using a PTFE Module, J. Ferment. Bioeng., 1989, vol. 67, no. 1, pp. 4045. 71. Kargupta, K., Datta, S., and Sanyal, S.K., Analysis of the Performance of a Continuous Membrane Bioreac tor with Cell Recycling during Ethanol Fermentation, Biochem. Eng. J., 1998, vol. 1, no. 1, pp. 3137. 72. Ghosh, K. and Ramachandran, K.B., Analysis of the Effect of In Situ Product Removal on the Stability and Performance of a Continuous Bioreactor with Cell Separator for Ethanol Production, Chem. Biochem. Eng. Q., 2007, vol. 21, no. 3, pp. 285296. 73. Moura, A.G. and Medeiros, J.R., Applying Consistent Technology for Fuel Ethanol Production, Sugar Tech nol., 2008, vol. 10, no. 1, pp. 2024. 74. Van Hoof, V., Abeele, L., Buekenhoudt, A., et al., Eco nomic Comparison between Azeotropic Distillation and Hybrid Systems Combining Distillation with Per vaporation for the Dehydration of Isopropanol, Sep. Purif. Technol., 2004, vol. 37, no. 1, pp. 3349.

58.

59.

60. 61.

62.

63.

64. 65.

66.

JOURNAL OF CTHEORETICAL FOUNDATIONS OF CHEMICAL ENGINEERING Vol. 44

No. 4

2010