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Distillation | Extractive Distillation

Chapter · December 2013

DOI: 10.1016/B978-0-12-409547-2.05949-7

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 DISTILLATION | Extractive Distillation A.A. Kiss

1 DISTILLATION | Extractive Distillation

2

3 Anton A. Kiss
4 AkzoNobel – Research, Development & Innovation, Zutphenseweg 10, 7418 AJ Deventer, NL
5 E-mail: Tony.Kiss@gmail.com, Tony.Kiss@akzonobel.com
6
7 Keywords
8 CAMD, dividing-wall column, entrainers, extractive distillation, industrial applications, ionic
9 liquids, mass separating agent, process design, residue curve map, solvent screening, solvent-
10 to-feed ratio, infinite dilution, liquid-liquid split
11
12 Abstract
13 This work provides a short review of extractive distillation technology, covering all relevant
14 topics: concept and working principles, residue curve maps, solvent design, screening and
15 selection, types of mass separating agents, influence on VLE, solvent-to-feed ratio, process
16 design, advanced extractive distillation in dividing-wall columns, and a list of applications.
17 Several important industrial applications are also briefly described: aromatic purification from
18 refining and petrochemical streams, cyclohexane recovery from naphta or natural gas liquid,
19 light olefin and paraffin separations, as well as bioethanol dehydration.
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32 Corresponding author’s e-mail address: Tony.Kiss@gmail.com

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 DISTILLATION | Extractive Distillation A.A. Kiss

1 1. Introduction
2 Distillation – the principal separation method used in industry – is a physical process for the
3 separation of liquid mixtures, based on differences in the boiling points or relative volatility
4 of the constituent components.1,2 However, the separation of azeotropic mixtures or close-
5 boiling components (with less than 20°C difference in boiling points) is usually not feasible in
6 a single conventional distillation column. Moreover, when the azeotropic composition is
7 insensitive to changes in pressure, then pressure-swing distillation (PSD) can not be employed
8 for separation. In such cases, the addition of another component – called entrainer, solvent or
9 mass separating agent – is used to alter the relative volatility of the close-boiling or azeotrope
10 forming components.3,4 This entrainer is selected to facilitate the separation by actually taking
11 advantage of the non-ideal behavior of a mixture of components having different chemical
12 structures. Typical entrainers include liquid solvents, solid salts, a combination of liquid
13 solvent and solid salts, or novel ionic liquids. Examples of separation processes that make use
14 of solvents are: liquid-liquid extraction, azeotropic distillation and extractive distillation. This
15 review focuses only on extractive distillation, addressing its working principle, residue curve
16 maps, solvent screening and design, types of mass separating agents, process design options,
17 and various industrial applications.
18
19 2. Working principle
20 By adding a solvent to interact with the components to be separated, the activity coefficients
21 are modified in such a way that the relative volatility is increased. The relative volatility of the
22 key components i and j in a given mixture with ideal vapor phase is given by:
yi / xi γ i pi0
23 α ij = = (1)
y j / x j γ j p 0j

24 where x and y are the molar fractions of each component in the liquid and vapor phase, γ is the
25 activity coefficient, and p0 is the vapor pressure of pure component. Since the ratio pi0/ pj0 is
26 constant for a given temperature, the solvent only affects the ratio of the activity coefficients
27 γi / γj. In the presence of a solvent S, this ratio is called selectivity:5
28 Sij = ( γ i / γ j ) (2)
S

29 Note that the activity coefficients depend on the liquid phase composition. As the effect of the
30 solvent tends to increase with its concentration, it is very common practice to evaluate the
31 selectivity at infinite dilution of the pure component in the solvent – which also represents the

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 DISTILLATION | Extractive Distillation A.A. Kiss

1 maximum possible selectivity:

2 Sij∞ = γ i∞ / γ ∞j (3)

3 The suitability of an entrainer can be also evaluated by its capacity, which is determined by:
4 C ∞j ,entrainer = 1/ γ ∞j (4)

5 where j denotes the solute. Smaller values of activity coefficient lead to stronger interactions
6 between component j and entrainer, which results in a larger capacity. However, note that
7 entrainers with a high selectivity often possess a low capacity hence the capacity is mostly
8 neglected, or at best used as a secondary decision variable.5 Moreover, the choice between an
9 extractive distillation (ED) and liquid-liquid extraction (LLX) process should clearly account
10 for the relative separation factors for equal-cost separation operations.6
11 In practice, extractive distillation is carried out in a sequence consisting of an extractive
12 distillation column (EDC) and a solvent recovery column (SRC) – as shown in Figure 1 (left).
13 One component is withdrawn at the top of EDC, while the other component together with the
14 solvent is removed as bottoms product. The second component is separated in the SRC unit,
15 where the solvent is recovered and recycled to the first column. Clearly, the separation in the
16 SRC is easier when no additional azeotropes occur in the mixture and a large difference in the
17 boiling points exists, between the high-boiling solvent and the second component.3 Moreover,
18 note that the solvent increases the liquid load inside the column hence the design of the liquid
19 channels is very important. Ideal solvents should decrease the solvent to feed ratio (S/F) and
20 the liquid load of the column, thus making the operation easy to implement in practice.
21 The two columns of the conventional sequence can also be conveniently integrated into a
22 dividing-wall column (DWC) – as the one illustrated in Figure 1 (right), also known as a split
23 shell column with divided overhead section and common bottoms section.7 Remarkable,
24 DWC is one of the best examples of proven process intensification technology in distillation,
25 as it allows significantly lower investment and operating costs (typically in the range of 25-
26 40%) while also drastically reducing the equipment and carbon footprint.8
27
28 Figure 1
29
30 3. Residue curve map
31 Residue curve mapping is a powerful tool for better understanding of the design and operation
32 of distillation columns, especially when the separation involves azeotropes. The ability to
33 visualize the physical constraints of the separation process allows quick generation of better

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 DISTILLATION | Extractive Distillation A.A. Kiss

1 design alternatives, even for complex highly non-ideal systems, resulting in significant time
2 and cost savings.8 A simple distillation residue curve shows how the composition of the liquid
3 residue changes over time (open distillation). A residue curve map (RCM) is a collection of
4 liquid residue curves originating from different initial compositions. RCM contain the same
5 information as phase diagrams, but represented in a more useful way for understanding how
6 to synthesize a distillation sequence.4,8,9. Thermodynamic data is of utmost importance in
7 getting reliable RCM, so the adequacy of models and the accuracy of interaction parameters
8 must be always checked.8 For example, Wilson is very accurate for homogeneous mixtures,
9 while UNIQUAC and NRTL are sufficiently accurate in many cases, being applicable to
10 vapor-liquid equilibrium (VLE) and liquid-liquid equilibrium (LLE). However, UNIFAC,
11 COSMO-RS and other predictive methods should be used only for exploratory purposes.
12 Figure 2 (left) shows a typical residue curve map (RCM) and the types of characteristic points
13 that can be encountered in a RCM.8 All of the residue curves originate at the light (lowest
14 boiling) pure component in a region, move towards the intermediate boiling component, and
15 end at the heavy (highest boiling) pure component in the same region. The lowest temperature
16 nodes are termed as unstable nodes (UN), as all trajectories leave from them; while the
17 highest temperature points in the region are termed stable nodes (SN), as all trajectories
18 ultimately reach them. The point that the trajectories approach from one direction and end in a
19 different direction (as always is the point of intermediate boiling component) are termed
20 saddle points (S). Residue curves that divide the composition space into different distillation
21 regions are called distillation boundaries. The concept of characteristic points is especially
22 important in classifying the azeotropic mixtures.10
23
24 Figure 2
25
26 Research studies have also determined the relationship between the number of nodes (stable
27 and unstable) and saddle points that can exist in a validly drawn RCM.8,10,11. The consistency
28 of RCM with the azeotropic data can be verified by a theoretical test, expressed by the next
29 relation based on topological arguments:
30 4(N3 - S3) + 2(N2 - S2) + (N1 - S1) = 1 (5)
31 where Ni and Si are the number of nodes and saddles, respectively, involving exactly i species
32 from the ternary mixtures. For example, in case of Figure 2 (left): N3=0, S3=0, N2=0, S2=1,
33 N1=3, S1=0, and therefore: 4(0-0)+2(0-1)+(3-0)=1.

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 DISTILLATION | Extractive Distillation A.A. Kiss

1 Residue curve maps have extremely useful applications, such as: testing of the consistency of
2 experimental azeotropic data; predicting the order and content of the cuts in batch distillation;
3 checking whether a given mixture is separable by distillation, identification of entrainers,
4 prediction of attainable compositions, qualitative prediction of composition profile shape;
5 identifying the limiting separation achievable by distillation, and synthesizing separation
6 sequences combining distillation with other methods.4,8,12 Based on the possible RCM types,
7 extractive distillations can be divided into three categories: separation of minimum-boiling or
8 maximum-boiling azeotropes (see Figure 2, right) and the separation of low relative volatility
9 non-azeotropic mixtures. Each category is basically represented by a single, unique residue
10 curve map.11
11
12 4. Solvent design, screening and selection
13 The selection of the most suitable solvent plays an important role in the economical design of
14 ED. Solvents with high selectivity (degree of separation) and high solubility (no liquid phase
15 splitting) are recommended, but typically the solvents with high selectivity have a reduced
16 capacity. When a suitable solvent is found, this should be further optimized to improve its
17 separation ability, decrease the solvent-to-feed ratio and thus reduce the liquid load in the ED
18 column.13 While a high selectivity is the main criterion for the selection of a solvent, there are
19 several other constraints that need to be fulfilled:13
20 • The entrainer should not form any new azeotropes with the components of the mixture.
21 • The solvent should be thermally and chemically stable, at temperatures encountered in the
22 extractive distillation process, in order to prevent degradation or undesired reactions.
23 • The entrainer should not cause any immiscible regions (L-L splitting should be avoided).
24 • The boiling point should be higher (cca 30-40°C) than that of the less volatile component.
25 • The solvent should have a proper balance in the affinity towards one component, to allow
26 a good separation in the ED column but also a relatively easy regeneration step, and thus
27 an energy-efficient separation in the solvent recovery column.14
28 • The selection should consider safety, environmental effects, corrosion, price, availability.
29 The type of possible entrainers can be also classified into: liquid entrainers that do not induce
30 liquid-phase separation in the ternary mixture, liquid entrainers that induce liquid-phase
31 separation in the ternary mixture, entrainers that react with one of the components in the
32 mixture and entrainers that ionically dissociate in the original mixture and alter the VLE.11
33 Practically, there are several classes of entrainers suitable for extractive distillation:

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 DISTILLATION | Extractive Distillation A.A. Kiss

1 Conventional solvents
2 Liquid solvents: This is the most common class of solvents, due to their easy operation and
3 handling. Liquid solvents can be easily recovered by distillation and then recycled. However,
4 the pollution of the top products of both the EDC and SRC is possible, despite their low vapor
5 pressure, due to the requirement of large solvent to feed mass ratios (reaching S/F=7-8).
6 Solid salt: In certain systems (e.g. ethanol and water) it is possible to use a solid salt dissolved
7 into the liquid phase, taking advantage of the salt effect – which refers to the ability of a solid
8 salt to alter the equilibrium by changing the activity coefficients in the liquid phase. The
9 process flowsheet is somewhat different from the conventional ED process, due to the need of
10 a salt recovery unit instead of SRC, typically an evaporator – as shown in Figure 3.13
11 Although the salt can be easily recovered, and the solvent to feed ratios are small, one must be
12 aware of the problems related to salt dissolution, reuse, corrosion and transportation.
13 Liquid solvent and solid salt combined: Using the same conventional ED process flowsheet,
14 the combination of two solvents integrates the advantages of liquid solvents (easy operation)
15 and solid salt (high separation ability with low solvent to feed ratios) and can be suitable for
16 separating polar or non-polar systems. The corrosive effect of the solid salts is a drawback
17 that is still present, and due to the solubility limitation of the solid salts, the amount added to
18 the liquid solvents is often small and the improvement of the separation is limited.
19 Novel solvents
20 Hyperbranched polymers: This class of highly branched, polydisperse, 3D macromolecules
21 has applications based on the non-volatility associated with these polymers and the large
22 number of functional groups that are attached to the molecule – thus allowing for tailoring of
23 their physical and thermodynamical properties. There are only a few hyperbranced polymers
24 commercially available which meet the requirements of an entrainer or solvent (large scale
25 availability, low viscosity, low melting temperatures, stability, selectivity and capacity).
26 Ionic liquids (IL): The term IL is used for a class of ionic chemicals with melting temperature
27 below 100 °C – an arbitrary limit defined as a response to the dramatically increasing number
28 of possible industrial applications of the IL below this temperature. They are formed by an
29 organic cation and an (in)organic anion. For ED applications, they are promising solvents due
30 to their unique characteristics: negligible vapor pressure, wide liquid range, chemically and
31 thermally stable, good solubility for most components, less corrosive than conventional
32 salts.14,15 However, for the successful industrial application of these chemicals, the toxicity,
33 corrosion behavior and physical properties of the ionic liquids should be sufficiently known.

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 DISTILLATION | Extractive Distillation A.A. Kiss

1 Other issues are the non-availability of characterization techniques, a deficient understanding

2 of the mechanism of synthesis and the presently high prices of these solvents.
3
4 Figure 3 Table 1 Table 2
5
6 An effective extractive distillation process depends on the choice of the extractive agent –
7 which should have a strong affinity towards one of the components to be separated, but still
8 allow a rather easy recovery of the solvent – since this have a major impact on the design and
9 economics of the process. The systematic synthesis framework for the conceptual design of
10 ED processes should include several steps.5 After the completion of these steps the optimal
11 entrainer choice, the optimal column design and the optimal operating point have been found.
12 1. Generating entrainer alternatives. Typically, this task can be done by using literature
13 studies or heuristic rules for entrainer selection, and the design of solvents through
14 computer-aided molecular design (CAMD). CAMD can be interpreted as the inverse of
15 the property prediction problem: given a set of desirable properties (e.g. high selectivity
16 for a certain component), a combination of structural groups (based on UNIFAC group
17 contribution method) is sought that satisfies the property specification. The heuristic rules
18 classify the entrainer candidates into five groups (Class I and II being successful solvents
19 in most cases), based on the extractive property related to the ability of forming hydrogen
20 bonds with one of the key components – see Table 1 for details.5 The recommended
21 solvents based on the polarity of the mixture are shown in Table 2. In addition,
22 experimental work (VLLE experiments) should be carried out to test solvents for new
23 applications.16 This is already used for conventional solvents, but it is especially needed
24 for new solvents, such as hyper-branched polymers or ionic liquids.14,15,17
25 2. Fast screening of alternatives. The resulting flowsheets for the different candidates are
26 screened to find the most economically attractive entrainers. It is advisable to screen the
27 entrainer alternatives based on shortcut calculations to narrow the choices down to 2-3
28 promising alternatives. Different screening methods are available, such as the classic one
29 based on selectivity at infinite dilution, or shortcut calculations combined with an
30 extended rectification body method. RBM allows the computation of the minimum energy
31 demand required for the selected separation, and the initialization of the MINLP (mixed-
32 integer nonlinear programming) optimization. This method is based on approximating the
33 column profile through the rectification bodies calculated from pinch points.18

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 DISTILLATION | Extractive Distillation A.A. Kiss

1 3. Detailed rigorous optimization. The results of the fast screening can be used to initialize a
2 detailed optimization of the entire ED flowsheet. Note that the shortcut calculations
3 cannot provide any information about the optimal number of trays or feed tray location, as
4 the minimum energy demand is calculated for columns with an infinite number of stages.
5 For a more detailed column design an economic trade-off has to be found between the
6 total investment cost (TIC) which is determined by the column diameter and number of
7 trays, and the total operating cost (TOC) that is defined by the energy duty of the columns.
8 Since the number of trays and the feed tray locations are discrete variables while the
9 energy duties, flowrates and compositions are continuous variables, MINLP optimization
10 is usually used for identifying the optimal column designs and the process operating point.
11
12 5. Industrial applications
13 ED can be applied as a stand-alone process, or in combination with azeotropic distillation,
14 reactive distillation or liquid-liquid extraction. Table 3 summarizes the industrial and potential
15 ED applications, while the next part focuses on the most important industrial applications.
3,8,14,15,17
16 Remarkable, extractive distillation gained much interest in industrial applications, as
17 it has several major advantages as compared to liquid-liquid extraction (LLX) processes:
18 • Lower capital costs. ED requires two major process units (EDC and SRC), while LLX
19 requires four: L-L extraction tower, extractive stripper, SRC and raffinate wash tower.
20 • Higher operational flexibility. LLX uses only solvent selectivity (polarity) for separation,
21 while ED uses also the boiling point as an extra degree of freedom for operation.
22 • Less physical property restrictions. Interfacial tension and density difference between the
23 liquid phases are important concerns for LLX, but not for ED.3
24
25 5.1 Aromatic purification
26 The ED technology for aromatics purification (i.e. BTX separation: benzene-toluene-xylene,)
27 must handle the possible formation of two liquid phases in the upper portion of the ED tower
28 where non-aromatics are concentrated. The second liquid phase is due to the reduced
29 solubility of non-aromatics in the polar solvent. The problem of two liquid phases can be
30 avoided by selecting a polar solvent that has enough solubility to dissolve both aromatics and
31 non-aromatics. But generally, solvents with a high selectivity have a reduced solvency
32 (capacity), and vice versa. Therefore, in order to avoid the two liquid phases, one may have to
33 compromise the solvent selectivity, sometimes to a great extent.3 A better approach is to cope

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 DISTILLATION | Extractive Distillation A.A. Kiss

1 with two liquid phases, without sacrificing the solvent selectivity, for the following reasons: 3
2 • Two liquid phases normally reduce the solvent selectivity in the VLL conditions in the ED
3 tower. But this can be compensated by intrinsic selectivity of a highly selective solvent.
4 For example, the performance of sulfolane – that leads to two liquid phases – is better than
5 alternative solvents such as NFM and NMP (Table 3) where a single liquid phase exists.
6 • Two liquid phases have no ill effects on the efficiency of small tray or packed columns
7 with diameters of less than 0.5 m. But in larger ED towers, the heavy liquid phase tends to
8 accumulate on the tray if the liquid phases are not well mixed. This issue can be avoided
9 by tray designs promoting gas agitation (hence liquid mixing), or in packed columns by L-
10 L redistributors specially designed to allow separate distribution of the two liquid phases.
11 The state-of-the-art ED technologies for aromatic purification are based on several solvent
12 systems, such as sulfolane, NFM and NMP – although proprietary cosolvents may be blended
13 into the base solvent to enhance the performance in specific ED applications. Table 4 makes a
14 comparison of the commercial aromatic technologies.3 The ED process can provide up to 25%
15 capital savings as compared to commercial LLX processes, but note that the ED process
16 recovers more xylenes, but less benzene than the counter LLX processes.
17 The Uhde’s Morphylane® process is accepted worldwide as a very effective and economical
18 process and it is now the world-leading technology for the recovery of BTX aromatics – with
19 55 plants worldwide with a total capacity of over 10 million mtpy aromatics. The classical
20 process consists of two columns (similar to Figure 1, left). The aromatics feed is added to the
21 EDC between the stripping and rectifying sections, and the NFM solvent above the rectifying
22 section. Solvent traces are separated from the non-aromatics in the solvent recovery section
23 from the top of EDC. The non-aromatic components are drawn off at the top of the EDC. The
24 aromatics contained in the feed leave at the bottom of EDC together with the solvent. The
25 aromatics are then stripped from the solvent in SRC. From the bottom of the SRC, the solvent
26 is recycled to the upper part of the EDC. The heat from the hot solvent is recovered almost
27 completely by means of heat exchangers within the ED process. Although already highly
28 optimized and flexible to a wide range of feedstock and product qualities, the Morphylane®
29 process was further developed by Uhde into a single-column ED configuration – shown in
30 Figure 4 – that allows 16% energy savings, 25% reduction in the number of main equipment
31 units, and 20-40% less space requirements for the plant.7
32
33 Table 3 Table 4

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 DISTILLATION | Extractive Distillation A.A. Kiss

1 5.2 Cycloparaffin recovery

2 ED technology has been also applied to the separation of paraffins and cycloparaffins, a much
3 more difficult separation than aromatics and non-aromatics. One major development was the
4 recovery of cyclohexane – an important raw material for the nylon industry – from naphtha or
5 natural gas liquid (NGL) streams. The recovery of pure cyclohexane through conventional
6 distillation is virtually impossible, due to the close-boiling C7 isomers in the streams. Since
7 the polarity difference between cyclohexane and C7 isomers is substantially smaller than that
8 for aromatic and nonaromatic compounds, no extractive solvent has been found that can
9 easily effect the separation. However, through the use of a cosolvent to enhance the solvency
10 of the mixed solvent (Table 3), an ED process has been commercialized to recover high purity
11 cyclohexane directly from an NGL fraction containing 85% cyclohexane.3
12
13 Figure 4 Figure 5
14
15 5.3 Light oleffin and paraffin separations
16 The ED technology was developed to recover high purity n-butenes suitable for producing
17 butadiene, used for synthetic rubbers. A mixture of 85% acetone and 15% water was used by
18 Shell as a selective solvent. Later, furfural was used as solvent for the separation of isobutane
19 from butene-1, n-butane from butene-2, and butene-1 from butadiene.3 Uhde’s Butenex®
20 extractive distillation process is using N-formyl morpholine as the selective solvent, for
21 recovering 1-butene and 2-butene from C4 hydrocarbon streams. On the basis of such a
22 feedstock (25.6% isobutane, 32.7% n-butane, 26.6% 1-butene and 15.1% 2-butene), the
23 following yields can be achieved: 1-butene 95.6%, 2-butene 99.1%, butanes 98.9%. The
24 purity of 1-butene and 2-butene products can be 99.6% and 95.9%, respectively.3
25 At industrial scale, butadiene is usually separated from C4 mixtures – consisting of butane,
26 butene-1, trans-butylene-2, cis-butylene-2, 1,3-butadiene and vinylacetylene (VAC) – by ED
27 with acetronitile (ACN) as solvent. The process includes the following sequence of columns:
28 extractive distillation (C1), solvent recovery (C2), extractive distillation (C3) and again
29 solvent recovery (C4). Column C1 separates butane and butene as one part, usable for fuel.
30 C3 separates butadiene as top product, while C4 delivers VAC and recovers the recyclable
31 solvent (ACN). The classic ED process was simplified to use only two extractive distillation
32 columns and an additional flash unit – as shown in Figure 5.13
33 The feasibility of using metal-ligand complexes as functionalized solvents in a reactive ED

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 DISTILLATION | Extractive Distillation A.A. Kiss

1 process, was reported for the separation and purification of alpha-olefins, such as 1-hexene
2 from other C6-olefin isomers (internal, branched, cyclic and diolefins) and paraffins by using
3 π-complexation.19 For silver / di (butyl) phosphoric acid (DBPA) – containing 20 %wt Ag, at
4 S/F = 3 – the highest selectivities obtained were 1.23 for 2-methyl-1-pentene and 1.42 for n-
5 hexane. Also, an equilibrium model was used to conceptually design a reactive ED column
6 applying the functionalized solvent silver-di (2-ethylhexyl)phosphoric acid (D2EHPA). For
7 99.5% purity and 99% recovery, the RED column should be operated at a solvent to feed ratio
8 S/F=5, P=0.2 bar, and T=311 K. Under these conditions, the minimum number of trays to
9 separate 1-hexene from 2-methyl-1-pentene is reduced to only 42, which is clearly a dramatic
10 decrease compared to about 310 trays required in the absence of silver.19
11
12 5.4 Bioethanol dehydration
13 The industrial bioethanol production uses various raw materials – e.g. corn, sugarcane and
14 lignocellulosic biomass – that undergo several pre-treatment steps before the fermentation. A
15 common feature of all technologies is the production of diluted ethanol (5-12 %wt) that needs
16 to be further concentrated beyond the azeotropic composition (95.63 %wt ethanol). A pre-
17 concentration distillation column (PDC) is used to concentrate bioethanol from 5-12 %wt up
18 to 92.4-94 %wt. Then, an extractive distillation process with various solvents is typically used
19 for further ethanol dehydration up to higher concentrations (over 99.8 %wt). The separation of
20 ethanol and water is actually the most important application of ED with solid salts. Figure 6
21 shows the change in VLE when ethylene glycol (EG), or EG and CaCl2 are used as entrainer.
22 In addition, Figure 7 shows the influence of various salts on the relative volatility of ethanol-
23 water, using a solvent to feed ratio of 1:1 (entrainer to ethanol-water azeotrope) and 0.2g salt
24 per mL solvent.13 The salt effect is stronger when the valence of the metal ion is higher: AlCl3
25 > CaCl2 > NaCl and Al(NO3)3 > Cu(NO3)2 > KNO3. Moreover, the effect of the acidic anion
26 decreases in the order of: AcO– > Cl– > NO3–.13
27 The EDC and SRC units of the classic ED process can be conveniently integrated into an
28 extractive DWC.20 Moreover, the pre-concentration step can be also integrated to allow the
29 processing of diluted ethanol streams, in a single E-DWC that combines three distillation
30 units into just one column – as illustrated in Figure 8.8,21 The feed side (prefractionator) acts
31 as the PDC unit of the conventional sequence. Water is removed as liquid side stream, but an
32 additional side reboiler is required in order to return the required amount of water vapors to
33 the column. The liquid feed stream is fed on top of the prefractionator side, thus serving as a

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1 reflux to the PDC section. The vapor leaving the feed side of the E-DWC has a near
2 azeotropic composition. Solvent is added at the top of the E-DWC, this section acting in fact
3 as the EDC unit of the conventional sequence. Ethanol is separated here as high purity top
4 distillate, and removed as the main product. The liquid flowing down the top section (EDC) is
5 collected and distributed only to the (SRC) side opposite to the feed side (prefractionator) and
6 further down the bottom of the E-DWC. This complete redistribution of the liquid flow is
7 required in order to avoid the presence and loss of solvent on the feed side (PDC section). In
8 the SRC section, the solvent is separated as bottom product and then recycled in the process.
9 Note that all components can be obtained as high purity products only in a narrow optimal
10 range of the solvent to feed ratio (S/F). Below the minimum ratio, ethanol can not be
11 sufficiently purified, while above the maximum ratio the excess of solvent leads to a situation
12 where the other products (water and recovered solvent) become an impurity for each other.
13 Remarkable, the single-step E-DWC alternative is much more efficient in terms of energy
14 requirements allowing 17% savings in the total annual costs with specific energy
15 requirements of only 2.07 kWh/kg bioethanol.8, 21
16
17 Figure 6 Figure 7 Figure 8
18
19 6. Concluding remarks
20 Extractive distillation technology is widely used in the petro-chemical industry for separating
21 azeotropic, close-boiling and low relative volatility mixtures. The developments in tailored
22 solvents and the advancement in internals design have made ED a competitive process at
23 industrial scale. In many cases, ED processes are more efficient and economical than liquid-
24 liquid extraction (LLX) in terms of capital investment, energy use and ease of operation.
25 Compared to other methods for separating azeotropes or close-boiling mixtures, extractive
26 distillation offers several benefits, such as: standalone operation, more degrees of freedom in
27 design, greater flexibility in implementation, possibility to process higher capacities than L-L
28 extraction, heat integration opportunities between the two distillation columns, rather easy
29 operability and controllability, solvent-free products, less solvent needed than for AD, no
30 need to vaporize the solvent, lower energy requirements than AD. Nonetheless, extractive
31 distillation also requires a substantial increase in the volatility difference among the
32 components to be separated, and it becomes less efficient with very wide boiling range feed
33 stocks, while not being suitable for thermally sensitive materials.

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1
2 Glossary
3 Activity coefficient – A factor used in thermodynamics to account for deviations, from the
4 ideal behavior in a mixture of chemical substances (e.g. by modifying the concentration)
5 Azeotrope – Constant boiling mixture that does not change in composition by distillation, and
6 generally it has a boiling point higher or lower than any of its pure constituents.
7 Ionic liquid (IL) – The term refers to a salt in liquid state, being restricted to salts whose
8 melting point is below some arbitrary temperature, typically 100 °C.
9 K value – Ratio of the concentration of a given component in the vapor phase to its
10 concentration in the liquid phase when the V-L phases are in equilibrium.
11 Mass separating agent (MSA) – A chemical species (also called entrainer or solvent) that is
12 added to ensure that the intended separation process takes place.
13 Relative volatility – Defined as the ratio of the K values of two components, it is a measure of
14 the ease with which the two components can be separated by distillation.
15 Residue curve – Describes the change of the composition of the liquid phase of a chemical
16 mixture during continuous evaporation at VLE condition (open distillation).
17 Residue curves map – A collection of multiple residue curves for a single system.
18 Vapor pressure – It is the pressure at which a liquid and its vapor are in equilibrium, at a
19 given temperature.

13
 DISTILLATION | Extractive Distillation A.A. Kiss

1 References
2 1. Resetarits, M. R.; Lockett, M. J., Distillation, Encyclopedia of Physical Science and
3 Technology 2003, 547-559. DOI: 10.1016/B0-12-227410-5/00182-4
4 2. Petlyuk, F. B., Distillation theory and its application to optimal design of separation,
5 Cambridge University Press, 2004.
6 3. Lee, F. M., Extractive distillation, Encyclopedia of Separation Science 2000, 1013-1022.
7 DOI: 10.1016/B0-12-226770-2/04801-8
8 4. Luyben, W.L.; Chien, I-L., Design and control of distillation systems for separating
9 azeotropes, Wiley-AIChE, 2010.
10 5. Kossack, S.; Kraemer, K.; Gani, R.; Marquardt, W., A systematic synthesis framework for
11 extractive distillation processes, Chemical Engineering Research & Design 2008, 86, 781-
12 792.
13 6. Seider, W. D.; Seader, J. D.; Lewin, D. R., Product & process design principles, 2nd
14 Edition, John Wiley & Sons: New-York, 2004.
15 7. Yildirim, O.; Kiss, A. A.; Kenig, E. Y., Dividing wall columns in chemical process
16 industry: A review on current activities, Separation & Purification Technology 2011, 80,
17 403-417.
18 8. Kiss, A. A., Advanced distillation technologies – Design, control and applications, John
19 Wiley & Sons, 2013.
20 9. Beneke, D.; Peters, M.; Glasser, D.; Hildebrandt, D., Understanding distillation using
21 column profile maps, Wiley, 2012.
22 10. Stichlmair, J. G.; Fair, J. R., Distillation - Principles and practice, Wiley-VCH: New York,
23 1998.
24 11. Doherty, M. F.; Malone, M. F., Conceptual design of distillation systems, McGraw-Hill:
25 New York, 2001.
26 12. Doherty, M. F.; Knapp, J. P., Distillation, azeotropic and extractive, in Kirk-Othmer
27 Encyclopedia of Chemical Technology, John Wiley & Sons, 2004.
28 13. Lei, Z. G.; Li, C. Y.; Chen, B. H., Extractive distillation: A review, Separation and
29 Purification Reviews 2003, 32, 121-213.
30 14. Jongmans, M. T. G.; Londono, A.; Mamilla, S. B.; Pragt, H. J.; Aaldering, K. T. J.;
31 Bargeman, G.; Nieuwhof, M. R.; ten Kate, A. J. B.; Verwer, P.; Kiss, A. A.; van Strien, C.
32 J. G.; Schuur, B.; de Haan, A. B., Extractant screening for the separation of dichloroacetic

14
 DISTILLATION | Extractive Distillation A.A. Kiss

1 acid from monochloroacetic acid by extractive distillation, Separation & Purification

2 Technology 2012, 98, 290-297.
3 15. Gutierrez Hernandez, J.P., Extractive distillation with ionic liquids as solvents: Selection
4 and conceptual process design, PhD Thesis, Eindhoven University of Technology,
5 Eindhoven, The Netherlands, 2013.
6 16. Tassios, D. P., Rapid screening of extractive distillation solvents, Advances in Chemistry
7 1974, 115, 46-63.
8 17. Jongmans, M. T. G.; Schuur, B.; de Haan, A. B., Ionic liquid screening for ethylbenzene /
9 styrene separation by extractive distillation, Industrial & Engineering Chemistry Research
10 2011, 50, 10800-10810.
11 18. Brüggemann, S.; Marquardt, W., Shortcut methods for nonideal multicomponent
12 distillation: 3. Extractive distillation columns, AIChE Journal 2004, 50, 1129-1149.
13 19. Kuipers, N. J. M.; Wentinkl, A. E.; de Haan, A. B.; Scholtz, J.; Mulder, H., Functionalized
14 solvents for olefin isomer purification by reactive extractive distillation, Chemical
15 Engineering Research & Design 2007, 85, 88-99.
16 20. Kiss, A. A.; Suszwalak, D. J-P. C., Enhanced bioethanol dehydration by extractive and
17 azeotropic distillation in dividing-wall columns, Separation & Purification Technology
18 2012, 86, 70-78.
19 21. Kiss, A. A.; Ignat, R. M., Innovative single step bioethanol dehydration in an extractive
20 dividing-wall column, Separation & Purification Technology 2012, 98, 290-297.

15
 DISTILLATION | Extractive Distillation A.A. Kiss

1 Tables
2 Table 1. Deviation from Raoult’s law for different classes of interacting components.5

Interacting classes Deviation H-Bonding

I+V Always positive (I + V usually show H-bonds are dissociated
II + V phase splitting)

III + IV Always negative H-bonds are formed

I + IV Always positive (I + IV usually More H-bonds are

II + IV show phase splitting) dissociated than formed
I + I, I + II, I + III Usually positive, but sometimes Some H-bonds are formed,
II + II, II + III negative and formation of maximum some are dissociated
azeotropes

III + III, III + V Nearly ideal systems; small positive No hydrogen bonds
IV + IV, IV + V deviations, seldom
V+V formation of minimum azeotropes
3 Note: Classification derived from the enthalpy of vaporization of a component in comparison
4 with Trouton’s constant (∆Hvap = 88 J/K·mol): a larger value indicates a large interaction in
5 the liquid phase while a lower value indicates the formation of associates in the vapor phase.
6 • Class I includes molecules that are capable to form three-dimensional networks of strong
7 hydrogen bonds in the liquid phase, e.g. water, glycol, hydroxylamine, hydroxyacids, amides.
8 • Class II includes molecules that are able to form one-dimensional chains through hydrogen
9 bonds, and where van der Waals’ forces become more important (e.g. ethanol, acetic acid).
10 • Class III includes molecules that act as a hydrogen bond acceptor, as for example: ethers,
11 ketones and nucleophilic aromatic compounds.
12 • Class IV consists of molecules that act primarily as hydrogen bond donors: chloroform,
13 dichlorethan, trichlorethan, etc.
14 • Class V molecules do neither act as hydrogen bond donors nor as acceptors, e.g. aromatic
15 compounds and tetra-chlorethan.
16
17
18
19 Table 2. Recommended solvents based on the polarity of the mixture.15

More volatile component Less volatile component Recommended solvent

Highly polar Highly polar Polar or non-polar
Moderately polar Moderately polar Polar or non-polar
Polar Non-polar Polar or non-polar*
Non-polar Polar Polar
Non-polar Non-polar Polar
*
20 The polar solvents may reverse the relative volatility
21

16
 DISTILLATION | Extractive Distillation
1 Table 3. Selected applications of extractive distillation.3,8,14,15
Application
Recovery of toluene
from paraffins
Aromatics purification
Cyclohexane recovery
from naphtha or NGL
Monomer separation
Light olefins and
paraffins separation
Cycloparaffins and
aromatics separation
Cycloparaffins and
paraffins separation
Acetic acid dehydration
Organic acids separation
Nitric acid dehydration
Close-boiling alcohols
Monomers separation
C3 splitting
C4 splitting
C5 splitting
Methyl acetate synthesis
Acetone-methanol
separation
Alcohols dehydration
Bioethanol dehydration
A.A. Kiss
Separation Solvent / entrainer
toluene / paraffins Phenol
aromatics / Diethylene glycol (DEG), triethylene
non-aromatics Glycol (TEG), dimethyl sulfoxide (DMSO),
N-methyl pyrrolidone (NMP), sulfolane, N-
formyl morpholine (NFM)
cyclohexane / toluene IL: [bmim]+[AlCl4]–
toluene, methyl- NMP, IL: [HMIM][TCB], [BMIM][TCB]
cyclohexane
cyclohexane / Ethylene glycol (EG), TEG, NMP,
C7 isomers sulfolane, MIST (mixed solvent by Philips)
ethylbenzene / styrene Sulfolane, IL: [3-mebupy] [B(CN)(4)], [4-
mebupy] [BF4], [EMIM] [SCN]
isobutane / butene-1 Sulfolane, furfural, acetone and water
n-butane / butene-2
butene-1 / butadiene
n-pentane / 1-pentene NMP, CHOL, NMEP or combinations
n-hexane / 1-hexene NMP, IL: [HMIM][TCB]
cyclohexane / benzene Acetone
cyclopentane / N-(b-mercaptoethyl)-2-pyrrolidone
2,2-dimethylbutane (NMEP), NMP, cyclohexanol (CHOL)
acetic acid / water Sulfolane, adiponitrile, benzophenone,
dimethyl sulfoxide, pelargonic acid,
cinnamic acid, neodecanoic acid, methyl
salicylate, heptanoic acid and isophorone,
acetophenone and nitrobenzene |
Tributylamine (extractive reactive
distillation)
Mono- / di-chloro Sulfolane, glymes: diethylene glycol
acetic acid dipentyl ether, DGDP, DGDB, TGDE
HNO3 / water Magnesium nitrate, sulfuric acid
n-propyl alcohol / sec- Sulfolane, others
butyl alcohol
isopropenyl styrene / Sulfolane, others
tert butyl styrene
propylene / propane Acetonitrile (ACN)
C4 hydrocarbons Acetone, acetonitrile, N,N-dimethyl-
formamide (DMF), NMP, NFM
C5 hydrocarbons N,N-dimethylformamide (DMF)
methanol/ methyl Water
acetate
acetone / methanol Water, ethylene glycol
ethanol, isopropanol, Ethylene glycol, DMF, EG with salts, CaCl2
tert-butanol / water (salt distillation), IL: [EMIM][DCA]
ethanol / water Ethylene glycol (EG), EG with salts: NaCl,
CaCl2, SrCl2, AlCl3, KNO3, Cu(NO3)2,
Al(NO3)3, CH3COOK, K2CO3 | glycerol,
hyperbranched polymers, ionic liquids
17
 DISTILLATION | Extractive Distillation A.A. Kiss

2 Table 4. Comparison of aromatic recovery technologies.3

System UDEX™ Arosolvan™ Sulfolane™ Morphylane™ GT-Aromex™

Solvent Tetra-EG NMP Sulfolane N-formyl Proprietary
morpholine
TIC (M$) 9.5 11.0 10.7 11.0 8.1

Utilities
Power (kWh/t) – 6.6 2.4 4.6 4.8
Steam (kcal/kg) 211 225 177 250 194
CW (L/kg) 158 – – 133 175

Min. recoveries
Benzene 99.9% 99.9% 99.9% 99.9% 95.0%
Toluene 99.5% 99.5% 99.0% 99.5% 99.5%
Xylene 95.0% 95.0% 95.0% 97.0% 100%

S/F ratio (v/v) 4:1 0.4 : 1 2:1 3:1 3:1

3
4 Note: Inside battery limit (ISBL) capital cost is considered as TIC. Only the extraction section
5 is included. All processes are pro rata for 1600 metric tons per day reformate feed. Sources
6 include SRI International, Handbook of Solvent Extraction, Petroleum Refining Technologies
7 & Economics, and licensor literature.3
8

18
 DISTILLATION | Extractive Distillation A.A. Kiss

1 Figure captions
2
3 Figure 1. Extractive distillation: conventional process in two columns (left) and integrated
4 process using a dividing-wall column (right)
5
6 Figure 2. Residue curve map (RCM) and types of characteristic points (left). RCM for
7 separating a maximum boiling azeotrope using a high-boiling solvent (right)
8
9 Figure 3. Flowsheet of extractive distillation using salt as mass separating agent
10
11 Figure 4. Uhde’s Morphylane® extractive distillation process using a single-column
12
13 Figure 5. Current ED process (top) and optimal ED process (btm) for the separtion of C4
14 mixtures with ACN as entrainer
15
16 Figure 6. VLE of ethanol and water for different entrainers (1:1 solvent / feed volume ratio
17 and 0.1g salt per ml solvent)
18
19 Figure 7. Influence of various solid salts and liquid solvents on the relative volatility of
20 ethanol and water
21
22 Figure 8. Bioethanol dehydration in an extractive dividing-wall column (E-DWC)
23

19
 DISTILLATION | Extractive Distillation A.A. Kiss

A B A B
Raffinate Extract
S product product
EDC SRC S

B,S

A,B A,B
E-DWC

S (recycle) S (recycle)
2
3 Figure 1. Extractive distillation: conventional process in two columns (left) and integrated
4 process using a dividing-wall column (right)
5
6
7
8
9
10
11
B
D (UN) UN – unstable node (UN)

SN – stable node

S – saddle point

Maximum boiling
Distillation boundary azeotrope
Distillation
boundary

A
Solvent (SN) (UN)
B (SN) C (S) A (SN)
12
13
14 Figure 2. Residue curve map (RCM) and types of characteristic points (left). RCM for
15 separating a maximum boiling azeotrope using a high-boiling solvent (right)
16

20
 DISTILLATION | Extractive Distillation A.A. Kiss

EDC S (recycle)

A,B
B

SR
2
3 Figure 3. Flowsheet of extractive distillation using salt as mass separating agent
4

Solvent recovery
section
Solvent

Nonaromatics
Feed Rectifying section

Stripping
section

Aromatics
Side rectifier

Solvent stripping
section

5
6 Figure 4. Uhde’s Morphylane® extractive distillation process using a single-column
7
8

21
 DISTILLATION | Extractive Distillation A.A. Kiss

ACN
Butane Butadiene
ACN Butene VAC

Liq
C4 ED1 ED2 Flash

2
3

ACN
Butane Butadiene
ACN Butene VAC

Liq
C4 ED1 ED2 Flash
Vap

Recycle
ACN
4
5 Figure 5. Current ED process (top) and optimal ED process (btm) for the separtion of C4
6 mixtures with ACN as entrainer
7
8

22
 DISTILLATION | Extractive Distillation A.A. Kiss

1
P = 1 atm EG + CaCl2
0.9
Vapor mole fraction ethanol / [-]

0.8
EG solvent
0.7
0.6
No solvent
0.5
0.4
0.3
0.2
0.1
0
0 0.2 0.4 0.6 0.8 1
Liquid mole fraction ethanol / [-]
1
2 Figure 6. VLE of ethanol and water for different entrainers (1:1 solvent / feed volume ratio
3 and 0.1g salt per ml solvent)
4

4.5
Relative volatility ethanol-water

4.15
4.05
4.0
3.5 3.13
3.0 2.60
2.87
2.60
2.56
2.40
2.5 2.31 2.35

1.90
2.0 1.85

1.5
1.01
1.0
0.5
0.0
ol

l3

3
t

)
K

K
l2

3
l

l2

3
aC
en

ed
3)
3)

O
O

O
O
lC
aC
yc

rC

2C
EG l(NO
O
lv

at
O

O
+N

+A
+S
gl

+K
+C

3C
so

ur
K
EG

u(

H3
EG
ne

EG

+
EG

at
EG

+A

H
o

+C

EG

(s
+C

C
le
N

EG
hy

EG

l2
aC
Et

5
6 Figure 7. Influence of various solid salts and liquid solvents on the relative volatility of
7 ethanol and water

23
 DISTILLATION | Extractive Distillation A.A. Kiss

1
2

Ethanol Water Ethanol

Solvent

Solvent (Ethylene glycol) EDC

(Ethylene glycol)
Feed

PDC
Feed
(near azeotropic)

SRC
E-DWC Water

E-DWC

Solvent Solvent
(recycle) (recycle)
3
4 Figure 8. Bioethanol dehydration in an extractive dividing-wall column (E-DWC)
5

24

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