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Extractive distillation
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• In the first half of the twentieth century, extractive

• distillation (ED) became an important industrial
• process when World War II demanded high purity
• toluene for explosive production and butadiene for
• synthetic rubber production. Over the years, substantial
• developments in ED have been carried out in
• terms of novel solvent discovery for a particular separation,
• as well as the development of more sophisticated
• ED tower internal designs. In the petroleum and
• petrochemical industries, ED has been found effective
• in separating mixtures of aromatics/nonaromatics,
• diolefins/olefins, olefins/paraffins and naphthenes/
• paraffins.
Introduction
• Extractive distillation is defined as distillation in
the presence of a miscible, high-boiling,
relatively non-volatile component, the solvent,
that forms no azeotrope with the other
components in the mixture. The method is used
for mixtures having a low value of relative
volatility, nearing unity. Such mixtures cannot
be separated by simple distillation, because the
volatility of the two components in the mixture
is nearly the same, causing them to evaporate
at nearly the same temperature at a similar
rate, making normal distillation impractical.
Azeotropic vs Extractive Distillation
• Azeotropic and extractive distillations are techniques used in the
field of chemistry and engineering. Major industries, especially
pharmaceuticals, are making use of these techniques to further
improve their research. Distillation is a very important process in
separating certain components from the mixture and is typically
based on the volatility of the components in the mixture of the
boiling liquid. Although these techniques are usually compared
with each other, many chemical engineering students are still
confused about the difference. Azeotropic and extractive
distillations have some similarities but they also have distinct
differences and these are observed on the processes. In chemistry,
these processes are very essential in separating certain mixtures to
form a new product. By comparing these two processes, you can
see their differences.
• The main difference between the two is in the process
of separating the mixture. Azeotropic distillation forms
an azeotrope right after combining the separation
solvent. This azeotrope can be a complicated way of
separating the mixture because it cannot be easily
changed by just a simple distillation. In extractive
distillation, a specific separation solvent is used in every
mixture that should not form an azeotrope. In this way,
extractive distillation is a better and easier method than
the azeotropic distillation. But you need to bear in mind
that if you have a mixture with very different volatilities,
Introduction
• The method of extractive distillation uses a
separation solvent, which is generally non-
volatile, has a high boiling point and is miscible
with the mixture, but doesn't form an azeotropic
mixture.
• The solvent interacts differently with the
components of the mixture thereby causing their
relative volatilities to change.
• This enables the new three-part mixture to be
separated by normal distillation.
• The original component with the greatest
volatility separates out as the top product.
Typical extractive distillation
Introduction

• The bottom product consists of a mixture of the

solvent and the other component, which can
again be separated easily because the solvent
does not form an azeotrope with it. The bottom
product can be separated by any of the
methods available
• applications in the following areas:
• 1. Aromatic puriRcation from reRning and
petrochemical
• streams.
• 2. CycloparafRn (cyclohexane or cyclopentane)
recovery
• from naphtha or natural gas liquid.
• 3. Light oleRns from light hydrocarbon mixtures.
• The azeotropic and extractive
• distillation processes that both involve the addition of an entrainer
are the most common
• [1e4]. We distinguish extractive from azeotropic distillation as the
entrainer is
• fed at a different location than the main mixture, bringing an
additional extractive section
• in the column, between the stripping and the rectifying sections.
Another major
• distinction is that products in azeotropic distillation are nodes of
the residue curve
• map, whereas they are mainly saddle points in extractive
distillation.
• Extractive distillation can be performed in
continuous operating mode in a
• sequence of two extractive and regeneration
columns or in a single-batch distillation
• column with at least three batch distillation
steps. Differences exist between both
• operating modes as the batch mode offers
more flexibility in terms of achievable
• product and larger operating parameter ranges.
+++
• Extractive distillation is more profitable than heterogeneous azeotropic distillation
• for many systems, in particular for the dehydration of aliphatic alcohols. The
• total annual cost (TAC) of the extractive distillation of an isopropyl alcoholewater
• mixture with dimethyl sulfoxide (DMSO) drops by 32.7% compared with the
• hetero-azeotropic distillation process using cyclohexane [4]. The most studied separation
• concerns the dehydration of ethanol, and heavy entrainer ethylene glycol
• (EG) (470.5 K) was proposed early [7,29e37]. Looking for entrainers less toxic
• than EG, glycerol (560.9 K) [38] and tetraethylene-glycol (587 K) [39] have been
• studied, among others. Optimization of the extractive column with the regeneration
• column process showed similar energy consumption for EG [40] and glycerol [38]
• but a larger consumption for tetraethylene-glycol [39]. Looking at capital and operational
• costs, glycerol seems more profitable than EG: less equilibrium trays in the
• extractive column (18 vs 24), a lower entrainer-feed flow rate ratio (0.45 vs 0.90),
• but a larger reflux (0.35 vs 0.26). Besides, the molar composition of EG in the
• extractive column bottom exceeds 0.90, imposing more demanding conditions for
• the entrainer recovery column.
• One application is separating hydrocarbons
with close
• 80 boiling point, such as C4, C5, C6 mixtures
and so on, the other is the
• 81 separation of mixtures which exhibit an
azeotrope, such as alcohol/water,
• 82 acetic acid/water, acetone/methanol,
methanol/ methyl acetate, ethanol/ethyl
• 83 acetate, acetone/ethyl ether and so on.
• In extractive distillation, an additional solvent, i.e. separating agent is
• used to alter the relative volatility of the components to be separated. In this
• way, it is possible to obtain one pure component at the top of one column
• and the other, together with the solvent at the bottom, which may be sep-
• arated easily in a secondary distillation column, due to a high boiling point
• of the solvent. The solvent doesn’t need to be vaporized in the extractive
• distillation process. However, in azeotropic distillation, which is also often
• used for the separation of close boiling point or azeotropic mixtures, both
• the solvent and components must be vaporized into the top of an azeotropic
• distillation column. Moreover, the amount of azeotropic solvent is usually large, which
leads to large energy consumption compared to extractive
• distillation. For this reason, extractive distillation is more attractive than
• azeotropic distillation
• The ease of separation of a given mixture with key
components i and j is given by the relative volatility:
𝑦𝑖
ൗ𝑥𝑖 𝞬𝑖 𝑝𝑖0
• α= 𝑦𝑗 =
ൗ𝑥𝑗 𝞬𝑗 𝑝𝑗0
• where
• 𝑥 is molar fraction in the liquid phase,
• 𝑦 is molar fraction in the vapor phase,
• 𝞬 is the activity coefficient,
• 𝑝𝑖0 is the pure component vapor pressure.
• The solvent is introduced to change the relative
volatility as far away from one as possible. Since
𝑝𝑖0
the ratio of is constant for small temperature
𝑝𝑗0
changes, the only way that the relative volatility
is affected is by introducing a solvent which
𝞬𝑖
changes the ratio . This ratio, in the presence
𝞬𝑗
of the solvent, is called selectivity 𝑆𝑖𝑗 :
𝞬𝑖
• 𝑆𝑖𝑗 = ( )𝑠
𝞬𝑗
The effect of solvent selectivity on the total annual cost of an extractive
distillation operation (2-methyl-1-butene/isoprene)
• It can be seen in Figures :
• the solvent selectivity increases, in general, the
total annual cost of the extractive distillation
decreases.
--
• Extractive distillation can’t obtain a very high
purity of product, but
• consumes less energy; however, azeotropic
distillation can obtain a very
• high purity of product, but consumes much
more energy.
SELECTION OF SOLVENT
• Extractive distillation works by the exploitation
of the selective solvent-induced enhancements
or moderations of the liquid-phase
nonidealities of the original components to be
separated. The solvent selectively alters the
activity coefficients of the components being
separated. To do this, a high concentration of
solvent is necessary. Several features are
essential:
SELECTION OF SOLVENT

• It should be inexpensive and easily available.

• It should be stable at operating condition of both of
column.
• It should be easily separable from the bottom product.
• It should be non-corrosive and non-toxic.
• It should be non-reactive with feed component.
• It should be higher boiling than the key components of
the separation.[
• Extractive distillation Column operation
• Continuous operating mode
• Batch operating mode
Continuous operating mode
• The extractive distillation process in continuous mode operates under steady-state
• conditions. The separation of the three components AeBeE usually involves a
• sequence of two connected columns, the extractive distillation column and the
• entrainer regeneration column. The classical sequence configurations for the direct
• and indirect splits are displayed in Figure 6.6, giving rise to three sections: rectifying,
• extractive, and stripping ones.
• As a general rule, a heavy entrainer FE is fed above the main feeding FAB (see
• Figure 6.6(a)) and a light entrainer is fed below FAB (see Figure 6.6(b)). Those conditions
• ensure a high concentration of the entrainer in the extractive section as light compound
concentration increases upward and heavy compound concentration
• increases downward. No thorough analysis has been made for an intermediateboiling
• entrainer that is fed like a heavy or a light entrainer. Other configurations,
• with FE fed along FAB or at the top of the column, exist for homogeneous continuous
• extractive distillation. For heterogeneous continuous extractive distillation, FE can
• be additionally fed at the decanter, giving rise to seven distinct configurations
• [21]. The column configuration with a heavy entrainer has dominated over the light
• entrainer one
• The key operational parameters of the extractive distillation column are the
• entrainer-feed flow rate ratio FE/FAB, along with the reflux ratio RR (RR ј LR/D)
• or the reboil ratio Rb (Rb ј VR/W). The choice of the physical state of the entrainer
• stream (e.g. a boiling liquid or a saturated vapor) has been partly discussed [17].
• The heavy entrainer configuration enables a direct split with the product removed
• from the distillate of the extractive column. Conversely, an indirect split with a light
• entrainer configuration allows one to withdraw the product from the extractive column
• bottom. Figure 6.6 shows that either A or B can be a product as it depends on
• the residue curve map class and the univolatility curve location (see Section 6.4.3).
• Finally, the entrainer-rich stream is sent with the other initial compound to the
• regeneration column to be recycled. In practice, an entrainer makeup stream (not
• shown) is added to compensate entrainer trace losses in the A- and B-rich products.
batch
• Extractive batch distillation is a semibatch process, as the main feed FAB is loaded
• initially in the boiler, whereas the entrainer is fed continuously at a higher tray. The
• entrainer regeneration task is performed in the same column, after the extractive
• task.
• Steger et al. [51] and Varga [52] have summarized batch extractive distillation,
• respectively, in a rectifier and in a stripper column configuration with a heavy, light,
• or intermediate entrainer for separating minimum- and maximum-boiling azeotropes
• and low-relative-volatility mixtures. Depending on the location of the entrainer
• feeding (fed continuously into the boiler, at the top, or at an intermediate tray position),
• batch extractive distillation variants can be imagined [51,52]. The one with an
• intermediate feed location later gives the best results and is the one we consider (see
• Figure 6.7) in both cases, as feasibility of extractive distillation requires the intersection
• of an extractive composition profile with a rectifying one for the rectifier configuration
• [11,12], or a stripping one for the stripping configuration [16,17].
• The use of a light entrainer would recommend using a batch stripper for
• running an indirect split, as the product being expected to be a heavy boiler could
• be removed from the boiler still [13,52,54], but a batch rectifier configuration is
• also possible [51,53].
• With a heavy entrainer, the main feed FAB is loaded initially in the still. The
• batch rectifier column exhibits an extractive and a rectifying section (see
• Figure 6.7(a)), and the direct split separation allows one to withdraw the product
• as distillate from the top. The operating parameters are the entrainer-vapor flow
• rate ratio of FE/V, the reflux ratio (RR ј L/D) established at the column top, and the
• number of equilibrium trays in each column section. FE/V is an entrainer-feed flow
• rate ratio, much like the continuous ratio FE/FAB considering that FAB is fed into the
• column as a vapor overflow V from the boiler. There exists a relation between the
• continuous and the batch entrainer-feed flow rate ratio for boiling liquid feeds
• With a light entrainer, the initial load is split into the top vessel and the boiler, the
• batch column is a stripper with an extractive and a stripping section, the product is
• removed as the bottom product, and the separation is an indirect split. The key operating
• variables are the entrainer-top liquid flow rate ratio FE/LT, the bottom reboil
• ratio Rb (Rb ј VS/W), and the number of equilibrium trays in each column section.
• FE/LT is an entrainer-feed flow rate ratio like FE/FAB, considering that FAB is fed to
• the column top through the liquid flow rate (LT) coming from the top vessel (see
• Figure 6.7(b)). Again, there exists a relation between the continuous and the batch
• entrainer-feed flow rate ratio With a light entrainer, the initial load is split into the top vessel and the boiler, the
• batch column is a stripper with an extractive and a stripping section, the product is
• removed as the bottom product, and the separation is an indirect split. The key operating
• variables are the entrainer-top liquid flow rate ratio FE/LT, the bottom reboil
• ratio Rb (Rb ј VS/W), and the number of equilibrium trays in each column section.
• FE/LT is an entrainer-feed flow rate ratio like FE/FAB, considering that FAB is fed to
• the column top through the liquid flow rate (LT) coming from the top vessel (see
• Figure 6.7(b)). Again, there exists a relation between the continuous and the batch
• entrainer-feed flow rate ratio
• vapor overhead by a single high-purity component. The dynamic of that
substitution
• is usually rapid and readily observed by a shift from the column top
temperature
• from the azeotrope temperature to the pure compound temperature.
Third, a product
• is removed under steady entrainer feeding. For the final step, the
entrainer is no
• longer fed and a classical distillation of the entrainer accumulated and of
the remaining
• original compound is performed. Several variants of the batch extractive
operation
• have been studied, and feeding the entrainer during the heating step may
in
• some cases shorten the operation without degrading the product [67,68].
Advantages and Disadvantages of
Extractive Distillation with the
Combination of Liquid Solvent and Solid
Salt:
• Extractive distillation with the combination of liquid solvent
and solid salt as the separating agent integrates the
advantages of liquid solvent (easy operation) and solid salt
(high separation ability). From the above discussion, we
know that whether it is of separating polar systems or non-
polar systems, extractive distillation with the combination of
liquid solvent and solid salt may be feasible. So it is
concluded that extractive distillation with the combination of
liquid solvent and solid salt is a promising separation
method. If we meet with the problems about extractive
distillation in the future, it is wise to try to solve it by
• adding solid salt. Unfortunately, many solid salts are
corrosive to the equipment and easies to decompose at high
temperature. In some cases the kinds of solid salts that we
can select are small. An economic calculation must be made
in determining the final salts. The benefit from adding salts
in the production should exceed the price of salts and other
charges. On the other hand, since the amount of solid salts
added to the liquid solvents is often small, the role of solid
salts in improving the separation ability is doomed to be
limited. Besides, liquid solvents are volatile, which inevitably
pollutes the top product of the extractive distillation column.
Accordingly, new separating agents should be explored to
avoid these problems brought out by liquid solvent and solid
salt.[