ENTRAINER SELECTION RULES

 for a minimum boiling azeotrope, use a high boiling component that introduces no additional
azeotrope, an intermediate boiling component that introduces no additional azeotrope, a
component which introduces no distillation boundary between the azeotropic constituents, and
either a low boiling component that introduces no additional azeotrope or a component that
introduces new minimum boiling azeotrope
 A good entrainer is a component that eliminates the azeotrope easily (i.e. even when it’s
concentration is small)
 A component that yields relative volatilities αAB between the two azeotrope constituents more
different from unity in the whole concentration range (0÷1).
 thermodynamics (selectivity and boiling point) and to process operation (entrainer–feed flow
rate ratio, low corrosion, price, toxicity, and high thermal stability) [
 Some entrainers enhance the volatility, while others reduce it
 Gerenally αAB is calculated from the ratio of the distillation coefficients Ki = yi /xi , which can be
written as follows if the pure liquid fugacity in a reference state is supposed to be equal to the
vapor pressure P0 I


 relative volatility is mainly affected by introducing an entrainer that changes the ratio of the
activity coefficients γA/γB
 the ratio P o A/Po B is almost constant for small temperature changes,
 SAB = γA.E/γB.E (selectivity)
 the activity coefficients of the components of the azeotropic mixtures are determined by
computing with a thermodynamic model like nrtl,….
 S ∞ AB departures from unity can only provide a preliminary guidance because the selectivity
may change as the solute concentration increases. The entrainer capacity for component B can
be evaluated from equation (4): C ∞ BE = 1/γ∞ BE
 The smaller the value of the activity coefficient γ ∞ BE is, the stronger are the interactions
between component B and the entrainer, which results in a larger capacity.
 The NRTL model usually represents binary equilibrium data quite well with its three parameters.
It is superior to the Wilson and UNIQUAC in that, it is applicable to a multicomponent system
with three phases Liquid–Liquid–Vapor.
 the changes of the activity coefficients which are a function of the solute concentration and the
entrainer - feed flow rate ratio ( we need to know flowrates of entrainer and feed through some
real industry example)
 for different ratios,find activity coeafficients and finally calculate relative volatility till it becomes
less than 1
 Although the final selection of entrainers must be determined by means of an economic
evaluation in which all variables and criteria are considered for the whole process including the
recovery process, screening entrainer at the preliminary stage should consider two aspects:
separation enhancement which can be expressed by relative volatility αAB (or selectivity) and
entrainer capacity (which can be expressed approximately by entrainer–feed flow rate ratio
S/F).
 First of all, the activity coefficients of the key components in the presence of entrainer are
determined by computing with one of the thermodynamic models (e.g. NRTL).
 Second, the relative volatility between the azeotropic constituent components at the different
entrainer - feed flow rate ratios S/F is determined. From the obtained results, we can
determine the value of the ratio (S/F)min at which the azeotropic point will be eliminated.
 Third, the final entrainer selection for the azeotropic separation is made by the criteria
“selectivity” αAB and “entrainer capacity” (S/F)min.

file:///C:/Users/Anil/Downloads/12952-103810387455-1-PB.pdf

 Depending on the boiling point of entrainer, three types of entrainer are observed which are
described below.
 Heavy entrainer: entrainer which have higher boiling point as compared to both the component
of azeotropic mixture.
 Intermediate entrainer: the boiling point of entrainer is in between boiling point of both the
component of mixture.
 Light entrainer: this type of entrainer have low boiling point with respect to the both the
component of mixture.
 The feasibility of entrainer is determined by residue curve map (RCM) technique. To determine
feasibility using RCM, vapour liquid diagram is necessary to understand.

 Based on the properties and role of the entrainer, distillation is divided in three main groups
 a) Homogenous azeotropic distillation: Entrainer used in distillation which is completely
miscible with component in original mixture. It forms homogenous azeotrope with component
in the original mixture, this carried out in single feed column.
 b) Heterogeneous azeotropic distillation Entrainer forms heterogeneous azeotrope with one or
more components in the original mixture which is carried out distillation column with a
decanter.
 c) Extractive distillation This process is carried out in two feed column in which entrainer is
introduced above the original mixture feed point and largely removed as bottom product.
Entrainer is used to enhance the relative volatility of low volatility component to precede the
separation of mixture. Entrainer has high boiling point (heavy entrainer) as compared to the
 original mixture component. It does not form any type of azeotrope. Other than above
distillation techniques some more are used now a day which are listed below:
 d) Reactive distillation Entrainer reacts with one or more component from original mixture. The
nonreacting component is produce as a distillate and the entrainer is recovered from reverse
reaction.
 e) Salt distillation It is the one type of extractive distillation in which relative volatility is altered
by addition of salt as an entrainer in the top reflux

Application of feasibility criteria defines the four general conditions to screen entrainer for separation of
minimum, maximum and close-boiling azeotropic binary mixture for batch distillation

a) No additional azeotrope is introduced

b) A minimum-temperature binary azeotrope exists between Entrainer (E) and either A or B
component.
c) A maximum-temperature binary azeotrope exists between Entrainer (E) and either A or B
component.
d) There might be a ternary azeotrope
e) Above four rules are applied for homogenous batch distillation but for heterogeneous batch
distillation additional two rules are :
f) E is not miscible with one of component of the original mixture (either A or B).
g) E forms minimum temperature heteroazeotrope with A or B.

(RCM) analysis is useful for the selection of entrainer for azeotropic and extractive distillation. RCM is
geometric representation of vapour liquid equilibrium (VLE) phase behaviour of multi-component
mixture which consists of collection of residue curve and trajectories compositions of components with
respect to time. The boiling points of pure components, binary, ternary or multicomponent mixture
indicated on the diagram. The composition trajectories move from lightest component to the heavy
component i.e. the temperature continually increases to as the liquid gets richer in heavier component.
Temperature indicated by arrow on residue curve from lighter component to heavier component. The
nature of RCM changes with extent of reaction i.e. depending upon the reaction kinetics. These curves
can be determined either experimentally or by mathematical simulation of the experiment

Evolution of Feasibility of entrainer using RCM technique consists of step wise procedure which is
explained briefly. First construct the RCM for given multicomponent mixture consisting of azeotropic
component and the given candidate entrainer. Next, check the phase behaviour of the system, whether
it is liquid-liquid or vapour-liquid phase. The tie-lines indicate the two phase compositions. Then draw an
envelope over the RCM composition space, superimposing the composition scale rather than
temperature scale.
1. Arrange the list of components and candidate entrainer

2. Prepare an RCM for each candidate entrainer: To construct RCM for the system of A, B, and the
candidate entrainer, requires thermodynamic physical property.

a. If it is not available then modelled using UNIFAC, provided the predictions are in agreement with
available azeotrope data.
b. If no physical property model is available, then construct RCM using available azeotropic
temperature, composition (approximate), and solubility (approximate) data.
c. If neither physical property nor azeotropic data available then required information can be
calculated using guessing or calculated experimentally.
d. 3. Determine the feasibility of candidate entrainer from the structure of the RCM:-
(a)The entrainer does not divide components (A and B) to be separated into different distillation
regions.
(b)The entrainer induces liquid-liquid phase separation; there exists liquidliquid equilibrium tie line
crossing distillation boundary.

4. Evaluate all separation sequences: - number of distillation column with decanters and also their
interconnections from the RCM of system for all feasible entrainer.

5. Determine the most promising entrainer for given feasibility conditions.

6. Design, stimulate and optimize separation sequences.

https://www.ripublication.com/ijcher16/ijcherv8n1_03.pdf

Batch distillation is an important separation technique in chemical industries. In particular, it is widely

used in pharmaceutical and speciality chemical manufacturing to recover valuable components from
wastesolvent mixtures.

 The frequent presence of multicomponent azeotropes in these streams can delimit distillation
regions in which the types of feasible separations are limited.
 Therefore, products generated by a separation process such as batch distillation are highly
dependent on the initial mixture composition.
 To split a mixture into its pure components, a sequence of batch processes might be required,
and several different configurations of columns might have to be used.
  a residuecurve-map analysis for the batch distillation of homogeneous mixtures with arbitrary
numbers of components led to an algorithm that permits the construction of batch distillation
regions
 Each batch distillation region is characterized by a product simplex, which is obtained when an
infinite reflux ratio, a large number of trays, and linear pot composition boundaries are
considered
 The synthesis and design of an azeotropic batch distillation process proceeds in two steps.
 The first step, process synthesis, involves the selection of one or more candidate entrainers, the
determination of the residue curve diagram and of the product cut sequence, and the choice of
one or more column configurations.
 The second step, process design, involves the search for optimal batch process parameter
values. The complexity of the second problem depends on the solutions obtained for the first
problem because efficiency in azeotropic distillation is largely determined by the choice of a
suitable entrainer.
 Most of the work published on the entrainer screening issue for distillation processes either
chooses the entrainer on the basis of its interaction with the mixture components or defines
guidelines for the selection of entrainers that produce feasible designs in continuous distillation
 However, the criteria obtained for continuous distillation processes cannot be applied directly
to batch distillation processes because continuous and batch distillation regions differ and the
product cut sequences are not alike. As a consequence, some entrainer selection rules
specifically suited for homogeneous batch azeotropic distillation have been derived

Refer below link for Entrainer selection using RCM for azeotropic batch distillation

https://sci-hub.se/https://doi.org/10.1021/ie000429z

entrainer selection SOFTWARE???... FIZ chemie

http://www.fiz-
chemie.de/fileadmin/user_upload/PDF_EN/Entrainer_Selection_manual_FIZ.pdf
PROPERTIES OF ISOPROPYL ALCOHOL
 Isopropyl alcohol is miscible in water, ethanol, ether, and chloroform. It
dissolves ethyl cellulose, polyvinyl butyral, many oils, alkaloids, gums and natural
resins.
 Unlike ethanol or methanol, isopropyl alcohol is not miscible with salt solutions
and can be separated from aqueous solutions by adding a salt such as sodium
chloride. The process is colloquially called salting out, and causes concentrated
isopropyl alcohol to separate into a distinct layer.
 Isopropyl alcohol forms an azeotrope with water, which gives a boiling point of
80.37 °C (176.67 °F) and a composition of 87.7 wt% (91 vol%) isopropyl alcohol.
Water–isopropyl alcohol mixtures have depressed melting points. It has a slightly
bitter taste, and is not safe to drink
 Isopropyl alcohol becomes increasingly viscous with decreasing temperature and
freezes at −89 °C (−128 °F).
 Isopropyl alcohol has a maximal absorbance at 205 nm in an ultraviolet–
visible spectrum
Solvent
Isopropyl alcohol dissolves a wide range of non-polar compounds. It also evaporates
quickly, leaves nearly zero oil traces, compared to ethanol, and is relatively non-toxic,
compared to alternative solvents. Thus, it is used widely as a solvent and as a cleaning
fluid, especially for dissolving oils.

Owing to its -OH group, isopropyl alcohol molecules can form weak bonds, called
hydrogen bonds, that help hold the molecules together. Consequently, it has a much
higher boiling and melting point than propane, which also contains three carbons and
eight hydrogens. The boiling point of isopropyl alcohol is 82 degrees Celsius; its
melting point is -89 C. Its boiling point is lower than that of 1-propanol (propyl
alcohol). The density of pure isopropyl alcohol at room temperature is about 78.6
percent of the density of water at the same temperature.

 Isopropyl alcohol is likewise less soluble in saltwater than in

pure water.
ETHYL ACETATE PROPERTIES
Ethyl acetate is immiscible with water.

 Ethyl acetate is an important solvent, raw material and intermediate widely

used in organic synthesis. Particularly, it is used as solvent in the production
of paints, rubber, resins, adhesives, leather, fiber and cellulose. Ethyl acetate,
similar to other esters, is a raw material to obtain flavors such as: banana,
pineapple and strawberry.
Ethyl acetate is a colorless, with fruity odor liquid. Its melting and boiling point are -83.6 ºC and
77.06 ºC and its density is 0.894 g mL-1. Ethyl acetate is not soluble in water, but it is soluble in
most of the organic solvents such as benzene, acetone, chloroform and toluene.

 Ethyl acetate and other esters can be hydrolyzed to the corresponding

carboxylic acid and ethanol. In the case of ethyl acetate, the reaction is
prepared using acids or bases as catalysts and the products: acetic acid and
ethanol are produced after a two step mechanism. Other important ethyl
acetate reaction is the transesteriferication, where the metoxy group from the
ester can be substituted by R- group from an alcohol.