UNIT OPERATIONS II. UNIT I. SEPARATION PROCESSES.

GENERALITIES. the content of some component that could inhibit the

behavior of the catalyst in a reaction or by it
Separation processes are of great importance in the
on the contrary, it is necessary to add some compound that
chemical industry, petrochemical industry, refining industry, of the
promote or inhibit some of the reactions present in the
food, polymers, energy, etc. In them
process, also in this block, the raw materials are
they obtain products by means of concentration
they carrya the thermodynamic conditions (pressure,
fractionation and/or purification of compositions
temperature, phase) that best fit the needs of
required and at reasonable prices.
reaction. The second block is the transformation process
Frequently in the industry it is necessary to separate the chemistry, generally consisting of a chemical reactor
components of a mixture in individual fractions. The adapted to carry out mass transfer and
fractions can be differentiated from each other by their state, by their associated energy, in the most efficient way possible.
chemical composition or by the size of the particles. Thus,
Because no reaction is totally selective towards
a crude product can be purified by removal of the
the product that is desired in the process. The effluent from
impurities that contaminate it, a mixture of two or more
the reaction system will consist of: a) product
components can be separated into pure components
deseado, b) subproductos de la reacción, c) materias primas
individuals, the current that comes out of a process can
that do not react, d) inert components to the reaction. The
contain a mixture of the product and non-material previously makes it necessary for a third block where the occurrence takes place
converted, and it is necessary to separate and recirculate the non-part
separation of the products contained in the effluent of the
converted to the reaction zone for its conversion to
reactor, obtain the quantity and quality of the products from
product; also a valuable substance, such as a
interest, mainly the main product; some
metallic material, dispersed in an inert material, is necessary
by-products that have commercial and economic value and
release it in order to proceed for its benefit and discard the
those by-products that have no commercial value whatsoever
inert material. ([Link]).
(waste products) that must be prepared for the
From the point of view of Chemical Engineering, matter environmental preservation.
it can be subjected to two types of industrial processes
The raw materials and some inert components, already
basics, separation and transformation. The processes of
isolated during the product separation stage are
separation refers to all those activities that
generally recycled for their reprocessing, which gives
they seek to separate and classify the different substances that
place to a fourth stage of the process, made up of the(s)
they constitute a flow of feed or raw material,
recirculation current(s), which depending on their quantity
using an industrial or laboratory process to obtain
and their composition integrates into the process at different points. In
specific products and those with higher added value.
All stages of the process involve exchanges.
transformation processes refer to a those
of energy with the outside, in order to incorporate the
procedures and activities that modify matter from
energy potential required for the preparation of the
its substance, that is to say new substances are obtained
raw materials, the reaction, the separation of the products and
completely different from the one that originates it. These
the reprocessing of the recirculation streams is
operations are carried out through chemical reactions,
the management and control of the kinetics of the reaction. The equipment
carry out properly.
chemical reactors are used. With the separation processes, changes are desired in
the chemical composition or physical changes in the material
In industrial processes, it is generally necessary to have a
that is prepared, processed, separated or purified. For
combination of transformation processes and those of
to achieve
separation for obtaining desirable products, such as
is shown in figure 1. Pure materials for applications in Engineering
semiconductors
2. Pure materials for processing
3. Remove toxins or inactive compounds from a
solution
4. High purity samples as references
5. Analysis of the components of a mixture (DNA)
Figure 1. Conceptual architecture of a chemical process.
Source: Aguilar R., E., 2007. 6. The separation of raw material into its components
(oil)
In figure 1, a first block can be seen where
prepares the raw material with the aim of making more These processes are carried out on specialized equipment and
efficient the following reaction process. That is to say, limit interconnected that work as their own units and with

FACILITADOR: ING. ZORAIDA J. CARRASQUERO C. MSc. UNEFM INTENSIVE 2019

 UNIT OPERATIONS II. UNIT I. SEPARATION PROCESSES.
a specific function where separation is achieved or • Modifying their conditions of movement (changes in
transformation of materials using scientific principles the direction, increase or decrease of speed
and common calculation techniques, and it is what defines the In all unit operations, there is a transfer.
operations unitary. You are operations they are simultaneously: mass, energy, and momentum.
based on principles and complementary laws and However, these operations are not controlled
they use some physical-mathematical instruments, as well as necessarily by the three transfers, but by one or to
specific calculation techniques that are mentioned in I sum two transfers, the most relevant ones.
continuation:
This transfer of properties originates a force.
1. Principles driving force, a gradient of some property, that accounts for
from the main transfer mechanism, as shown
a. Laws of Conservation or changes of properties in table 1. Table I.1. Characteristics of the transfers
extensivas
Transfer Mechanism Driving Force
• Matter (Law of Lavoisier)
Matter Gradient of
• Energy (First Law of Thermodynamics) Diffusion
concentration
• Quantity of Motion (Newton's Law) Heat Driving
Gradient of
Convection
• Entropy Temperature
Radiation
b. Laws of equilibrium of physicochemical systems Quantity of Gradient of
Friction
(Second Law of Thermodynamics) Movement Speed
• Kinetic Laws
Economic laws A particular case, if the system reaches a condition such that
•
it cannot experience any change spontaneously,
• Environmental laws it is said that the driving force is 'null', that is to say the system
• Safety and hygiene laws, etc. it is in a state of equilibrium. Therefore, it is possible
establish certain operational conditions under which everything
2. Complementary the system is in a state of equilibrium.
a. Stoichiometric laws The separation processes developed include different
b. P-V-T state equations unit operations, among which are mentioned:
a. Distillation. Which consists of to separate by means of
c. Physical-mathematical instruments
vaporization, a liquid mixture of miscible substances and
d. Physical-mathematical models volatile in their individual components or in some.
e. Systems of magnitudes and units cases in cuts or fractions if several are present
components, for example crude fractionation
f. Dimensional analysis
b. Absorption of gases. A soluble vapor contained in a
g. Analysis of design variables in operations, mixed with an inert gas, is absorbed by a
etc. liquid in which the gaseous solute is more or less
3. Calculation techniques. soluble. The solute is then recovered by distillation and
the adsorbent liquid can be reused or disposed of.
a. Presentation of experimental data
c. Liquid-liquid extraction. Also called extraction with
b. Adjustment and correlation of experimental data solvent, in which a liquid mixture is treated with a
c. Methods for solving equations and systems of solvent that preferentially dissolves one or more
equations components of the mixture. The mixture treated in this
the form is referred to as refined and the solvent-rich phase is
d. Tensor calculation operations, etc. denominated extract, The component that is transmitted
The purpose of every unit operation is to modify the from the refined to the extract is the solute, and the
conditions of a quantity of matter, in a more useful form to The component that remains in the refining is the solvent.
our purposes. This is achieved: [Link]. It is a simultaneous transfer operation of
• Modifying its mass or its composition (mix or heat and mass transfer gas-solid, where humidity
phase separation contained in the solid is transferred by evaporation to
• Modifying the level or quality of energy it has the gaseous phase, based on the pressure difference of
(cooling, vaporization) vapor exerted by the wet solid and the partial pressure

FACILITADOR: ING. ZORAIDA J. CARRASQUERO C. MSc. UNEFM INTENSIVE 2019

 UNIT OPERATIONS II. UNIT I. SEPARATION PROCESSES.
from the vapor of the gas flow. When these two Unit operations can be considered in two
pressures are equal, it is said that the solid and the gas are in types:
equilibrium and the drying process ceases.
• Key operations: those where the reaction occurs
e. Crystallization. It is a unit operation of transfer. chemistry, the separation of phases and the separation of
simultaneous matter and energy in which the chemical products. For example: distillation, absorption,
formation of a solid (crystal or precipitate) from liquid extraction, reactor.
a homogeneous phase (solute in solution or in a
• Auxiliary operations: where heat is supplied or removed,
melted). The driving force in both stages is the
supplies or removes work, the solids accumulate due to
oversaturation and the possible temperature difference
size reduction or solids are separated by size,
between the crystal and the liquid originated by the phase change.
there is no change in the chemical composition. For example:
f. Adsorption. It is the process by which an atom or a Pumps, heat exchangers, filters.
substance molecule adheres to the surface of a
Figure I.1 shows a series of unit operations.
solid or at the interface between two fluids. Adsorption
coupled that represent the production of ETBE, where
it is a means to neutralize or satisfy the forces of
the key and auxiliary operations are identified.
attraction that exists on a surface or an interface, and
that are due to the discontinuity in the nature of the
structure. Consequently, adsorption produces a
decrease of interfacial free energy (or tension if so
deal of a phase fluid/fluid) .
[Link]/[Link] J.L.
1998
g. Evaporation. It is an operation in which separation occurs.
through boiling, a volatile solvent of one or several
non-volatile solutes, with which it is mixed
forming a dissolution o suspension.
([Link]
engineering/operations
basicas/contenidos1/topic10/page_16.htm
h. Filtration. It is a physical-mechanical method for the Figure I.1. Identification of key operations (lines
separation of mixtures of compound substances of red) and the auxiliary operations (blue lines).
different phases (phase: homogeneous component in a
The sequence of chemical, physical, biological operations that
determined state of aggregation). A filtering medium
are necessary for the transformation and/or separation, the
porous is traversed by a liquid or gas (phase 1) and the
transport and storage of materials or energy can
solid particles or droplets of a liquid (phase 2) remain
they can be represented through block flow diagrams,
retained on the surface or inside the medium
flow process diagrams and piping diagrams
filtering.
instrumentation In this work, the ...
i. The use of chromatography and separation methods block flow diagrams and flow diagrams of
analytics, to determine the composition of mixtures processes.
complex.
Block flow diagram: it is a simple representation
j. Membranes. This is a separation operation of an industrial production process. Each block
controlled by the transfer of matter and whose force represents an operation or a complete stage of the process.
a driver is a gradient of pressure and concentration, Its In the block diagram, each of the operations
the objective is the transfer of a solvent from a solution units are represented as a block, on which is
concentrated to a more diluted one through a membrane they can list some of the characteristics of the
semipermeable. ([Link]/operations). operation (pH, temperature, pressure, etc.) and even that
relevant information (mass reason of the)
k. Bioseparators. Bioseparation processes involve
diferentes corrientes, rendimientos, etc.). Los bloques van
the recovery and purification of products derived from
united by arrows that represent flows of matter, being
of the bioreactor. They include all the treatments that
convenient to reflect next to each arrow the data
requires the culture medium for the production of the product
known about the current. In this type of diagram, it does not
under the conditions of desired purity and activity.
they include auxiliary operations. For the preparation of the
([Link]
block diagrams are used in different programs

FACILITADOR: ING. ZORAIDA J. CARRASQUERO C. MSc. UNEFM INTENSIVO 2019

 UNIT OPERATIONS II. UNIT I. SEPARATION PROCESSES.
IT professionals, such as: AutoCAD, Microsoft Visio, Microsoft Figures I.4 and I.5 show the process flow diagram.
PowerPoint, etc. for the production of methanol and the production of benzene,
respectively.
Figure I.2 shows an example of a diagram of
blocks of a production process of surfactants
encapsulated extreme in which the information is reflected
supplied in Patent US5847229A1. It can be observed in it
four operations: two reactions (1 and 2), a separation of
phases (3) and the final drying (4) until obtaining the product
desired. It also reflects other information provided by the
patent (temperature, molar relationships, etc.) are not defined
the flows nor the energy exchanges; and in Figure I.3
show the block flow diagram of the process for the
production of benzene. (www.
[Link]/̴aulavirtualpfciq/[Link]
In general, in block flow diagrams, the
operations are represented by blocks, most of
the lines are represented with arrows that point in the direction of
Figure I.3. Block flow diagram for production of
flow, the direction of the flow goes from left to right while Benzene. Source: [Link]
If possible, the light currents (gases) go through the top.
while the heavy currents (liquids and solids) go
through the background, critical information about the process is provided,
if the lines intersect, the horizontal line is continuous and the
vertical is cut off and operations are not represented
auxiliaries.

Figure I.4 Flowchart of the process for obtaining

methanol

Figure I.2. Example of a block diagram of a process

production of surfactants. Source: Patent US5847229A1
Flowchart of the process. It is a graphic representation.
of a process. Each stage of the process is represented by
a different symbol that contains a brief description of
the stage of the process. The graphic symbols of the process are
united by arrows that indicate the direction of the flow and are
they identify the main flows. This type of diagram provides
more information than block diagrams, includes the
numbers and identification names of the team, the
pressures and temperatures, service identifications, and flow
mass/volumetric of the selected flows and a
material balance table linked by a key of
process lines, auxiliary operations are included. In Figure I.5. Flow diagram for the production of benzene.

FACILITADOR: ING. ZORAIDA J. CARRASQUERO C. MSc. UNEFM INTENSIVE 2019

 UNIT OPERATIONS II. UNIT I. SEPARATION PROCESSES.
Characteristics of Unit Operations. VSublimation or condensation to solid state
(cooling)
Each of the unit operations is characterized by:
VCrystallization (Heat)
• Principle of separation VDrying (Heat)
• Separation agent 2. Reduction of pressure, pressure gradient (gradient
• Factor of separation of pressure more membrane)
VInstant vaporization (pressure reduction)
The principle of separation is what indicates the basis on which it is based.
VGas diffusion (pressure gradient plus
unit operation for the separation to occur. It also
membrane)
define as the inherent physical or chemical property of the
VReverse osmosis (pressure gradient plus membrane)
components of the mixture that allows it to be carried out
VUltrafiltration (pressure gradient plus membrane)
separation. Table I.2 shows some of the
3. Non-condensable gas or condensable gas
most common operations indicating their principle of
VDesorption (non-condensable gas)
separation.
VSweeping diffusion (condensable gas)
4. Non-volatile liquid or immiscible liquid or solvent
Table I.2. Principle of separation of some of the VAbsorption (non-volatile liquid)
most well-known unit operations. (Source: Taken from VExtraction (Immiscible liquid)
King. J. 1998 VLeaching or washing (solvent)
5. Adsorbent solid, solid resin.
Unit Operation Principle of separation
VAdsorption (adsorbent solid)
Distillation Difference of points of VIon exchange (solid resin)
boiling 6. Concentrated saline solution plus membrane
VReverse Osmosis
Gas absorption Preferential solubility
7. More active tense air bubbles
Evaporation Difference in volatility VBubbling or foaming
VFlotation (surfactant added)
Crystallization Difference in tendency to 8. Capillarity plus paper or gel phase or solid gel
to crystallize VPaper chromatography (capillarity plus paper)
Drying of solids Evaporation of water VFiltration through a gel (solid gel)
9. Membranes
Sedimentation Difference in density VDialysis (Selective membrane: solvent)
Leaching Preferential solubility VElectrodialysis (anion exchange membranes and cation exchange membranes;
electric field
VGas permeation or permeability (membrane)
The separation agent is responsible for creating or adding a selective, pressure gradient
second phase to promote the separation of the 10. Magnetic field, electric field or electrical energy
components that make up the original mixture. They are known VMass spectrometry (magnetic field)
two types: VElectrophoresis (electric field)
VElectrolysis with reaction (electric energy)
1. Matter separation agent. 11. Centrifugal or mechanical force
VIt may be partially miscible with one or more of the VCentrifugation (centrifugal force)
species of the mixture VUltracentrifugation (centrifugal force)
VIt is generally the largest component.
concentration. The separation factor (α)jjthes degree of separation that
2. Energy separation agent. It can be obtained through any separation process in
VHeat transfer and/or work to or from the particular and is defined in terms of the compositions of the
mix separation object. productos:
VA second phase can be generated by reduction of ⁄
= (I.1)
the pressure. ⁄

Most commonly used separation agents in operations The separation factor, , between components i and j is the
unitary relationship of molar fractions (mass fractions,
molar flow rates or mass flow rates of the components
1. Supply of heating or cooling.
VEvaporation (Heat) individuals) of the two components in product 1
VDistillation (Heat) divided by the relation in product 2.
VMolecular distillation (Heat and vacuum) Thus, yes:

FACILITADOR: ING. ZORAIDA J. CARRASQUERO C. MSc. UNEFM INTENSIVE 2019

 UNIT OPERATIONS II. UNIT I. SEPARATION PROCESSES.
s °
αijThe separation of components i and j is not applicable. = ° (I.6)
αijs > 1 The component i tend a to concentrate
preferably in product 1 and component j tends to The inherent separation factor αijin a steam system
preferably focus on product 2. liquid is referred to as relative volatility.
s
αijThe j component tends to concentrate on the product At sufficiently low pressures, the K ratioiP must be
1 more than the component i and the component i tends regardless to of the level of pressure, so that it can
focus on product 2 more than component j. maintain the ideal gas hypothesis and that the correction
of Poynting pressure is negligible. When Ki*P and Kj*P
King, J. (2003) indicates that the separation factor reflects the
they are independent of the pressure, αijit will necessarily be
differences in equilibrium compositions and speeds
independent of the pressure. The vapor pressures of i and j
of transport due to fundamental physical phenomena
they depend on the temperature; therefore Kiy Kjits functions
that cause separation. For this reason, a is defined a
of the temperature. Since αijit is proportional to the relationship
inherent separation factor, αijwhat is the factor of
of vapor pressures, and since the vapor pressures of
separation that would be obtained under ideal conditions, as follows:
Vapors increase when the temperature rises, αijit will be
• For equilibrium separation processes, the factor of less sensitive to temperature than the constants of
inherent separation corresponds those a equilibrium of components i and j. In small intervals of
compositions of the product that would be obtained when temperature αijthey can be taken at a constant frequency. In
the complete equilibrium between the phases is reached. the case that Raoult's and Dalton's laws are fulfilled αijis
• For separation processes controlled by velocity independent of the pressure and composition, and it is
the inherent separation factor corresponds to those insensible to temperature (King, J., 2003).
compositions of the product that would occur in the presence
En los procesos de separación vapor-líquido, la mayoría de las
of
found solutions are not ideal, that is to say they do not obey
a single controlling mechanism of physical transport.
Raoult's law. In these cases, equation I.4 is modified.
Inherent separation factor: equilibrium processes. normally including an activity coefficient of the
liquid phase ϒ,
For separation processes in phase equilibrium
= ∗ = ∗ °∗
immiscibles is defined for each species i a value called (I.7)
equilibrium relationship, Ki, and it is the relationship of the molar fraction
At high pressures, a coefficient is also necessary.
from the phase 1 to the molar fraction of i in phase 2 at the
vapor phase activity and fugacity coefficients of the
balance
liquid phase and vapor. The activity coefficient of the phase
= (I.2) liquid depends on the composition. The standard state of
the reference is usually chosen as ϒi= 1.0 for the
The inherent separation factor is given by the relationship pure component i. Yes ϒi1.0, it is said that there are
of the equilibrium constant of component i divided by the positive deviations from ideality in the liquid solution, and
equilibrium constant of component j is given by the if ϒI< 1,0, there are negative deviations from ideality in the
equation (I.3): liquid solution.
⁄
= = (I.3) For non-ideal solutions, equations (I.5) and (I.6) are
⁄
they turn into:
VVapor-Liquid Systems ∗°
= (I.8)
For processes based on the equilibrium between phases
carbonated and liquid αij, KIy Kjcan be related to the Y
vapor pressures and activity coefficients. If the ∗°
= ∗°
(I.9)
components of the mixture obey Raoult's laws and
Dalton, Now, Kiy αijdepends on the composition due to the
= ∗ = °∗
(I.4) dependency on the composition of ϒiy ϒjHowever, it is still
it is true that αijit is relatively insensitive to temperature,
where andiyxithey are the molar fractions of i in the phases pressure and composition.
soda and liquid, respectively, P is the total pressure, pIes
the partial pressure of i and PI° it is the vapor pressure of the liquid In a binary mixture containing only i and j, making the
pure i. From there, substitutions andj = 1 - yiy xj= 1 - xiin the definition of factor of
°
separation, is obtained:
= = (I.5)
= (I.10)
y
FACILITATOR: ENG. ZORAIDA J. CARRASQUERO C. MSc. UNEFM INTENSIVE 2019
 UNIT OPERATIONS II. UNIT I. SEPARATION PROCESSES.
It can be readjusted as follows: % ∗ ∗
$ = (I.15)
&' ∗(
∗
= (I.11) where: Niflow of component i across the barrier
!

Equation I.11 relates yia αijy xiin as steam system- P1y P2pressures from the high and low pressure sides,
binary liquid. If the liquid and vapor phases in a system respectively.
binary vapor-liquid are in equilibrium, it can be replaced y1iy y2imole fractions of component i on the sides of
s
αijby αijin equation I.11. high and low pressure, respectively.
∗
= (I.12) T = temperature
" #
MiMolecular weight of component i
The systems where there are large deviations from the
ideal conditions and/or close boiling points of the components a = geometric factor dependent only on the structure of the
pure substances often produce azeotropes, where barrier.
the curve of yi= xi; therefore, αij= 1.0 and the separation is not It will be assumed that the composition of the high-pressure side does not
possible.
changes appreciably throughout the depletion of one of
VLiquid-liquid system. the gaseous species. All the material on the low side
pressure has arrived through the process in state
For the equilibrium between two immiscible liquid phases, it can be
stationary described by the equation I.15, so that
use equation I.7 for the two phases with the postulate of
)
a unique vapor phase that is necessarily in = (I.16)
)
equilibrium with both liquid phases and obtain:
To simplify, it will be assumed that P2<< P1Combining the
= (I.13) From equations I.15 and I.16, a relationship is obtained that does not

What relates the molar fractions of component i in the it depends on the composition:
phases 1 and 2 in equilibrium. For the separation between the = = &* ⁄ * I.17)
components i and j in a liquid-liquid equilibrium process
it can be written (King, J., 2003): The inherent separation factor can, in principle, at
⁄ ∗ smaller, also to be calculated from molecular theory to
= = (I.14)
⁄ ∗ a number of other processes controlled by speed,
such as sweeping diffusion and thermal diffusion, even when the
Therefore, it can be seen that the equilibrium processes
analysis is more complex.
liquid-liquid must necessarily involve solutions not
ideals ( ϒ≠ 1,0) if αijit will depend on the composition in a Basic techniques of separation.
liquid-liquid system unless the system is so diluted
In each separation operation, the components of the
in component i in both phases that the coefficients of
sound mixtures are induced a different movements,
activity will remain constant and equal to the values
separable spatial locations or phases by one or more of
for infinite dilution.
the five basic separation methods. However, the
Inherent separation factor: Processes controlled by the separation is not perfect, and if the food contains more
speed. of two species, two or more separation operations
they may be required (Seader, E. J.; Henley, J. D. & Roper, K.,
A simplified process of gas diffusion is considered,
2010).
like shown in Figure I. 4. The gas mixture to
separate is located on one side (the left) of a The most common separation techniques are mentioned in
porous barrier. A pressure gradient is maintained across continuation:
from the barrier, with pressure on the food side
• Separation by the creation of a phase: immiscible with the
(left) much greater than on the side of the product
feeding phase, by transfer of energy or
(right). This pressure gradient causes a flow of
pressure reduction, distillation example, condensation
molecules from left to right across the barrier of the
partial vaporization, instant distillation (Flash)
gas mixture to separate.
extraction with supercritical fluid.
If the barrier has sufficiently small pores, and if the
• Separation by phase addition: which can
the gas pressure is sufficiently low, the free path
absorb, extract or selectively strip certain
the average of gas molecules will be large compared to
species of nutrition. Example: gas absorption,
the dimensions of the pore. Therefore, the molecular flow will have
liquid-liquid extraction, extractive distillation, drying
place by the Knudsen flow mechanism, and will come
expressed by the equation:

FACILITATOR: Eng. ZORAIDA J. CARRASQUERO C. MSc. UNEFM INTENSIVE 2019

 UNIT OPERATIONS II. UNIT I. SEPARATION PROCESSES.
• Barrier separation: less common but not less
important is the use of barrier, usually membranes
polymeric, which involves a feed in phase
liquid or gas and take advantage of the difference in
permeability of species through the barrier, it
they are governed by diffusive processes. Example: Reverse osmosis,
Figure I.7. Continuous operation.
dialysis, micro filtration, ultrafiltration, per evaporation
Source:[Link]/basicoperations
Gas permeation.
• Separation by fields of forces or gradients: it Operation Semicontinuous. The regime of
•
they use fields of external forces, taking advantage of the
operation is non-stationary. It is said that a
different responses of ions and molecules to forces and operation is semi-continuous when one or more
to the gradients. Example: centrifugation, diffusion materials are loaded into the unit
thermal, electrolysis, electrodialysis, and electrophoresis.
process, where they remain for a certain time
Unit operations are mainly classified into while other materials come in and out
function of the property (matter, energy, and quantity of continuously from the same (See Figure I.8).
movement) that is transferred or of the property that is more
relevant. However, below are various
forms used by some authors (Henley, E. J., et al.;
King, J.), to classify the unit operations according to
a:
To the variation over time.
• Discontinuous Operation: The operation works in Figure I.8. Semi-continuous operation.
non-stationary regime. The characteristic variables Source:[Link]/basicoperations
the system is modified increasingly or
decreasing, but continuously over time for
2. To the type of circulation
the same position. They are characterized by dividing
temporarily in loading stage, carrying out the • Parallel flow. If the phases shift in the same
operation, unloading and conditioning stage direction and sense, as shown in Figure I.9.
repeating these operations cyclically. In
in many cases, there is a downtime for
conditioning of the equipment between the stage of
descarga (valor final de la variable) y carga (valor inicial
of the variable) of the following cycle (see Figure I.6).

Figure I.9. Parallel flow operation.

Source:[Link]/basicoperations

Figure I.6. Discontinuous operation. • Countercurrent flow. If the phases shift in the
Source:[Link]/basicoperations same address but in opposite directions (see Figure)
I.10)
• Continuous Operation. The operation operates in state
stationary, so that the characteristic variables
the system has no variation over time
for a fixed position in space, although they can
to do it from one point to another of the system. In this type of
operations eliminate loading times and
download, is carried out through input currents
and system exit. On the contrary, there is usually a
short initial non-stationary period during
in which the system variables reach the Figure I.10. Countercurrent flow operation.
working conditions (See Figure I.7). Source:[Link]/basicoperations

FACILITADOR: ING. ZORAIDA J. CARRASQUERO C. MSc. UNEFM INTENSIVE 2019

 UNIT OPERATIONS II. UNIT I. SEPARATION PROCESSES.
• Cross flow. If the phases move differently.
address, as shown in figure I.11. this type • Simultaneous transfer of matter and energy. They are the
operation is primarily presented when the operations in which contact occurs between
phases are immiscible. phases, involving the transport of matter and energy
between both phases, such transportation can be in the
same address or in opposite directions. They are very
related to air interaction operations-
water, drying, crystallization, lyophilization.
• Transfer of momentum. It occurs in
those systems in which a part of it
moves with respect to another one or to the walls of the
container. Fluid displacement systems
includes pumps, compressors, valves, filtration,
Figure I.11. Crossflow operation. sedimentation, flotation, centrifugation, agitation and
Source:[Link]/basicoperations mixtures, between others. (Source:
3. To the property that is transferred [Link]/basicoperations).
4. To the phases involved
• Transfer of matter. The operations of
transfer of matter encompasses all the • Vapor-liquid. Among the unit operations
operations in which the controlling stage is the involved in the vapor-liquid phases are mentioned:
material transfer and aim to separate Distillation, absorption-desorption, humidification-
components or groups of components of a phase deshumidificación, evaporación.
originally homogeneous. It is the displacement of • Liquid-liquid. Unit operation involved in
one several constituents of a fluid mixture with liquid-liquid equilibrium is: Liquid extraction
regarding a global mass due to the action of a force liquid
impeller generally a gradient of • Vapor-solid. In vapor-solid equilibrium, it is named
concentration. The transfer mechanism of adsorption-desorption.
mass, depends on the dynamics of the system in which it • Solid-liquid. Typical unit operations in the
It is carried out. There are two modes of mass transfer: solid-liquid equilibrium involves adsorption, exchange
a) convective: the mass can be transferred according to the ionic, leaching.
global fluid movement. It may happen that the 5. Its application and importance.
movement occurs in laminar flow or
turbulent. b) molecular or ordinary diffusion: can The following are some of the operations
to define oneself as the displacement of molecules most well-known units in order of importance and
individuals through a fluid by means of the applicability: distillation, liquid-liquid extraction,
individual or disorderly displacements of the ["gas absorption","desorption","evaporation","crystallization"]
molecules, due to the difference in concentration. ["humidification","dehumidification","adsorption","exchange"]
This can occur in stagnant fluid systems or ionic.
in fluids that are moving. (Source: Criteria for the selection of separation processes.
[Link]/repository). Between the
unit operations whose controlling stage is the Once the different unit operations are known, their
matter transfer is mentioned: distillation, characteristics, the most well-known separation techniques are
gas absorption, solvent extraction, adsorption focus attention on separating the components or
ionic exchange. components of a mixture and the units or stages
• Heat transfer. It is the process by which necessary to obtain the desired products or
exchanges energy in the form of heat between different specified. Thus, it is necessary to distinguish the characteristics
bodies or between different parts of the same body most important physical and chemical properties of the mixture to be separated,
by the action of a driving force, generally a product specifications that are desired and the possible
temperature gradient. Heat is transferred formation of corrosive products, foaming, stability
through conduction, convection, or radiation. Although thermal among others.
these mechanisms they can to have place Among the most important criteria to consider for the
simultaneously, it may happen that one of them selection and sequence of the different stages necessary for
predominates over the other two. Examples of the the separation, it is mentioned:
unit operations controlled by transfer
Heat mentions: evaporation, heat exchangers • Composition of the diet and desired purity of the
of heat ovens. (Source: productos
[Link]/basicoperations).
FACILITADOR: ING. ZORAIDA J. CARRASQUERO C. MSc. UNEFM INTENSIVE 2019
 UNIT OPERATIONS II. UNIT I. SEPARATION PROCESSES.
• Property of pure components: vapor pressure, Table I.3. Factors influencing the selection of the
boiling point, melting point, solubility in a certain feasible separation operations
solvente, densidad.
Composition, particularity of the
• Thermal stability species a be recovered o
Condition of the
• Foam formation separated
nutrition
Flow velocity
• Formation of corrosive products Temperature
• Design, engineering and development: commercial availability Pressure
Phase (solid, liquid or gas)
• Fixed costs: investment, installation, costs of Purity requirements
maintenance Temperature
Condition delete
• Operationality and security Pressure
producto
Phase
• Environmental implications Differences of Molecular
The first consideration that must be made is the selection of thermodynamic properties
type of separator. If the mixture to be separated is homogeneous, the the components Transport
separation can only be achieved by the creation of another phase Easy to scale
inside the system. For example, if the mixture is gaseous it Easy design
can create another phase by partial condensation. The vapor that Temperature pressure y
the result of the condensation will be richer in the components Characteristics of phase state requirements
more volatile and the liquid will be richer in the components the operations Physical size limitations
less volatile. This is the case of a capacitor and of separation Energy requirements
flash separator.
Economic Cost of capital
Another alternative is to add a liquid phase solvent, the Operating costs.
which would dissolve the desired component(s) of the mixture
soda. The equipment used is an absorber. In this case, it
requires an additional separation stage to recover the Example I.1. Feasible separation method. (Example 1.1 of
solvent to be reused and obtain the absorbed product Seader, E. J.; Henley, J. D. & Roper, K., 2010)
available for the next stage of separation.
For each of the following binary mixtures, one
If the mixture is heterogeneous or of multiple phases, then it separation operation is suggested. Explain why it is.
you can use a physical separation operation operation will be appropriate or not.
taking advantage of the difference in densities between the phases
presents. This separation is simple and the most common are: a. Air separation into oxygen-rich and rich products
in nitrogen by distillation.
• Vapor-liquid
b. Separation of m-xylene and p-xylene by distillation.
• Liquid-liquid (Immiscible)
• Solid-liquid c. Separation of benzene and cyclohexane by distillation.
• Solid-vapor d. Separation of isopropyl alcohol and water by distillation.
• Solid-solid e. Separation of penicillin from water in a broth of
fermentation by evaporation of water.
For the development of a separation process, the following is required:
selection of (see Table I.3): Solution:
• Separation method: to select it, one must a. The normal boiling point of oxygen (-183 °C) and of
consider the condition of the feeding, the factor of nitrogen (-195.8 °C) are sufficiently different that
separation. they can be separated by distillation, but they are
• Transfer agent, energy, mass or quantity of high pressures and cryogenic temperatures are required.
movement In moderate to low productions, they usually
• Separation equipment: differences should be taken into account.
are separated by adsorption or gas permeation through
of the properties of the components.
of a membrane, at low cost.
• Optimal arrangement or sequence of equipment: considering
the condition of the product. b. The boiling points of m-xylene (139.3 °C) and p-
• Optimization of operating conditions. Considering xylene (138.5 °C) are close to making the separation by
the characteristics of separation operations and the impractical distillation. However, their melting points
economic aspect. differ widely from -47.4 ° C for the m-xylene and 13.2

FACILITADOR: ING. ZORAIDA J. CARRASQUERO C. MSc. UNEFM INTENSIVE 2019

 UNIT OPERATIONS II. UNIT I. SEPARATION PROCESSES.
°C for p-xylene makes crystallization the method of Case 2: 50% of O is recovered.2in the permeate product
most appropriate separation. with 50% mol of O2.
c. The boiling points of benzene (80.1 °C) and the cycle
Case 3: 85% mol of N2in the rejection product and 50% mol
hexane (80.7 °C) are close and make it impractical to
of O2in the permeate product.
separation by distillation. The most suitable method is the
distillation in the presence of phenol (boiling point Case 4: 85% mol of N2in the rejection product and a
181.4 °C), which reduces the volatility of benzene, oxygen ratio in the permeate to rejection of 1,1 [(P/R)]O2
allowing for nearly pure cyclohexane to be obtained. = 1,1].
another product is a mixture of benzene and phenol, which
Solution:
then it is easily separated by distillation.
d. The normal boiling point of isopropyl alcohol
(82.3 °C) and water (100.0 °C) indicate that they can be
separated by distillation. However, they form a
minimum boiling point azeotrope at 80.4 °C and 1
31.7% molar of water and 68.7% mol of alcohol
isopropyl, which makes its separation by distillation difficult
if you want to obtain alcohol concentrations greater than
68.5% molar. A feasible separation method is the
distillation in the presence of benzene, using two stages
of process. In the first stage, alcohol is obtained. Figure I.2.1. Diagram of the process.
high purity isopropyl and a heterogeneous azeotrope of Caso 1: Datos: (FRO2)P= 0.50 and (FRN2)R0.875
three components. The azeotrope is separated into two phases,
the benzene-rich phase is recycled to the first stage and the The recovery of oxygen in the permeate product,
water-rich phase is sent to a second stage, where allows to determine the amount of oxygen that comes out per P and the
the almost pure water is obtained by distillation, with the other recovery of N2in the rejection current allows
recycled product to the first stage. determine the quantity of N2what comes out for R.
e. Penicillin has a melting point of 97 °C, but it Amount of N2y O2y N2in P:
break down before reaching its normal point of
boiling. Therefore, it seems that it can be isolated from PO2= F*xF,O2*FRO2(100 kmol/h)(0.21)(0.50) = 10.5 kmol/h
water through evaporation of water. However, penicillin PN2= F*xF,N2– RN2=(100 kmol/h)(0.79) - 69.1 kmol/h = 9.9
and most other antibiotics are sensitive to kmol/h
heat, so they must be kept close to
Amount of N2and O2in R:
ambient temperature. Therefore, the evaporation of
water would have to take place in impractical conditions RN2= F*xF,N2*(FR,N2)R= (100 kmol/h)(0,79)(0,875) = 69,1
and high vacuum. A practical method of separation of the kmol/h
penicillin is the liquid-liquid extraction with n-butyl
RO2= F*xF;O2– PO2=(100 kmol/h)(0.21) - 10.5 kmol/h = 10.5
acetate or n-amyl acetate.
kmol/h
Example I.2. Using purity as the specification and the
Total amount of P:
recovery. (Example 1.3 from Seader, E. J.; Henley, J. D. &
Roper, K., 2010 P = PO2+ PN2= 10.5 kmol/h + 9.9 kmol/h = 20.4 kmol/h

A feed, F, of 100 kmol/h of air containing 21% Total amount of R:

mole of oxygen and 79% mole of nitrogen is partially
R = RO2+ RN2= 10.5 kmol/h + 69.1 kmol/h = 79.6 kmol/h
separated by a membrane unit according to each
one of the specifications of the four stages. Calculate the Molar fraction of O2y N2en P:
quantities, in kmol/h, and the compositions, in % molar, of xP,O2(10.5 kmol/h) / (20.4 kmol/h) = 0.515
the two products (Reject, R, and permeate, P). The membrane
is more permeable to O2. xP,N2(9.9 kmol/h) / (20.4 kmol/h) = 0.485

Case 1: 50% of O is recovered.2in the permeate product and Molar fraction of O2y N2in R:
87.5% of N2in the rejection product. xR,O2(10.5 kmol/h) / (79.6 kmol/h) = 0.132
xR,N2(69.1 kmol/h) / (79.6 kmol/h) = 0.868

FACILITADOR: ING. ZORAIDA J. CARRASQUERO C. MSc. UNEFM INTENSIVO 2019

 UNIT OPERATIONS II. UNIT I. SEPARATION PROCESSES.
Case 2: Data: (FRO2)P= 0.50 and xP,O2= 0.50 P = 100 kmol/h - 82.857 kmol/h = 17.143 kmol/h
∗ ,-/ 050"+ ∗ 0,-/ # Amount of O2y N2 en P:
"+,- # = = 0,50 ∴ =
+∗ 0,-/ ,-/ PO2(17,143 kmol/h)(0.50) = 8,572 kmol/h
⁄
0,501005678 90,21# PN2= 17,143 kmol/h – 8,572 kmol/h = 8,572 kmol/h
= = 215678 9⁄
0,50
Amount of O2y N2in R:
Applying a global balance in the membrane unit, we
he/she has: RO2= (82,857 kmol/h)(0.15) = 12.429 kmol/h

F = P + R → R = F - P = 100 kmol/h - 21 kmol/h = 79 kmol/h RN2= 82,857 kmol/h – 12,429 kmol/h = 70,428 kmol/h

P = 21 kmol/h y R = 79 kmol/h Case 4: Data: xR,N2= 0.85 and (P/R)O2= 1.10

Amount of O2y N2en P: Molar fraction of O2in R:

PO2(0.50)(100 kmol/h)(0.21) = 10.5 kmol/h xR,O2= 1- 0,85 = 0,15

PN2= 21 kmol/h – 10,5 kmol/h = 10,5 kmol/h Applying a material balance on O2in the unit of
membrane:
Amount of O2y N2in R:
F*xF,O2= P*xP,O2+ R*xR,O2→FO2= PO2+ RO2
RO2= 21 kmol/h – 10,5 kmol/h = 10,5 kmol/h
(100 kmol/h)(0.21) = 21 kmol/h = PO2+ RO2 (I.2.3)
RN2= 79 kmol/h – 10,5 kmol/h = 68,5 kmol/h
PO2= 1.10 * RO2 (I.2.4)
Molar fraction of O2y N2en P:
By solving the system of equations (I.2.3) and (I.2.4), we have:
xP,O2= (10.5 kmol/h) / (21 kmol/h) = 0.50
21 kmol/h = 2.1 * RO2→RO2= 10.00 kmol/h and PO2= 11.00
xP,N2(10.5 kmol/h) / (21 kmol/h) = 0.50 kmol/h
Molar fraction of O2y N2in R: Total quantity of P and R:
xR,O2(10.5 kmol/h) / (79 kmol/h) = 0.133 RO2= 10.00 kmol/h = R*xR,O2R = (10.00 kmol/h)/xR,O2
xR,N2= (68,5 kmol/h)/(79 kmol/h) = 0,867 R = (10.00 kmol/h) / 0.15 = 66.67 kmol/h
Case 3: Data: xR,N2= 0.85 y xP,O2= 0.50 P = 100 kmol/h - 66.67 kmol/h = 33.33 kmol/h
Mole fraction of O2in R: Individual amount of N2in P and R:
xR,O21 - 0.85 = 0.15 PN2= 33,33 kmol/h – 11,00 kmol/h = 22,33 kmol/h
Mole fraction of N2in P: RN266.67 kmol/h - 10.00 kmol/h = 56.67 kmol/h
xP,N21 - 0.50 = 0.50 Molar fraction of O2y N2en P:
Applying a global material balance in the unit of xP,O2(11.00 kmol/h) / (33.33 kmol/h) = 0.33
membrane
xP,N2= (22,33 kmol/h)/(33,33 kmol/h) = 0,67
F = P + R → 100 kmol/h = P + R (I.2.1)
Table I.2.1. Summary of Results example I.2
Material balance in O2in the membrane unit:
F*xF,O2= P*xP,O2+ R*xR,O2
(100 kmol/h)(0.21) = P(0.50) + R(0.15) → 21 kmol/h = 0.50*P +
0.85*R (I.2.2)

By solving the system of equations (I.2.1) and (I.2.2), we have:

Example I.3. Feasible separation alternatives. (Example 1.5
21 kmol/h = 0.50(100 kmol/h - R) + 0.15*R de Seader, E. J.; Henley, J. D. & Roper, K., 2010
-29 kmol/h = -0.35*R → R = 82.857 kmol/h Propylene and propane are among the
light hydrocarbons obtained by cracking fractions of
FACILITADOR: ING. ZORAIDA J. CARRASQUERO C. MSc. UNEFM INTENSIVE 2019
 UNIT OPERATIONS II. UNIT I. SEPARATION PROCESSES.
heavy oil. Propane is valuable as fuel and
as raw material to produce propylene and ethylene. The
Propylene is used to produce acrylonitrile for making
synthetic rubber, isopropyl alcohol, cumene, oxide of
propylene and polypropylene. Although propylene and propane
they have close boiling points, traditionally they are
separated by distillation. In Figure I.3.1 it is observed that
they need a large number of stages and that the reflux and the
Vaporization is high. Consequently, it is required.
replace distillation with a more economical process and
with lower energy consumption. Based on the factors that
they influence the selection of the separation, shown in the
Table I.3, and the scaling (enlargement) characteristics,
shown in Table I.4, and the basic separation techniques
previously mentioned, propose alternatives that
allow the separation of the process shown in the Figure
I.3.1.
Solution:
Figure I.3.1. Distillation of the propane-propylene mixture.
First, check the power flows and currents. Source: Seader, E. J.; Henley, J. D. & Roper, K., 2010
the product of Figure I.3.1 satisfies the law of the
Table I.5. Properties of the mixture from example I.3
mass conservation. Table I.5 shows the
properties mainly taken by Daubert and Danner.
The only listed property that can be leveraged is the
dipole moment. Due to the asymmetrical location of the double
link in propylene, its dipole moment is
significantly higher than that of propane, so the
Propylene is a weakly polar compound.
operations that take advantage of this difference are:

a. Extractive distillation with a polar solvent such as the

furfural or an aliphatic nitrile which reduces volatility
of propylene.
b. Adsorption with silica gel or zeolite that selectively
it adsorbs propylene.
c. The method of membranes impregnated with nitrate Source: Seader, E. J.; Henley, J. D. & Roper, K., 2010
silver to selectively carry propylene through the
Formative Task
membrane.
What is a key operation in chemical engineering?
Table 1.4. Scalability (expansion) of the
most common separation operations. 2. What are the basic separation techniques, and what
What do they have in common?

3. What is the difference between a separation agent

matter (ASM) and energy separation agent (ASE)?
Mention three disadvantages of using an agent
separation of matter.
4. What is the most common method used to separate two
fluid phases?
5. Examine a process flow diagram and identify
What are the key and auxiliary operations?
Indicate the principle of separation, agent of
separation, predominant transfer, phase of the
Source: Seader, E. J.; Henley, J. D. & Roper, K., 2010
FACILITATOR: Eng. ZORAIDA J. CARRASQUERO C. MSc. UNEFM INTENSIVE 2019
 UNIT OPERATIONS II. UNIT I. SEPARATION PROCESSES.
raw material and the products obtained from the • GEANKOPLIS, C. J. (1998) Transport Processes and
key operations. Unit Operations. Third edition. Cecsa Editorial
6. What is the difference between absorption and adsorption? • TREYBAL, R. (1980) Transfer Operations
Masa. Second Edition. McGraw Hill Publishing.
7. The degree of separation in a separation operation
often specified in terms of • MARCILLA GOMIS A. (1998). Introduction to the
recovery of components and/or product purity. Separation Operations. Stage-wise Calculation of
What do they differ in? Equilibrium. Publications of the University of Alicante.
Electronic edition Espagrafic.
8. When an ethanol-water mixture is distilled at pressure
atmospheric, the top product has a composition • AGUILAR RODRIGUEZ, ENRIQUE. (2007). Design of
close to the azeotrope (89.4% mol of ethanol) and the product Processes in Chemical Engineering. Mexican Institute of
in the background close to the pure water. Based on the Petroleum - National Polytechnic Institute. ISBN 968-489-
differences in the properties of ethanol and water 037-0 FIPN-2007-113. Printed and made in Mexico. Edition
explain how the following operations should be skilled digital.
to recover pure ethanol in the distillate: a)
• PERRY R.; GREEN, D. W.; MALONEY, J. O. (1998). Manual
["extractive distillation","azeotropic distillation"]
from the Chemical Engineer. Sixth Edition. McGraw Publishing
liquid-liquid extraction, d) crystallization, e)
Hill.
pervaporation, f) adsorption.
• [Link]/~aulavirtualpfciq/[Link].
9. In the manufacturing of synthetic rubber, a is obtained
Reviewed 12/27/2017.
wax fraction, of low molecular weight, like a
byproduct that forms in the solvent solution • [Link]/2010/09/diagram
reaction, what is normal heptane. The byproduct has _flow.pdf. Reviewed 27/12/2017.
a negligible volatility. Indicate which of the following
• [Link]/files/notebooks/S160A_Adsorption
operations could be suitable for the
[Link]. Reviewed 12/30/2017.
solvent recovery and for what reason. Please indicate.
why the others are not suitable. a) Distillation; b) • [Link]
Evaporation and c) Filtration. basicas/contenidos1/topic10/page_16.htm Reviewed
30/12/2017.
10. Discuss the similarities and differences between the following
operaciones: a) vaporización flash; b) condensación • [Link]/operations. Reviewed 30/12/2017.
partial and c) evaporation.
• [Link] Reviewed
Bibliographic References 30/12/2017. Sergio Huerta Ochoa.
• KING, J. (2003). Separation Processes. Reverté Publishing.
Spanish edition.
• Henley, E. J.; Seader, J. D. (1998). Operations of
stepwise separation of equilibrium in Chemical Engineering.
Second Edition. Reverté Publishing.
• Henley, E. J.; Seader, J. D. y Roper, D. K. (2010).
Separation Process Principles. Chemical and Biochemical
Operations. Third edition. John Wiley & Sons publishers.
• FOUST, A.; WENZEL, L.; CLUMP, C.; MAUS, L.; ANDERSEN,
B. (1980). Principles of Unit Operations. Second
Edition. John Wiley & Sons publishers.
• WANKAT, P. (2008). Process Engineering
Separation. Second Edition. Prentice Hall Publishing.
• WANKAT, P. (2012).Separation Process Engineering
Includes Mass Transfer Analysis Third Edition. Publisher
Prentice Hall.
• McCABE, W.; SMITH, J.; HARRIOTT, P. (2007) Operations
Units in Chemical Engineering. McGraw Hill Publishing.
Seventh Edition.

FACILITADOR: ING. ZORAIDA J. CARRASQUERO C. MSc. UNEFM INTENSIVE 2019