Separation Processes

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UNIT OPERATIONS II. UNIT I. SEPARATION PROCESSES.

GENERALITIES. phase) that best suit the reaction needs. The second block is
the chemical transformation process, generally made up of a
Separation processes are of great importance in the chemical,
chemical reactor conditioned to carry out the transfer of mass
petrochemical, refining, food, polymers, energy, etc. industries.
and associated energy, in the most efficient way possible.
In them, products are obtained through concentration,
fractionation and/or purification to the required compositions Because no reaction is totally selective towards the product
and at reasonable prices. desired in the process. The effluent of the reaction system will
consist of: a) desired product, b) by-products of the reaction, c)
Frequently in industry it is necessary to separate the
raw materials that do not react, d) components inert to the
components of a mixture into individual fractions. The fractions
reaction. The above makes it necessary to have a third block
can be differentiated from each other by their state, by their
where the separation of the products contained in the reactor
chemical composition or by the size of the particles. Thus, a
effluent occurs, obtaining the quantity and quality of the
raw product can be purified by removing contaminating
products of interest, mainly the main product; some
impurities, a mixture of two or more components can be
byproducts that have commercial and economic value and
separated into the individual pure components, the stream
those byproducts that have no commercial value (residual
leaving a process can contain a mixture of the product and
products) that must be conditioned for the preservation of the
unconverted material, and it is necessary to separate and
environment.
recirculate the unconverted part to the reaction zone for its
conversion to product; Also a valuable substance, such as a The raw materials and some inert components, already isolated
metallic material, dispersed in an inert material, must be during the product separation stage, are generally recycled for
released in order to process it and discard the inert material. reprocessing, which gives rise to a fourth stage of the process,
(depa.fquim.unam.mx.pdf). made up of the recirculation stream(s), which depending of its
quantity and composition are integrated into the process at
From the point of view of Chemical Engineering, matter can be different points. In all stages of the process, energy exchanges
subjected to two types of basic industrial processes, separation with the outside are present, in order to incorporate the energy
and transformation. Separation processes refer to all those potential required for the preparation of the raw materials, the
activities that seek to separate and classify the different reaction, the separation of the products and the reprocessing
substances that constitute a feed or raw material flow, using an of the recirculation streams. carried out appropriately.
industrial or laboratory process to obtain specific products with
greater added value. Transformation processes refer to those With separation processes, it is desired to obtain changes in the
procedures and activities that modify matter from its chemical composition or physical changes in the material that is
substance, that is, new substances are obtained that are prepared, processed, separated or purified. To obtain:
completely different from the one that originates it. These 1. Pure materials for engineering applications
operations are carried out through chemical reactions, (semiconductors)
management and control of the kinetics of the reaction. The
2. Pure materials for processing
equipment used is chemical reactors.
3. Remove toxins or inactive compounds from a solution
In industrial processes, a combination of transformation and
separation processes is generally necessary to obtain desirable 4. High purity samples as references
products, as shown in Figure 1. 5. Analysis of components of a mixture (DNA)
6. The separation of raw material into its components
(petroleum)
These processes are carried out in specialized and
interconnected equipment that works as their own units and
with a specific function where the separation or transformation
of materials is achieved using scientific principles and common
Figure 1. Conceptual architecture of a chemical process. calculation techniques, and this is what defines unit operations.
Source: Aguilar R., E., 2007. These operations are based on complementary principles and
laws and use physical-mathematical instruments, as well as
Figure 1 shows a first block where the raw material is
certain calculation techniques that are mentioned below:
conditioned in order to make the reaction process that follows
more efficient. That is, limit the content of some component 1. Beginning
that could inhibit the behavior of the catalyst in a reaction or, a. Conservation Laws or changes to extensive properties
on the contrary, it is required to add some compound that
promotes or inhibits some of the reactions present in the • Matter (Lavoisier's Law)
process, also in this block, the raw materials They are brought • Energy (First Law of Thermodynamics)
to the thermodynamic conditions (pressure, temperature,

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


UNIT OPERATIONS II. UNIT I. SEPARATION PROCESSES.
• Momentum of Movement (Law ofNewton) Amount of Gradient
Friction
Motion Speed
• Entropy
b. Laws of balance of physical-chemical systems (Second
Law of Thermodynamics) In a particular case, if the system reaches a condition such
that it cannot experience any change spontaneously, the
• Kinetic Laws driving force is said to be “null”, that is, the system is in a
• Economic laws state of equilibrium . Therefore, it is possible to establish
certain operating conditions, under which every system is in a
• Environmental laws state of equilibrium .
• Safety and hygiene laws, etc. The separation processes developed include different unit
2. Complementary operations, among which are mentioned:

a. Stoichiometric laws a. Distillation. Which consists of separating, by vaporization,


a liquid mixture of miscible and volatile substances into its
b. PVT equations of state individual components or in some cases into cuts or
c. Physical-mathematical instruments fractions if several components are present, for example
crude oil fractionation
d. Physical – mathematical models
b. Gas absorption . A soluble vapor contained in a mixture
e. Systems of magnitudes and units
with an inert gas is absorbed by a liquid in which the
f. Dimensional analysis gaseous solute is more or less soluble. The solute is then
g. Analysis of design variables in operations, etc. recovered by distillation and the adsorbent liquid can be
reused or discarded.
3. Calculation techniques.
c. Liquid liquid extraction . Also called solvent extraction, in
a. Presentation of experimental data which a liquid mixture is treated with a solvent that
b. Fitting and correlation of experimental data preferentially dissolves one or more components of the
mixture. The mixture treated in this way is called raffinate
c. Methods for solving equations and systems of equations
and the solvent-rich phase is called extract. The
d. Tensor calculus operations, etc. component that is transmitted from the raffinate to the
The purpose of every unit operation is to modify the conditions extract is the solute, and the component that remains in
of a quantity of matter in a way that is more useful for our the raffinate is the diluent.
purposes. This is achieved: d. Drying . It is a simultaneous heat and mass transfer
• Modifying its mass or composition (mixing or phase operation of gas-solid contact, where the moisture
separation) contained in the solid is transferred by evaporation to the
• Modifying the level or quality of energy it has (cooling, gas phase, based on the difference in vapor pressure
vaporization) exerted by the wet solid and the partial pressure. of the
vapor of the gas stream. When these two pressures
• Modifying its conditions of movement (changes in become equal, the solid and gas are said to be in
direction, increase or decrease in speed) equilibrium and the drying process ceases.
In all unit operations, mass, energy and momentum are e. Crystallization . It is a unitary operation of simultaneous
transferred simultaneously. However, these operations are transfer of matter and energy in which the formation of a
not necessarily controlled by the three transfers, but by one solid (crystal or precipitate) occurs from a homogeneous
or at most two transfers, the most relevant. phase (solute in solution or in a melt). The driving force in
This transfer of properties creates a driving force, a gradient both stages is supersaturation and the possible
of some property, which accounts for the main transfer temperature difference between the crystal and the liquid
mechanism, as shown in Table 1. Table I.1. Transfers caused by the phase change.
characteristic
Transfer Mechanism Driving force
Subject Concentration
Diffusion
gradient
Heat Conduction
Temperature
Convection
Gradient
Radiation

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


UNIT OPERATIONS II. UNIT I. SEPARATION PROCESSES.
f. Adsorption . It is the process by which an atom or molecule
of substance adheres to the surface of a solid or between
the interface between two fluids. Adsorption is a means to
neutralize or satisfy the attractive forces that exist at a
surface or interface, and which are due to discontinuity in
the nature of the structure. Consequently, adsorption
produces a decrease in interfacial free energy (or tension if
it is a fluid/fluid phase). (
www.firp.ula.ve/AdsorciónMojaibilidad.Salager , JL, 1998)
g. Evaporation. It is an operation in which a volatile solvent is
separated by boiling from one or more non-volatile solutes,
with which it is mixed forming a solution or suspension. (
http://ocwus.us.es/arquitectura-e- ingenieria/operaciones-
basics/contents1/topic10/page_16.htm)
Figure I.1. Identification of key operations (red lines) and
h. Filtration. It is a physical-mechanical method for the auxiliary operations (blue lines).
separation of mixtures of substances composed of different
The sequence of chemical, physical, biological operations that
phases (phase: homogeneous component in a certain state
are necessary for the transformation and/or separation,
of aggregation). A porous filter medium is passed through
transport and storage of materials or energy can be
by a liquid or gas (phase 1) and solid particles or droplets of
represented by block flow diagrams, process flow diagrams and
a liquid (phase 2) are retained on the surface or inside the
piping and instrumentation diagrams. This work briefly defines
filter medium.
block flow diagrams and process flow diagrams.
i. The use of chromatography and analytical separation
Block flow diagram : It is a simple representation of an
methods to determine the composition of complex
industrial production process. Each block represents an
mixtures.
operation or a complete stage of the process. In the block
j. membranes. It is a separation operation controlled by the diagram, each of the unit operations is represented as a block,
transfer of matter and whose driving force is a pressure and on which some of the characteristics of the operation can be
concentration gradient. Its objective is the passage of a recorded (pH, temperature, pressure, etc.) and even that
solvent from a concentrated solution to a more dilute one information that is considered relevant (reason mass of the
through a semipermeable membrane. different currents, yields, etc.). The blocks are linked by arrows
(www4.ujaen.es/operaciones). that represent flows of matter, and it is convenient to reflect
next to each arrow the known data about the flow. Auxiliary
k. Bioseparators. Bioseparation processes involve the recovery
operations are not included in this type of diagram. Different
and purification of products from the bioreactor. They
programs are used to create block diagrams.
include all the treatments required by the culture broth to
obtain the product under the desired purity and activity
conditions. ( http://sgpwe.izt.uam.mx )
Unit operations can be considered of two types:
• Key operations : those where chemical reaction, phase
separation, and chemical separation occur. For example:
distillation, absorption, liquid extraction, reactor.
• Auxiliary operations : where heat is supplied or removed,
work is supplied or removed, solids are agglomerated by
size reduction or solids are separated by size, there is no
change in chemical composition. For example: Pumps, heat
exchangers, filters.
Figure I.1 shows a series of coupled unit operations that
represent the production of ETBE, where the key and auxiliary
operations are identified.

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


UNIT OPERATIONS II. UNIT I. SEPARATION PROCESSES.
computer software, such as: AutoCAD, Microsoft Visio, Figure I.4 and I.5 show the process flow diagram for obtaining
Microsoft PowerPoint, etc. methanol and producing benzene, respectively.
Figure I.2 shows an example of a block diagram of a
production process for end-encapsulated surfactants, which
reflects the information provided in Patent US5847229A1.
Four operations are observed in it: two reactions (1 and 2), a
phase separation (3) and final drying (4) until the desired
product is obtained. Other information provided by the patent
is also reflected (temperature, molar ratios, etc.). Flow rates
or energy exchanges are not defined; and Figure I.3 shows the
block flow diagram of the process for production of
benzene. (www.
ugr.es/̴aulavirtualpfciq/diagramadeblocks.html)
In general, in block flow diagrams, operations are represented
by blocks, most lines are represented by arrows going in the
direction of the flow, the flow direction is from left to right as
long as possible, light currents ( gases) go at the top while the Figure I.3. Block flow diagram for the production of
heavy streams (liquids and solids) go at the bottom, the critical Benzene. Source: www.kardauni08.files.wordpress.com
information of the process is provided, if the lines intersect
the horizontal line is continuous and the vertical line is cut and
the operations are not represented auxiliaries.
Figure I.2. Example of a block diagram of a process
production of tensile assets. Source: Patent US5847229A1

Figure. I.4 Process flow diagram for obtaining


methan

Process Flow Diagram . It is a graphic representation of a


process. Each process stage is represented by a different
symbol that contains a brief description of the process stage.
The graphical symbols of the process are linked by arrows that
indicate the direction of flow and the main flows are
identified. This type of diagram provides more information
than block diagrams, including equipment identification
numbers and names, pressures and temperatures, service
identifications, and mass/volume flow of selected streams,
and a material balance table linked by By means of a process
line key, auxiliary operations are included. In

Figure I.5. Flow chart for benzene production.

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


UNIT OPERATIONS II. UNIT I. SEPARATION PROCESSES.
Characteristics of Unitary operations . / Instant vaporization (pressure reduction)
/ Gaseous diffusion (pressure gradient plus membrane)
Each of the unit operations is characterized by:
/ Reverse osmosis (pressure gradient plus membrane)
Separation principle / Ultrafiltration (pressure gradient plus membrane)
Separation agent Separation factor 3. Non-condensable gas or condensable gas
/ Desorption (non-condensable gas)
The separation principle is what indicates what the unit
/ Sweep diffusion (condensable gas)
operation is based on for the separation to occur. It is also
4. Non-volatile liquid or immiscible liquid or solvent
defined as the physical or chemical property inherent to the
/ Absorption (non-volatile liquid)
components of the mixture that allows the separation to take
/ Extraction (Immiscible liquid)
place. Table I.2 shows some of the most common operations
/ Leaching or washing (solvent)
indicating their separation principle.
5. Solid adsorbent, solid resin.
/ Adsorption (adsorbent solid)
Table I.2. Separation principle of some of the best-known unit / Ion exchange (solid resin)
operations. (Source: Taken from King. J. 1998) 6. Concentrated saline solution plus membrane
/ Inverse osmosis
Unitary Operation Separation principle
7. Active tighter air bubbles
Distillation Boiling point difference / Bubbling or foaming
/ Flotation (surfactant added)
8. Capillarity plus paper or gel phase or solid gel
gas absorption Preferential solubility
/ Paper chromatography (capillarity plus paper)
Evaporation Volatility difference / Filtration through a gel (solid gel)
9. membranes
Crystallization Difference in tendency to / Dialysis (Selective membrane: solvent)
crystallize / Electrodialysis (anionic and cationic membranes; electric
Solids drying water evaporation field)
/ Gas permeation or permeability (selective membrane,
Sedimentation Density difference pressure gradient)
Leaching Preferential solubility 10. Magnetic, electric field or electrical energy
/ Mass spectrometry (magnetic field)
/ Electrophoresis (electric field)
The separation agent is responsible for creating or adding a / Electrolysis with reaction (electrical energy)
second phase to promote the separation of the components 11. Centrifugal or mechanical force
that make up the original mixture. Two types are known: / Centrifugation (centrifugal force)
/ Ultracentrifugation (centrifugal force)
1. Matter separation agent.
/ May be partially miscible with one or more of the The separation factor (α ij ) is the degree of separation that can
s

species in the mixture be obtained with any particular separation process and is
/ It is generally the component with the highest defined based on the compositions of the products:
concentration. ÍÜ ⁄
Xj1
Xi1 ⁄ Xj2
2. Energy separation agent.
/ Transfer of heat and/or work to or from the mixture The separation factor,
^ ÍJ , between components i and j is
being separated. the ratio of the mole fractions (mass fractions, mole flow rates
/ A second phase can be generated by reducing the or mass flow rates of the individual components) of the two
components in product 1 divided by the ratio in product 2.
pressure.
So, if:
Separation agents most used in unit operations:
1. Heat or cooling supply.
(I.1)
/ Evaporation (Heat)
/ Distillation (Heat)
/ Molecular distillation (Heat and vacuum)
/ Resublimation or condensation to the solid state (cooling)
/ Crystallization (Heat)
/ Drying (Heat)
2. Pressure reduction, pressure gradient (pressure gradient
plus membrane)

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


UNIT OPERATIONS II. UNIT I. SEPARATION PROCESSES.
α ij = 1 The separation of components i and j does not take
s a_PL
M1 1 — ,°
p (I.6)

place
The inherent separation factor α ij in a liquid vapor system is
α ij > 1 Component i tends to concentrate preferentially in
s

called relative volatility.


product 1 and component j tends to concentrate preferentially
in product 2. At sufficiently low pressures the relationship K i *P must be
independent of the pressure level, so that the perfect gas
α ij < 1 Component j tends to concentrate on product 1 more
s

hypothesis can be maintained and the Poynting pressure


than component i, and component i tends to concentrate on
correction is negligible. When K i *P and K j *P are independent
product 2 more than component j.
of pressure, α ij will necessarily be independent of pressure.
King, J. (2003) indicates that the separation factor reflects The vapor pressures of i and j depend on temperature;
differences in equilibrium compositions and transport rates due therefore K i and K j are functions of temperature. Since α ij is
to the fundamental physical phenomena that cause separation. proportional to the ratio of vapor pressures, and since vapor
For this reason, an inherent separation factor , α ij , is defined, pressures increase as temperature increases, α ij will be less
which is the separation factor that would be obtained under sensitive to temperature than the equilibrium constants of
ideal conditions, as follows: components i and j. In small temperature intervals α ij can be
• “For equilibrium separation processes, the inherent taken with constant frequency. In the case that Raoult and
separation factor corresponds to those product Dalton's laws are fulfilled, α ij is independent of pressure and
compositions that would be obtained when complete composition, and is insensitive to temperature (King, J., 2003).
equilibrium between the phases was achieved.” In vapor-liquid separation processes, most of the solutions
• “For rate-controlled separation processes the inherent found are non-ideal, that is, they do not obey Raoult's law. In
separation factor corresponds to those product these cases, equation I.4 is normally modified by including a
compositions that would occur in the presence of liquid phase activity coefficient ϒ,
a single controlling mechanism of physical transport.” P í = p ∗ and í = YÍ ∗ p ° ∗
x
i (I.7)
Inherent Separation Factor: Equilibrium Processes . At high pressures, an activity coefficient of the vapor phase and
For separation processes in the equilibrium of immiscible fugacity coefficients of the liquid and vapor phase are also
phases, a value called equilibrium ratio, K i , is defined for each necessary. The activity coefficient of the liquid phase depends
species i, and is the ratio of the mole fraction of i in phase 1 to on the composition. The reference standard state is usually
the mole fraction of i in phase 2 in the balance, chosen as ϒ i = 1.0 for pure component i. If ϒ i > 1.0, it is said
that there are positive deviations from ideality in the liquid
K = il solution, and if ϒ i < 1.0, there are negative deviations from
1 Xi2
ideality in the liquid solution.
The inherent separation factor is given by (I.2)
the ratio of the equilibrium constant of component i divided by
the equilibrium constant of component j and is given by
equation (I.3):
X Xj1_K For non-ideal solutions, equations (I.5) and (I.6) become:
(I.3)

/ X2 ¡2 ⁄X K
Vapor-Liquid Systems (I.8)
For processes based on the equilibrium between the gas and
liquid phases α ij , K i and K j can be related to vapor pressures
(I.9)
and activity coefficients. If the components of the mixture obey
Raoult's and Dalton's laws,
Now, K i and α ij depend on the composition due to the
" either .. ..
Pí=p∗yí=Pí*X (I.4) composition dependence of ϒ i and ϒ j . However, it is still true
where y i and x i are the mole fractions of i in the gas and liquid that α ij is relatively insensitive to temperature, pressure and
phases, respectively, P is the total pressure, p i is the partial composition.
pressure of i, and P i is the vapor pressure of the pure liquid i.
°
In a binary mixture containing only i and j, making the
Thence, substitutions y j = 1 – y i and x j = 1 – x i in the definition of
separation factor, we obtain:

(I.5) DC-- y i (i- xj)


^IJ
xid-yi)
(I.10)

and
FACILITATOR: ING. ZORAIDA J. CARRASQUERO C. MSc. UNEFM INTENSIVE 2019
UNIT OPERATIONS II. UNIT I. SEPARATION PROCESSES.
%
Which can be reset as follows: (Pl Y-P2 Y20) ∗ ∗
(I.15)

(I.11) where: N i = flow of component i through the barrier


Equation I.11 relates y i to α ij yx i in a binary vapor-liquid
s
low pressure sides, respectively.
system. If the liquid and vapor phases in a binary vapor-liquid
T = temperature
system are in equilibrium, α ij can be replaced by α ij in
s

equation I.11. M i = Molecular mass of component i

(I.12) a = geometric factor dependent only on the structure of the


barrier.
Systems where there are large deviations It will be assumed that the composition of the high pressure
from ideality and/or close boiling points of the pure side does not change appreciably throughout the depletion of
components involved frequently produce azeotropes, where one of the gas species. All the material on the low pressure
the curve of y i = x i ; therefore, α ij = 1.0 and separation is not side has arrived through the steady-state process described by
possible. equation I.15, so that ) Í
/ Liquid-liquid system. ■ = Y21
)
Yo y2j
For the equilibrium between two immiscible liquid phases,
equation I.7 can be used for the two phases with the postulate For simplicity, we will assume that P 2 << P 1 . Combining
of a single vapor phase that is necessarily in equilibrium with equations I.15 and I.16, a relationship that does not depend on
both liquid phases and obtain: the composition is obtained: (I.16)
^ ij
Xi1.= Yi2 v,, yn = (,/M
X2 Yi (I.13) Yo
Which relates the mole fractions of component i in phases 1 The inherent separation factor can, in principle at its lowest,
and 2 at equilibrium. For the separation between components i also be calculated from molecular theory for I.17)
and j in a liquid-liquid process in equilibrium it can be written a number of other rate-controlled processes,
(King, J., 2003): such as scanning diffusion and thermal diffusion, even though
X ⁄ Xj1_ Yiz ∗ the analysis is more complex.
Yj1 (I.14)
X2 ⁄ Xj2 Yi ∗ Yj2 Basic separation techniques.
Consequently, it can be seen that liquid-liquid equilibrium In each separation operation the components of the mixture
processes must necessarily involve non-ideal solutions (ϒ≠ 1.0) are induced into different motions, separable spatial locations
if α ij will depend on the composition in a liquid-liquid system or phases by one or more of the five basic separation methods.
unless the system is so dilute in the component i in both However, separation is not perfect, and if the feed contains
phases that the activity coefficients will remain constant and more than two species, two or more separation operations
equal to the values for infinite dilution. may be required (Seader, E. J.; Henley, J. d. & Roper, K., 2010).
Inherent separation factor: Speed controlled processes. The most common separation techniques are mentioned
A simplified gaseous diffusion process is considered, as shown below:
in Figure I. 4. The gas mixture to be separated is located on one • Separation by creation of a phase : immiscible with the feed
side (the left) of a porous barrier. A pressure gradient is phase, by energy transfer or pressure reduction, for
maintained across the barrier, with the pressure on the food example distillation, condensation-partial vaporization,
side (left) much greater than on the product side (right). This instantaneous distillation (Flash), extraction with
pressure gradient causes a flow of molecules from left to right supercritical fluid.
across the barrier of the gas mixture to be separated.
• Phase addition separation : which can selectively absorb,
If the barrier has sufficiently small pores, and if the gas extract or strip certain species from the feed. Example: gas
pressure is sufficiently low, the mean free path of the gas absorption, liquid liquid extraction, extractive distillation,
molecules will be large compared to the dimensions of the drying
pore. Therefore, the molecular flow will take place through the
Knudsen flow mechanism, and will be expressed by the
equation:
P 1 and P 2 = pressures of the high and low pressure sides,
respectively.
y 1i and y 2i = mole fractions of component i on the high and

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


UNIT OPERATIONS II. UNIT I. SEPARATION PROCESSES.
• Separation by barrier : less common but no less important
is the use of a barrier, usually polymeric membranes, which
involves feeding in a liquid or gas phase and takes
advantage of the difference in permeability of the species
through the barrier, they are governed by diffusional
processes. . Example: Reverse osmosis, dialysis, Figure I.7. Continuous operation.
microfiltration, ultrafiltration, evaporation, gas permeation. Source: www.uc3m.es/operacionesbasicas
• Separation by force fields or gradients: external force fields I.8).
are used, taking advantage of the different responses of
ions and molecules to forces and gradients. Example:
centrifugation, thermal diffusion, electrolysis, electrodialysis
and electrophoresis.
Unit operations are classified primarily based on which property
(matter, energy, and momentum) is transferred or whichever
property is most relevant. However, various forms used by
some authors are presented below (Henley, E. J., et al.; King, J.), Figure I.8. Semi-continuous operation.
to classify unit operations according to: Source: www.uc3m.es/operacionesbasicas
1. To variation over time.
2. To the type of circulation
• Discontinuous Operation : The operation works in a non-
steady regime. The characteristic variables of the system • Parallel flow . If the phases move in the same direction and
are modified in an increasing or decreasing manner, but sense, as shown in Figure I.9.
continuously over time for the same position. They are
characterized by being temporally divided into loading
stage, carrying out the operation, unloading and
conditioning stage, these operations being repeated
cyclically. In many cases, there is a downtime for
equipment conditioning between the unloading (final
value of the variable) and loading (initial value of the
variable) stages of the following cycle (see Figure I.6).

Figure I.9. Parallel flow operation.


Source: www.uc3m.es/operacionesbasicas
• Countercurrent flow . If the phases move in the same
direction but in opposite directions (see Figure I.10)

Figure I.6. Discontinuous operation.


Source: www.uc3m.es/operacionesbasicas

• Continuous operation . The operation operates in a


steady state, so that the characteristic variables of the
system do not vary with time for a fixed position in
space, although they can vary from one point to another
in the system. In this type of operations, charging and Figure I.10. Countercurrent flow operation.
discharging times are eliminated; they are carried out Source: www.uc3m.es/operacionesbasicas
using currents entering and exiting the system. On the
contrary, there is usually a short initial non-stationary • Cross flow . If the phases move in different directions, as
period of time during which the system variables reach shown in figure I.11. This type of operation occurs
working conditions (See Figure I.7). primarily when the phases are immiscible.

• Operation Semicontinuous . The regime of


operation is non-stationary. An operation is said to be semi-
continuous when one or more materials are loaded into the
process unit, where they remain for a certain time while
other materials continuously enter and leave it (See Figure

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


UNIT OPERATIONS II. UNIT I. SEPARATION PROCESSES.
one part of it moves with respect to another or to the
walls of the container. Fluid displacement systems
include pumps, compressors, valves, filtration,
sedimentation, flotation, centrifugation, agitation and
mixing, among others. (Source:
www.uc3m.es/operacionesbasicas ) .
4. To the phases involved
• Vapor-liquid. Among the unit operations involved in the
Figure I.11. Cross flow operation. vapor-liquid phases are mentioned: Distillation,
Source: www.uc3m.es/operacionesbasicas absorption-desorption, humidification-dehumidification,
3. To the property being transferred evaporation.
• Liquid-liquid. Unit operation involved in liquid-liquid
• Material transfer . Mass transfer operations encompass equilibrium is: Liquid-liquid extraction
all operations in which the controlling stage is the • Vapor-solid. Vapor-solid equilibrium is called adsorption-
transfer of matter and are intended to separate desorption.
components or groups of components from an originally • Solid-liquid. Typical unit operations in solid-liquid
homogeneous phase. It is the displacement of one or equilibrium are adsorption, ion exchange, and leaching.
more constituents of a fluid mixture with respect to a
global mass by the action of a driving force, generally a 5. To its application and importance.
concentration gradient. The mass transfer mechanism Some of the best-known unit operations are mentioned
depends on the dynamics of the system in which it takes below in order of importance and applicability: distillation,
place. There are two modes of mass transfer: a) liquid-liquid extraction, gas absorption, desorption,
convective : mass can be transferred according to the evaporation, crystallization, humidification,
global movement of the fluid. It may happen that the dehumidification, adsorption, ion exchange.
movement is carried out in a laminar or turbulent
regime. b) molecular or ordinary diffusion : it can be Criteria for the selection of separation processes.
defined as the movement of individual molecules Once the different unit operations and their characteristics are
through a fluid through the individual or disordered known, the most well-known separation techniques focus
movements of the molecules, due to the difference in attention on separating the components or constituents of a
concentration. This can occur in stagnant fluid systems mixture and the units or stages necessary to obtain the desired
or in fluids that are moving. (Source: or specified products. Thus, it is necessary to distinguish the
www.frro.unt.edu.ar/repositorio ) . Among the unit most notable physical and chemical characteristics of the
operations whose controlling stage is the transfer of mixture to be separated, the specifications of the desired
matter are mentioned: distillation, gas absorption, product and the possible formation of corrosive products,
solvent extraction, adsorption, ion exchange. foam, thermal stability, among others.
• Heat transfer . It is the process by which energy is
exchanged in the form of heat between different bodies Among the most important criteria to take into account for the
or between different parts of the same body by the selection and sequence of the different stages necessary for
action of a driving force, generally a temperature separation, the following are mentioned:
gradient. Heat is transferred by conduction, convection • Feed composition and desired product purity
or radiation. Although these mechanisms can take place
simultaneously, it may happen that one of them • Property of pure components: vapor pressure, boiling point,
predominates over the other two. Examples of unit melting point, solubility in a certain solvent, density.
operations controlled by heat transfer are mentioned: • Thermal stability
evaporation, heat exchangers, heat,
ovens. (Fountain: • Foaming
www.uc3m.es/operacionesbasicas ). • Formation of corrosive products
• Simultaneous transfer of matter and energy . They are • Design, engineering and development: commercial
the operations in which a contact between phases availability
occurs, transporting matter and energy between both • Fixed costs: investment, installation, costs
phases, said transport can be in the same direction or in maintenance
opposite directions. They are closely related to the
operations of air-water interaction, drying, • Operation and security
crystallization, and freeze-drying. • Environmental implications
• Momentum transfer . It occurs in those systems in which
The first consideration that must be made is the selection of the

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


UNIT OPERATIONS II. UNIT I. SEPARATION PROCESSES.
type of separator. If the mixture to be separated is Easy to scale
homogeneous, the separation can only be carried out by Easy design
creating another phase within the system. For example, if the Temperature, pressure, and
mixture is gaseous, another phase can be created by partial Characteristics of phase status requirements
condensation. The vapor resulting from condensation will be the operations Physical size limitations
richer in the more volatile components and the liquid will be from separation Power requirements
richer in the less volatile components. This is the case of a flash
Economical Capital costs
condenser and separator.
Operating costs.
Another alternative is to add a solvent in the liquid phase,
which would dissolve the desired component(s) of the gas
mixture. The equipment used is an absorber. In this case, an Example I.1. Feasible separation method. (Example 1.1 from
additional separation step is required to recover the solvent to Seader, E. J.; Henley, J. d. & Roper, K., 2010)
be reused and obtain the absorbed product available for the For each of the following binary mixtures, a separation
next separation step.
operation is suggested. Explain why the operation will or will
If the mixture is heterogeneous or multi-phase, then a physical not be appropriate.
separation operation can be used taking advantage of the
difference in densities between the phases present. This a. Separation of air into oxygen-rich and nitrogen-rich
separation is simple and the most common are: products by distillation.
b. Separation of m-xylene and p-xylene by distillation.
• Vapor-liquid
c. Separation of benzene and hexane cycle by distillation.
• Liquid-liquid (Immiscible)
d. Separation of isopropyl alcohol and water by distillation.
• Solid-liquid
e. Separation of penicillin from water in a fermentation broth
• Solid-vapor
• Solid-solid by evaporation of water.

For the development of a separation process, the selection of Solution:


(see Table I.3) is required: a. The normal boiling points of oxygen (-183 °C) and nitrogen
• Separation method: to select it, the feed condition and the (-195.8 °C) are sufficiently different that they can be
separation factor must be considered. separated by distillation, but high pressures and cryogenic
• Transfer agent, energy, mass or momentum temperatures are required. At moderate to low
• Separation equipment: differences in component properties production, they are usually separated by adsorption or
must be considered. gas permeation through a membrane, at low cost.
• Optimal arrangement or sequence of equipment: b. The boiling points of m-xylene (139.3 °C) and p-xylene
considering the condition of the product. (138.5 °C) are close making separation by distillation
• Optimization of operating conditions. Considering the impractical. However, their melting points differ widely
characteristics of separation operations and the economic from -47.4 °C for m-xylene and 13.2
aspect.
Table I.3. Factors influencing the selection of feasible
separation operations

Composition, particularity of the species


Feeding condition
to be recovered or separated
Flow rate
Temperature
Pressure
Phase (solid, liquid or gas)
Purity requirements
Temperature
Condition of Pressure
product Phase
Differences of Molecular
properties of Thermodynamics
the components Transport

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


UNIT OPERATIONS II. UNIT I. SEPARATION PROCESSES.
c. °C for p-xylene make crystallization the most suitable Solution:
separation method.
d. The boiling points of benzene (80.1 °C) and the hexane cycle
(80.7 °C) are close and make a separation by distillation
impractical. The most suitable method is distillation in the F = 100 kmol/h
presence of phenol (boiling point 181.4 °C), which reduces 21% mol Oz
the volatility of benzene, allowing almost pure cyclohexane 79% mol N2
to be obtained. The other product is a mixture of benzene
and phenol, which is then easily separated by distillation.
e. 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 an azeotrope with a Figure I.2.1. Scheme of the
minimum boiling point at 80.4 °C and 1 atm of 31.7 mol% of process.
water and 68.7 mol% of isopropyl alcohol, which makes Case 1 : Data: (FRo2)p = Membrane
their separation by distillation difficult if we want to obtain 0.50 and (FRn2)r = 0.875 Unit
alcohol concentrations greater than 68.5% molar. A feasible
separation method is distillation in the presence of The recovery of oxygen in
benzene, using two process steps. In the first stage, high the permeate product
purity isopropyl alcohol and a three-component allows us to determine the
heterogeneous azeotrope are obtained. The azeotrope is amount of oxygen that comes out through P and the recovery
separated into two phases, the benzene-rich phase is of N 2 in the rejection stream allows us to determine the
recycled to the first stage and the water-rich phase is sent amount of N 2 that comes out through R.
to a second stage, where almost pure water is obtained by Amount of N 2 and O 2 and N 2 in P :
distillation, with the other product recycled to the first
PO2 = F*XF,O2*FRO2 = (100 KMOL/H)(0.21)(0.50) = 10.5 KMOL/H
stage. stage.
f. Penicillin has a melting point of 97°C, but decomposes PN2 = F*XF,N2 – RN2 = (100 KMOL/H)(0.79) – 69.1 KMOL/H = 9.9
before reaching its normal boiling point. Therefore, it seems KMOL/H
that it can be isolated from water by evaporation of water.
Amount of N 2 and O 2 in R :
However, penicillin and most other antibiotics are sensitive
to heat, so they should be kept near room temperature. RN2 = F*XF,N2*(FR,N2)R = (100 KMOL/H)(0.79)(0.875) = 69.1
Therefore, water evaporation would have to take place KMOL/H
under impractical, high vacuum conditions. A practical RO2 = F*XF;O2 – PO2 = (100 KMOL/H)(0.21) – 10.5 KMOL/H = 10.5
method for separating penicillin is liquid-liquid extraction KMOL/H
with n-butyl acetate or n-amyl acetate.
Total amount of P :
Example I.2. Using purity and recovery as specifications.
(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
Total amount of R :
A feed, F, of 100 kmol/h of air containing 21 mol% oxygen and
79 mol% nitrogen is partially separated by a membrane unit R = Ro2 + Rn2 = 10.5 kmol/h + 69.1 kmol/h =79.6 kmol/h
according to each of the four stage specifications. Calculate the Mole fraction of O 2 and N 2 in P :
quantities, in kmol/h, and the compositions, in molar %, of the
two products (Rejection, R, and permeate, P). The membrane is xp,o2 = (10.5 kmol/h)/(20.4 kmol/h) = 0.515
more permeable to O 2 . xp,n2 = (9.9 kmol/h)/(20.4 kmol/h) = 0.485
Case 1 : 50% of O 2 is recovered in the permeate product and Mole fraction of O 2 and N 2 in R :
87.5% of N 2 in the reject product.
xr,o2 = (10.5 kmol/h)/(79.6 kmol/h) = 0.132
Case 2: 50% of O 2 is recovered in the product permeated with
50 mol% of O 2 . xr,n2 = (69.1kmol/h)/(79.6 kmol/h) = 0.868

Case 3 : 85 mol% of N 2 in the reject product and 50 mol% of O 2


in the permeate product.
Case 4 : 85 mol% of N 2 in the rejection product and an oxygen
ratio in the permeate to rejection of 1.1 [(P/R)o2 = 1.1].

FACILITATOR: ING. ZORAIDA J. CARRASQUERO C. MSc. UNEFM INTENSIVE 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
"+, - 2 # p P∗xP Amount of O 2 and N 2 in R :
,-/
= 0.50 ∴ p= -0.50 )"+∗ X 0,-/ #
+∗ X X RO2 = (82.857 KMOL/H)(0.15) = 12.429 KMOL/H
0,-/ P
,-/
= 21 5678⁄9 RN2 = 82.857 KMOL/H – 12.429 KMOL/H = 70.428 KMOL/H
-0,50)" -100 5678⁄9)0,21#
Case 4 : Data: xr,n2 = 0.85 and (P/R)o2 = 1.10
0,50
Applying a global balance in the Mole fraction of O 2 in R :
membrane unit we have: xr,o2 = 1- 0.85 = 0.15
F = P + R → R = F – P = 100 kmol/h – 21 kmol/h = 79 kmol/h Applying a material balance in O 2 in the membrane unit:
P = 21 kmol/h and R = 79 kmol/h F*XF,O2 = P*XP,O2 + R*XR,O2 →FO2 = PO2 + RO2
Amount of O 2 and N 2 in P : (100 kmol/h)(0.21) = 21 kmol/h = Po2 + Ro2 (I.2.3)
PO2 = (0.50)(100 KMOL/H)(0.21) = 10.5 KMOL/H PO2 = 1.10*RO2 (I.2.4)
PN2 = 21 KMOL/H – 10.5 KMOL/H = 10.5 KMOL/H Solving the system of equations (I.2.3) and (I.2.4) we have:
Amount of O 2 and N 2 in R : 21 kmol/h = 2.1*Ro2 →Ro2 = 10.00 kmol/h and Po2 = 11.00
RO2 = 21 KMOL/H – 10.5 KMOL/H = 10.5 KMOL/H kmol/h

RN2 = 79 KMOL/H – 10.5 KMOL/H = 68.5 KMOL/H Total amount of P and R :

Mole fraction of O 2 and N 2 in P : RO2 = 10.00 KMOL/H = R*XR,O2 →R = (10.00 KMOL/H)/XR,O2

xp,o2 = (10.5 kmol/h)/(21 kmol/h) = 0.50 R = (10.00 kmol/h)/0.15 = 66.67 kmol/h

xp,n2 = (10.5 kmol/h)/(21 kmol/h) = 0.50 P = 100 kmol/h – 66.67 kmol/h = 33.33 kmol/h

Mole fraction of O 2 and N 2 in R : Individual quantity of N 2 in P and R :

xr,o2 = (10.5 kmol/h)/(79 kmol/h) = 0.133 PN2 = 33.33 KMOL/H – 11.00 KMOL/H = 22.33 KMOL/H

xr,n2 = (68.5 kmol/h)/(79 kmol/h) = 0.867 RN2 = 66.67 KMOL/H – 10.00 KMOL/H = 56.67 KMOL/H

Case 3 : Data: xr,n2 = 0.85 and xp,o2 = 0.50 Mole fraction of O 2 and N 2 in P :

Mole fraction of O 2 in R : xr,o2 = 1 – 0.85 = 0.15 xp,o2 = (11.00 kmol/h)/(33.33 kmol/h) = 0.33

Mole fraction of N 2 in P : xp,n2 = (22.33 kmol/h)/(33.33 kmol/h) = 0.67

xp,n2 = 1 – 0.50 = 0.50 Table I.2.1. Summary of Results example I.2

Applying a global material balance in the membrane unit: Case 1 2 1 4


Product stream p R p R p R p R
F = P + R → 100 kmol/h = P + R (I.2.1) Composition (Molar N2 0,485 0,868 0,500 0,867 0,500 0,850 0,667 0,850
Fraction) I 0,515 0,132 0,500 0,130 0,500 0,150 0,333 0,150
heard
Material balance in O 2 in the membrane unit: Neith 9,90
Individual Quantity er 69,10 10,50 68,50 8,57 70,43 22,33 56,67
kmol/h 0, 10,50 10,50 10,50 10,50 8,57 12,43 11,00 10,00

F*XF,O2 = P*XP,O2 + R*XR,O2 Total quantity, kmol/h 20,40 79,60 21,00 79,00 17,14 82,86 33,33 66,67

(100 kmol/h)(0.21) = P(0.50)+R(0.15)→21 kmol/h = 0.50*P +


Example I.3. Feasible separation alternatives. (Example 1.5
0.85*R (I.2.2)
from Seader, E. J.; Henley, J. d. & Roper, K., 2010)
Propylene and propane are among the light hydrocarbons
Solving the system of equations (I.2.1) and (I.2.2) we have: obtained by cracking fractions of
21 kmol/h = 0.50(100 kmol/h –R) + 0.15*R
-29 kmol/h = -0.35*R → R = 82.857 kmol/h
Amount of O 2 and N 2 in P :
PO2 = (17.143 KMOL/H)(0.50) = 8.572 KMOL/H
PN2 = 17.143 KMOL/H – 8.572 KMOL/H = 8.572 KMOL/H

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


UNIT OPERATIONS II. UNIT I. SEPARATION PROCESSES.
heavy oil. Propane is valuable as a fuel and
as raw material to produce propylene and ethylene. Propylene 5,060 5,590
van der Waals area, m2/kmolx10 3
is used to produce acrylonitrile to make synthetic rubber,
isopropyl alcohol, cumene, propylene oxide and polypropylene. Acentric factor 0,142 0,152
Dipole moment, debyes 0,4 0,0
Although propylene and propane have close boiling points, they
Turning radius, mx1010 2,254 2,431
are traditionally separated by distillation. Figure I.3.1 shows that
Normal melting point, K 87,9 85,5
a large number of stages are needed and that reflux and
Normal boiling point, K 225,4 231,1
vaporization are high. Consequently, it is necessary to replace Critical Temperature, K 364,8 369,8
distillation with a more economical process with lower energy Critical Pressure, MPa 4,61 4,25
consumption. Based on the factors influencing separation Source: Seader, E. J.; Henley, J. d. & Roper, K., 2010
selection shown in Table I.3, and the scaling characteristics
shown in Table I.4, and the basic separation techniques
mentioned above, propose alternatives that allow the
separation of the process shown in Figure I.3.1.
Solution:
First verify that the feed flows and product streams in Figure
I.3.1 satisfy the law of conservation of mass. Table I.5 shows the
properties taken mainly by Daubert and Danner. The only
property listed that can be exploited is the dipole moment. Due
to the asymmetric location of the double bond in propylene, its
dipole moment is significantly larger than that of propane,
making propylene a weakly polar compound. The operations
that take advantage of this difference are:
a. Extractive distillation with a polar solvent such as furfural or
an aliphatic nitrile which reduces the volatility of propylene.
b. Adsorption with silica gel or zeolite that selectively adsorbs
propylene.
c. The method of membranes impregnated with silver nitrate
to selectively carry propylene through the membrane.

Figure I.3.1. Distillation of the propane-propylene mixture.


Source: Seader, E. J.; Henley, J. d. & Roper, K., 2010
Table I.5. Properties of the mixture of example I.3

Property Propylene Propane


molar mass 42,081 44,096
0,03408 0,03757
Van der Waals volume, m3/kmol
UNEFM INTENSIVE 2019
Training Task UNIT OPERATIONS II. UNIT I. SEPARATION PROCESSES.
Table 1.4. Ease of scaling (extension) of the most common condensation and c) evaporation.
separation operations.
Bibliographic references
Separation operations in Scaling Need for parallel units • KING, J. (2003). Separation processes. Reverté Editorial.
descending order of scaling Spanish edition.
Distillation Easy Does not need • Henley, E. J.; Seader, J. d. (1998). Separation operations by
Absorption Easy Does not need
Azeotropic and extractive Easy Does not need
equilibrium stages in Chemical Engineering. Second edition.
distillation Reverté Editorial.
Liquid-liquid extraction Easy Sometimes
membranes Requires pressurizing Almost always • Henley, E. J.; Seader, J. d. and Roper, D. K. (2010).
between stages Separation Process Principles. Chemical and Biochemical
Adsorption Easy Only for regeneration Operations. Third edition. John Wiley & Sons editors.
cycle
Crystallization Is not easy Sometimes • FOUST, A.; WENZEL, L.; CLUMP, C.; MAUS, L.; ANDERSEN,
Drying Not convenient Sometimes
l. b. (1980). Principles of Unit Operations. Second edition.
1. What is a key operation in chemical engineering? John Wiley & Sons editors.
2. What are the basic separation techniques, and what do • WANKAT, P. (2008). Separation Process Engineering.
they have in common? Second edition. Prentice Hall Publishing.
3. What is the difference between matter separation agent • WANKAT, P. (2012). Separation Process Engineering
(ASM) and energy separation agent (ASE)? Name three Includes Mass Transfer Analysis Third Edition. Prentice Hall
disadvantages of using a matter separation agent. Publishing.
4. What is the most common method used to separate two • McCABE, W.; SMITH, J.; HARRIOTT, P. (2007) Unit
fluid phases? Operations in Chemical Engineering. McGraw Hill
5. Examine a process flow diagram and identify what are the Publishing. Seventh edition.
key and auxiliary operations? Indicate the principle of • GEANKOPLIS, C. J. (1998) Transportation Processes and
separation, separation agent, predominant transfer, phase Unit Operations. Third edition. Cecsa Editorial
of the raw material and the products obtained from the
key operations. • TREYBAL, R. (1980) Mass Transfer Operations. Second
edition. McGraw Hill Publishing.
6. What is the difference between absorption and
adsorption? • MARCILLA GOMIS A. (1998). Introduction to separation
operations. Calculation by Equilibrium Stages. Publications
7. The degree of separation in a separation operation is of the University of Alicante. Espagrafic electronic edition.
frequently specified in terms of component recovery
and/or product purity. How do they differ? • AGUILAR RODRIGUEZ, ENRIQUE. (2007). Process Design in
Chemical Engineering. Mexican Petroleum Institute –
8. When an ethanol-water mixture is distilled at atmospheric National Polytechnic Institute. ISBN 968-489 037-0 FIPN-
pressure, the top product has a composition close to the 2007-113. Printed and made in Mexico. Digital edition.
azeotrope (89.4 mol % ethanol) and the bottom product
• PERRY R.; GREEN, D. W.; MALONEY, J. EITHER. (1998).
close to pure water. Based on the differences in the
Chemical Engineer's Manual. Sixth edition. McGraw Hill
properties of ethanol and water, explain how the following
Publishing.
operations must be performed to recover pure ethanol in
the distillate: a) extractive distillation, b) azeotropic • www.ugr.es/~aulavirtualpfciq/diagramadeblocks.html .
distillation, c) liquid liquid extraction, d) crystallization, e) Reviewed 12/27/2017.
pervaporation, f) adsorption. • www.kardauni08.files.wordpress.com/2010/09/
9. In the manufacture of synthetic rubber, a low molecular diagrama_de_flujo.pdf . Reviewed 12/27/2017.
weight waxy fraction is obtained as a byproduct that is • www.firp.ula.ve/archivos/cuadernos/S160A_Adsorción
formed in solution of the reaction solvent, which is normal Mojaibilidad.pdf . Revised 12/30/2017.
heptane. The byproduct has negligible volatility. Indicate
which of the following operations might be appropriate for • http://ocwus.us.es/arquitectura-e-ngenieria/operaciones-
solvent recovery and why. Indicate why the others are not basicas/contenidos1/tema10/pagina_16.htm . Revised
suitable. a) Distillation; b) Evaporation and c) Filtration. 12/30/2017.
• www4.ujaen.es/operaciones. Revised 12/30/2017.
10. Discuss the similarities and differences between the
following operations: a) flash vaporization; b) partial • http://sgpwe.izt.uam.mx . Bioseparators. Revised
12/30/2017. Sergio Huerta Ochoa.
Source: Seader, E. J.; Henley, J. d. & Roper, K., 2010
FACILITATOR: ING. ZORAIDA J. CARRASQUERO C. MSc.
FACILITATOR: ING. ZORAIDA J. CARRASQUERO C. MSc. UNEFM INTENSIVE 2019

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