UNIVERSITI TEKNOLOGI MARA

FAKULTI KEJURUTERAAN KIMIA

CHE522
TRANSPORT PHENOMENA
ASSIGNMENT 2

No. Name Student No.

1 Wan Ahmad Radhi Bin Wan 2015996719
Abdullah
2 Che Muhammad Fikri Bin 2015429556
Che Salim
3 Muhammad Aqil Bin 2015102711
Zulaidi
Question 1

Heat exchangers are a ubiquitous feature of modern industry, vital not only in order to keep
expensive equipment from overheating, but also in harnessing that very same heat for other
purposes. In fulfilling this important role, heat exchangers are subject to numerous issues and
problems. One of the most common is known as heat exchanger fouling. As a chemical
engineer responsible to report the problem to your client, describe how fouling can affect heat
exchanger’s efficiency and how to mitigate the problem from recurring again. You should use
the fundamental law involved in the process and include any relevant figure (s) to defend your
statement.

ANSWER

What is Fouling?

The simplest way to define what fouling is where it can be said as the deposition and
accumulation of foreign substance to the external or the internal surfaces of the heat
exchanger’s pipes or tube such as algaes, suspended solids and insoluble salts.

There are many factors that affect the rate and extent of fouling in the heat exchanger
such as the properties and conditions of the chemicals that flows in the heat exchanger where
some chemicals may not be compatible with the surface of heat exchangers and also the
stability of the components itself which may leads to increasing in the rate of fouling. The
chemicals that enters the heat exchanger also may be affected by the surrounding conditions
before entering the heat exchanger such as the exposure of the chemicals in the storage or may
be affected by the operating parameters of the heat exchanger itself.

Mechanism and stages of Fouling

There are a five main stages of fouling in a unit operation that requires different types
of prevention techniques or ways to overcome the problems. These stages may occurs at the
same time which will further increases the rate of fouling.

The first stage is the initiation period where it is the stage where the internal surface of
the heat exchanger starts to be accumulated by the foreign substances. This stage is continuous
where the foreign substances that accumulates on the surface are accumulated bit by bits from
time to time where after a long time it will accumulate into a large amount of foulant at the
wall of the heat exchanger.
 The second stage is the particulate fouling where small particles from an unstable
chemicals that flows in the heat exchanger deposits onto the wall of the heat exchanger. The
particles that is been said are divided into two groups where the first group is particles which
is originally carried by from unit operations before entering the heat exchanger and particles
formed in the heat exchanger due to various reactions such as aggregation and flocculation.

The third stage is the mass transport and migration of the foulants from the chemical
flowing to the fouling sites which is the wall of the heat exchanger. The foulants is the foreign
substances that is said before that will deposit itself to the wall of heat exchanger in the next
stage.

The fourth stage is the phase separation and deposition of the foulants which involves
in the nucleation or initiation of fouling sites which will lead to the attachment to the wall of
heat exchanger which will lead to a mass of deposit at the wall of heat exchanger.

The fifth stage is the aging and hardening stage of the deposits where the deposits will
increase its strength by hardening and become more sticking to the wall of heat exchanger
which will gives it more protection from being removed during cleaning.

How fouling affect the heat exchanger

The buildup of fouling agents on the surfaces of a heat exchanger increases the overall
resistance to the flow of heat. This can be illustrated by the Figure 1.1 which demonstrates the
lowering of temperatures across the fouled surfaces of a heat exchanger.

Figure 1.1: Temperature distribution across fouled heat exchanger surfaces.

 T1 and T6 are the temperatures of the hot and cold fluids respectively. The fouling
deposits create layers that offer a resistance to heat flow due to their near stagnant conditions.
Moreover, the thermal conductivity of foulants, in general, is comparatively low to metals’.
For these, in order to overcome this compication, large temperature differences are required
thus creating more difficulties like increase in the energy consumption. So let’s get to know
how the fouling agents contribute to the resistance of heat flow. The resistance to heat flow
across a solid surface is given as:

𝑥
𝜆

Where x is the solid thickness (parallel to the path of the heat) and λ is the thermal conductivity
of the particular solid or stagnant fluid. To shorten things, the resistances to heat flow put up
by the cold fluid, hot fluid and metal wall of the exchanger are ignored.
𝑥1
For Deposit 1, its thermal resistance is , λ1 is the thermal conductivity of Deposit 1.
𝜆1

𝑥2
For Deposit 2, its thermal resistance is , λ2 is the thermal conductivity of Deposit 2.
𝜆2

Under steady state conditions, the heat flux is given by:

∆𝑇
𝑞=
𝑅𝑇

Where ΔT is the temperature difference between the hot and cold fluids and R T is the total
resistance contributed in the heat exchanger. In this case the total resistance only combines the
resistance provided by the foulants. Hence,

𝑥1 𝑥2
𝑅𝑇 = +
𝜆1 𝜆2

In a heat exchanger, the main concern is the amount of heat being transferred. From the
heat flux equation, we can see that the total resistance plays a role in producing the value of
heat flux. To give the highest possible amount of heat, the total resistance shall be minimized.
From here, we can understand that the thickness of the foulants, x1 and x2 affects the value of
the total resistance. A direct proportionality between the foulants thickness and the resistance
of heat flow does exist. This means, the greater the deposits of the foulants, the greater the heat
flow will be restricted. Thus the efficiency of the heat exchanger reduces unless cleaned or
other mitigation methods are introduced.
How to mitigate the fouling from recurring again.

From the reading and research in article and journal about how to mitigate the fouling in
heat exchangers, various kind of methods have been developed to control fouling from occur
again. The methods can be classified to three methods which are chemical method, mechanical
method and changing the phase of the solution.

For the chemical method, reduction of fouling happened when the solution was added
foreign chemicals (chemical additives). Many companies now days have developed chemical
additives to be used extensively for mitigate fouling in the industrial sector.

The chemical additives act in different kind of ways such as sequestering agent, threshold
agents, crystal modifiers and dispersants. One of the example of sequestering agents is
ethylenediaminetetraacetic acid (EDTA) where the EDTA complex strongly with the scaling
cations such as Ca+, Mg+ and Cu+ in exchange with Na+. So, the scaling can be prevent and any
scale formed previously had been removed. For the threshold agents, polyphosphates and
polyphosphonates also been used to reduce scaling in boilers and cooling water systems. Both
of the threshold agents prevent the formation including prevent cystallisation and diminished
fouling. Only small amout of these agents are needed in reducing scaling from supersaturated
salt solutions because of the effectiveness.

For the crystal modifying agents such as polycarboxylic acid, it distort the crystal habit
and inhibit the formation of large crystals. However, the distorted crystals remain suspended
in the bulk solution and particulate fouling may take place if the concentration increases beyond
a certain limit. The particulate fouling can be prevent by using dispersing agents along with the
crystal modifying agents. Although crystallization additives cannot prevent completely fouling
from occur, the results from the crystallize are different from those formed in the absence of
any additives. The layer that formed become looses its strength and can be removed easily. In
addition, by controlling the pH, crystallization fouling can be minimised.
 While for the dispersants, its been used to reduce the surface tension of the deposits.
Dispersants helps in disintegrating the suspended particles into smaller fragments that do not
settle so readily. Beside that, dispersants also very helpful in keeping the foulants away from
the surface.

Different from chemical method, as the technology nowadays had become more advanced,
several mechanical methods have been developed in recent years which the following
mechanisms predict the modern methods:

1. Breakage of deposits during brief overheating due to differential thermal expansions of heat
transfer surface and deposits.

2. Mechanical vibration of the heat transfer surfaces.

3. Acoustical vibration of the surface.

4. Increased shear stress at the fluid/ deposit interface.

5. Reduced stickiness of the heat transfer surface.

Lastly, beside the chemical method, mechanical method and changing the phase, the heat
exchangers need to be clean. Either the clean up operation done on line to maintain acceptable
performance without interruption of operation or off-line cleaning where the operation need to
be shut down for a time for further inspection and cleaning.
Question 2

Mass transport is a transport of components under a chemical potential gradient. Mass transfer
operation plays an important role in many industrial processes. A group of operations for
separating the components of mixtures is based on the transfer of material from one
homogeneous phase to another such as gas absorption and stripping, liquid-liquid extraction,
leaching, distillation, humidification, drying, crystallization and number of other separation
techniques.bn bn

Summarize TWO (2) of these techniques to describe the mass transfer operation. Also,
specifically highlight the driving force for each of the techniques and include any relevant
figure (s) to describe the fluxes involved.

1. Liquid-Solid Leaching

Leaching is one of the techniques to separates the components of mixture based on the transfer
of material from one homogeneous phase to another. The solid is contacted with a liquid phase,
in order to separate the desired solute component or remove an undesirable solute component
from the solid phase.

The separation process is called liquid-solid leaching or simply leaching when the two phases
are in closed contact and the solute or solutes can diffuse from the solid to liquid phase, then
resulting in a separation of the components originally in the solid. In leaching, when an
undesirable component is removed from a solid with water, the process is called washing.

Leaching process usually use in the metals industry for removing mineral from ores (acid
solvents), the sugar industry for removing sugar from beets (water is solvent) and the oilseeds
industry for removing oil from soybeans (hexane or similar organic solvents).

In leaching, it can either be batch, semibatch or continuous. Leaching process usually operates
at higher temperature to increase the solubility of the solute in the solvent. Calculations involve
three component which are the solid, solvent and solute.

For preparation of solids for leaching, there are two kind of method which are first, inorganic
and organic material and second is animal and vegetable materials. In method of inorganic and
organic materials, the solids depends to a large amount of the proportion of the soluble
component present, its distribution through out the original solid. If the soluble material is
surrounded by a matrix of insoluble matter, the solvent must diffuse inside to contact and
dissolve the soluble material and then diffuse out. For the animals and vegetable materials,
biological materials are cellular in structure and the soluble constituents ar generally found
inside the cells. The rate of leaching may be slow, because the cell walls provide another
resistance to diffusion.

For the rates of leaching, in general the rate transfer of the solvent from the bulk solution to the
solid surface is quite rapid, while the rate of transfer of the solvent into the solid may be
somewhat rapid or slow. The rate of diffusion of the solute through the solid and solvent to the
surface of the solid is often the controlling resistance in the overall leaching process and may
depend on various of factors.

In the rate of leaching when dissolving a solid, the rate of mass transfer from the solid surface
to the liquid is the controlling factor. There is no resistance in the solid phase if it is a pure
material. The equation for the rate of mass transfer can be derived as follows for a batch system.

The rate of mass transfer of solute A being dissolved to the solution of volume V m3 is

NA
 k L (c AS  c A )
A

N A : kg mol of A dissolving to the solution/s.

A : Surface area of particles in m2

kL : Mass-transfer coefficient in m/s

cAS : Saturation solubility of the solid solute A in the solution in kg.mol/m3

cA : Concentration of A in the solution at time t sec in kg.mol/m3.

By material balance, the rate of accumulation of A in the solution is equal to Eq.(12.8-1) times
the area A:

Vdc A
 N A  Ak L (c AS  c A )
dt

Integrate from t = ) and cA = cA0 to t = t and cA = cA,

cA t
dc Ak
c cAS AcA  V L  dt
t 0
A0

c AS  c A
 e ( k L A / V )t
c AS  c A0

The solution approaches a saturated condition exponentially. Frequently the interfacial area A
will increase during the extraction if the external surface becomes very irregular. However, if
the soluble material forms a high proportion of the total solid, disintegration of the particles
may occur. If the solid completely dissolving, the interfacial area changes markedly including
the mass of transfer coefficient may changes.

For the rate of leaching when diffusion in solid controls, when the case where unsteady-state
diffusion in the solid is the controlling resistance in the leaching of the solute by an external
solvent, the following approximations can be used. If the average diffusivity D Aeff of solute A
is approximately constant, then for extraction in a batch process, unsteady-state mass-transfer
equations can be used.

N A  kc (cL1  cLi )

kc : Mass transfer coefficient in m/s

cLi : Bulk fluid concentration in kg mol A/m3.

cLi : Concentration in the fluid just adjacent to the surface of the solid.
Driving force of leaching
In leaching, the criterion that greatly drives the process to occur is the concentration gradient
of the travelling solutes (solid). Although there are many influential aids that help catalysing
the process such as solubility, the solutes’ concentration gradient itself is the main reason they
move from one point to another. This can be simply aided by the equation explained earlier
which is:

NA
 k L (c AS  c A )
A
Consider two streams being mixed in a vessel through time; one carries soluble solute A while
another does not. When these two streams mix, a concentration gradient will be created since
there is a difference in concentration of solute A between them. Hence the solutes diffuse into
the other stream. After the solutes are evenly spread, equilibrium of its concentration is reached
on both sides and the transfer process will stop. But then, this will not happen since both
streams are continuously being fed in and flown out. For this, the equilibrium is far from
occurring thus the diffusion process shall always happen inside the mixing vessel.
2. Crystallization

From the separation techniques that is been mention, the first technique I choose to
summarize is the crystallization technique. The best way to describe crystallization is that it is
the process where solid particles are formed from a homogeneous phase. In industries the
crystallization technique used is a solid-liquid separation process where mass transfer occurs
from the solute of a liquid solution from the feed to a pure solid crystalline phase. The easiest
way to know what crystallization is from what occurs in our everyday lives such as the process
of freezing of water to form ice.

The main technique used in the industries is done by using the crystallizer. The crystals
formed from the process have different sizes and shapes depending on the type of crystallizer
used and the chemical used for the crystallization. There are seven type of crystals formed
which depends on the arrangement of the axes and their angles according to the figure below:

Seven types of crystals formed

The driving force that is important for the crystallization process is the supersaturation which
can be said as the driving force for all solution crystallization processes. The engineers in the
industries controls the crystallization process by cautiously controlling the supersaturation
levels during the process. Supersaturation is the difference between the actual concentration
and the solubility concentration of a substances at a given temperature
Supersaturation is very important because it is the driving force used for nucleation and growth
of the crystals. Nucleation is the creation of new crystal nuclei by primary nucleation which
crystals are created spontaneously from solution or by secondary nucleation where crystals are
created by existing crystals. Next, the growth of crystal is the growth in the crystal’s size after
the nucleation phase. The growth is very important because it will affect in the final crystal
size whether all the crystals form will have uniform size or not. The relation between
supersaturation and nucleation and growth can be defined by the following equations.

𝐺 = 𝑘𝑔 Δ𝐶 𝑔

𝐺 = 𝑘𝑏 Δ𝐶 𝑏

𝐺 = Growth Rate

𝑘𝑔 = Growth constant

𝑔 = Growth order

𝐵 = Nucleation Rate

𝑘𝑏 = Nucleation constant

𝑏 = Nucleation order

ΔC = Supersaturation

From the equation above the graph below can be formed to show the relationship between
supersaturation and nucleation and growth and also the crystal size.
Relationship Graph between supersaturation and
nucleation, growth and crystal size.