Assignment – 1

Chemical Process
Technology
1. Petrochemical’s End Product:
Polymers & Polymerization Techniques.
a) Nylon 11 has the following structure [- NH –
(CH2)10 – CO -]n . If the number - average degree
of polymerization, Xn, for nylon is 100 and Mw =
120,000, what is its poly dispersity?
Answer:
We note that Xn and n(DP) define the same quantity for
two slightly different entities. The degree of
polymerization for a single molecule is n. But a polymer
mass is composed of millions of molecules, each of which
has a certain degree of polymerization. X n is the average
N

∑ ni Mr
of these. Thus, Xn = i=1 ,
N

where N = total number of molecules in the polymer mass

Mr = molecular weight of repeating unit
ni = DP of molecule i.
Now Mn = Xn Mr = 100 (15 + 14 ×10 + 28) = 18,300
Mw 120 000
Polydispersity = Mn = 18300 = 6.56
b) Briefly explain the role of surfactant in emulsion
polymerization system with the mechanism of polymer
growth and product isolation.
Answer:
Role of Surfactants
Surfactants are employed in emulsion polymerizations
to facilitate emulsification and impart electrostatic and
steric stabilization to the polymer particles. Steric
stabilization was described earlier in connection with non
- aqueous dispersion polymerization; the same mechanism
applies in aqueous emulsion systems. Electrostatic
stabilizers are usually anionic surfactants, i.e., salts of
organic acids, which provide colloidal stability by
electrostatic repulsion of charges on the particle surfaces
and their associated double layers. (Cationic surfactants
are not commonly used in emulsion polymerizations.) The
presence of free surfactant is not preferred in some
applications of polymer emulsions. It may, for instance,
result in water sensitivity of dried latex coatings or affect
the properties of particles used as substrates in solid phase
peptide syntheses. Colloidal stability can be conferred by
so-called "copolymerizable surfactants" in cases when it
is not feasible to add surfactants. These "surfactants" are
actually comonomers that are intended to provide surface
activity. It is desirable that they be located preferentially
on the particle surfaces and this can be accomplished by
methods outlined below in the section on Core-Shell
polymerization. For example, incorporation of
methacrylic acid (in copolymers with styrene or acrylics)
or vinyl sulfonic acid (in copolymers with vinyl acetate)
provides electrostatic stabilization under the alkaline
conditions used to store most emulsions (acid storage
favors corrosion of metal containers). Copolymerizable
steric stabilizers include esters of methacrylic acid and
polyethylene glycol, which can be made by
transesterification of methyl methacrylate.
Mechanism of Polymer growth and Product isolation
The first successful theory to explain the distinct
features of emulsion polymerization was developed by
Smith and Ewart, and Harkins in the 1940s, based on their
studies of polystyrene. Smith and Ewart arbitrarily
divided the mechanism of emulsion polymerization into
three stages or intervals. Subsequently it has been
recognized that not all monomers or systems undergo
these particular three intervals. Nevertheless, the Smith -
Ewart description is a useful starting point to analyze
emulsion polymerizations.
Interval 1
When radicals generated in the aqueous phase
encounter the monomer within the micelle, they initiate
polymerization. The conversion of monomer to polymer
within the micelle lowers the monomer concentration and
generates a monomer concentration gradient.
Consequently, the monomer from monomer droplets and
uninitiated micelles begin to diffuse to the growing,
polymer-containing, particles. Those micelles that did not
encounter a radical during the earlier stage of conversion
begin to disappear, losing their monomer and surfactant to
the growing particles. The theory predicts that after the
end of this interval, the number of growing polymer
particles remains constant.
Interval 2
This interval is also known as steady state reaction
stage. Throughout this stage, monomer droplets act as
reservoirs supplying monomer to the growing polymer
particles by diffusion through the water. While at steady
state, the ratio of free radicals per particle can be divided
into three cases. When the number of free radicals per
particle is less than 1/2, this is called Case 1. When the
number of free radicals per particle equals 1/2, this is
called Case 2. And when there is greater than 1/2 radical
per particle, this is called Case 3. Smith - Ewart theory
predicts that Case 2 is the predominant scenario for the
following reasons. A monomer - swollen particle that has
been struck by a radical contains one growing chain.
Because only one radical (at the end of the growing
polymer chain) is present, the chain cannot terminate, and
it will continue to grow until a second initiator radical
enters the particle. As the rate of termination is much
greater than the rate of propagation, and because the
polymer particles are extremely small, chain growth is
terminated immediately after the entrance of the second
initiator radical. The particle then remains dormant until a
third initiator radical enters, initiating the growth of a
second chain. Consequently the polymer particles in this
case either have zero radicals (dormant state), or 1 radical
(polymer growing state) and a very short period of 2
radicals (terminating state) which can be ignored for the
free radicals per particle calculation. At any given time, a
micelle contains either one growing chain or no growing
chains (assumed to be equally probable). Thus, on
average, there is around 1/2 radical per particle, leading to
the Case 2 scenario. The polymerization rate in this stage
can be expressed by Rp = kp [M][P] where kp is the
homogeneous propagation rate constant for
polymerization within the particles and [M] is the
equilibrium monomer concentration within a particle, [P ]
represents the overall concentration of polymerizing
radicals in the reaction. For Case 2, where the average
number of free radicals per micelle are ½ [P] can be
N micelles
calculated in following expression: [P] = 2N A where
Nmicelles is number concentration of micelles (number of
micelles per unit volume), and NA is the Avogadro
constant (6.02×1023 mol−1). Consequently, the rate of
polymerization is then
N micelles
Rp = kp [M] 2N A

Interval 3
Separate monomer droplets disappear as the reaction
continues. Polymer particles in this stage may be
sufficiently large enough that they contain more than 1
radical per particle. Depending on the particular product
and monomer, additional monomer and initiator may be
continuously and slowly added to maintain their levels in
the system as the particles grow. The final product is a
dispersion of polymer particles in water. It can also be
known as a polymer colloid, a latex, or commonly and
inaccurately as an 'emulsion'. Smith - Ewart theory does
not predict the specific polymerization behavior when the
monomer is somewhat water-soluble, like methyl
methacrylate or vinyl acetate. In these cases homogeneous
nucleation occurs: particles are formed without the
presence or need for surfactant micelles.

2. Production and Purification of galacto -

oligosaccharides (GOS) from milk lactose.
a) Draw a schematic showing the feed recycle
loop and enzyme recycle loop for the production
of GOS through enzymatic process in a batch
reactor.
Answer: Feed Recycle loop
PI – Pressure indicator
PP – Peristaltic pump
M - Motor

Enzyme Recycle Loop

b) Compare the merits and demerits of GOS

purification through anti - solvent technology and
enzyme immobilized membrane bioreactor.
Answer:
Merits of GOS purification through anti – solvent
technology:
 Low energy consumption
 Large production capacity
 Fast action
 Easy continuous operation
 Ease of automation
Demerits of GOS purification through anti – solvent
technology:
 High concentrations of the solvent, which needs to be
recycled to the plant.
 High temperature requirement requires utility section
development, especially in cold countries.
 Serving both the requirement (maximum percentage
recovery and less lactose contamination) in a single plant
requires two simultaneous downstream process because of
two different feedstock concentration
 Leading to a process of membrane separation.

Merits of GOS purification through enzyme

immobilized membrane bioreactor:
 Increased enzyme stability
 Reduced enzyme costs
 Greater ease of enzyme separation and recovery for
reutilization
 Possibility of operating continuously
 Reduced effluent problems
Demerits of GOS purification through enzyme
immobilized membrane bioreactor:
 Enzymatic reaction of GOS is mainly limited by the
content of water, monosaccharides (Glucose and
Galactose). Presence of water enhances the possibility of
hydrolysis reaction instead of transgalactosylation
reaction. Presence of monosaccharides increases the
possibility of enzyme inhibition. These limit the
application of batch reaction towards the yield of GOS.
  Downstream application for making purified GOS
increases the cost.
 Compare to these, single membrane reactor, where,
enzyme has been immobilized on the membrane might
increase the chances of GOS yield
 Fouling takes place in the membrane sometimes
 Leakage of enzyme may occur.

3. Blast Furnace operation in steel plant.

a) What are the important Blast Furnace
Performance Indicators and explain how they are
maintained and useful w.r.t Shell Cooling i.e.,
STAVES?
Answer:
Important Blast Furnace Performance Indicators:
 Maximum Furnace Campaign Life
 +20 years
 Refractory
 Cooling System components (Plates/Staves/Tuyeres)
 Maximize Maintenance and Operational Costs
 Hot Blast Valve
 Tuyeres
 Staves and Plates
 Furnace Availability
Shell Cooling i.e., STAVES
In Blast Furnace, refractory cooling would take place
through Copper and Cast iron staves. The copper plate has
a much higher heat transfer coefficient (HTC) than the
cast iron stave and has a much lower tendency for fouling.
The mild steel pipes in the cast iron stave can quickly
develop an insulating layer of iron oxide corrosion
product that would reduce heat flux and bring about
reduced refractory cooling. The advantage of stave
cooling over flat plate cooling is the blanket cooling
effect of the staves as compared to point to point cooling
effect of flat plate cooler. This ensures a more uniform
cooling performance. Cast iron staves in the blast furnace
bosh and stack area have an average life expectancy of
around 8 to 10 years. Cast iron staves typically fail due to
loss of cast iron material and exposure of internal pipe
coil. Cast iron cracks in service due to high heat loads it is
exposed to. Further cast iron has a low thermal
conductivity (about 45 W/m K). Random gaps between
the cooling tubes and the cast iron reduce the amount of
heat that is removed. Cast iron staves have the advantage
of lower costs and increased structural integrity and
protection of the furnace shell when furnace refractories
have been worn away. The use of cast iron coolers in
which the tubes are closer to the cast iron complicates the
design of the shell while not necessarily increasing the
life of the cooling system. Copper flat coolers have a
greater uniformity of material properties over the
complete cooling element. In those regions of the blast
furnace which are subject to mechanical damage, the front
side of the cooling elements is usually reinforced with
special materials. These coolers are mostly welded to the
blast furnace shell to ensure gas tight sealing. The copper
flat plate coolers have normally multiple channels with
one or two independent chambers. These coolers are
designed to maintain high water velocities throughout the
cooler, thus have an even and high heat transfer
coefficient.

b) With a labelled Diagram, give all the Reactions

involved in Blast Furnace Operation in various
regions and explain their importance pertaining to
Temperature and Heat?
The main chemical reaction producing the molten iron is:
Fe2O3 + 3CO → 2Fe + 3CO2
This reaction might be divided into multiple steps, with
the first being that preheated blast air blown into the
furnace reacts with the carbon in the form of coke to
produce carbon monoxide and heat:
2 C(s) + O2(g) → 2 CO(g)
The hot carbon monoxide is the reducing agent for the
iron ore and reacts with the iron oxide to produce molten
iron and carbon dioxide. Depending on the temperature in
the different parts of the furnace (warmest at the bottom)
the iron is reduced in several steps. At the top, where the
temperature usually is in the range between 200 °C and
700°C, the iron oxide is partially reduced to iron (II,III)
oxide, Fe3O4.
3 Fe2O3(s) + CO(g) → 2 Fe3O4(s) + CO2(g)
At temperatures around 850 °C, further down in the
furnace, the iron (II, III) is reduced further to iron(II)
oxide:
Fe3O4(s) + CO(g) → 3 FeO(s) + CO2(g)
Hot carbon dioxide, unreacted carbon monoxide, and
nitrogen from the air pass up through the furnace as fresh
feed material travels down into the reaction zone. As the
material travels downward, the counter-current gases both
preheat the feed charge and decompose the limestone to
calcium oxide and carbon dioxide:
CaCO3(s) → CaO(s) + CO2(g)
The calcium oxide formed by decomposition reacts
with various acidic impurities in the iron (notably silica),
to form a fayalitic slag which is essentially calcium
silicate, CaSiO3:
SiO2 + CaO → CaSiO3
As the iron (II) oxide moves down to the area with
higher temperatures, ranging up to 1200 °C degrees, it is
reduced further to iron metal:
FeO(s) + CO(g) → Fe(s) + CO2(g)
The carbon dioxide formed in this process is re-
reduced to carbon monoxide by the coke:
C(s) + CO2(g) → 2 CO(g)
The temperature-dependent equilibrium controlling the
gas atmosphere in the furnace is called the Boudouard
reaction:
2CO ⇌ CO2 + C
The "pig iron" produced by the blast furnace has a
relatively high carbon content of around 4–5% and
usually contains too much sulphur, making it very brittle,
and of limited immediate commercial use. Some pig iron
is used to make cast iron. The majority of pig iron
produced by blast furnaces undergoes further processing
to reduce the carbon and sulphur content and produce
various grades of steel used for construction materials,
automobiles, ships and machinery. Desulphurisation
usually takes place during the transport of the liquid steel
to the steelworks. This is done by adding calcium oxide,
which reacts with the iron sulfide contained in the pig iron
to form calcium sulfide (called lime desulfurization). In a
further process step, the so-called basic oxygen
steelmaking, the carbon is oxidized by blowing oxygen
onto the liquid pig iron to form crude steel.

4. Fertilizer Industry (Nitrogen Based)

a) What are different ways of H2 generation from
Ammonia synthesis and which is cheapest one?
Answer: Different ways of H2 generation from Ammonia
synthesis are:
1. Natural Gas (Methane) Steam Reforming (SMR):
CH4(g) + H2O + heat  CO + 3 H2
Cost of H2 generation – 2.08 to 2.27 $/Kg
2. Naphtha Steam Reforming:
C8H18 + 16 H2O  8 CO2 + 25 H2
Cost of H2 generation – Almost same as SMR
(Sometimes, it may varied due to the availability of
Naphtha)
3. Partial Oxidation of Heavy Oil:
C12H24 + 6 O2  12 CO + 12 H2
Cost of H2 generation – about 1.8 times costlier than
SMR.
4. Gasification of Coal:
2C + O2 + H2O  H2 + CO2 + CO
Cost of H2 generation – about 1.4 to 2.6 times costlier
than SMR
5. Electrolysis of Water:
2 H2O  2 H2 + O2
Cost of H2 generation – about 2.2 times costlier than SMR
at high temperatures.
Production of H2 through Natural gas (methane) Steam
Reforming is the cheapest one among all.
b) What are the important morphological
properties of Urea and how it affects end usage?

Answer:
Important Morphological Properties of Urea:

By,
Name: Abishek Kumar L,