CPT Slides Endsem 040522

Chemical Process Technology
CHE F 419
Second semester 2021-2022
Dr. Ramesh-Babu Adusumalli

Department of Chemical Enginerring
BITS-Hyderabad campus
Chamber: D 207
E-mail: [email protected]
09/11/2023 Chemical Process Technology 1

Course contents
• To know the present status of chemical industries in India
• Unit operations and Unit Process concepts
• To understand the Cement manufacturing processes
• To understand the chronological development in the Sulfuric acid production
• To understand the chronological development in the Nitrogen based fertilizers
production
• To understand the importance of NPK fertilizer and its production
• To understand the extraction of edible and essential oils
• To understand the Pulp and paper production processes
• To understand the Coal based technologies
• To understand the Crude oil refining processes
• To understand the Petrochemical processes (C1-C2 compounds)
• To understand the processing of Polyolefins, Phenolic resins and Composites
• To understand the Aluminium manufacturing processes
• To understand the Paracetmol Tablet manufacturing
i
GR-S: Government rubber styrene was produced in World war-2 because of supply cut-off from south east asia.
OEM= Original equipment manufacturers; CEFIC = European Chemical Industry Council
Polymer for insulation and fittings
Courtesy:
CEFIC =
European Chemical
Industry Council

Introduction
• Chemical Industry contributed 3 % GDP and 17 % of the
manufacturing sector (2005-06).
• Raw materials (self-sufficient!): Coal, Natural gas, Iron, Mica
and Manganese. Coking coal. Mica = 80 % of the world output
• But we don't have enough petroleum reservoirs. Total
requirement 70 MT !!! but western offshore is contributing
only 25 MT (million tons)
• Bihar is major source of mineral wealth in India
• We are extracting around 58 minerals from 4000 mines.
Among them, three are fuel minerals, dozen metallic and
rest are non-metallic type.
• Al output is rising rapidly, but bauxite reserves are almost 5
% of the world total
Mineral reserves of India (1994)
UNIT Reserves % of world total
Bauxite Million of tons 1080 4.5
Beryllium tons 64000 17
Chromite Million of tons 18.1 4.3
Iron Ore Million of tons 3300 5.1
Manganese Million of tons 17 2.1
Rare Earth Million of tons 2.3 2.7
Titanium Million of tons 43 15
Zinc Million of tons 11 7.3
Zirconium Million of tons 2.1 4.3

Classification of Minerals
14
Mineral Belts of India
• 11 states account for 90 % of the total number of operational mines: Andhra
Pradesh, Orrisa, Chhattisgarh, Jharkhand, West Bengal, Maharashtra, Tamil Nadu,
Gujarat, Madhya Pradesh, Rajasthan, and Karnataka.
• There are three major mineral belts in India namely −
a) The North-Eastern Plateau Region which includes Chhotanagpur (Jharkhand),
Odisha, West Bengal, and parts of Chhattisgarh. Iron ore, coal, manganese,
bauxite, and mica are the major minerals of the north-eastern plateau region.
b)The South-Western Plateau Region: Major parts are Karnataka, Goa, and
contiguous Tamil Nadu uplands and Kerala. Major mineral resources of south-
western plateau region are iron ore, manganese, and limestone. Kerala has
deposits of monazite and thorium, and bauxite clay and Goa has deposits of iron
ore.
c) The North-Western Region: The north-western region covers the areas of
Aravalli in Rajasthan and parts of Gujarat. Major minerals of north-western
regions are copper, zinc, sandstone, granite, marble, Gypsum and Fuller’s earth
deposits. In addition, Gujarat and Rajasthan, both have rich sources of salt. The
Himalayan belt is also an important mineral belt, as it has rich deposits of
copper, lead, zinc, cobalt, and tungsten. 15
Mineral Distribution in India
16
Energy consumption in India (2004-05)
Gross energy (mill Gcal) Share (%)
Coal and Lignite 3372 48

Nuclear energy 187 3
(uranium)
Hydrocarbons 2057 29
Fuel-wood 805 11
Dung-cake and 527 7
agricultural waste
Hydroelectric 137 2

Natural Gas Consumption
Industry-wise off-take of Natural Gas in India during 2017-18
18
Consumption of Petroleum Products
Sector-wise Consumption of Petroleum Products during 2017-18
19
Electricity Consumption
Consumption of Electricity by Sectors in India during 2017-18
20
Important minerals found in india: Coal, Iron, Mica, Copper,
Bauxite, Manganese, and Gold
Transportation picture for India: Air, Pipe

lines, Water transport, Road, Rail transport
Nuclear power (Tarapur and Kalpakam, etc):

50 % cheaper and can be installed
anywhere. Ex. France
Unit processes and Unit operations
Commercial production of chemicals from raw materials =

f(chemical changes+ Physical changes)
Unit operation Unit process Industry

Calcination Cement
Ammonooxidation Plastics/synthetic
fibres
Distillation
Drying

Solids /pastes without
Dryers agitation
-Tray dryer
- Screen conveyor dryer
(Spray dryer)
Solids / pastes with agitation
- Tower dryer & Rotary dryer
- Screw-conveyor dryer
- Fluid-bed dryer
Tray dryer - Flash dryer
The dryer is made out of angle frame; double walled from CRCA mild steel, thermally
insulated with 3 inch thick glass wool between the walls. Inner body is finished with
heat resistant aluminium paint, outside in grey hammer tone.
Adiabatic, non-adiabatic or combined both
TRAY
DRYER
Fluidised Bed Dryer
• Fluidized Beds have been used for heat exchange in both
physical operations and chemical processes because of
rapid transport. Also, because of mixing, uniform
temperatures throughout the bed can be maintained.
• To plot the drying curve under fluidized bed condition.
• Here silica particles are circulated within the fluidized
bed. This circulation has a direct bearing on the heat
transfer properties of air- silica fluidized bed systems.
• CALCULATION OF DRYING CURVE FROM THE RECORD OF
MOISTURE CONTENT OF THE DRYING MEDIUM.
Fluidised Bed Dryer
Residence time of 30-120 sec, surface liquid is vaporised

15-30 min, if internal diffusion is required
Natural draft tray Dryer
• To plot the graph between time vs. moisture content, time
vs. rate of drying , moisture content vs. rate of drying.
• To determine the drying rate and critical moisture content
of the given material .
• Drying of solids is considered to occur in two stages, a
constant rate period followed by a falling rate period. In
the constant rate period, the rate of drying corresponds to
the removal of water from the surface of the solid. The
falling rate period corresponds to the removal of water
from the interior of the solid. The rate in either case is
dependent on solid (here bric material) characteristics and
tray material.
Natural draft tray Dryer
ROTARY DRYER
Suitable for drying free-flowing granular solids which do not dust
/stick; high temperature versions are kilns for calcining cement/ lime.
Mass velocity: 2000-25,000 Kg/m2.hr; 120-175 OC for steam heated
Dryer diameter= 1-3 mt;
Flash dryer
Drying takes place in a
matter of seconds (3-
4). Wet material is
dispersed into a
stream of heated air
(or gas) which
conveys it through a
drying duct.
Inlet air temperature ranges from (100 -650 degree centigrade)

while airflows can exceed (200,000 m3/hr). Solid temperature will
not exceed 50 OC
Batch sedimentation
• The separation of dilute slurry by gravity settling into a clear liquid
and thick sludge is known as Sedimentation
• In this experiment for slurry of known concentration, the height of a
clear liquid-solid interface is obtained as a function of time. Slopes of
this curve at any point of time represent settling velocities of the
suspension at that time and are characteristics of specific solid
concentration.
• To plot a graph between the height of interface (z) and time () for
slurries having five different concentration (5, 7.5, 10, 12.5, and 15 %)
of CaCO3
• To plot settling rate (dz/d)0 vs initial concentration (Co) on a log-
log-scale.
• To determine the critical constant (c, Cc) for each concentration (Co).
• Use these critical parameters of slurry for the determination of Area
(A) for continuous thickener / clarifier
Sedimentation
studies
https://www.youtube.com/watch?v=2IUZza3ohlo
ROTARY DRUM VACUUM FILTER
Objective : To study the performance of a Rotary Drum Filter operating under Vacuum
Aim: To determine the specific cake resistance (α) for a given slurry of CaCO3.
Procedure:
1.Prepare a slurry of CaCO3 in water of known concentration (10-15 %)
2.Pour the prepared mixture in the tank and switch on the agitator to get the homogeneous slurry
3.Allow the slurry to pass through the rotary drum filter and switch on the vacuum pump.
4. Fix the pressure gauge reading at one value and record filtrate collected in the receiver for
known amount of time (Here water is collected every 2 minutes and repeated 4 times at the same
pressure gauge)
5. Increase the pressure by slightly closing the air by-pass line and repeat the above procedure.
6. Remove the cake deposited using doctor blade and wash the filter assembly.
7. During above steps collect the cake deposited per revolutions of drum.
α is Cake resistance, υ porosity of the bed, slope = t/V vs V

t is the time for cake formation, ρF = density of filtrate, µF = viscosity of filtrate, V= Vol. filtrate
Rotary drum vacuum filtration
PLATE & FRAME FILTER PRESS
Objective: To study the operation of plate and frame filter press. It consists of 7 plates and 6
frames. Here pore of the medium (canvas cloth) will be larger than the particles which are to be
removed, and the filter will work efficiently only after an initial deposit has been trapped in the
medium.
A * P * b
Aim : To determine the Specific cake resistance (α) and medium resistance (R) R 
Experimental Procedure:

1. Prepare slurry of CaCO3 in water (5%).Filter the prepared solution and feed it in the feed
tank.
Open slightly the by pass valve for recycling/mixing. Switch on the agitator of the feed tank.
2. Fix the plate and frames on the press. Keep the canvas cloth on the frames and tighten it
2 * A 2 * P * a
3. Connect the outlet of the filter press to the filtrate tank. 
 *c
4. Start the pump and allow feed to enter the press.
5. Record the Inlet slurry pressure, Pi and Outlet slurry pressure, Po .
6. Collect the filtrate in the receiver. Record the amount of filtrate collected v in time t.
7. Run the filtration till there is appreciable fall in rate of filtrate collection.
a=slope of the graph (t/v vs v); ∆p=pressulre drop; A= total filtration area;
µ=Viscosity of the filtrate; C= concentration of the slurry; b=intercept of the graph (t/v vs v)
Plate and frame filter press
Double Effect Evaporator
Adsorption in
Packed bed
• Plotting the breakthrough curve of adsorption

for a given system & Calculation of Length of unused bed
• One of the well known operations for solid liquid contacting is
adsorption. The colored material can be removed by contacting
the liquid solutions with activated carbon (colored substances are
retained on the surface of the solid carbon).
• In adsorption the molecules distribute themselves between two
phases, one of which is a solid whilst the other can be the liquid
or gas. At intervals, the adsorbent has to be removed from the
process and regenerated, that is, restored to its original condition.
• Activated Charcoal , KMNO4 solution, colorimetry, optical density
Adsorption in
Packed bed
Cement is made by heating
limestone (calcium
carbonate) with small
CEMENT
quantities of other
materials (such as clay) to
1450 °C in a kiln, in a
process known as
calcination, whereby a
molecule of carbon dioxide
is liberated from the
calcium carbonate to form
calcium oxide, or quicklime,
which is then blended with
the other materials that
have been included in the
mix. The resulting hard
substance, called 'clinker', is
then ground with a small
amount of gypsum into a
powder to make 'Ordinary
Portland Cement', the most
commonly used type of
cement (often referred to as
OPC).
By definition —
a hydraulic cement produced
by pulverizing clinker
consisting essentially of
hydraulic calcium silicates,
usually containing one or
more of the forms of calcium
sulfate as an interground
addition
Source: PCA, 2003

Calcium Iron Silica Alumina Sulfate
Alkali waste Blast-furnace Calcium silicate Aluminum-ore Anhydrite
Aragonite flue dust Cement rock refuse Calcium
Calcite Clay Clay Bauxite sulfate
Cement-kiln Iron ore Fly ash Cement rock Gypsum
dust Mill scale Fuller’s earth Clay
Cement rock Ore washings Limestone Copper slag
Chalk Pyrite cinders Loess Fly ash
Clay Shale Marl Fuller’s earth
Fuller’s earth Ore washings Granodiorite
Limestone Quartzite Limestone
Marble Rice-hull ash Loess
Marl Sand Ore washings
Seashells Sandstone Shale
Shale Shale Slag
Slag Slag Staurolite
Traprock
Source: PCA, 2003

Traditional Manufacture of Portland
Cement
1. Stone is first reduced to 125 mm (5 in.)

Source: PCA, 2003
size, then to 20 mm (3/4 in.), and stored.
-5- 10 hour shifts
-Haul trucks
- 2 – 796C cat
- 1 – 35R Euclid
988 Cat Loaders
Natural Cement Rock

- Two Benches
- No Blasting only Ripping
2. Raw materials are ground to powder and blended.
3. Burning changes raw mix chemically into cement clinker.

3. Burning changes raw mix chemically into clinker. Note
four stage preheater, flash furnaces, and shorter kiln.
Source: PCA, 2003

C4AF
Source: Mindess, Young, and Darwin, 2004

Pyro- Processing
four stage preheater, flash
furnaces, and shorter kiln
•Modernized in 1999 by HBZ and

Fuller
•1500 tpd to 2000 tpd
•Fuel Consumption decreased by
15%
•Modern – State of the Art Preheater
Kiln –2,000 stpd
/ Precalciner System with down draft
calciner/ & DeSox
12’ x 165’
3.1 RPM
Source: PCA, 2003
4. Clinker is ground with gypsum into portland cement and
shipped.
Source: PCA, 2003

Clinker Gypsum
clinker is formed by burning calcium and siliceous raw materials in a kiln, it is about 20
mm in diameter. Gypsum, a source of sulfate, is interground with portland clinker to
form portland cement. It helps control setting, drying , shrinkage properties, and
strength development.
Source: PCA, 2003

Grinding
• Clinker is ground with gypsum
(calcium sulfate) to produce
portland cement
• Fine grinding is necessary for
high early strength
– 85-95% -325 mesh (45
microns)
– ~ 7 trillion particles per
pound
• Gypsum absorbs water and
prevents setting of C3A during
shipment
Source: van Oss and Padovani, 2002
Process of Clinker Production
Source: PCA, 2003

Source: PCA, 2003
Belite or 2CaO• SiO2 or C2S
Alite or 3CaO•SiO2 or C3S Alite Crystals
Aluminate or 3CaO• Al2O3 or C3A
Ferrite or 4CaO• Al2O3 • Fe2O3 or C4AF
Source: PCA, 2003

Source: Taylor, 1997
Clinker Phases
• Alite or 3CaO•SiO2 or C3S
– Hydrates & hardens quickly
– High early strength
– Higher heat of hydration (setting)
• Belite or 2CaO• SiO2 or C2S

– Hydrates & hardens slower than alite
– Gives off less heat
– High late strength (> 7 days)
• Modern cements are

manufactured to be higher in alite
for early strength
Clinker Phases
• Aluminate or 3CaO• Al2O3 or
C 3A
resistance
– Very high heat of hydration

5. High
sulfate
– Some contribution to early

strength
– Low C3A for sulfate resistance
• Ferrite or 4CaO• Al2O3 • Fe2O3 or

C4AF
– Little contribution to strength
– Lowers clinkering temperature
– Controls the color of cement
Microscopic Images of Clinker
Alite
Belite
Aluminate
Ferrite
Types of Portland Cement
ASTM C 150 (AASHTO M 85)
I Normal
II Moderate sulfate resistance
III High early strength
IV Low heat of hydration
Overview of Cement Manufacturing Process by Dalmia

http://www.youtube.com/watch?v=BDckapx5hTM
Calcium Sulfoaluminate (CSA) Cement Gypsum (CSH2)

Thickener
Silica, mica, Talc
Limestone Beneficiation (reducing the % of

Silica, Iron content)

Portland Cement
Manufacturing
1-3 hrs, 3-10 mm size

Sulphuric Acid
M.P = 10.5 OC, B.P = 340 OC
Contact Process: yields 98 % sulphuric acid
S (solid) + oxygen SO2 (gas)…..-70.9 Kcal

SO2 (gas) + 0.5 O2 (gas) SO3 (gas) …-23 Kcal
- S can come from…….Sulphur; Iron Pyrites (FeS2); CuS, ZnS, PbS; 2
- Combustion yields very pure SO2 which requires only filtration, drying
- Iron Pyrites containing 40-45 % S are roasted, dust removed, cooling,

Scrubbing, filtering, drying by conc. acid scrubbing to remove dust,
moisture, catalyst poisons
S contains Arsenic and attack
catalyst. It can be removed
- Vanadium pentoxide, porous carrier by contacting with milk of
- Multistage catalytic converter lime in autoclave

Sulphur melting point = 112.8 OC; Boiling point = 444.6 OC; S.G = 2
Soluble in organic solvents/liquid ammonia
Oleum = H2SO4 + SO3
Sulphuric acid is used majorly in Phosphate fertilisers
Hindustan Copper and Hindustan Zinc produce S from smelter gases from
copper and zinc smelters respectively…Bihar, Rajasthan
Kashmir, recovery of elemental Sulphur from petroleum refineries,
Elemental Sulphur from Pyrites::
Thermal Dissociation = FeS2 ----0.5 S2 (gas) +FeS (liquid) (1300 OC, +16 Kcal)
Roasting of FeS (Pyrrhotite) for SO2 recovery

2FeS + 3.5 O2 ….Fe2O3 + 2SO2 (1000 OC, -295 Kcal).
General combustion reaction =

C+H+S+O2 ……SO2, H2S, CO, H2CO2, H2O

Contact Process: Sulfuric acid manufacturing
• https://www.youtube.com/watch?v=BkdjR5DZBl0
•
https://www.youtube.com/watch?v=w11F74O2uV8
150 OC
Ziegler-Natta Process HDPE/PP
https://www.youtube.com/watch?v=cVXy8sAregg
https://www.youtube.com/watch?
v=DEEjNQN2dIQ

Nitrogen
Occurrence
• most abundant element in the atmosphere (N2)
• very low abundance in Earth’s crustal rocks
Recovery
• by fractional distillation of air
Industrial Uses
• fertilizers (nitrates, ammonia, ammonium salts, and urea)
• propellants and explosives (nitro-organics, nitrates, hydrazines)
Most Important Industrial Reaction

• the Haber process for the production of ammonia (NH3)
Mixed Fertilizer N-P-K:
: 5-10-5 is 5wt % Nitrogen; 10 wt% available P2O5; 5 wt% K2O
Continual cropping, heavy monsoon (leaching)
Muriate of potash (KCl), Sulphate of Potash; insoluble potash bearing silicates and
highly soluble KCl; sea water deposits, ashes from the burning of wood/plant waste;
UREA: NH2 . CO . NH2 ; melts at 132 OC ; Soluble in water; 46 % N; granules

coated with non-hygroscopic dust such as Phosphate rock or lime stone
Liquid – mixtures of urea in NH3 solution (45 % total N; 30 % free NH3; 15 % as

Urea)
Slow release (low MW Urea formaldehyde..)
Urea-ammonium nitrate solution; Urea is replacing highly acidic ammonium salts..
Melamine is synthesized by condensation of urea molecules. Melamine-

formaldehyde and Phenol-formaldehyde are thermoset resins….FORMICA

2 hrs
2 seconds
Manufacturing of UREA from Ammonium Cabamate
Manufacturing of AMMONIA NITRATE
Ammonium Nitrate (NH4NO3) is in the first place a nitrogenous fertilizer

representing more than 10% of the total nitrogen consumption worldwide. Due to
its powerful oxidizing properties it is used as commercial explosive (Amatol is a
mixture of TNT and granular ammonium nitrate)…decomposes to N2, H20, O2
It is applied as a straight material or in combination with calcium carbonate,

limestone, or dolomite. The combination is called calcium ammonium nitrate (CAN)
or ammonium nitrate-limestone (ANL)
The nitrogen in ammonium nitrate is more rapidly available to some crops (not rice
paddy) than urea or ammonium sulfate; most crops take up nitrogen mainly in
nitrate form; thus, ammoniacal nitrogen must be converted to nitrate in the soil
before it becomes effective.
Ammonium nitrate is a white crystalline substance with a nitrogen content of 35%

and a density of about 1.725 kg/m3 and M.P of 170 OC and decomposes >200 OC.
The melting points depend on the content of the water, and it is practically
impossible to obtain dry product in the industrial conditions.

Kieselguhr, a diatomaceous earth (diatomite) is a form of silica composed of the
siliceous shells of unicellular aquatic plants of microscopic size. Kieselguhr is heat
resistant and used here to avoid explosions.
Prilling tower can be replaced by centrifugal oil-quenching process.
Prilling Process:
Stengel process: Vapour phase reaction in SS reactor (304, ELC)
Nitrolime is recommended, because AN has too high leaching rate on soil

application
Conditioned air…free of oil and other combustibles
Byproduct from coke ovens of the steel plant

70 mt
1.5 mm
75 %, 140 OC
75 OC, SS(ELC); 160 OC, Ta
Fluidized bed, 0.6 % H2O
Stengel process
Manufacturing of AMMONIA NITRATE and NITROLIME

What do you mean by mixed fertilizer and why they are promoted compare to
mono-fertilizers? (4)
ANSWER: N-P-K fertilizers, generally in the form of granular soilds are called
mixed fertilizers. The composition is expressed as wt % of total N, available
P2O5, and soluble K2O. Growing plants in various areas have widely differing
requirements of N, P and K depending on the nature of the plant, the
composition of the soil, the physical type of soil and irrigation of the soil. These
requirements can be fulfilled by mixed fertilizers in which N is known for
development of stems and leaves, P is known for accelerating the seeding
or fruit formation and K is known for development of sugars of fruits and
fibrous materials of the plants. Heavy monsoon rains causes rapid leaching of
N, P, K elements, so mixed fertilizers need to applied to soil regularly depending
on the soil condition.

Phosphorous
- Fluorapatite Ca 10 (PO4)6 F2= Phosphate rocks are essentially fluorapatite

- Silica
Yellow phosphorous P4 44.1 OC 280 OC 1.82
Red Phosphorous…P4…… 593 OC 2.36 formed by

heating yellow grade to get the stable grade (oxidation resistance)
Phosporic acid
Ammonium phosphate, calcium phosphate, Nitrophospate: Fertilizers

High grade rock with >30 % P2O5 is used for superphosphate manufacture
b. Write the relation between P2O5 and BPL and what do you mean by << beneficiation>> ? After
production which phosphorus is stored in water and why? (3)
ANSWER: Phosphorous content of rock phosphate is expressed as percentage P2O5. In trade it is

expressed as Bone Phosphate of Lime (BPL) having the chemical formula Ca3(PO4)2.
1 % BPL = 0.458 % P2O5. Beneficiation of phosphate rock is carried out to increase the available P2O5
content in the rock. Yellow Phosphorous, because it ignites spontaneously in air.

100 to 150 cm diameter carbon electrode
Slight vacuum
2 Ca3 (PO4)2 + 10 C+6 SiO2 -----P4 (yellow grade) + 6 CaSiO3 + 10 CO

P4+10CO+10O2 ……2P2O5+10CO2
P2O5+xH2O….2H3PO4 + x-3 (H2O)
Q.8: Write the reaction and description of making H3PO4 by strong sulfuric acid leaching process
(5)
ANSWER: 42.4 OC
Ca3(PO4)2 + 3 H2SO4+6 H20 2 H3PO4 + 3 (CaSO4.2H20)..gypsum 213 OC (loses
water of
Side reactions:
hydration)
CaF2 + H2SO4 + 2 H20 2HF+ CaSO4.2H20 1.83
6 HF+ SiO2 H2SiF6 + 2H20
 Beneficiated phosphate rock (32% P2O5) and Sulfuric acid from the contact process is used as raw
materials
 200 mesh size rocks are pumped to the reaction tank using weak H3PO4 recycle stream where sulfuric
acid is also pumped using automatic control devices which maintains the acid and rock feed ratio
 A single reactor or a series of reactors are used to permit 98 % conversion in 4-6 hrs
 Gypsum-phosphoric acid slurry goes to a travelling pan vacuum filter where the 40 % acid is removed
and cake is washed with water
 The 2-inch gypsum cake is can be dried to use in plaster, paints, cements and fertilsiers
 The dilute acid is concentrated in a single effect evaporator to grades >50% acid.

Ammonium Phosphates Manufacturing
NH3+H3PO4 NH4H2PO4 (Monoammonium Phosphate) exothermic, BP 130 OC
NH3+ NH4H2PO4 (NH4)2HPO4 (Diammonium Phiosphate)
Melting points: Decomposes Quick dissolving

Density: 1.8 for mono..which is higher than di...(1.62) fertilizer, fire
retarding agent
NH3+H2SO4 NH4HSO4 for wood/paper
NH3+ NH4HSO4 (NH4)2SO4
NH3 loss should be minimised ..3% Nutralisation and granulation...
First reactor: 80 % neutralisation....2nd and 3rd reactors to obtain Diammonium salts if

higher N fertiliser is needed..
Slurry from the 3rd neutralizer is mixed with KCl and absorbed in a bed of dry recycle
fertiliser.. Tumbling action to coat recycle material with a slurry film
Lower screen: 6-12 is sent for bagging;;;;;Weight ratio of recycle to product: 6: 1-1.5
<1 % MC, 10 mint
SS316 for hot acid/fume ducts; carbon steel

b. Write the two principal steps involved in making DAP (Diammonium Phosphate) from NH3. How much
is the final moisture content of DAP and which ammonium phosphate is used in dental applications? (4)
ANSWER: Neutralisation and granulation (alternate answer could be reaction between ammonia and
phosphoric acid and ammonia and monoammonium phosphate). Final moisture content will be less than
1 %. Monoammonium Phosphate is used in Dental applications.
c. Write the chemical reactions involved in making Triple superphosphate? (2)
ANSWER: [Ca3(PO4)2]3. CaF2 + 14 H3PO4 10 CaH4(PO4)2+2HF
Phosphate rock Phosphoric acid triple superphosphate

Phosphate rock used for Superphosphate production: 16-20 % P2O5
Sulfuric acid
Phosphate rock used for Triple superphosphate production: 40-50 % P2O5

Phosphoric acid
In India only superphosphate are produced until 1960.
Continious blender:

Pulp-Paper making
• Cotton paper is made from cotton linters or
cotton from used cloths (rags) as the primary
material source, hence the name rag paper.
Cotton paper is superior in both strength and
durability to wood pulp-based paper, which
may contain high concentrations of acids.

Stem
Sapwood
Macroanatomy
and Anatomical
Heartwood
Directions
Radial
Tangential
Lignin and cellulose

Wood con…
Cell wall is considered as Fibre
reinforced Composite
Fibre: Cellulose microfibrils.
Matrix: Lignin-hemicellulose
Deviation angle of the microfibrils to
the cell axis ins known as Micro Fibril
Angle (MFA). The fibrils give the fiber
its elastic modulus and tensile strength
in the axial direction
Cell wall
properties
Normal wood Compression wood

Lumen
Cell wall Courtesy: Dr. Herbert Sxita (Pulp Chemistry) and Dr. Ingo
Burgert (Holzforschung)
102
Wood con…
Cell wall consists of

50% cellulose (hydrophilic)
25% hemicellulose (hydrophilic) l=2-4 mm
25% lignin (hydrophobic).
d=30-40 µm
20 µm
Refining, dr
Softwood Hardwood
50 µm
Cooking Kraft or Chemical (68%) cooking uses NaOH

and Na2S and removes the lignin. Bleaching
103
Mechanical properties of wood fibres: FIB and Microcompression
Cell wall
Cell wall
Cell wall 3 µm
Top surface gold Lumen

Lumen
coated
Top view Side view

1000 µm 10 µm
30 KeV, 3500 pA – rough milling

30 KeV, 75 pA – fine polishing
104
Common Hardwood Cell Types
Overview - Softwood Cells
• Rays - generally uniseriate
• Resin canals - only in 4 genera
• Longitudinal Tracheids
– dominant cell (90-95% of wood volume)
– elongated 75-100 times their diameter (note picture)
– relatively uniform radial arrangement
– denser latewood from smaller radial diameter (flattening of
the cell) and thicker wall
– Pinus
– Picea
– Larix
– Pseudotsuga
Chemical Composition of Wood
% of Dry Weight
Primary components:
Wood Type Cellulose HemiCellulose Lignin

Hardwood 40-44 15-35 18-25
Softwood 40-44 20-32 25-35
Secondary components:
Minor Constituents:
Pectins and Starch: ~6%
Extractives: ~1-40%, typically 5%
Inorganics: 0.1-0.5%, Ca, K, Mg, Si
Debarking by tumbling and rubbing
In all cases where eucalyptus is debarked in a debarking drum, the bark is removed
from the log surface in the first 8-12 m of the drum length. These studies clearly show
that, as far as the pure debarking process is concerned, the remainder of the drum
length, the final 15-25 m, are unnecessary and cause wood breakage and
unreasonably high wood losses.
The drum shell has an

essential amount of
longitudinal holes (bark slots)
through which the loose bark
should come out of the drum.
In other words, the barking
drum is a combination of a
debarker and a bark
separation unit.
108
Steam
Deaerator-preheater, 30 mt tall digestion tower, minimum

cellulose hydrolysis, Hydrogen peroxide
Preparation of Wood pulp by Sulfate Process
2017A1PS0884H .,MANYAM VINEETH
2016A1PS0442H .,SHOEB AHMED KHAN 7.5 2017A1PS0915H .,SAI SRI HARSHA INDURTI 7.0
2016A1PS0481H .,JAY NANDLAL PANDIT 6.0 2017A1PS0953H .,PANICKER RAHUL RAKESH 5.5
2016A1PS0529H .,P RAGHUL 2017A1PS0963H .,CHIVUKULA KAUSHIK 9.5
2016A1PS0538H .,K SANJEEV RAJ 2017A1PS0964H .,KARAN GROVER
2016A1PS0625H .,ETI SINGH 7.5 2017A1PS1014H .,ARYAN MITTAL
2016A1PS0657H .,UDIT SINGH 2017A1PS1032H .,SANKEERTH REDDY ANUMANDLA 8.5
2016A1PS0659H .,SAKTHI GNANASUNDARAM S 2017A1PS1037H .,ISHITA KUKRETI
2016A1PS0708H .,THOLE DARPAN NARESH 2017A1PS1038H .,MISBAHUL HAQUE 3.0
2016A1PS0924H .,CHEMBETI KAVAL SAI ABHILASH 2017A1PS1042H .,KAMATH KRUTARTH KIRAN 7.5
2016A1PS0930H .,SHRISTI TRIPATHI 2017A1PS1059H .,SUMAYYA KHAN 5.5
2016A1PS0963H .,RAHUL SHARMA 2017A1PS1068H .,SHASHWAT PREM

2017A1PS1072H .,AAKASH DWIVEDI
2016A1TS0629H .,PRANAV RAJ 8.5
2017A1PS1100H .,DHARESH VATSA 5.0
2016A1TS0660H .,SIDDHARTH SINGH TOMAR
2017A1PS1106H .,P ARYAN
2016B1A10671H VENKATARAMA PUPPALA,NAVINCHANDRA
2017A1PS1118H .,POORNIMA SUMAJA V 6.0
2016B1A10717H .,YASHVARDHAN SHUKLA
2017A1PS1136H .,HARISH S 8.5
2016B2A10623H .,VENKATA SRIRAM D
2017A1PS1200H REDDY SYAMALA,SAI PRASANTH 6.0
2016B2A10661H .,IYER AMADHYA AMUTHAN 5.0
2017A1PS1307H .,SUHANI GUPTA 6.5
2016B3A10374H .,CHEEMALAMARRY SAI KARTHIK 6.0
2017A1PS1432H .,BIBIN TONY
2016B3A10455H .,SAKSHAM SHARMA 5.5
2017A1PS1481H .,PANICKER SURAJ RAKESH 5.5
2016B4A10501H .,MRINAL JHA
2017A1PS1605H .,PRIYANKA GOYAL 9.0
2016B4A10513H .,THANGELLA RAHUL RAJU 2017A1PS1649H .,HARSHAL DILEEP MAHAJAN
2016B5A10604H .,HIMANSHU ACHRA 2017A1PS1652H .,SIDDHI SATNALIKA
2017A1PS0696H .,BISHMAYA RANJAN SWAIN 2019PHXPO407H Dasika Prabhat 8.0
2017A1PS0801H .,SATCHIT NAGPAL 2016A1B10664H .,KRITIKA KASLIWAL 7.0
2017A1PS0831H .,DWAIPAYAN BHATTACHARYYA 8.0 2017A1PS1054H .,GAURI CHATURVEDI 5.0
2017A1PS0848H .,AYUSHI NIGAM 2017A1PS0991H .,RAKSHIT KHANDELWAL 6.5
2017A1PS0850H .,TANISHQ THAKUR 2017A1PS1357H .,JAIN SHUBHAM VINOD 6.0
2017A1PS0871H .,PERURI NIKHIL Avg= 6.6
2017A1PS0883H .,VASA MAUREEN SHAMA 6.5 Max= 9.5
2017A1PS0884H .,MANYAM VINEETH Min= 3.0

Seminar Topics as on 13.02.20
2017A1PS0831H DWAIPAYAN BHATTACHARYYA 16 13 81.25
2017A1PS1481H PANICKER SURAJ RAKESH 16 13 81.25
2016A1TS0629H PRANAV RAJ 16 13 81.25
2017A1PS0953H PANICKER RAHUL RAKESH 16 12 75
2017A1PS1605H PRIYANKA GOYAL 16 12 75
2017A1PS1032H SANKEERTH REDDY ANUMANDLA 16 12 75
2017A1PS0883H VASA MAUREEN SHAMA 16 12 75
2016B3A10374H CHEEMALAMARRY SAI KARTHIK 16 11 68.75
2017A1PS0963H CHIVUKULA KAUSHIK 16 11 68.75
2017A1PS1100H DHARESH VATSA 16 11 68.75
2017A1PS1136H HARISH S 16 10 62.5
2016A1B10664H KRITIKA KASLIWAL 16 10 62.5
2017A1PS1200H SAI PRASANTH REDDY SYAMALA 16 10 62.5
2017A1PS1059H SUMAYYA KHAN 16 10 62.5
2017A1PS0915H SAI SRI HARSHA INDURTI 16 9 56.25
2016A1PS0442H SHOEB AHMED KHAN 16 9 56.25
2016A1PS0538H K SANJEEV RAJ 16 8 50
2017A1PS1307H SUHANI GUPTA 16 8 50

• Baggase – Dirt and pith (thin walled, short cells); – fibres are stronger than pith material.
• Chemical pulping- digestion time is very low- fibres are loosened- penetration is very easy
• For each 10 tonnes of sugarcane crushed, a sugar factory produces nearly 3 tonnes of wet bagasse.
• The high moisture content of bagasse, typically 40 to 50%, is detrimental to its use as a fuel. In
general, bagasse is stored prior to further processing. For electricity production, it is stored under
moist conditions, and the mild exothermic reaction that results from the degradation of residual
sugars dries the bagasse pile slightly. For paper and pulp production, it is normally stored wet in order
to assist in removal of the short pith fibres, which impede the papermaking process.
• A typical chemical analysis of bagasse might be (on a washed and dried basis):
Cellulose 45–55%; Hemicellulose 20–25%; Lignin 18–24%; Ash 1–4%; Waxes <1%
• Bagasse is an extremely inhomogeneous material comprising around 30-40% of "pith" fibre, which is
derived from the core of the plant and is mainly parenchyma material, and "bast", "rind", or "stem"
fibre, which comprises the balance and is largely derived from sclerenchyma material. These
properties make bagasse particularly problematic for paper manufacture and have been the subject of
a large body of literature.

Table 1 Characterization of whole and depithed bagasse (prior to cooking)
Water Water Ash

Sample Lignin Retention Absorption (%)
(%) Value - WRV Capacity
(%)
Whole bagasse 26.7±0.1 4.52±0.39 0.56±0.15 0.85±0.35
Depithed bagasse 26.9±0.3 1.91±0.26 1.19±1.32 1.17±1.05

Table 2 Characterization of whole and depithed bagasse pulps (after cooking)
Sample Cooking Yield Residual Cellulose Water Water Ash /

Temperature (%) Lignin Content Retention Absorption Inorganic
(oC) (%) (%) Value - Capacity Content
WRV (%) (%)
140 34 1.66± 0.04 57.94±2.7 4.39±0.13 1.29±0.14 2.87±0.38
Whole
Bagasse
165 31 1.53±0.02 69.41±0.9 4.72±0.12 1.78±0.16 4.52±0.38
pulp
140 32 1.48±0.03 67.72±1.1 5.52±0.18 2.41±0.26 1.38±0.35
Depithed
Bagasse
165 30 1.08±0.04 75.42±1.7 6.44±0.17 4.31±0.33 1.75±0.07
pulp
Table 3 Mechanical properties of bagasse handsheets made from unbleached pulp
Bagasse Cooking Tensile Tensile Tensile Tensile Erichsen

handsheet Temperature strength strength index strain modulus cupping
(N/mm2) (Nm/g) (%) (KN/mm2) test depth
(oC)
(mm)
140 34.1+7.4 10.63+2.7 1.1+0.30 4.09+0.03 4.00

Depithed
bagasse 165 20.4+1.3 7.95+0.5 1.0+0.33 3.10+0.02 3.65
Whole 140 46.7+5.7 7.21+1.4 1.4+0.27 4.61+0.02 5.00
bagasse
165 63.6+10 13.77+1.6 1.9+0.28 4.96+0.03 4.45
Pulp
1800 Oscillation
Cooking @ 1400C &
1650C for 1hr
Black liquor
Fig 2 . Rotary Pulp Digester equipment for kraft cooking of Pithed (Whole) & Depithed bagass
at two different temperatures,140 and 1650C
Whole
Whole Bagassse Whole Bagasse
Fig.1 Images of bagasse samples before kraft cooking (a) and after kraft cooking
(b, c)
Fig 6: Optical images of bagasse revealing bark, pith and fibers
(a) (b)
um
m
h 290
777 u
t
Leng
th
Leng
200 um 100 um
Bark Fibers Pith Fibers Pith
Fig 4 Stereomicroscopy images of bagasse revealing bark, pith and fibers (prior
to cooking). a: Depithed bagasse; b: Whole Bagasse
(a) (b)
Fig. 2 Sample residues after the ash test. (a) Whole bagasse (Ash content
is 0.85 %) and (b) Whole bagasse pulp @165 oC (Ash content is 4.5 %)
(a) (b)
100 µm 100 µm
(c) (d)
Pith cells forming a
glue like structure
100 µm 100 µm
Fig 3 Stereomicroscopy images of bagasse pulp fibers. fiber diameter of 11 -22 µm and vessel
diameter of 40, 50, 80 and parenchyma cell diameter of 140 µm are visible. a: Depithed
bagasse pulp @140 oC; b: Whole bagasse pulp @140 oC; c: Depithed bagasse pulp @165 oC;
d: Whole bagasse pulp @165 oC
@ 140 oC
------ @165 oC @ 140 oC
------ @165 oC
whole depithed
bagasse bagasse
pulp pulp
a Temperature (oC) b Temperature (oC)
Fig 5. Thermogravimetric analysis of (a) whole bagasse pulp and (b) depithed bagasse pulp.
Note the thermal stability of whole bagasse pulp @165 oC (45 wt % remaining at 350 oC).
Whole bagasse pulp @140 oC, 1hr Whole bagasse Pulp @165 oC, 1hr
Before After
After
Before
500 um 500 um
100 um 100 um
Fig 6. Microscopic images of whole bagasse pulp before Thermogravimetric

analysis (TGA) test and pulp reside after TGA test.
oC
165
oC
140
oC
Stress (N/mm2 X 10)

140
oC
165 Whole bagasse
Depithed bagasse
Strain
Fig 8: Tensile stress-strain plots of handsheets made from unbleached bagasse pulp. Note
the strain ranging from 0.8 % to 2 % and strength ranging from 20 N/mm 2 to 60 N/mm2
(a) (b) (c) (d)
depithed bagasse pulp whole bagasse pulp depithed bagasse pulp whole bagasse pulp
Fig. 9. Microscopic images of tensile fractured handsheets made from unbleached bagasse
pulp. Note the angle of fracture -20o, +20o, 0o, +20o from left to right respectively. a:
Depithed bagasse pulp @140 oC; b: Whole bagasse pulp @140 oC; c: Depithed bagasse
pulp @165 oC; d: Whole bagasse pulp @165 oC. Angles between +15 to +45o indicates
strong bonding between fibres.
Fig 10: Optical images of Tensile tested handsheets from bagasse pulp
Fig 12 : Optical images of handsheets after Burst strength testing
6
5
@1400C
4 @1650C
Depth (mm)
@1400C
3 @1650C
0
Pithed bagasse Depithed Bagasse
Fig 11: Burst strength of bagasse handsheets

Depithed Bagasse 140oC 0.5 h
Depithed Bagasse 165oC 0.5 h
Depithed Bagasse 140oC 1 h
Depithed Bagasse 165oC 1 h
Fig. 10 UV-Visible spectroscopic analysis of depithed bagasse black liquor collected

from digester at 0.5 h and 1 h of cooking.
Paper making process (Schematic drawing)

Black liquor separation
131
Basics of the Kraft Recovery System II
132
Black Liquor The combined liquids, known as black liquor
(so called because of its color), contain lignin
fragments, carbohydrates from the breakdown
of hemicellulose, sodium carbonate,
sodium sulfate and other inorganic salts.
Chips
NaOH Inorganics
Na2S Digester Pulp NaOH (7%)
Na2S (19%)
Na2CO3 (36%)
Black Liquor Na2SO3 (9%)
Na2SO4 (13%)
14-18% Solids
pH 12+ Na2S2O3 (16%)
65% Organics
35% Inorganics
133
Basics of the Kraft Recovery System
Cooking
The object of this system is to Pulp
&
Chips
Washing
regenerate the cooking
chemicals and to generate
heat = steam & power. BLACK LIQUOR
WHITE LIQUOR
Alkali Lignin
Hydrolysis Salts NaOH
Sulfonation Products Na2S
Ca(OH)2 + Na2CO3  CaCO3 + 2 NaOH
Evaporation GREEN LIQUOR

& Na2CO3 Causticizing
Burning Na2S
Heat Water
CaCO3
Makeup Chemicals CaO
134
Chemical recovery from sulfate pulp digestion liquor
Black liquor
Green liquor
Ca(OH)2 + Na2CO3  CaCO3 + 2 NaOH White liquor

• In order to burn the black liquor, the solids content needs to be
raised to over 60%.
– This means that over 80% of the water needs to be removed.
• This is accomplished through the use of multiple effect evaporators.
• Evaporation is accomplished through:

– Direct contact with flue gasses (old)
– Indirect contact with steam
• Falling film (new)
• Raising film (old)
• With indirect contact, steam is applied countercurrent to the
liquor (high temperature/pressure steam is applied to thickest liquor).
The steam produced from the liquor is used to heat the next
effect (evaporator) at a lower temperature and pressure.
This continues to the first effect (most dilute liquor) which is
run under vacuum.
136
Evaporation III
Thick black liquor
lower temperature and pressure.
137
Reduction of Inorganics
• Formation of sodium carbonate (Na2CO3)

– Combustion of organics results in the formation of CO2 and
CO. Sodium compounds are converted into Na2O.
– Na2O + CO2  Na2CO3
– Na2S + H2O + CO2  Na2CO3 + H2S
• Reductive reactions in the char results in the
formation of sodium sulfide (Na2S)
– Na2SO4 + 2C  Na2S + 2CO2
– Na2SO4 + 4C  Na2S + 4CO
138
Recovery Furnace
• Concentrated black liquor is burned in a recovery
furnace. The functions of the recovery furnace
are:
– Remove remaining water from black liquor.
– Burn the black liquor organic compounds
• Solves disposal issues.
• Produces steam (for heating and energy).
– Reduce sulfur species to sulfide.
– Generate Na2CO3 which will later be converted to NaOH
Ca(OH)2 + Na2CO3  CaCO3 + 2 NaOH
139
Recovery Furnace III
System for recovery
of heat to generate power
(A)
Combustion
Zone
Air (C)
Liquor
Air
(B) Reduction
Gasses from Pyrolysis Air
Zone
(D)
Smelt (molten Na2CO3, Na2S, etc)
140
Recovery Furnace IV
•Liquor is sprayed
to char bed (droplet size 2-
3mm)
•Particles should be
dry before landing
the char bed
•Char is required in
bed for effective
reduction of
sulfates
141
Smelt
• The molten inorganics at the bottom of the recovery

furnace are known as the smelt. This material at
1500°F leaves the furnace and is added to water in the
smelt tank.
– This results in the formation of green liquor
– This is also a dangerous operation. The extremely hot smelt
causes the water to instantly vaporize in a violent reaction.
– Green liquor composition: NaOH (8%), Na2S (20%), Na2CO3
(60%), Na2SO3 ( 3%), Na2SO4 (6%), Na2S2O3 (3%).
142
Caustizing
• Caustizing is the process in which sodium
carbonate is converted into sodium hydroxide.
• In the first step, green liquor is clarified to
remove insoluble materials.
– Calcium compounds
– Unburned carbon
– Metals
• Clarified green liquor is sent to a “slaker”
where lime (CaO/Ca(OH)2) is added .
143
Slaker (Causticizing) Chemistry
• Calcium carbonate (CaCO3) has extremely low solubility in

water while sodium carbonate (Na2CO3) has fairly high
solubility. When lime (CaO) is added to a Na2CO3 solution,
the following reaction occurs: (important to note that CaO + H2O
 Ca(OH)2 this is the slaking reaction).
– Ca(OH)2 + Na2CO3  CaCO3 + 2 NaOH
– The calcium carbonate precipitates out of solution driving the reaction
to the right side of the above equation thus forming sodium hydroxide.
– Calcium carbonate is removed through clarification forming white
liquor. This step completes the circle as the white liquor is returned to
the digester for pulping.
144
Lime Kiln
• The wet calcium carbonate slurry is treated in
a lime kiln.
– This is a very long, refractory brick lined, slightly
tilted, rotating tube which is extremely hot (1500
to 2100°F).
– The calcium carbonate slurry is dried in the first
section of the kiln and then the calcium carbonate
is converted to CaO: CaCO3 + heat  CaO + CO2
145
Black versus green liquor
146
Production of Lignin chemicals
• Methyl mercaptan, or methanethiol, is a colorless, flammable gas with a distinct
odor that smells like rotten eggs or cabbage. It is found in coal tar and petroleum
distillates and as an emission from paper and pulp mills.

Manufacturing of Dimethyl sulfide and Dimethyl sulfoxide from wood liquor
5 % DMS
45 %
solids

Grasim Joint ventures
Birla Jingwei Fibres Company Limited in China AV Cell and AV Nackawic in Canada
Currently, this plant has a capacity to produce AV Cell and AV Nackawic supply
viscose staple fibreFibre
of 30,000 tpa. The capacity dissolving grade pulp to the Group’s
is being increased to 70,000 tpa by May 2010 viscose staple fibre units in India,
along with a captive cogeneration power plant Thailand and Indonesia.
of 15 MW. Pulp
Owning a plantation, manufacturing of Birla Lao Pulp & Plantation Limited in Laos
rayon grade pulp, production of principal This will provide a low cost source for wood to
raw material namely, caustic soda, meet future requirements of a green field
intermediate inputs namely CS2, sulphuric Wood
pulp plant in due course of time.
acid along with captive power and steam
generation facilities, usage of by product
Na2SO4 in paper and pulp, detergent, Cellulose (I) Pulp – Cellulose (II) fibre
glass and textile industries indicates their production
dedication in this sector.
(C6H10O5)n + nNaOH → (C6H9O4ONa)n + nH2O (C6H9O4ONa)n + nCS2 → (C6H9O4O-SC-SNa)n
C6H9O4O-SC-SNa)n + ½nH2SO4 → (C6H10O5)n + nCS2 + ½nNa2SO4

Factfile: Aditya Birla group
The world's largest aluminium rolling company
 World leader in viscose staple fibre
 One of the three biggest producers of primary aluminium in Asia
 One of the leading cement producers in India and the ninth-largest globally
 Fourth-largest producer of carbon black in the world
 Fourth-largest producer of insulators in the world
 World's fifth-largest producer of acrylic fibre
Group companies (India)

Nagda – viscose staple fibre - M.P
:: Grasim Industries Ltd. Harihar – viscose staple fibre , rayon grade pulp - Karnataka
Kharach – viscose staple fibre - Gujarat
:: Hindalco Industries Ltd.
Veraval – viscose filament yarn - Gujarat
:: Aditya Birla Nuvo Ltd.
Viscose Staple fibre: A man-made cellulose fibre, which is
:: UltraTech Cement Ltd. biodegradable and having charactristics akin to cotton.
WOOD – PULP – LYOCELL FIBRE
Pulping Regeneration
Raw Cellulose (I) - Regenerated Cellulose (II)

Unpurified - Purifed
Mechanical properties of
Kraft pulping uses NaOH
and Na2S - Lignin is
removed from
Cellulose (I) >> Cellulose (II)
Middlelamella & Cell wall
Mechanical pulping
involves metal disks
which grinds the wood -
Lignin is removed from
Middlelamella only
(more yield-less quality)
BIRLA Cellulose / Lenzing Lyocell
11/03/2015 ABSTC Mumbai 151

WOOD – BIOCOMPOSITE MATERIAL
Cell wall
250
~ 5 MPa
200 Lumen
Stress (MPa)
150
Top view 10~ 100

µmMPa
100
50 COMPRE 45°
SSION
0
0 0.05 0.1 0.15 0.2 0.25 0.3
Strain
TENSILE
Normal Compression
wood wood
11/03/2015 ABSTC Mumbai 152
Grasim Research and Development
• Grasim Forest Research Institute, Harihar is involved in R&D of forestry.
• Birla Research Institute for Applied Sciences (BRI), Nagda is involved in the
development of different generations of cellulosic fibres.
• Textile Research Application Development Centre (TRADC) at Kharach, a NABL

accredited Lab, is involved in addressing research and development related to
downstream textile value chain comprising various fibres, yarns, processing,
garments, etc.
 high performance viscose fibres aptly named Viscose Plus,

 High Wet Modulus Fibres (Modal)
 new generation Solvent Spun Fibres
 Birla Excel.
http://www.birlacellulose.com
• http://www.youtube.com/watch?v=qpy_uZyV
7L0
• http://www.youtube.com/watch?
v=JWRQSuYruB8&feature=fvsr

Vegetable Oils
• Vegetable fats and oils are lipid materials derived from plants. Physically, oils are liquid
at room temperature, and fats are solid. Chemically, both fats and oils are composed of
triglycerides, as contrasted with waxes which lack glycerin in their structure. Although
many different parts of plants may yield oil, in commercial practice, oil is extracted
primarily from seeds.
• Wax: mixed esters of polyhydric alcohols other than glycerin
• Per capita consumption of edible oils and derivatives: 7.5 Kg/ year. (worldwide: 15.5)
• India: 11% of the total land is used for oil production (after food grains)
• Application of Oils:
•Liquid oil: 57%
•Vanaspati (hydrogenated oil): 19% R1, R2, R3 are not
•Soaps and detergents: 10% neccesarily the same 155
•Cosmetics: 9%
•Paints: 2%
The doubly unsaturated linoleic acid
(14.2-17%).
The triply unsaturated α-linolenic acid
(51.9-55.2%),
The monounsaturated oleic acid (18.5-
22.6%),
09/11/2023 Chemical Process Technology
Example of an unsaturated fat triglyceride. Left part:
glycerol, right part from top to bottom: palmitic acid,
oleic acid, alpha-linolenic acid, chemical formula: C55H98O6
Triglycerides are formed by combining glycerol with three molecules of fatty acid.
The glycerol molecule has three hydroxyl (HO-) groups. Each fatty acid has a
carboxyl group (COOH). In triglycerides, the hydroxyl groups of the glycerol join the
carboxyl groups of the fatty acid to form ester bonds

12-14: Coconut oil,
16-18: Vegetable oil;
20-24: Fish oil;
• Even no of carbon atoms

• Stearic acid: saturated (non drying oil), Melting point: 69 OC, reactivity to oxygen: Nil
• Oliec (one DB, 14 OC) , linoleic (2 DB, -5 OC) and linolenic acids (3 DB, -11OC): unsaturated
(semi dry and dry oils); reactivity to oxygen: Extremely rapid
Vegetable Oils -2: Edible oils
Oil source World consumption
(million tons)
Palm - 41.31- The most widely produced tropical oil. Also used to make biofuel.
Soybean -41.28- Accounts for about half of worldwide edible oil production.
Rapeseed- 18.24- One of the most widely used cooking oils, Canola is a (trademarked)
variety (cultivar) of rapeseed.
Sunflower - 9.91- A common cooking oil, also used to make biodiesel.

Vegetable oil is synonym for
Peanut- 4.82- Mild-flavored cooking oil. edible oil?
Cottonseed -4.99- A major food oil, often used in industrial food processing
Palm kernel- 4.85- From the seed of the African palm tree
Coconut -3.48- Used in soaps and cooking
Olive -2.84 - Used in cooking, cosmetics, soaps and as a fuel for traditional oil lamps
Vegetable Oils -4:
Corn oil, one of the most common, and inexpensive cooking oils.
Grape seed oil, used in cooking and cosmetics

Hazelnut and other nut oils
Linseed oil, from flax seeds
Caster oil: from seeds
Rice bran oil, from rice grains
Safflower oil, a flavorless and colorless cooking oil.
Sesame oil, used as a cooking oil, and as a massage oil (India).

Animal source: Lard from Hog fat
Tallow from beef and mutton fat
Ocean source: Menhaden fish

Sperm whale
Cod fish

Vegetable Oils -3: Non-edible oils
CASTOR OIL
LINSEED OIL

The "modern" way of processing vegetable oil is by chemical extraction, using solvent
extracts, which produces higher yields and is quicker and less expensive. The most
common solvent is petroleum-derived hexane (69 OC). This technique is used for most of
the "newer" industrial oils such as soybean and corn oils. Other solvents are
Trichloroethylene (89 OC) and Propane.
Another way is physical extraction, which does not use solvent extracts. It is made the
"traditional" way using several different types of mechanical extraction. This method is
typically used to produce the more traditional oils (e.g., olive, coconut etc.), and it is
preferred by most "health-food" customers in the USA and in Europe. Expeller-pressed
extraction is one type, and there are two other types that are both oil presses: the screw
press and the ram press. Oil seed presses are commonly used in developing countries,
among people for whom other extraction methods would be prohibitively expensive. The
amount of oil extracted using these methods varies widely, as shown in the following table
for extracting mowrah butter in India:
Method Percentage extracted

Ghani 20-30%
Expellers 34-37%
Solvent 40-43%
“RBD” or Refined, Bleached & Deodorized
Precoat rotary
09/11/2023 Chemical Process Technology vacuum filters
162
Protein rich &exported
Screw Oil Press
Before the oil can be taken out of the oilseed, the seeds are first ground up into a paste. Next, those around up seeds a washed or purged with
a solvent (also known as a petroleum distillate) such as hexane, to release the fat in the seed.To remove that solvent from the oil, it is “flashed
off” through heat in a sealed chamber.

Cold pressed seed oils must be produced below 122˚ F (as is legally defined in
Europe) and should only apply to fully unrefined oils that are not heated later during
the refining process.

Ghee: 1-2 atm, 135-180
OC
Vanaspati: 2-3.5 atm,

120-160 OC (high MP)
5-15 kg of catalyst / ton

of oil
Steam to drive-off air
and water
Iodine number
Mildly exothermic

Hydrogenated vegetable oil
Vanaspati is also an Indian/South Asian slang for Vansaspati ghee,
a fully or partially hydrogenated vegetable cooking oil, often used
as a cheaper substitute for ghee. In India, vanaspati ghee is usually
made from palm oil. Hydrogenation is performed using a catalyst
known as "supported nickel catalyst", in reactors at low-medium
pressure (3-10 bar). Vanaspati ghee is an important source of
trans fats in India, and may contain up to 50% trans fats.[1]
http://www.youtube.com/watch?v=PC4DT4ier2Q&feature=related
Example of an unsaturated fat triglyceride. Left part:
glycerol, right part from top to bottom: palmitic acid,
oleic acid, alpha-linolenic acid, chemical formula: C55H98O6
Triglycerides are formed by combining glycerol with three molecules of fatty acid.
The glycerol molecule has three hydroxyl (HO-) groups. Each fatty acid has a
carboxyl group (COOH). In triglycerides, the hydroxyl groups of the glycerol join the
carboxyl groups of the fatty acid to form ester bonds

R

• Soaps are compounds of the type R.COO.M where
R.COO. is fatty acid radical representing oleic, stearic,
palmitic, etc. M is alkali element such as Na or K.
Soaps
• Process of formation is known as saponification
– Types of soaps:
• Sodium soap – ordinary hard soap
• Potassium soap – soft soap (shaving soaps are potassium
soaps of coconut and palm oils)
• Castile soap – sodium soap of olive oil
• Green soap – mixture of sodium and potassium linseed oil
• Transparent soap – contains sucrose
• Floating soap – contains air
• Calcium and magnesium soaps are very poorly water soluble
(hard water contains calcium and magnesium salts –these
insolubilize soaps)
Analytical methods to evaluate lipids
• Saponification number
• Iodine value (Hanus method)
• Free fatty acids
• Acetyl number
• Reichert-Meissl number
• HPLC/GC (for more precise analysis)
Saponification number
• gives some clue as to the average size of fatty
acids in a given sample of fat
• defined as the number of milligrams of KOH
needed to neutralize the fatty acids in 1 gm of
fat
• butter (large proportion of short chain FAs) sap. no. 220
– 230
• oleomargarine (long chain FAs) sap. No is 195 or less
SOAP MANUFACTURING
Saponification
and other
ingredients
such as Rosin
ZnO
• Acid hydrolysis of glycerides followed by alkali addition
(Saponification) (Twitchell process)
• flexibility in control of product distribution
• Higher glycerin yields
• Less off-colour production during the short time hydrolysis step
(R.COO)3. C3H5 + 3 H2O …..3RCOO.H + C3H5 (OH)3
Triglyceride Fatty acid glycerin
• 3RCOO.H + M.OH …..R. COO. M (soap) + H2O
• http://www.youtube.com/watch?v=aoB88WggvbI
• A detergent is a surfactant or a mixture of surfactants
having "cleaning properties in dilute solutions."[1]
Commonly, "detergent" refers to
alkylbenzenesulfonates, a family of compounds that
are similar to soap but are less affected by hard water
. In most household contexts, the term detergent by
itself refers specifically to laundry detergent or
dish detergent, vs hand soap or other types of
cleaning agents. Detergents are commonly available
as powders or concentrated solutions.

Detergents are classified into three broad groupings, depending on the electrical
charge of the surfactants.
Anionic –Give R- in water (sulfated fatty alcohols, Sulfonates, etc.)

Cationic -- Give R+ in water
Nonionic—Alkyl-aryl-ethylene oxide derivatives

Fossil Fuels
Coal
(C3H4)n
Hydrogen deficiency
hydrocarbon…many
interlocked
aromatic rings
Energy consumption
Source wise Consumption of Energy during 2017-18
179
Formation of Coal Deposits
A swampy setting, in which plant growth is lush and where there is
water to cover fallen trees, dead leaves and other plant debris, is
ideal for the initial stages to create coal. The formation of coal from
dead plant matter requires burial, pressure, heat and time . The
process works best under anaerobic conditions (no oxygen) since
the reaction with oxygen during decay destroys the organic matter.
It is the carbon content of the coal that supplies most of its heating
value. The greater the carbon to oxygen ratio the harder the coal.
Formation of Coal Deposits
The products of coalification are divided into four major categories based on
the carbon content of the material
Peat is the first stage in the formation of coal

Peat
Peat is an accumulation of partially decayed
Lignite vegetation matter
Bituminous Peat forms in wetlands or peatlands, variously called
Anthracite bogs and tropical swamp forests
It contains a large amount of water and must be dried
before use
Historically, it has been used as a source of heat and
burns with a long flame and considerable smoke
Peat
Peat is still mined as a fuel in Ireland and England
The peat is stacked to slowly

dry out
Approximately 60% of the world's

wetlands are peat
Lignite
Lignite is the second step in the formation of coal and is formed when peat is
subjected to increased vertical pressure from accumulating sediments
Lignite, often referred to as brown coal, is the lowest rank of coal and used
almost exclusively as fuel for steam-electric power generation
It is brownish-black and has a high inherent moisture content, sometimes as
high as 66 percent, and very high ash content compared to bituminous coal
It is often burned in power stations

constructed very close to the mines
Bituminous
Bituminous Coal is the third stage of coal formation
Additional pressure over time has made it compact and virtually all traces
of plant life have disappeared
It is of higher quality than lignite coal but of poorer quality than
anthracite coal
It is greatly used in industry as a source of heat energy
Bituminous coal is usually black, sometimes dark brown, often with well-
defined bands of bright and dull material
It is a relatively hard coal containing a tar-like substance called bitumen
Bituminous
Bituminous coal is a complex molecular mix of 60-80% carbon, plus
oxygen, hydrogen and nitrogen, plus some occasional impurities like
sulfur
Coking Coal
When used for many industrial processes, bituminous coal must first be
"coked" to remove volatile components
Coking is achieved by heating the coal in the absence of oxygen, which drives
off volatile hydrocarbons such as propane, benzene and other aromatic
hydrocarbons, and some sulfur gases and a considerable amount of the
contained water of the bituminous coal
Coking coal is used in the manufacture of steel, where carbon must be as
volatile-free and ash-free as possible
Anthracite
Anthracite is formed during the forth stage of coal formation
It is the most valuable and highest grade of coal, and has a carbon content of
92-98%
Physically, anthracite differs from bituminous

coal by its greater hardness and higher density
Plus, it burns far more efficiently with less smoke
Fuel Efficiency
As the coals becomes harder,
their carbon content increases,
and so does the amount of heat
released
Anthracite produces twice the
energy (BTUs) of lignite
World Coal Reserves
46% of the U.S. reserves
are bituminous and
anthracite
The remaining 54% is
lignite
Nichahom Bikaner
Bharuch
Lignite
and Coal
Deposits Neyveli
in India
190
COKING OF COAL
900-1150OC ….batteries of tall vertical ceramic chambers..separated by heating flues

Chamber (13 feet high, 40 feet long, width: 18 &16 feet)
Battery = 10-100 ovens (200 – 2000 tons of coal)
COKING OF COAL
• Begin to soften = 300OC (what is Charcoal?)
• Fluidity of mass reaches maximum and finally the mass solidifies
to form coke
• Gases and vapors…swell the mass…coke to have a porous
structure
• 4 (C3H4)n ----nC6H6+5nC+3nH2+nCH4
• Crushed coal is preheated to 1100OC, 17 hrs (red hot coke)
• The gases are cooled to remove tars, scrubbed with H2SO4 to
remove ammonia, scrubbed with light oil to remove aromatics
• Coal gas is treated to remove sulfur—fuel in steel blast furnace
• one ton of coal produces 750 kg of coke and 15 gallons of liquid
•
192
DISTILLATION OF COAL TAR
• Light oil - Coal tar, phenolic and aromatic
hydrocarbon constituents
• Hydrodesulphurization and solvent extraction
• Corrosion due solid particles, water,
ammonium chloride, and chemicals
• Petroleum distillation
193
Coal Gasification
Left: One of the most advanced - and cleanest - coal power plants in the
world is Tampa Electric's Polk Power Station in Florida It uses a coal
gasification process that turns coal into a gas that can be cleaned of almost
all pollutants
Right: This 2544-ton-per-day coal gasification demonstration pilot plant in
Pennsylvania, will have energy conversion efficiencies 20 to 35% higher than
those of conventional pulverized-coal steam power plants
Coal Gasification
Coke or non-coking coal is heated inside a large oven and blasted with steam
The coal is converted into carbon monoxide and hydrogen gas (town gas)
Hydrogen gas burns very easily.
Syngas consists primarily of hydrogen, carbon monoxide, and very Coke or non-
often some carbon dioxide, and has less than half the energy density coking coal
of natural gas. Syngas is combustible and often used as a fuel source
or as an intermediate for the production of other chemicals.
Alternatively, the coal gas (also known as "town gas") can

be converted into transportation fuels such as gasoline
and diesel through additional treatment via the Fischer-
Tropsch process.
Koppers totzek process

Carbon or fire brick
Liquid fuel can also be feeded
Hot gases leaves from top and ash falls in water sealed
chamber
Lurgi process (fixed bed gasifier)

Coal particles are feeded 1700 degrees
centrigade
Flux material such a lime may be added
3C (i.e., coal) + O2 + H2O → H2 + 3CO

Production of polymer-based products
Primary Basic Polymer End product applications

Resources Petrochemical Materials
Plastics
Plastics
Crude
Crude HDPE
Oil HDPE
Oil LDPE
LDPE
Ethylene
Ethylene LLDPE
LLDPE
Propylene
Propylene PP
PP Elastomer
Elastomer
Styrene
Styrene PVC
PVC
Vinyl
VinylChloride
Chloride ABS
ABS
Butadiene
Butadiene PA
PA
Cyclohexane
Cyclohexane Acetal
Acetal
Acetylene
Acetylene PC
PC Fibers
Fibers
PUR
PUR
Natural
Natural PBT
Gas PBT
Gas etc.
etc.
Adhesives
Adhesives++
Coatings
Coatings
INTRODUCTION TO POLYMER MATERIALS
• Natural polymers: Cellulose, starch, protein, isoprene, etc.

• Synthetic polymers: Polystyrene, polyethylene, polypropylene, nylon, etc.
• ELASTOMERS: Polymers capable of high extension under ambient conditions

ex: Natural rubber, nitrile and butyl rubber
• FIBERS: Polymers which permit their formation into long fibers for textiles and composites
ex: Nylon, polyester, cotton, wool, and silk
• PLASTICS: Except elastomers and fibers, all other synthetic polymers
•THERMOPLASTCS and THERMOSETS are the two categories of plastics
• Plastics contain various additives and fillers

• ADDITIVES: For better processability, environmental stability and to enhance
mechanical properties of the final product
Types of plastics
Thermoplastics e.g. PS, PP, PE, PMMA,

PVC, PC, Nylon, etc.
Plastics capable of softening and flowing
when heated, hardening when cooled, and
softening when reheated -
REVERSIBLE PROCESS
Thermosets
Plastics which become permanently rigid e.g. Epoxies, Phenol, etc.
when heated and cooled -
IRREVERSIBLE PROCESS
Ex: Colored PE, Flexible PVC are

Resin is chemically homogeneous  plastics……..But PE, PVC, epoxy, SBR
lack of filler, plasticizer, stabilizer, etc are resins
The chemistry of polymer molecules
Ethylene (C2H4) is a gas at ambient temperature (T) and pressure (P). If it is subjected catalytically to
appropriate conditions of T, P, it will transform to PE. (Explanation: Chapt. 2)
For Polyethylene, (a) a schematic representation of mer and chain structures, and (b) a perspective of the
molecule, indicating the zigzag backbone structure. In (a) angle between the singly bonded carbon atoms is not
180 °C, but rather close to 109 °C. More accurately 3-D model in which carbon atoms form a zig-zag pattern
shown in (b), the C-C bond length being 0,154nm
Homopolymers
Homopolymers: Polymers whose structure can be represented by
multiple repetition of a single type of repeat unit which may contain
one or more species of monomer unit.
–(M)n– M: monomer unit or repeat unit;

n: number of repeat units or
degree of polymerization (DP)
n = 2 (dimer), 3 (trimer), 4 (tetramer), 5

(pentamer), 6 (hexamer), …...
< 10: oligomer (e.g., MW < 2,000)
> 10 or MW >10,000: polymer
Nomenclature:
Source-based : Monomers name in parentheses unless it is a simple single word
e.g., poly(methyl methacrylate) (PMMA), polyethylene (PE)
Structure-based: Chemical structure of the repeat unit in parentheses

e.g., poly(ethylene terephthalate) (PET)
- here repeat (mer) unit contains more than one monomer units
Common homo-polymers
Monomer Polymer
Common homopolymers con..
Monomer Polymer
Common homopolymers con..
Monomer Polymer
Copolymers
Copolymer: Polymers whose molecules contain two or more different types
of repeat units.
Random copolymers : distribution of repeat units is truly random.

-B-A-B-B-A-B-A-A-B-A-B-B-B-A-
Alternating : repeat unit are arranged alternately along the polymer chain
-A-B-A-B-A-B-A-B-A-B-A-B-A-B-
Block: linear copolymers in which the repeat units exit only in long sequences, or
blocks, of the same type.
E.g., AB diblock copolymers -A-A-A-A-A-A-A-A-A-A-A-A-B-B-B-B-B-B-B-B-B-
ABA triblock copolymers -A-A-A-A-A-A-A-B-B-B-B-B-B-B-B-A-A-A-A-A-A-
Graft copolymers: branched polymers in which the branches have a different chemical
structure to that of the main chain.
B-B-B-B-B-B-B- B-B-B-B-B-B-B-B-B-B-B-
B B
-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A--A-A-A-A-A-A-A-A-A-A-
B B
B-B-B-B-B-B-B-B-B-B-B-B- B-B-B-B-B-B-B-B-B-B-B-B-
Repeat units used in copolymer rubbers
Molecular Weight and Polydispersity
Molecular Weight : mass of 1 mole of polymer, in unit of g mol -1.
M = xMo
where x (or n): degree of polymerization, Mo: molar mass of repeat unit.
Molecular Weight Distribution: polymers consist of macromolecules with a range
of molecular weights.
Number-average molecular weight (Mn):

NiMi
Mn = 
Ni
imagine N1 molecules with molecular weight M1, N2 molecules with molecular
weight M2, …, Nj molecules with molecular weight Mj
Weight-average molecular weight: Mw = (wiMi) = NiMi2/ NiMi
The ratios of different molecular weight averages Mw/Mn is often used as

characteristics of polymer polydispersity.
For most polymers Mw/Mn: 1.5–2.5
Molecular weight distribution
MW and Distribution affect:

• Tensile Strength
• Impact Toughness
• Thermal Properties
• Crystallinity
• Processing: Heat and
work
Molecular structure
The physical characteristics of a polymer depend not only on its molecular weight and
shape, but also on differences in the structure of the molecular chains
Note: Predominantly linear polymers might have some limited branching

and cross-linking ( not limited to single distinctive structural type)
POLYMERIZATION MECHANISM
Polymerisation: Synthesis of the large molecular weight polymers from monomers
Types: 1) Chain growth 2). Step growth
Chain growth polymerisation (Addition polymerisation)

• Bifunctional monomer units are attached one at a time in chain like fashion to
form a linear macromolecule
• The composition of the resultant product molecule is an exact multiple for that of
the original reactant monomer
• no reaction product
• Stages: Initiation, propagation and termination
• Types of polymerization: Free-radical, Cationic and Anionic
• Initiators for free-radical polymerizations: azo (-N=N-), disulfide (-S-S-), or
peroxide (-O-O-) compounds
• Ex: PE, PP, PVC and PS, etc.
• PS can be polymerized by free-radical and anionic mechanisms ( Chemical
nature of the substituent group)
Addition polymerization:
Free radical (shown for ethylene or ethene)
polymerization of ethene to form (poly)ethene
nCH2 CH2 peroxides CH2 CH2

200oC, 3000 atm n
O O O
O O O
2 mol
Chain initiation
O
peroxides radicals
O
+ CO2
Free-radical: Chain propagation
Rad
CH2 CH2 Rad CH2 CH2
Rad CH2 CH2 CH2 CH2 Rad CH2 CH2 CH2 CH2
Rad CH2 CH2 CH2 CH2 etc.
Chain termination:
Any time 2 radicals collide, no new radical is
formed and the chain terminates
R.+R.→R-R
Rad CH2 CH2 + Rad CH2 CH2 Rad CH2 CH2 CH2 CH2 Rad
Termination doesnot occur at the samepoint for each molecule 

leads to distribution of molecular weights
Another chain termination
“disproportionation”
2 Rad CH2 CH2 Rad CH CH2 + Rad CH2 CH3
Rad CH CH2 Rad CH CH2

H H
Rad CH2 CH2 Rad CH2 CH2
Rad CH CH2 + Rad CH2 CH3
Note: This termination gives two terminated chains compare to single terminated chain
discussed previously. In both termination models, free radical groups caps (both) ends of the
chain unlike fully recoverable catalysts used in other mechanisms.
Step growth (Condensation) polymerization
• Formation of polymers by stepwise intermolecualr chemical reactions that normally
involve more than one monomer species
• Homobifunctional (diacid, diamine) or heterobifunctional (amino acid)
• large chains cannot be produced until almost all of the starting materials have been
consumed (~99%)  high yield reactions are necessary
• various chain lengths are produced, yielding a molecular weight distribution
• leads to trifunctional monomers capable of forming network polymers
• Ex: thermosetting polyesters, Phenol-formaldehyde, nylons, etc.
• Condensation: liberation of a small molecule in the form of a gas, water, or salt
• Non condensation: no liberation of small molecules
Condensation Noncondensation
Classification Monomer 1 Monomer 2 Classification Monomer 1 Monomer 2
Polyamide Dicarboxylic acid Diamine
Polyurethane Diisocyanate Diol or
Polycarbonate Bisphenol Phosgene polyol
Polyester Dicarboxylic acid Diol or polyol PPO 2,6- Oxygen
Disubstituted
Polyimide Tetracarboxylic acid Diamine phenol
Step growth requires 2 functional groups to react
A A + B B A A B B
A A B B
can react here with B-B can react here with A-A
or
A B+ A B A B A B
A B A B
can react here with can react here with
B end of A-B A end of A-B
Polymerization of nylon through condensation
O
HOOC(CH2)4COOH + H2N(CH2)6NH2 HOOC(CH2)4C NH(CH2)6NH2
amide linkage
Amide linkage is a mixture note: can react with NH2 note: can react with COOH
of adipic acid and of next amine molecule of next dicarboxylic acid molecule
hexamethylenediamine.
O O
C(CH2)4C NH(CH2)6NH
n amide group: (-CO-NH-)
polymer notation for "nylon 6,6"

Aliphatic polyamides are called nylons. When at least 85% of the amide groups are
attached to aromatic groups, the polyamides are called aramids. Nylon 6,6 indicates six
carbon atoms in the diamine and six carbon atoms in dicarboxylic acid
Comparison of polymerisation mechanisms
Addition Condensation
Mechanism Chain reaction Step-by-step
Initiator Yes No ( “T, p”)
Monomer, numbers Olefinic;1 Bifunctional; 2
of types needed
By-product No Yes
Chain Few, long chains Many chains
characteristics
Branching Yes No
Time of reaction Fast Slow
Comparison of polymer mechanisms con…
Addition Polymer
n H2 C = C H2 -> -CH2 CH2 CH2 CH2 CH2 CH2 -

Monomer Polymer
Condensation Polymer
R – COOH + H2N-R’ -> H2O + R-CO – NH – R’
Monomer 1 Monomer 2 Copolymer

Polymer crystals
Crystallinity: Packaging of molecular chains so as to produce an ordered atomic array.
Conditions for crystallinity: Chemically simple, regular and symmetrical chain structurers
Metal specimens: totally crystalline
Ceramics: totally crystalline or totally non-crystalline
Polymers: semi crystalline (0-95% crystalline)
 Complexity of atomic arrangement because of
molecules makes polymers to be semicrystalline
Models to describe polymer crystallinity:

• Fringed – micelle model (small crystalline regions
or micelles are embedded within the amorphous matrix)
• Chain-folded model (polymer single crystals grown

from dilute solutions)
• Spherulites (bulk polymers that are crystallized from a melt

form spherulites)
• PE, PP, PVC, PTFE, and nylon form a spherulitic Fringed-micelle model of a semicrystalline polymer,
showing both crystalline and amorphous regions
structure when they crystallize from a melt
Ethylene monomers – Addition polymerisation
H Y X=H, Y=H Poly(Ethylene)

X=CH3, Y=H Poly(Propylene)
X=C6H5, Y=H Poly(Styrene)
C C X=COOH, Y=H Poly(Acrylic Acid)
X=COOCH3, Y=CH3 Poly(Methyl Methacrylate)
H X
For easy understanding of chemical structures!!!
Difference between a grocery bag, syrup bottle, coffee cup, disposable
diaper, shatter resistant window is the difference in those substituents
Processes in Polymer technology
Ethenic Polymer Processes (PE) M. P = -163 OC
1. Addition polymerization
2. - (CH2-CH2)n – Mol. Wt. : 1500 – 100,000
3. : MP: 85-110 OC Density: 0.91-0.93 (high pressure), 0.96 low pressure
4. Grades: 1.5 – 3 mm pellets, flakes, powdered solid
Low pressure: HDPE, Dr. Karl Ziegler, aluminium triethyl activated with heavy
metal derivative TiCl4
High pressure, LDPE, films, Liner for jute bags (fertiliser, cement), seepage barrier
LLDPE..LDPE at lower Pressure…apha olefin (1-butane) as comonomer, 100 OC, 2

Mpa, gasphase

production of polyolefins (PE) by low pressure Ziegler process
C5-C7 saturated
paraffin diluent
Re-distillation
Solvent Polymerization
7 atms. Gauge, 70 OC
Flash drum: Remove the

solvent from catalyst
Water is added to destroy

the residual catalyst, which
is highly flammable (dry)
centrifuged Extruded, 95-98 % yield

Blow molding, injection,
HDPE
Natta, PP (textile fibre)

190 OC, 30 %
Demethanizer, deethanizer
1000 – 2500 atms
Peroxide catalyst
100-300 OC, LDPE

PVC, 80-140 OC softening point
Decomposes at 140 OC, HCl
Emulsion Polymerization
Pressure reactor, 50 OC, 72 hrs
More emulsifying agent..vinyl latex
90 %, 0.1 to 1 micron
Vinyl chloride, ethylene

Tiny globules by dichloride monomer
stirring
Sodium lauryl Self-extinguishing,
sulfate electrical
Phenolic Resin
• Phenol and formaldehyde in varying ratios
• Has 2 forms : Novolac and Resole, determined by
formaldehyde : Phenol ratio
– Novolac ratio < 1; - Resole ratio > 1
• Novolac phenolic requires an additional hardener (two stage),
while resole does not (one stage)
Condensation
polymerization
Hexamethylene
tetramine..white
solid which
breaks down to
HCHO and NH3.
228
Phenol- formaldehyde resin (resole, liquid B stage)
* Acid or
Base
CH2OH
* -
OH
+ HCHO -
OH
* Monomethylolphenol
Bifunctional-Linear; Phenol by
Cresol..OH-C6H4-
Trifunctional- CH3….linear
Structure of novoloc polymers
tridimensional network
229
PF (Novolac and Resole)
PF: Novolac PF: Resole
• Acid catalyzed, excess phenol, • Base catalyzed, One stage
limited formaldehyde • excess formaldehyde
• Powder B stage, will not crosslink • Liquid B stage for storage or
further by itself shipping
– Curing agents: HMTA w/ heat • Finished by heat or acid
• Two-stage resins • Used as adhesive/impregnant
– Usually filled: wood flour, • Easily foamed
fibers
Phenolic product issues:
• Density of -OH groups: adhesive
• Need for mold release, external or internal
• High heat/flame resistance, low thermal conductivity, dark color
– Rocket nozzles, pan handles, capacitors, knobs, sandpaper, pulleys
HMTA = Hexamethylene tetramine
231
Pores in phenolic resin (cured)
Pores are formed due to

the release of water
(condensation
polymerization)
232
Ribbon blender/ball mill

FIBRES, TEXTILES,
Cotton, viscose, lyocell….wool (Australia)…SUITINGS
Polyester, Polyamide, PP, Acrylic…Staple, filament yarn

Polyamide (nylon)….garments, tire cord
Polyester-wool, Polyester-viscose…crimped

Wood – Pulp – Paper / Fibre
Pulping / cooking aims to separate cellulose fibers from the wood structure.
Pulping Regeneration
Raw Cellulose (I) - unpurified Regenerated Cellulose (II) -

Purifed
Kraft or Chemical pulping Mechanical properties of

uses NaOH and Na2S, here
Lignin is completely
removed. It accounts for 70 Cellulose (I) >> Cellulose (II)
% pulp production.
Mechanical pulping involves

metal disks which grinds the
wood, here lignin is partially
removed.
Lenzing AG
Cost E54/WG2, 17.10.2008 / Budapest 235
Micromechanics of singl
Factfile: Aditya Birla group
The world's largest aluminium rolling company
 World leader in viscose staple fibre
 One of the three biggest producers of primary aluminium in Asia
 One of the leading cement producers in India and the ninth-largest globally
 Fourth-largest producer of carbon black in the world
 Fourth-largest producer of insulators in the world
 World's fifth-largest producer of acrylic fibre
Group companies (India)

Nagda – viscose staple fibre - M.P
:: Grasim Industries Ltd. Harihar – viscose staple fibre , rayon grade pulp - Karnataka
Kharach – viscose staple fibre - Gujarat
:: Hindalco Industries Ltd.
Veraval – viscose filament yarn - Gujarat
:: Aditya Birla Nuvo Ltd.
Viscose Staple fibre: A man-made cellulose fibre, which is
:: UltraTech Cement Ltd. biodegradable and having charactristics akin to cotton.
Grasim Joint ventures
Birla Jingwei Fibres Company Limited in China AV Cell and AV Nackawic in Canada
Currently, this plant has a capacity to produce AV Cell and AV Nackawic supply
viscose staple fibreFibre
of 30,000 tpa. The capacity dissolving grade pulp to the Group’s
is being increased to 70,000 tpa by May 2010 viscose staple fibre units in India,
along with a captive cogeneration power plant Thailand and Indonesia.
of 15 MW. Pulp
Owning a plantation, manufacturing of Birla Lao Pulp & Plantation Limited in Laos
rayon grade pulp, production of principal This will provide a low cost source for wood to
raw material namely, caustic soda, meet future requirements of a green field
intermediate inputs namely CS2, sulphuric Wood
pulp plant in due course of time.
acid along with captive power and steam
generation facilities, usage of by product
Na2SO4 in paper and pulp, detergent, Cellulose (I) Pulp – Cellulose (II) fibre
glass and textile industries indicates their production
dedication in this sector.
(C6H10O5)n + nNaOH → (C6H9O4ONa)n + nH2O (C6H9O4ONa)n + nCS2 → (C6H9O4O-SC-SNa)n
C6H9O4O-SC-SNa)n + ½nH2SO4 → (C6H10O5)n + nCS2 + ½nNa2SO4

Role of BITS Hyderabad…..
• Designing the new reactor to obtain the pulp
suitable for fibre production
• Chemical analysis of viscose dope after mixing
with reagents (antimicrobial, hydrophobic, etc.)
• Mechanical (single fibre tests, bonding with
polymers, etc.) and Chemical analysis of fibres
• Finding the new application such as
transparent cellulose film..
Regenerat Cellulose fibres
• Regenerated cellulose: Wood pulp is converted in a series of
controlled and co-ordinated steps to a spinnable solution and
then into longer filaments which may be precisely controlled in
terms of length, denier, physical properties and cross-section, etc.
•Viscose: Alkali solution + CS2

• Lyocell: Solution in an amine oxide (NMMO)
• Regenerated cellulose fibers are avilable in a wide range
• Homogenous cross section and low quality difference
• Good mechanical properties, especially high elongation at break
• Easy to make user-defined reinforcements
• Scope for new market besides its huge market in textiles
• Fibrillated and Micro fibers are the new choice (ex. Microlyocell
has high moisture absorption)
240
• NMMO monohydrate is used as a solvent in the Lyocell process to produce
Tencel fiber.It dissolves cellulose to form a solution called dope, and the
cellulose is reprecipitated in a water bath to produce a fiber. The process is
similar but not analogous to the viscose process. In the viscose process,
cellulose is made soluble by conversion to its xanthate derivatives. With
NMMO, cellulose is not derivatized but dissolves to give a homogeneous
polymer solution. The resulting fiber is similar to viscose; this was observed,
for example, for Valonia cellulose microfibrils. Dilution with water causes the
cellulose to reprecipitate, i.e. the solvation of cellulose with NMMO is a water
sensitive process.
• Cellulose remains insoluble to most solvents since it has a strong and highly
structured intermolecular hydrogen bonding network, which resists common
solvents. NMMO is able to break the hydrogen bonding network that keeps
cellulose insoluble to water and other solvents.
241
• http://www.youtube.com/watch?v=W_oq6I_7
Khg
• Rayon tirecord

244
245
246
247
248
249
Microscopic examination of single fibers
Viscose Modal Lyocell
Fibers were embedded in epoxy resin, cured at 60°C

Fiber cross-sections were made by using ultramicrotome and diamond knife
Gentiana violet was used to stain the fiber-cross sections
Image was captured by Light microscopy equipped with CCD camera
Fiber diameter and perimeter was measured by fitting the fiber cross-section with an ellipsis
Difficult to extract single fibres from natural fiber bundles
Hemp Flax Sisal

Coconut - Coir fibre
Sweet water
Eating flesh
Cooking oil
Fiber
Seafaring tree
Coir fibre, threads & yarns
Coconut husk
251
CARBON FIBRE
E-glass fibre density = 2.55 g/cm3; water density = 1 g /cm3;
wood density= 0.7 – 1.2 g/cm3; Cellulose fibre = 1.5 g/cm3;
Aluminium = 2.7 g/cm3; Polyethene fibre = 0.97 g/cm3;
Carbon = 2.26 g/cm3; Carbon fibre= 1.66 – 2.2 g/cm3;
Precursor fibre = polymeric fibre consists of long

chain molecules (0.1-1 micron) …random
orientation….poor mechanical behavior.low cost…
Ex. PAN (Poly acrylonitrile), Rayon, PVAc,

Polyimides, Phenolics, Pitch based (PVC,
Petroleum Asphalt and coal tar)… 252
CARBON FIBRE
Thermal decomposition of an organic fibre under well-
controlled conditions of rate and time of heating
environment and stretching while heating
• Fiberization to make precursor fibre: Wet or dry or

melt spinning followed by some drawing or stretching
• Stabilization: prevents the fibre from melting in the
subsequent high-temperature treatments
• Carbonization: thermal treatment (1000-1500 OC)
which removes most noncarbon elements
• Graphitization: optional thermal treatment (>2500 OC)
for better properties
• https://www.youtube.com/watch?v=kaoq8Mc4xxw
253
Along a axis = 1000 Gpa; along c axis= 35 GPa due to van der
waals bond
K.K. Chawla, Composite Materials, 1998, Springer. 254

Carbon Fibre
Short duration
Black fibres are heated slowly (fibre texture, elastic
modulus) Yield = 50 %
255
256
Glass Fiber Reinforced
Polymer composites – GFRP
Carbon Fiber Reinforced
Woven Carbon
Polymer Composites – CFRP Fiber Mat
Aramid Fiber Reinforced
Polymer composites-AFRP
Temperature Range of matrix (OC)

 Glassfibres : 8-20 m
 Carbonfibres: 5-8 m
 Aramidfibres: ca. 12 m
257
CARBON FIBRE WOVENMAT
1000 µm
258
POLYMER COMPOSITES
Polymer Matrix Composites (PMC):
- Low modulus matrix
- High modulus fibers
• High potential for lightweight constructions

• Tailoring of properties in user-defined way
• High damping properties?
• Good corrosion resistance
• Environmental toxicity?
• Production and life cycle costs ??
09/11/2023 259
Reinforcing agents  Glassfibres : 8-20 m
 Carbonfibres: 5-8 m
- Fibres
 Aramidfibres: ca. 12 m
Diameter
• Size
Volume fraction
• Quantity
Aspect ratio
s= ¥ s=0
• Form
• Orientation
Arrangement,
• Distribution Homogenity
Reinforcement Types (Graphically)
Laminar reinforcment Particle reinforcment
Continuious woven Discontinuious (Chopped)

fibre reinforcment fibre reinforcment
Skeletal (honeycomb)
Flake reinforcment
reinforcment
261
Verstärkungskomponenten
Microstructure of typical Reinforcement materials
Long C-fibers Short C-fibers Short fibers - Saffil Woven fibers
SiC particles, 10 TiC, 1-50 µm Al2O3, 1-10 µm SiO2, 250 nm,

µm spherical particles dispersoids
OM- und SE-micrographs
262
Verstärkungskomponenten
Flexure Testing Fractography (DS)
Epoxy Phenolic
15.11.2016 CHARACTERIZATION OF FIBRE/MATRIX INTE 263

RFACE IN ADVANCED COMPOSITES
WIND TURBINE BLADES
- Danish 3-blades Rotor Design

- 15-20 tonnes of Glass-epoxy composites
- Volume fraction 60 %
- Average life time: 20 years
264
Bauteil für Messmaschine (Fa. Carl Zeiss in Oberkochen)
Carbon/EP
Schaumkern
Besondere Anforderung: hohe Maßhaltigkeit bei Temperaturänderung
Material:
• Carbonfasergewebe
• Epoxidharz
• Rohacell-Schaum
265
PMCs
Processing of Polymer Composites
Money spent to reduce the 1 kilo weight:
Advantages of Composites: Space agencies 25,000 Euro
High potential for lightweight constructions Aeronautics 250 - 750 Euro
Tailoring of properties in user-defined way Automobile 0 - 2.5 Euro
Good corrosion resistance
Carbon Fiber
Aramid Fiber Polypropylene matrix
Glass Fiber + Epoxy matrix
Natural Fibers Unsaturtated polyester
matrix
Advantage of Natural fibers

1) CO2 neutral 2) low price (ca. 0.6 EURO / Kg compare to 1.2 EURO / kg of glass)
3) low density (Natural fibers 1500 kg/m3 – Glass 2500 kg/m3) 4) Non toxic (Glass: Skin irritations)
5) Fibers are not abrasive to the processing equipment
Today almost 20 kg of natural fibers are used per vehicle produced in

Germany!!!
Purification of alumina from Bauxite
Precipitator: Dilute mixture of Na3AlO3 is seeded

with Al(OH)3 to induce crystals of Al(OH)3 in magma
solution of NaOH.
In calciner Al(OH)3 crystals are subjected to 1100

O
C temperature to drive-off water of hydration (leads
to pure alumina) and excess water.
Supernatant
sodium
aluminate
Iron oxide and Particle size

sodium
aluminium
silicate
Bauxite = 50-60 % Al2O3 Ore, silica, Iron Ore
Jaw crusher…2-5 cm lump size…wetground..100 mesh

40 % of the cost if for
power, Hindalco, building,
consumer, defence,
automobile
3-5 % Al2O3 conc..

99.7 % Al not good
for electric
conductor
5-7 volts with 40-100 cells in series, DC of 8000-50,000 amperes


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Chemical Process Technology

Dr. Ramesh-Babu Adusumalli

09/11/2023 Chemical Process Technology 1

09/11/2023 Chemical Process Technology 7

Bauxite Million of tons 1080 4.5

Beryllium tons 64000 17

Chromite Million of tons 18.1 4.3

Iron Ore Million of tons 3300 5.1

Manganese Million of tons 17 2.1

Rare Earth Million of tons 2.3 2.7

Titanium Million of tons 43 15

Zinc Million of tons 11 7.3

Zirconium Million of tons 2.1 4.3

Coal and Lignite 3372 48

09/11/2023 Chemical Process Technology 17

Transportation picture for India: Air, Pipe

Nuclear power (Tarapur and Kalpakam, etc):

Commercial production of chemicals from raw materials =

Unit operation Unit process Industry

09/11/2023 Chemical Process Technology 22

Residence time of 30-120 sec, surface liquid is vaporised

Inlet air temperature ranges from (100 -650 degree centigrade)

α is Cake resistance, υ porosity of the bed, slope = t/V vs V

• Plotting the breakthrough curve of adsorption

Source: PCA, 2003

Source: PCA, 2003

1. Stone is first reduced to 125 mm (5 in.)

Natural Cement Rock

3. Burning changes raw mix chemically into cement clinker.

Source: PCA, 2003

Source: Mindess, Young, and Darwin, 2004

•Modernized in 1999 by HBZ and

Source: PCA, 2003

Source: PCA, 2003

Source: PCA, 2003

Source: PCA, 2003

• Belite or 2CaO• SiO2 or C2S

• Modern cements are

– Very high heat of hydration

– Some contribution to early

• Ferrite or 4CaO• Al2O3 • Fe2O3 or

Overview of Cement Manufacturing Process by Dalmia

Source: Mindess, Young, and Darwin, 2004

Limestone Beneficiation (reducing the % of

09/11/2023 Chemical Process Technology 73

09/11/2023 Chemical Process Technology 74

S (solid) + oxygen SO2 (gas)…..-70.9 Kcal

- S can come from…….Sulphur; Iron Pyrites (FeS2); CuS, ZnS, PbS; 2

- Iron Pyrites containing 40-45 % S are roasted, dust removed, cooling,

09/11/2023 Chemical Process Technology 75

Sulphuric acid is used majorly in Phosphate fertilisers

Kashmir, recovery of elemental Sulphur from petroleum refineries,

Elemental Sulphur from Pyrites::

Roasting of FeS (Pyrrhotite) for SO2 recovery

General combustion reaction =

09/11/2023 Chemical Process Technology 76

09/11/2023 Chemical Process Technology 80

Most Important Industrial Reaction

Continual cropping, heavy monsoon (leaching)

UREA: NH2 . CO . NH2 ; melts at 132 OC ; Soluble in water; 46 % N; granules