CL – 308
OVERVIEW OF INDIAN
CHEMICAL INDUSTRY
A REPORT ON ‘COURSE ON WHEELS’
ALKYL AMINES CHEMICALS LIMITED
UPL LIMITED
Date: 03rd February, 2019
Submitted by:
Nimish Pankhedkar 183020051
Yash Kadam 160020014
Anil Pal 160020085
Instructor:
Prof. S. M. Mahajani
Department of Chemical Engineering
Indian Institute of Technology, Bombay
COURSE ON WHEELS
ABSTRACT
The document is based on the ‘Course on Wheels - 2018’ conducted by Department of
Chemical Engineering, IIT-Bombay. Various industries from chemical and allied sectors were
visited, and participants were assigned one or two companies for detailed study. Alkyl Amines
Chemicals Ltd from Speciality chemicals and UPL Limited from Agrochemical sector, are
mentioned in this report. Basic commercial aspects, company profile, product profile, and
process description for the plants visited in these industries are studied in detail.
Continuous plant for Methyl amines majorly producing Dimethyl Amine was visited in Alkyl
amines chemicals ltd. Flowsheet for the same is described in the report. Some safety aspects of
designing tank for volatile material is also covered owing to a session conducted in the
company.
Process for ‘Pendimethalin’ a fungicide manufactured in UPL Limited is discussed along with
a major raw material for agrochemical sector, i.e. ‘Carbon Disulfide’
The information here is as observed in the industry and literature for the processes have been
referred as and when required to cover the missing points, and to have a better understanding.
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ACKNOWLEDGEMENTS
It gives us immense pleasure in presenting the report on visit to ‘Alkyl Amines Chemicals Ltd.
and UPL Limited’ as a part of Course on Wheels (Course CL – 308 Overview of Indian
Chemical Industry)
We would like to express gratitude towards Prof. S. M. Mahajani for developing this course
and being with us during entire visit, guiding us at every point, that helped us gain rich
experience in Operations in chemical and allied industries. We also thank Prof. R. D. Gudi –
Head, Chemical Engineering Department, for granting permission for this visit and introducing
to us, the control aspects in industry.
We are also grateful to Prof. Leja Hattiangadi, for sharing her knowledge and huge experience
during initial visits. We thank all other professors from IIT-Bombay, who accompanied us in
the entire journey.
We also acknowledge the teaching assistants: Mr. Akash Shinde, Mr. Vikram Uday and Mr.
Mritunjoy Roy for making all the necessary arrangements, they were indeed major pillars to
make this course a success.
Nimish Pankhedkar
Yash Kadam
Anil Pal
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Table of Contents
ABSTRACT ............................................................................................................................... 2
ACKNOWLEDGEMENTS ....................................................................................................... 3
LIST OF FIGURES ................................................................................................................... 6
INTRODUCTION ..................................................................................................................... 7
ALKYL AMINES CHEMICALS LTD ..................................................................................... 8
COMPANY PROFILE .......................................................................................................... 8
MANUFACTURING FACILITIES .................................................................................. 9
MANUFACTURING STRENGTHS .............................................................................. 10
COMMERCIAL ASPECTS ............................................................................................ 10
PRODUCT PROFILE .......................................................................................................... 11
PRODUCT RANGE ........................................................................................................ 12
CONSUMERS STATISTICS .......................................................................................... 13
OVER VIEW OF METHYL AMINES ............................................................................... 15
COMMERCIAL ROUTES FOR ALKYL AMINE MANUFACTURE ......................... 15
PROCESS DESCRIPTION ................................................................................................. 16
RAW MATERIALS ........................................................................................................ 16
REACTOR ....................................................................................................................... 17
DISTILLATION SECTION ............................................................................................ 18
PACKAGING .................................................................................................................. 19
COOLING WATER CIRCUIT (USE OF AIR-COOLED HEAT EXCHANGER) ....... 19
BOILER DETAILS ......................................................................................................... 20
FIRE FIGHTING SYSTEM ............................................................................................ 21
EFFLUENT TREATMENT PLANT .............................................................................. 21
USAGE OF METHYL AMINES ........................................................................................ 22
SECTOR WISE DETAILS .............................................................................................. 22
SAFETY ASPECTS IN DESIGNING ................................................................................ 23
UPL LIMITED......................................................................................................................... 24
HISTORY AND OVERVIEW ............................................................................................ 24
MARKET STATISTICS ..................................................................................................... 24
INTERNATIONAL MARKET ....................................................................................... 24
NATIONAL MARKET ................................................................................................... 24
COMMERCIAL ASPECTS ................................................................................................ 24
ACQUISITION OF ARYSTA ......................................................................................... 25
IMPORTANT ASPECTS FOR UPL ............................................................................... 26
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STRONG BACKWARD & FORWARD INTEGRATION ............................................ 27
CARBON DI-SULFIDE PLANT ........................................................................................ 28
PENDIMETHALIN PLANT ............................................................................................... 29
SAFETY MEASURES INCORPORATED BY UPL ......................................................... 31
REFERENCES ........................................................................................................................ 32
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LIST OF FIGURES
Figure 1. Gross Revenue of Alkyl Amines from FY.2011 to FY. 2019 .................................. 10
Figure 2. EBIDTA / PAT details of Alky Amines from FY2011 to FY2019 ......................... 11
Figure 3. Yearwise statistics for Employed Capital................................................................. 11
Figure 4.Alkyl Industry Profile 2017-18 ................................................................................. 13
Figure 5. World consumption of aliphatic amines (End use wise) .......................................... 14
Figure 6. Various customers of Alkyl amines (Sector wise) ................................................... 14
Figure 7. Methyl Amines flowsheet......................................................................................... 17
Figure 8. Schematic diagram of Air cooled heat exchanger .................................................... 20
Figure 9. Induced draught air cooled heat exchanger .............................................................. 20
Figure 10. Block Diagram of ETP ........................................................................................... 21
Figure 11. Financial summary of UPL .................................................................................... 25
Figure 12. Acquisition of Arysta ............................................................................................. 25
Figure 13. Product Integration in UPL .................................................................................... 27
Figure 14. Block Diagram of CS2 Plant .................................................................................. 28
Figure 15. Pendimethalin Reaction .......................................................................................... 29
Figure 16. Block Diagram for Pendimethalin plant ................................................................. 30
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INTRODUCTION
This report is made about the industries which were visited during 3rd December – 24th
December 2018 under the course “Course of wheels: Overview of Indian Chemical Industry”.
The objective of this course is to give students an exposure to different segments of chemical
and allied industries and visit a representative industry in almost each of these sectors, see the
processing facility, hear the practicing chemical engineers, and understand the commercial and
business aspects.
The different sectors chosen as a part of this visit were: Coal based industry (power plant), Oil
refinery, Petrochemical complex, Fertilizer complex, Oil fields, Natural and associated gas
processing, Fine and specialty chemicals (e.g. agrochemicals, pharmaceuticals etc.),
Chloroalkali etc. In addition to these production facilities, we visited a plant under
commissioning phase and also a unit that manages waste from chemical industries. The
companies include: Gujarat Industries Power Corporation (GIPCL), Surat; Reliance
Petrochemicals, Dahej ; UPL, Jhagadia; ONGC; Alkyl Amines Chemicals Ltd; Deepak Nitrite,
Nandesari; Bharuch Enviro Infrastructure Limited, Bharuch; JB Chemical and
Pharmaceuticals; ATUL limited;Gujarat Narmada valley Fertilizers and Chemicals (GNFC);
Reliance Refinery Complex, Jamnagar and Nirma.Chemicals, Bhavnagar
We have submitted brief reports on every visit listed above and this report contain detailed
information about ALKYL AMINE & UPL.
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ALKYL AMINES CHEMICALS LTD
COMPANY PROFILE
Alkyl Amines Chemicals Limited is a global supplier of amines and amine-based chemicals to
the pharmaceutical, agrochemical, rubber chemical & water treatment industries, among
others. Alkyl Amines Chemicals Ltd (AACL) is a public Limited Listed Company promoted
in 1979. The Company is in the business of manufacturing and marketing various aliphatic
amines, amine derivatives and other speciality chemicals for the last 30 years.
It has two manufacturing sites with 9 production plants and related utilities at Patalganga and
Kurkumbh in Maharashtra. The company has an R&D centre at Hadapsar, Pune. Over the last
decade, the company had added various new product processes which were developed in the
R&D to expand its product range through inhouse technology.
The first plant was commissioned in 1982 at Patalganga to make ethylamines with technology
from Leonard Process Company, USA. Subsequently, the capacity at the site was expanded to
manufacture other amines with technical know-how of Acid Amines Technologies, USA, and
now hosts 2 multipurpose amines plants with a capacity exceeding 25000 MT/annum.
In 1995 it started on its Kurkumbh complex where various amines and amine derivatives are
currently being manufactured in 7 production plants with a capacity exceeding 30000
MT/annum. In the last decade, the company has added various facilities to manufacture a wide
range of speciality chemicals with its inhouse developed technologies.
AACL is a global supplier of amines and amine-based chemicals to the pharmaceutical,
agrochemical, rubber chemical and water treatment industries, among others. It has established
a leading position in the domestic market and presence in the international market with a
reputation for reliable service and quality products with annual sales of Rupees 400 Crores.
In 2014-15 the company was awarded ‘Responsible Care Certification’, and became one to
join group of less than 50 companies in India.
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MANUFACTURING FACILITIES
SITE PLANT DESCRIPTION
Multipurpose aliphatic amines plant
based on a catalytic vapour phase
PATALGANGA Aliphatic Amines Plant I & II reaction process. Capable of producing
C2-C6 aliphatic amines (mono-di-tri)
Multipurpose plant capable of
producing solutions of various amine
Amine-Hydrochloride Plant
hydrochlorides
Indian FDA approved plant capable of
producing mosquito repellents like
Multipurpose Plant I
DEET & DEPA
Plant capable of producing amine
oxides and downstream products like
Multipurpose Plant II
diethyl hydroxyl amine
Multipurpose plant that is capable of
synthesising and distilling various
products based on hydrogenation using
KURKUMBH Multipurpose Plant III
catalysts like Ni, Pd-C, Pt, etc. The
plant has two high-pressure reactors
Plant dedicated to hydrogen
production for captive as well as
Hydrogen Plant
contract & toll manufacturing use
Plant capable of making various types
of betaines and other surfactants for
Surfactants Plant
personal care applications
Multipurpose aliphatic amines plant
based on a catalytic vapour phase
Aliphatic Amines Plant
reaction process
Methyl amines plant based on a
catalytic vapour phase reaction
DAHEJ Methyl Amines Plant process. Capable of producing methyl
amines (mono-di-tri)
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MANUFACTURING STRENGTHS
Reactions:
• Reductive Amination
• Hydrogenation
• Cyanoethylation
• Oxidation
• Amidation
Distillations:
• Pressure /Atmospheric / Vacuum
• Fractional / Azeotropic
• Continuous / Batch
• Powder making facilities
Multi-purpose plants
o A wide palette of products (100+). Most developed in house.
o Global leader in Ethyl amines.
o One of the leading players globally in DEHA (Diethyl hydroxyl amine)
o One of the largest producers of DMA-HCL
o Leading producer of Acetonitrile with a unique process
o Globally leading manufacturer of various specialty amines
o Dominant Indian manufacturer of most of our product range
o Strong in commercialization of processes through in –house team
o Reputation as a reliable, ethical supplier.
COMMERCIAL ASPECTS
Gross Revenue: (Rs. Crores)
Figure 1. Gross Revenue of Alkyl Amines from FY.2011 to FY. 2019
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EBIDTA/PAT:
Figure 2. EBIDTA / PAT details of Alky Amines from FY2011 to FY2019
Capital Employed (Rs. Crores)
Figure 3. Yearwise statistics for Employed Capital
PRODUCT PROFILE
Amines are products derived from Ammonia (NH3) by displacement of H2 in the Ammonia
molecule by other radicals (R) such as Methyl, Ethylene and Propanol. Structurally, three types
of amines are formed – Primary/Secondary/Tertiary based on number of hydrogen atoms
displaced.
Primary Amine: R – NH2
Secondary Amine: R2 – NH
Tertiary Amine: R3 – N
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The ‘Nitrogen’ in an amine has the property of 3 valences. This versatility allows the ‘Amine’
compound to shuttle between various phases and act as a carrier of the ‘Active’ compounds.
This property finds varied applications.
Alkyl Amine manufactures over 100 amines & amine - based chemicals across all its plants.
The composition of the ‘R’ group in the amine structure defines the categories of the amines.
• Aliphatic: Where ‘R’ is the alkyl group with 6 carbons or less.
Examples are Methylamines, Ethylamine's etc.
• Ethylene: Where ‘R’ is the ‘Ethylene’ group. Typically, these amines have more than
one ‘NH3’ group and are also called ‘Diamines’.
Examples are Ethylene Diamine (EDA), Diethylene Triamine (DETA)
• Alkanol: Where ‘R’ is the alkanol group.
Examples are Ethanolamine's, Propanolamines.
• Mixed/Complex: These are amines where more than one type of ‘R’ group combines
with a ‘Amine’ group.
Examples: Dimethyl Amino Propylamine, Dimethylethylamine, Diethyl
hydroxylamine, etc.
Currently the company produces 43 mono- amines, 12 diamines, 4 polyamines, 5 amine
hydrochlorides, 2 amides, 20 long chain amines (Other amines) and 18 amine – based
speciality products.
PRODUCT RANGE
Monomethyl amine
(MMA)
Methyl amine Dimethyl amine (DMA)
Ethyl amine Trimethyl amine (TMA)
Iso propyl amine
Aliphatic amines Propyl amine
Butyl amine
Ethyl hexyl amine
Alkyl Amines
Cyclo hexyl amine
Mixed Amines
Amine Derivatives Amides
Speciality
Hydrochlorides
Chemicals
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CONSUMERS STATISTICS
These products find wide area of application spanning many industries. Major market for
amines and amine-based chemicals is Pharmaceuticals that accounted for 61% in 2017-18
followed by agrochemicals to take share of only 6%. Graphical representation of figures is
mentioned below:
Figure 4.Alkyl Industry Profile 2017-18
As far as aliphatic amines are concerned, they mainly dominate the raw material market for
industrial solvents. Absorption of carbon dioxide is majorly done by using amines solvent.
Following pie chart represents the market consumption of aliphatic amines.
On and average price for 40% DMA is between Rs. 40 – 60 per kg.
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Figure 5. World consumption of aliphatic amines (End use wise)
Figure 6. Various customers of Alkyl amines (Sector wise)
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OVER VIEW OF METHYL AMINES
Methyl amines i.e. Monomethylamine (MMA), Dimethylamine (DMA),
Trimethylamine (TMA) are major industrial chemical intermediates. They are mainly used in
res such s pesticide production, water treatment and pharmaceuticals. It has a very strong fishy
smell which is more prominent at a concentration lower 10ppb.
Although many routes are available for synthesis of methyl mines, only few are significant
commercially.
COMMERCIAL ROUTES FOR ALKYL AMINE MANUFACTURE
1. Alkylation of Ammonia with alcohols in the presence of either dehydration or
dehydrogenation catalysts.
The vapour phase transformation is carried out by mixing appropriate alcohol
and ammonia at high operating temperatures around 250 to 500 °C and low to
moderate pressures (1 to 200 atm) in the presence of dehydration catalysts such
as aluminium oxide, silica, aluminium phosphate, thorium oxide, tungsten
oxide, magnesium oxide, or chromium oxide. A problem associated with this
process is that it gives rise to a mixture of mono, di & tri alkylated amines. This
can be overcome by judicious selection of the reaction temperature, pressure,
flowrate, ratio of reactants and catalysts. Combining with the recycle of the
undesired reaction products, allows one to optimize within certain limits the
extent of alkylation. The selectivity and overall efficiency of this reaction is
dramatically affected by subtle variations in the catalyst as, particle size
activation temperature, aging and the presence of cocatalysts or promoters.
This is the most widely practiced, synthetic route for production of lower
aliphatic amines. It has also been carried out in presence of hydrogen and a
hydrogenation catalyst, i.e. copper, nickel, cobalt, platinum. The presence of
hydrogen has proven mandatory since nitriles are readily formed in its absence.
2. Catalytic reductive amination of aldehydes and ketones.
Interaction of aldehydes as well as ketones with ammonia and hydrogen in the
presence of certain hydrogenation catalysts provides for the formation of
amines. Although this reaction has not enjoyed the wide industrial acceptance
afforded the previously discussed alcohol ammonolysis procedure for the
production of the lower aliphatic monoamines, it is nonetheless an extremely
efficient, effective, synthetic procedure and mostly the choice for certain higher
aliphatic amines. Compared to the above procedure, this route requires much
facile reaction conditions; typically, temperature below 200°C and pressures
less than 10 atm. Many mixed specialty alkylamines are produced via this
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procedure. The crude reaction mixture derived from this process also consists
of primary, secondary and usually tertiary amines.
3. Acid catalysed addition of Hydrogen cyanide to olefins
Unique tertiary – alkyl, primary, monoamines can be synthesized via the
addition of hydrogen cyanide to a branched olefin in the presence of a strong
acid such as sulfuric acid to which one or more moles of water have been added.
The resulting intermediate tertiary – alkylformamide provides the amine upon
hydrolysis.
PROCESS DESCRIPTION
Methyl amines are commercially formed by reacting methanol and ammonia in a fixed
proportion in the presence of Silica/Alumina catalyst. This gives rise to a mixture of Mono -
methyl amine (MMA) Di-methyl amine (DMA), Tri-methyl amine (TMA) and water along
with the unreacted Ammonia and methanol. Thermodynamics favours the production of TMA
while the largest demand is for DMA. Following are the main reactions and their Gibbs free
energies:
Amination ΔG° (kcal/gmol)
MeOH + NH3 → MMA + H2O -4.13
MeOH + MMA → DMA + H2O -7.24
MeOH + DMA → TMA + H2O -8.39 (Most Favoured)
Disproportionation
2MMA → DMA + NH3 -3.11
MMA + DMA → TMA + NH3 -4.15
2DMA → TMA + MMA -1.15
The products thus formed in the reactor are then stored in an intermediate hold up tank from
where they are fed in a series of distillation column for the separation of MMA, DMA and
TMA. The unreacted ammonia and methanol go back to the reactor as recycle and water is
removed and sent to ETP for the treatment.
RAW MATERIALS
• Nearly half of the ammonia is imported and half is obtained from fertilizer company
like GSFC and GNFC.
• Methanol is imported
• Methyl alcohol and ammonia storage needs to be licensed under PESO (Petroleum and
Explosives Safety Organization) regulations.
Usually materials, having vapour pressures above 1.5 bar at 15°C come under PESO
regulation.
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• Methanol inventory is sufficient for about 10 days, and that for ammonia is 3days.
• Ammonia is either stored in bullets or tanks, and transported via tankers. Reciprocating
compressors is used to feed ammonia vapours from the tank into the tanker, that creates
a pressure in tanker whereas suction in the tank, this creates a net pressure difference
from tanker to tank, and ammonia is filled in the tank.
Figure 7. Methyl Amines flowsheet
Equipment Wise description:
REACTOR
• The reaction is carried out in a Fixed bed type of reactor loaded with
Silica/Alumina catalyst.
• It is operated at 450 °C and at 18 bar pressure.
• Reaction is exothermic in nature takes and place in vapour phase. The chemistry
consists of three simultaneous reversible reaction as mentioned earlier where
methyl amines are produced and water is a by-product.
• The primary desired product is DMA and the equilibrium mixture leaving the
reactor contains more TMA than can be sold. Therefore, the excess amounts of
these components are recycled back to the reactor from the separation section.
• Excess of ammonia is used that takes up the per-pass conversion of methanol
close to 100%.
• Methanol is first vaporised and then fed to the reactor.
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• The reactions are exothermic, but the feed is cool enough and also large
ammonia recycle make it necessary to add small amount of heat. Medium
pressure steam is used as heating medium.
• The reactor effluent is cooled and passed to a crude product storage tank. Small
amounts of by-product hydrogen and mono oxide separate in this tank.
DISTILLATION SECTION
The separation section consists of 5 distillation columns that separates total 5
components. Following table gives the boiling points of all components at 1atm.
MMA DMA TMA Water Ammonia Methanol
Boiling Point (°C) 41.03 69.93 59.29 157.9 -271.1 80.5
at 5.87 bar
i. Column 1:
• Ammonia has very low boiling point and can be easily separated from
the mixture in the first column itself.
• Column consisting of sieve trays is used.
• Recovered ammonia is recycled back to the reactor.
ii. Column 2: (Extractive Distillation)
• The ternary system of MMA/DMA/TMA system contains binary azeotropes
between MMA/TMA and TMA/DMA.
Components Boiling Point (°C) Composition
(at 85 psia)
MMA/TMA 40.68 88% MMA
TMA/DMA 55.87 60.27% TMA
MMA/DMA No Azeotrope
• An extractive distillation column is used to remove TMA, so that the
separation of MMA & DMA can be achieved in single column.
• Water is used as a solvent, that carries away DMA, MMA, Methanol to
the bottom of the column and TMA is withdrawn from top.
• This is also a sieve tray column.
iii. Column 3:
• This sieve tray column separates Methanol-Water mixture from MMA-
DMA mixture.
• MMA-DMA is the distillate that is sent further, and bottoms is methanol
and water.
• Some processes also separate Water as top product in this (3rd) column,
and DMA, MMA & methanol are passed to the fourth column.
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iv. Column 4:
• MMA that is low boiling comes out as distillate, part of which is
recycled back to the reactor.
• DMA is withdrawn from bottom as its boiling point is higher than that
of MMA.
• DMA is completely stored in a tank and sold in various forms. Mainly
aqueous solutions of 40% and 60% as well as anhydrous form.
v. Column 5:
• Methanol and water are separated in this column.
• Many a times this column is replaced by ‘Falling Film Evaporator’,
where in water is evaporated from methanol.
• Water separated is sent to ETP plant and methanol is recycled.
PACKAGING
• The product is filtered to avoid any entrainment of dust particles, just for
filling/drumming.
• DMA is packed in drums mainly in 3 different grades viz; 40% aqueous, 60%
aqueous and anhydrous, depending on the requirement.
• An ejector is mounted on top of the amine filling setup, which sucks all the
vapours that are generated while filling, with the help of a breaded hose.
• Earthing is provided to the set up to prevent any spark due to static electricity
that could cause any fire incidence.
• The outlet of ejector is fed to the scrubber, to neutralise the vapours with water.
• DMA is also directly filled in tankers and transported. This is done by sucking
the vapours from tanker and filling it the tank, thereby creating pressure in the
tank, that makes DMA flow in the tanker. Thus, there is a suction in the tanker.
Reciprocating compressor is used for this.
COOLING WATER CIRCUIT (USE OF AIR-COOLED HEAT EXCHANGER)
• Cooling water is used as utility to remove heat in various parts of process. After
increase in the temperature it needs to be cooled so it can be used again.
• In alkyl amines, it is first fed to Air Cooled Heat Exchanger to reduce the
temperature maximum up to the ambient air temperature, then fed to the cooling
tower.
• An air-cooled heat exchanger avoids the need for the many high costs associated
with using water like corrosion of metal parts. Since it uses ambient air instead
of water, there are no increased water costs when using an air-cooled heat
exchanger, nor are there added costs associated with the treatment of water
before it can be used as coolant. This also eliminates the possibility of polluting
water resources through chemical or thermal pollution. It also has less
installation cost and requires less space.
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• Disadvantages of this cooler is higher horsepower requirements, less accessible
fans when it’s time for maintenance, and the need to remove plenums to replace
bundles.
• Another limitation is water cannot be cooled below ambient air temperature,
which is usually higher than operating temperature of cooling water; in
summers.
Figure 8. Schematic diagram of Air cooled heat exchanger
Figure 9. Induced draught air cooled heat exchanger
BOILER DETAILS
• Alkyl amine uses Coal Fired Boiler which is Fluidised Bed type, having bed
height of around 1m.
• It generates high pressure steam of 30bar which is around 350-380°C.
• 500tonnes per day is the steam requirement, from which 80-85% is recovered
and 120-125 tonnes per day is produced daily.
• Boiler feed water has to be checked for mainly 2 specifications:
i. ph: Between 6.5 – 7
ii. Conductivity: Must be less than 0.5 μS
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• Indonesian coal is used in boiler which costs around Rs. 3000 – 5000 per
tonne.
FIRE FIGHTING SYSTEM
• Water sprinklers are fixed around the circumference of columns and tanks at
gradual height, that automatically sprinkles water at a pressure of 7 kg/cm2.
• Jockey pumps are used to maintain the pressure header at this pressure. If the
pressure in the header drops below 7 kg/cm2, then the pump starts and
increases the pressure.
• Purpose of jockey pump is to maintain the header pressure.
• In case of power failure, Diesel Generators (DG Sets) are used to run the
pump. It is designed for fighting up to 2.5 hrs.
EFFLUENT TREATMENT PLANT
The waste generated from process operation (distillation) is collected into collection sump.
They are treated by process such as neutralization followed by biological oxidation where
neutralization is done by adjusting the pH of water through the addition of an acid or a base,
depending on the target pH and biological oxidation as bacteria are added to breakdowns the
organic particles present in that waste water. Treated effluent is left out with nitrogen present
in it in major quantity. For NOx balance, Buds are added in aerobic condition which convert it
to nitrate compounds. Further, Buds are added in an anaerobic condition to reduce it to Nitrogen
gas. Which lead to form a slurry. The treated and degasified mixed liquor enters the clarifier to
separate the biomass. This biomass has to be wasted periodically to sludge drying bed to
maintain Mixed liquor suspended solids (MLSS). The clarified waste water which may contain
some refractory COD, will be collected in intermediate tank for onward tertiary treatment of
filtration by pressure sand filter and adsorption in activated carbon. The treated water is
collected in final sump. Blowdown from cooling tower is also collected in final sump. From
final sump treated effluent is disposed to Gujarat Govt. CETP and this Slurry is used for
landfilling under government provision.
Block Diagram of ETP:
Figure 10. Block Diagram of ETP
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Effluent Characteristics:
S.no. Parameter Unit Untreated Effluent Treated Effluent MPCB Limits
1 pH mg/l 7–9 6.9 6 – 8.5
2 COD mg/l 2000 – 3000 151 Less than 250
3 BOD mg/l 1000 – 1500 40 Less than 100
4 TDS mg/l 1000 - 2000 1182 Less than 2000
Source:http://www.environmentclearance.nic.in/writereaddata/FormB/EC/EIA_EMP/13082016W60QYLUWEI
A.pdf
USAGE OF METHYL AMINES
The following table presents usage of Methyl amines in various sectors along with the
product in which it is used.
SECTOR WISE DETAILS
Alkyl Amines
Sector Usage Product in which it is used
Product
Dimethoate, Carbaryl,
Insecticide
Cabofuronl
Agrochemicals
An intermediate for
Monomethyl Aceto acetamide
Monocrotophos
Bronchodilator Ephedrine
Monomethyl Pharmaceuticals
Vasodilator Theophylline & Caffine
amine
Rubber & Stabilising &
Natural rubber latex
Chemicals Preservative agent
N-Methyl-J Acid and Fischer base.
Paints & Dyes
Antibacterial Trimethoprim
Pharmaceuticals Antiulcer Ranitidine
Anaesthetic Pentocaine, Tetracaine
Tetramethyl thiuram
Rubber & Vulcanisation disulphide (TMTDS), Zinc
Dimethyl Amine Chemicals accelerator dimethyl dithio carbamate
(Sodium & Potassium salts)
Paints & Dyes Purification of Phthalocynaine pigments.
Weedicide Isoproturon
Agrochemicals Herbicide 2,4-D, Diuron, Monuron
Fungicide Ziram, Thiram
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Ampicillin, Amoxycillin,
Pharmaceuticals Antibiotics
Cephalexin & their derivatives
Trimethyl amine
Plant growth
Agrochemicals Cycocel
regulator
SAFETY ASPECTS IN DESIGNING
Throughout our visits in different plants, safety aspects and measures were given the highest
priority and it’s important as well. We had a very informative lecture from the team of Alkyl
Amine about how safety is incorporated while designing the plant.
Three levels of safety are followed. First, there are alarms which activate if the control sensors
for level, temperature or pressure show high readings which are automated. There are alarms
along with air analysis sensors as well. Second, Alarms along with interlocks to immediately
stop inflow or outflow from any or all the vessels. Third, relieving devices which include safety
valves and rupture discs or both, which lead to a scrubber, tank or sometimes to the flare
directly (if the flue gas is not very harmful), There are always 2 safety valves in case 1 fails.
The scrubbing system and flare are also designed at the very beginning. The scrubbers are
designed such that it can take load of the entire plant at its peak performance. Also, the scrubber
vessels should be able to handle the heat of solution as well. The flare should be always ready
with pilot flame always functional. The height of the flare depends on the radiation flux at the
top of the flare.
The scrubbing systems and flare also ensure environmental protection. Other than these,
sprinklers are built around storage tanks so that any gas leakage can be absorbed in the water.
For avoiding liquid spillages which are hazardous to life, dykes are built around the storage
tank farms such that all the volume that can be stored in the tanks is contained in a boundary
formed by the dyke. There should always be standby tanks to transfer material in case of
leakages or other emergencies.
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UPL LIMITED
HISTORY AND OVERVIEW
UPL, United phosphorus Limited is an India based multinational company that was established
in 1969 at Vapi, India. Started as manufacturing red phosphorus is now engaged in
manufacturing of various industrial chemicals, speciality chemicals and agrochemicals.
Currently it is among the top five companies in the world under generic agrochemical domain.
With the main focus toward producing product for the benefits of farmers, UPL has become
the largest producer of crop protection products in India. UPL offers a comprehensive product
portfolio of crop protection chemicals- fungicides, herbicides, insecticides, plant growth
regulators, speciality chemicals, nutrifeeds and seeds. The Company markets branded generics
and proprietary branded products in all major agro economies across the globe, reinforcing its
identity as one of the most profitable agrochemicals companies in the world. UPL Limited has
entrenched its presence in 122 countries across six continents. UPL operates 35 manufacturing
units with 7400+ employee base globally after merging with Arysta. Their key product are –
acephate (insecticide), propanil (herbicide), Glufosinate (an active ingredient in several non-
selective herbicides), Mancozeb (fungicide), Metamitron (systemic and selective herbicide),
Devrinol (selective systemic pre-emergence herbicide), sulphur and copper. UPL exports its
products to 128 countries having a revenue of more than $2 billion with a growth rate higher
than sector average. With more than 3% of its total revenue on research and development, UPL
has in total has 240+ patents registered and 25+ Successful acquisition integrations in the past
20 years.
MARKET STATISTICS
INTERNATIONAL MARKET
Global market of agrochemicals is very diverse and offer a wide range of products suitable for
different conditions (i.e. soil and pest). Major companies in the market are Syngenta, BASF SE
(Germany), Dow Chemical Limited (U.S.), Bayer AG. They all together account for 70% of
the global agrochemical market. Global market of agrochemicals was valued at USD 207.5
billion in 2014 and with a CAGR of 3.2%, it is expected to achieve USD 250.5 billion by
FY2020.
NATIONAL MARKET
India is the fourth largest global producer of agrochemicals after the US, Japan and China. This
segment generated a value of USD 2.7 billion in FY18 and is expected to grow at 7.5% per
annum to reach USD 4.7 billion by FY19. Approximately 30% of the demand comes from
domestic consumers while the rest goes towards exports.
COMMERCIAL ASPECTS
In last few years, its revenue is continuously increasing because they always took step which
make them compete with international companies and improve them self like they have very
strong backward and forward integration within their plants which make them easy to make
more profit and escape them from dependence of other companies for raw materials and other
inputs.
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Figure 11. Financial summary of UPL
ACQUISITION OF ARYSTA
After the acquisition, UPL will get 5th position from 7th position in terms of Agrochemical
Revenue by increasing from 2.7 billion USD to 4.7 USD.
Figure 12. Acquisition of Arysta
UPL and Arysta, one of the well-known companies gets combined and shared lots of
facilities like
UPL Arysta
Strong geographies – India, Americas, Strong geographies – Africa, Russia, Eastern Europe
Western Europe
Differentiated formulations, mixtures Strong R&D platform that supports growth activities
and combination products
Accelerated product development and 160 FTEs in global product development and
launch capabilities formulation research teams and 150 Regulatory FTEs
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6,150+ registrations 6,850+ registrations
The New UPL will improve in manufacturing capacity, RnD capability and Product capability
After combination, Each company will have 13000+ product registrations and revenue 4.7
billion USD.
They will have access to new AI’s and J-makers and Late stage product development combined
with innovative formulations, mixtures, combinations product strategy as UPL has greater
focus on innovative formulations, combinations, mixtures and label extensions and have local
registrations expertise across geographies whereas Arysta has late stage development
capabilities and access to J-makers and strong relationships with innovators source of AI’s.
IMPORTANT ASPECTS FOR UPL
• Sustainability: Proper uses of resources and promoting recycling and all.
• Safety: Applied many precautions to avoid accidents and disaster.
• Self-Dependent: Have good backward integration and reliable
• Adopting new better technology
• Quality {that is customer satisfaction} of their products
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STRONG BACKWARD & FORWARD INTEGRATION
Figure 13. Product Integration in UPL
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CARBON DI-SULFIDE PLANT
CS2 plant was set up in 2010 in Jhagadia plant and this plant helped them increase the
production of other products. The technology was provided by Akzonobel, Netherland. The
design production capacity of the plant is 110 TPD, but after relevant debottlenecking of the
plant, they operate it at nearly 133 TPD and can operate at a maximum of 150 TPD. CS2 is
majorly used as a raw product for production of Mancozeb, WDG and Antrocol. The by-
product which is formed while producing CS2 is H2S is either converted back to Sulphur or
used for NaHS synthesis. The raw products used for CS2 production is Methane (from Gujarat
Gas) and Sulphur (from Reliance).
The reaction takes place in a furnace and methane is used as fuel. Sulphur is kept in 15% excess
to reduce coke formation. The sulphur provided to the furnace is maintained between 120oC
to 150oC because above 150oC, sulphur is highly viscous and below 120oC sulphur will
solidify. The reaction takes place in vapour phase at 650°C.
Figure 14. Block Diagram of CS2 Plant
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PENDIMETHALIN PLANT
Pendimethalin is an herbicide used to control most annual grasses and certain broadleaf weeds
in fields of corn, potatoes, rice, cotton, soybeans, tobacco, peanuts and sunflowers. It is used
both pre-emergence, that is before weed seeds have sprouted, and early post-emergence.
Pendimethalin is available as emulsifiable concentrate, wettable powder or dispersible granule
formulations.
We saw its production in 2 plants of the UPL Jhagadia complex with the production capacity
of 2850 MTA and 5000 MTA. It is produced using a semi-batch process. The formation of the
complete product takes 7 days. UPL is the largest supplier of pendimethalin in India. Their
biggest competitors is Rallis, a TATA Chemicals Subsidiary and Meghmani Organics LTD
The chemicals used in the process is 4-nitroorthoxylene (raw material), Diethyl Ketone (raw
material), HNO3, H2SO4, H2, HCl, Heptane, Acetone, EDC, SBC and promoter catalyst.
The Hydrogenation takes place in a continuous manner in a loop reactor. A loop reactor is a
reactor in which the material is pumped round one or more vessels or stages in a continuous
process. Its structure is like a continuous tube or pipe into which reactants are fed and from
which the product of the reaction is withdrawn.
A mild nitrating agent is used (20% HNO3, 30% H2SO4) for better reaction control.
The minimum purity that needs to be achieved is 97% and the impurity in this is 1ppm of
compounds containing nitroso group. To achieve this purity, denitrosossation is done, which
include two parts, one is chemical denitrosossation and followed by thermal denitrosossation.
Chemical Denitrosossation is done by adding HCl and acetone at 70 to 73 degree Celsius which
converts nitroso group to nitro and the purity after this stage is 70%. This is followed by a
falling film evaporator to recover acetone. Thermal Denitrosossation is similar to vacuum
distillation at 1 mm Hg pressure and at about 140 to 145 degree Celsius.
Figure 15. Pendimethalin Reaction
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Figure 16. Block Diagram for Pendimethalin plant
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SAFETY MEASURES INCORPORATED BY UPL
UPL has adopted the Japanese method of 5S of Safety:
Seiri (Sort) - Sort out unnecessary items in the workplace and discard them.
Seiton (Set in Order) - Arrange necessary items in good order so that they can be easily picked
for use.
Seiso (Shine) - Clean your workplace thoroughly so that there is no dust on floors, machines
and equipments
Seiketsu (Standardise) - maintain high standards of workplace at all times
Shitsuke (Sustain) - train people to follow good housekeeping automatically
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REFERENCES
Books:
• K. Weissermel, H-j Arpe, ‘Industrial Organic Chemistry’, Fourth Edition, 2003,Wiley
Publication.
• William L Luyben, ‘Plantwide Dynamic Simulators in Chemical Processing and
Control’, 2002, Marcel Dekker Inc.
• Stephen A Lawrence, ‘Amines: Synthesis, Properties & Applications’, 2004,
Cambridge University Press.
• Lohn J McKetta, ‘Encyclopedia of Chemical Processing & Design’, Volume 3, 1977,
Marcel Dekker Inc.
Journal Articles/Papers:
• David R Corbin et al, ‘Methyl Amines Synthesis: A review’, 1997, Catalysis Today
Websites:
• https://www.uplonline.com/
• http://alkylamines.com/index.asp
• http://www.thermopedia.com/content/551/
• https://www.omnicalculator.com/chemistry/Boliling-point
Patents:
• Ashina et al, Patent no. 4485261, 1984, United States Patent
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