MANCOZEB – (A Protective Leaf Fungicide)

A part of its long objective of meeting the entire demand of environment friendly pesticides
used for public health and enhancing its market share in the agrochemical sector, the company
introduced two pesticides namely Mancozeb & Acephate. The company has also entered the area
of biotechnology and physiochemical for pest control. The Mancozeb plant in Udyogamandal unit
has a rated capacity of 1000 TPA (formulated product –1133 TPA). Udyogamandal unit is
producing MANCOZEB 75 WP only. Mancozeb belongs to less toxic category (LD 50 > 5000 mg/Kg
weight – green triangle) used for the control of wide range of plant disease and seed treatment.
Molecular formula: [C4H6N2S4]x [Zn] y, Molecular weight – 541.04.
MANCOZEB TECHNICAL SPECIFICATION (IS: 8707 – 1978)
1. MANCOZEB Content (% / mass) – 85 % Min
2. ZINC Content of Mancozeb content (%by mass) – 2.5 % Min.
3. MANGANESE Content of Mancozeb content (% by mass) – 20 %Min.

MANCOZEB 75 WP SPECIFICATION (IS: 8708 – 1978)

1. MANCOZEB Content - % / mass – 75% [-3% / + 5%] Min.
2. ZINC Content of Mancozeb content (% by mass) – 2.5 % Min.
3. MANGANESE Content of Mancozeb content (% by mass) – 20 %Min.
4. SUSPENSIBILITY : 50% minimum after ATS
RAW MATERIALS
 Carbon Disulphide : CS2, colourless to light yellowish liquid. Boiling Point – 46.3°C.
Distillation below 46.6°C yield % / weight – 95.0%min. Specific gravity / 27OC: 1.257 – 1.261.
H2S, SO2 and other reducing substances max: 5% shall not show any acidic reactions.
Molecular weight: 76, Flash Point – 300C, Auto Ignition temp – 1000C
 Ethylene Di amine : EDA (C2H8N2) – Corrosive, inflammable, colourless to light amber
coloured, viscous, liquid with fishy odour. Assay: 98% min., Molecular weight: 60.1
Specific gravity: 0.900/ 200C. Boiling Point – 1160C, Auto Ignition temp – 3800C.
Flashpoint : 340C.
 Manganese Sulphate: MnSO4 :Pale pinkish powder or liquid, Assay pure grade 97-98%,
Technical grade 83 – 85% max. Fe content - 0.05% max. Chloride - 2% max.
 Zinc Sulphate ( Zn SO4 7H2O) free flowing powder or crystal form(Commercial).Zinc Content
21.0% min.
 Sodium / Calcium lignum sulphonate – act as wetting and dispersing agent.
 Jeemol DN or CBZ – used as a surfactant.
 Sodium Hydroxide lye: Specific gravity 1.480 – 1.500 (Strength 47.5 to 49.5 %).
 Hexamine – Assay: 99% min. It is used as a stabilizer and a fire retardant
 Step I (PREPARATION OF NABAM)

Nabam is the sodium salt of Ethelene bis – dithio carbamic acid and is prepared by reacting
Ethylene diamine with Carbon Disulphide and Sodium Hydroxide. EDA is the limiting reagent and
the reaction medium is water. S S
CH2—NH2 CH2-NH-C-SH CH2-NH-C-SNa
+ 2 CS2 + 2 NaOH + 2H2O
CH2—NH2 CH2-NH-C-SH CH2-NH-C-SNa

S S
EDA Ethylene bis-dithio carbamic acid NABAM
 EDA solution is prepared by taking water in the vessel V102 and necessary
quantity of EDA is pumped using air pressure while cooling with chilled water in the Jacket.
Agitated for a few minutes and find the EDA content. 55.0% EDA solution is used for the first step
reaction.
Close the bottom valve of Reactor R 101(Jacketed stainless steel vessel with
agitator). Check the strength of caustic solution in Scrubber. Switch on scrubber pump. Ensure
Brine cooling in condenser. Circulate cooling water in jacket. Close CS 2 recovery valve & open CS2
reflux valve. Pump in required quantity of water and start agitation. Create an inert atmosphere by
nitrogen blanketing. By maintaining the temperature between 20 – 25 OC, charge CS2. Agitate
(about 10 minutes) until an emulsion is formed. The calculated quantity EDA 55.0% solution is
added. After adding about 1/3rd of EDA solution immediately start the addition of caustic lye. The
rate of addition of both EDA & Caustic lye is adjusted to complete within a period of two hours.
Keep the reaction temperature between 40 – 43 OC, and make sure the reflux is returned back to
the system. The pH of NABAM after the caustic lye addition should be in between 8.6 – 9.4.
Once the pH is achieved close nitrogen. Close the reflux valve and open the distillate
line to D103 (CS2 recovery vessel) and slowly raise the reaction temperature to 62 OC to recover
excess CS2. After complete CS2 recovery, maintain temp 60 + 2OC and keep in nitrogen
atmosphere. Find the pH, specific gravity of the NABAM formed. In the presence of excess of
NaOH / CS2 the following gases formed at high temperature and are absorbed in the scrubber.

2 NaOH + CS2 Na2S + H2S + CO2

Step II (PREPARATION OF MANEB)

Maneb is the Manganese salt of Ethylene bis-dithio carbamic acid. To Concentrated Nabam
solution, Manganese sulphate solution is added with agitation. Maneb is obtained as yellow
crystals in slurry form with mother liquor. It is washed with water to remove Na 2SO4.

S S

CH2-NH-C-S
CH2-NH-C-S-Na
MnSO4 Mn + Na2SO4
+ CH2-NH-C-S
CH2-NH-C-S-Na
S
NABAM S MANEB

Required quantity of water is taken in vessel V–104 and necessary quantity of MnSO4 is
charged to make 27.0% solution. Agitated for a few minutes and settled. Analyse the strength and
Specific gravity. From V –104 the solution is pumped into V–107. Required of MnSO4 27.0%
solution. Find the ratio for adding NABAM to MnSO 4. Set the ratio in ratio meter. To R–102 charge
the initial quantity of MnSO 4 27.0% solution, start agitation and raise the temperature to 45 OC. To
the reaction mass start the addition of NABAM from R – 101through dip line and simultaneously
MnSO4 solution (from V–107) is sprayed from the top. Temperature will reach up to 55 + 2 OC and
the addition should be completed within 1½ hours. During the addition check the excess MnSO 4
content in the reactor at intervals and keep in between 0.5 – 0.9%. After complete addition check
the excess MnSO4 again and should be around 0.6 – 0.9%. Cool to room temperature for filtration.
The Na2SO4 formed during 2nd step is removed by water washing. The Maneb and Na 2SO4
formed is transferred to Nutsche filter, fitted with a unique style agitator, which can stir up, down,
clock & anti clockwise directions. The slurry is stirred, washed and filtered until the sulphate
content becomes less than 1.0%. The Na2SO4 solution is pumped to ETP.
 Step III (PREPARATION OF MANCOZEB)
The washed Maneb is reacted with ZnSO4 forming Mancozeb. It is a coordination product
of Manganese Ethylene bis-di thio-carbamate and zinc ion, which is greenish yellow coloured
powder. It is formulated using wetting – dispersing agent, surfactants and stabilizer cum fire
retardant. S S
CH2-NH-C-S
CH2-NH-C-S Mn
Mn + ZnSO4 CH2-NH-C-S Zn
CH2-NH-C-S
S
X Y
S
Water is taken in vessel V104 and required quantity ZnSO4 is charged to make 32.0% Zinc
Sulphate solution. Agitated for a few minutes. Find the strength and Specific gravity. Solution is
pumped from V – 104 to V – 107. Washed Maneb is taken in R–103 and agitation started. ZnSO4
solution is added slowly to the reactor and after the addition is complete the mass is agitated for 3
hours. (Make sure the agitator is always working when
Maneb or Mancozeb slurry is in the reactors/ storages). Mancozeb slurry is transferred to
tank T – 105 A or T– 105B using slurry pump P – 105. The stabilizer Hexamine and Sodium /
Calcium lignum sulphonate – wetting and dispersing agent are added here and agitated for uniform
mixing.
Due to the highly combustible and easy decomposition nature, slurry containing 30%
Mancozeb is dried in two steps. The moisture content is reduced to 10 – 12 % in a spray drier in
the first step and the moisture content of < 1% is achieved in a rotary vacuum drier in the final
drying stage. The spray drying is a perfect process, which help to minimise residual moisture,
increase bulk density and develop particle shape & to form uniform particle size. The spray drying
unit consists of a feed pump which can change its RPM according to the outlet temperature (75 –
80 OC) of the chamber, an atomiser having an RPM of 12500, an air heater – inlet temperature
between 230 OC to 250 OC and an air disperser, drying chamber and systems for exhaust air
cleaning and powder recovery. The slurry is pumped and atomized in the form of a fine spray and
fed into the spray chamber into which hot air is also admitted. Moisture evaporation takes place
from the surface of droplets and product gets dried. Best part of the product falls to the base of the
chamber and the rest passes out entrained in the air. It is scrubbed in the scrubber and air is
vented out. The water evaporation capacity of spray drier is 1200 litre/ hour. The moisture content
of spray-dried sample is analyzed.
In Rotary vacuum evaporator the moisture content of spray dried material is reduced below
1.0%. Ensure the moisture content below 1% by analyzing. Ensure no leak in RVD by checking the
vacuum. Charge the whole S.D. material to RVD. Then steam is admitted through the jacket of the
RVD and apply vacuum in RVD to remove moisture. Initially the vacuum seems to drop down at
the beginning and then vacuum will start building up. Cool the temperature of the material below
40 OC and slowly release the vacuum while balancing with nitrogen purging. Ensure the bottom
valve of the blender closed well and transfer the material from RVD to the blender. Charge fillers
(lavigated clay) and surfactants (about 3% - Jeemol DN & CBZ). Close the blender lid, start
agitation and blend the material for 4 to 5 hours to ensure a homogeneous product. The product
from blender bagged using bagging machine in 25 Kg paper bags with two polythene liners inside.
The inner liner is sealed with nitrogen filling. The bagging sample sends for content &
Suspensibility analysis.