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MANUFACTURING PROCESS
o Alkylation
o Carboxylation
o Acetylation
o Condensation
o Cyclization,
o Dehydration
o Halogenation
o Oxidation
o Sulfonation
o Nitration
o Amination
In each reaction, state some raw material remain un-reacted, and some unwanted
product are formed which remain in the system. Desired products are carefully
recovered in each step from the system. Unwanted products are discarded, but not
carefully. These inevitably become pollutants in wastewater and solid waste. Some are
vented out in the atmosphere. Although in some cases some recyclable materials are
also profitably taken back in to the system. Impurities present in raw materials may also
react with one another and in many cases show up as a scum, froth or tar or simply as
un-reacted raw material. In order to understand generation of wastewater, solid waste
and emission understanding of unit process and operation is required. The typical unit
operation of chemical synthesis is depicted in Fig. 1. Within this backdrop the
manufacturing process of some of the technical grade pesticides and associated air
pollutants are discussed in the subsequent paragraphs.
6
Energy
Oil , coal, natural gas,
electricity, steam etc.
Chemical Auxiliaries
Recycling especially
Chemical Raw of catalysts
materials
Chemical operations /
process/ reactions and Unit Products
Operations
By Products for
internal or external use
Waste Heat
Gaseous
Wastages
Waste Water
7
2.1. Acephate
Process starts with the addition of Dimethyl Sulphate to Dimethyl thio phosphoramide
(DMPAT) to give Methamodophos, which is acetylated with acetic Anhydride in presence
of sulphuric acid to give crude acephate. Crude acephate is neutralised with ammonia
solution and extracted in methylene chloride. The extracted acephate liquor is
crystallised under chilled condition in presence of Ethyl acetate. Crystallised Acephate
is then centrifuged and dried. The chemistry of Acephate production is stated below:
Step 1: Isomerisation
CH3CO S CH3CO O
70oC
P NH2 + DMS P - NH2
CH3CO CH3CS
Dimethyl
Sulphate Methamodophose
DMPAT
Step 2:Acetylation
CH3CO O CH3CO O O
CH3-C 65-70oC
P NH2 + O P-N-C-CH3 + CH3COOH
H2SO4
CH3CS CH3-C CH3CS
H
O
Acephate
Methamodophose Acetic Anhydride
Liquor ammonia is slowly added under stirring to neutralize sulphuric acid and acetic
acid. Liquor ammonia is added till pH is about 7. Layers are separated. Organic layer is
washed with water. Aqueous layer is sent to effluent treatment plant.
8
Step 4:Crystallisation of Acephate Liquor
DMPAT
DMS
Methylene
chloride ISOMERISATION MeCl2 (Recycle)
MeCl2
Acetic
ACETYLATION
Anhydride
Ammonia
NEUTRALISATION Sulphuric Acid
Liquor
Aqueous Phase
MeCl2
EXTRACTION
(Recycle)
[1] Acetic Acid (50%)
[2] Ammonium Sulphate
Ethyl Acetate CRYSTALISATION
CENTRIFUGATION
ACEPHATE W/C
9
2.2 Aluminium Phosphide
MIXING
UNIT Vent P2O5 (as H3PO4 mist)
735 Kg
H3PO4
WATER ABSORBER BY PRODUCT
100
700 Kg Liters WASTEWATER TO ETP
CRUSHING
700 Kg
Urea/MR-17 210 Kg WAX
30 Kg.
Zn St 20
GRAPHITE BLENDING
40 Kg. OVER SIZE
RECYCLE
SEIVING
TABLETING POUCHING
PACKING
Aluminium Phosphide
10
2.2.1. Associated Air Pollutants
During the course of reaction, P2O5 fumes (as H3PO4 mist) generated, which are
pass through scrubber, followed with mist eliminator so as to control the emission
of pollutants. Also, dilute phosphoric acid is generated as a by-product by the
industrial units.
2.3 Captafol
2S + Cl2 S2Cl2
Cl Cl
Cl Cl
C=C + SCl2 Cl C C H
Cl H
SCl Cl
Tri-chloro Ethylene
TCESCl
11
Step 4: Condensation
Cl Cl 0
C
Cl C C H + N + NaOH
C
SCl Cl 0
TCESCl Tetrahydro Phthalic Imide
Cl Cl
C
N S C C H + NaCl + H2O
C
0 Cl Cl
Captafol
In the manufacturing of Captafol pesticide, S2Cl2 & SCl2 are formed during
chlorination of sulphur and subsequent chlorination of sulphur monochloride. It is
observed that there is no direct emission of S2Cl2 & SCl2. But, only chlorine
emission takes place during process, which is confirmed during in-depth study.
2.4 Captan
12
Step 3: Condensation
O O
Cl
C C
CSCl4 + NaOH + NH N S C Cl + NaCl
C C
Cl
O O
Tetra Hydro Pthelic Amide Captan
Step 4: Washing
Step 5: Filtration & Drying
EDC
Cl2 CHLORINATION
Water
Toluene CSCl4
dilution
THPI
NaOH
CONDENSATION
H2O
Recycled ML
Water
Aqueous Phase to ETP
WASHING
Toluene
FILTERATION ML to Recycle
& DRYING
CAPTAN
Fig. 4: Process Flow Diagram of Captan Manfuacturing
13
2.4.1 Associated Air Pollutants
The air pollutants identified from the process of manufacturing of Captan are
Hydrochloric Acid (HCl) and Chlorine (Cl2).
2.5 Cypermethrin
Dichloro Vinyl Cyclo propane Carboxylic Acid Chloride (DVACl) also known as
Cypermethric Acid Chloride (CMAC) and Meta Phenoxy Benzaldehyde (MPBAD)
are taken in an agitator reactor, in a solvent (Hexane). Sodium cyanide and
water are added to the mass. Mass is agitated in reactor for the required time. At
the end of reaction, the reaction mass is separated into two phases, organic layer
and aqueous layer.
-
Aq. CN LAYER Cyanide Treatment)
CYPER + HEXANE
1st Water wash
1st Soda wash
2nd Soda wash
2nd Water wash
2-WASHING
CYPER + HEXANE
3-CONCENTRATION
CYPER TECH.
14
DVA chloride
MBBA is reacted with phenol in presence of catalyst, KOH and Toluene to form
Meta Phenoxy benzaldehyde acetal (MPBA). MPBA is further treated with
caustic lye in presence of water. Aqueous layer is separated from organic layer
and treated with sulphuric acid. KBr solution formed during the course of
treatment is then taken for Bromine recovery. Organic layer containing MPBA
and toluene is taken for hydrolysis in next stage.
15
2.5.1 Associated Air Pollutants
2.6 Dimethoate
S
S S
OCH3
P S P + 4 CH3OH P + H2S
S S HS OCH3
20% Sodium carbonate is added to the DDPA solution prepared as above till pH
7.0. The layers are separated. The toluene layer goes for purification and the
aqueous layer containing sodium salt of DDPA is taken for next step.
S S
OCH3
CH3O
P + Na2CO3 P + CO2
DDPA Na-DDPA
16
Step 3: Methyl monochloro acetate (MMCA)
Monochloro Acetic Acid, Methanol and Catalytic amount of sulphuric acid are
refluxes and MMCA formed is distilled out at 140oC and used for the next step.
Step 4: Condensation
Na-DDPA prepared as in step 2 and MMCA prepared as in step 3 are mixed and
heated for four hours at 60oC under stirring. After the reaction is over same is
washed with water and carried out amidation reaction with MMA at –2oC. The
reaction mass is neutralised to pH 5.5 – 6.0 with 10% sulphuric acid and the
product is extracted with ethylene dichloride solvent. The solvent is then
removed from the separated organic layer under vacuum at 70 -75oC and
dimethoate is packed.
The air pollutants identified from the process of manufacturing of demethoate are
Hydrogen Sulphide (H2S) and Methanol (CH3OH). Methanol is not reported by
the industrial units.
17
P2S5 H2S to Scurbber
Methanol DDPA
PREPARATION
Toluene
Na2CO3 NEUTRALISATION
(20%)
MMCA CONDENSATION
PREPARATION
Ice
EDC
40% MMA AMIDATION
10% H2SO4
EDC to Recycle
DRYING Loss
FINISHED
DIMETHOATE
18
2.7 2,4 – Dichlorophenoxy acetic acid (2,4 – D)
Q1 SCRUBBER CHLORINATION
HCl 1. PHENOL
2. ACETIC ACID
CONDENSATION
Q2
FILTRATION 2,4-D SODIUM
ACIDIFICATION
OF
2,4-D SODIUM
Q3 E1
FILTRATION
2,4-D ACID
19
2.8 Dichlorvos (D.D.V.P)
In the first step Tri-Methyl Phosphite (TMP) is slowly allowed to react chemically
with tri chloro acetaldehyde at controlled conditions of temperature and at
ambient pressure to produce crude DDVP.
Product obtained from step 1 is purified under vacuum by film evaporator to get
final product having purity around 95%. The chemistry of DDVP manufacturing
process is stated below:
O
DRYING
PACKING
Dichlorvos 1000 kg
(DDVP) %
Methyl chloride (CH3Cl).is identified air pollutant from the manufacturing process
of D.D.V.P.
20
2.9 Ethion
Toluene is taken in the reactor and phosphorus pentasulfide is added under stirring.
Temperature is raised and ethanol is slowly added under controlled temperature
conditions. During the reaction, hydrogen sulphide gas is evolved. It is absorbed in dilute
sodium hydroxide solution in a scrubber.
With Dithioacid formed in step No. 1, sodium hydroxide solution is added slowly and
temperature is controlled by circulating cooling water in the jacket of reactor. At the end
of reaction, two layers are separated. Aqueous layer is taken for next step and organic
layer is sent for toluene recovery.
Step 3: Condensation
To the aqueous solution of sodium salt of dithioacid, methylene bromide is added, and
temperature is raised under maintain condition. At the end of reaction, layers are
separated. Aqueous layer contains sodium bromide and organic layer contain product is
steam stripped to remove impurities.
S
C2H5O
4 C2H5OH + P2S5 2 P - SH + H2S
C2H5O
S S
C2H5O C2H5O
P - SH + 2NaOH 2 P - S - Na + H2O
C2H5O C2H5O
S S S
C2H5O C2H5O OC2H5
2 P - S - Na + Br - CH2 - Br 2 P - S - CH2 - S - P + 2 Na Br
C2H5O C2H5O OC2H5
21
The process flow diagram of Ethion manufacturing is given at Fig. 9.
CATALYST
METHYL DIBROMIDE
CAUSTIC LYE
INDUSTRIAL ALCOHOL
PHOSPHOROUS
PENTASULPHIDE
PROUCT - ETHION
NaOH ETHION ETHION
DDPA REACTION PREPARATION REACTOR PURIFICATION
Hydrogen Sulphide (H2S) and Ethyl Mercaptan (C2H5SH) are identified air
pollutants from the manufacturing process of Ethion.
22
2.10 Endosulphan
Cl Cl HOH2C Cl
Cl CH2OH
Cl Cl + HC Cl Cl H
H
Cl
Cl Cl HC CH2OH
Cl
HCCP HOH2CBut.Diol Het Diol
But. Diol
Step 3: Het Diol is then reacted with Thionyl chloride in Carbon tetrachloride
solvent to give Endosulphan solution.
Cl Cl
Cl CH2OH CH2O
Cl
Cl Cl H H
+ SOCl2 Cl Cl
H H S = O + 2HCl
Cl Cl
CH2OH CH2O
Cl Cl
Hydrochloric Acid (HCl) is identified air pollutant from the manufacturing process
of Endosulphan.
23
Hexachlorocydapentadiene
Butene Diol Solvent
Reactor-I
Tower
Unit
Endosulphan (Technical)
2.11 Fenvalerate
Para chloro toluene (PCT) is chlorinated to Para chloro benzyl chloride (PCBC).
The HCl and Cl2 gases liberated are scrubbed with water and caustic solution.
The chlorinated mass is distilled to remove excess PCT. PCBC is reacted with
Sodium cyanide to form PCCN. The aqueous layer is treated with Sodium
hypochlorite to reduce cyanide content.
The para chloro benzyl cyanide is reacted with Isopropyl bromide in presence of
caustic to form PCAN. The reaction mass is washed with water. Aqueous layer
is taken for NaBr recovery. The organic layer is taken for fractional distillation.
PCAN thus obtained is hydrolysed with sulphuric acid to form PCA.
PCA is further reacted with Thionyl chloride to obtain PCA chloride. The gases
liberated are scrubbed with water to remove HCl and with caustic to remove SO2.
PCA chloride thus obtained is condensed with MPBAD, alongwith sodium
cyanide and washed with water. Organic mass containing solvents is taken for
solvent distillation. Fenvalerate (Tech) thus obtained is packed in drums.
24
The aqueous layer containing excess cyanide is treated with Sodium
hypochlorite and is drained to ETP. The process flow diagram is given at Fig.
11A to Fig. 11 E
PCT - 1908 Kg
CATALYST - 9.54 Kg TO SCRUBBER (30% HCl)
DCM - 19.08 Kg
Cl2 - 279.84 Kg HCL - 143.1 Kg (100%)
CHLORINATION
C/PCBC + PCT
2073.36 Kg
Rec. PCT
Mid CUT
DISTILLATION
PCBC
D/PCBC(96%) - 596 Kg
NaCN - 200 Kg
H2O - 200 Kg
Catalyst - 22.4 Kg
Reactor
1st. Dilution water - 440 Kg
1st. Wash Water - 900 Kg
Washer
(1st. Dilution + 1st. Wash)
-
CN Effluent
-
(For CN Treatment)
C/PCCN
25
C/PCCN (96%) - 543.543 Kg
IPBr. (98% min.) - 427.284 Kg
Catalyst - 34.32 Kg
Caustic Lye (47%) - 1029.6 Kg
Reactor
WASHER
(1st. DILUTION)
Aq. NaBr - 1716 Kg
(For Br2 - Recovery)
Ref. IPBr
1st. Fraction
D/PCAN (96%)
DISTILLATION
Residue (Incineration)
26
D/PCAN (96%)
H2SO4 (98%)
H2O
EDC
1 - HYDROLYSIS
2 - ISOLATION
EDC
Effluent to ETP
PCA + HEXANE
HCl
To Scrubber
SO2
SOCl2
SO2
DMF
Rec. Hexane
3 - PCACl
Reaction
DMF Layer
C/PCACl
Rec. Hexane
1st Fraction
D/PCACl
4 - DISTILLATION
Residue (Incineration)
27
NaCN
H2O
CATALYST
MPBAD (99%)
D/PCACl (96%)
TOLUENE
Salt Sln.
1. FEN. REACTION
FEN. + TOLUENE
SODA-WASH
WATER-WASH
2. WASHING
FEN. + TOLUENE
Rec. TOLUENE
3. CONCENTRATION
FENVALERATE (TECH.)
28
2.11.1 Associated Air Pollutants
Hydrochloric Acid (HCl), Chlorine (Cl2) and Sulphur Dioxide (SO2) are identified
air pollutant from the manufacturing process of Endosulphan.
2.12 Malathion
CHCO CHCOOC2H5
C6H6
O + 2C2H5OH + H2O
H2SO4
CH3O CHCOOC2H5
(DEM)
CH3O S CHCOOC2H5 CH3O S
P + HQN P
CH3O SH CHCOOC2H5 CH3O SCHCOOC2H5
(DEM)
CH2COOC2H5
29
DDPA PREPARATION
NaOH + WATER
142 335
H2S GAS SCRUBBER
P2S5 800
METHANOL 480 DDPA
TOLUENE 300 PREPARATION SPENT NaOH SOLUTION
600
Reaction Mass
1458
FILTERATION 1
P2S5 Residue
1457
DDPA
DEM PREPARATION
90
H2SO4 VAPOUR LOSS
CRUDE DEM
1007
SODA SOLUTION 60
240 NEUTRALISATION 370
TO ETP
WATER
937
NEUTRALISED DEM
MALATHION PREPARATION
1457 937
DDPA DEM
CONDENSATION
CRUDE MALATHION
CAUSTIC 110 2424
WATER 1890 NEUTRALISATION TO ETP
230
DRYING TOLUENE
1740
MALATHION TECHNICAL
30
2.12.1 Associated Air Pollutants
Methyl Alcohol and Bromine are reacted in a glass lined reactor. After completion
of Bromination, distillation of Methyl Bromide is started. As the boiling point of
Methyl Bromide is 4.5º C, chilled brine having temperature less than – 8º C is
circulated in the Reflux condenser as well as Product condenser.
Dense ash
column
31
2.13.1 Associated Air Pollutants
2.14. Monocrotophos
Step 2: Condensation
(MMAA) (MMACl)
CH3O CH3O O
MMACl + P - OCH3 P + CH3Cl
CH3O O - C = CH - CO - NHCH3
CH3O
CH3
Monocrotophos
TMP
32
Mathanol + Water 1544 Kg HCl Fumes 48 Kg
MMAA 450 Kg
2251 Kg.
3004 Kg.
METHANOL
Reuse (16% Water) 1128 Kg
DISTILLATION Recovered Methanol (50%) 630 Kg
1201 Kg.
EDC 1244 Kg
EXTRACTION
Aqueous to ETP g
1687 Kg.
658 Kg.
TMP 381 Kg
CONDENSATION Methyl Chloride 125 Kg.
EDC 84 Kg
998 Kg.
PURIFICATION TMP + EDC + Impurities to EDC
Recovery
MONOCROTOPHOS
Hydrogen Chloride (HCL) and Methyl Chloride (CH3Cl) are identified air pollutant
from the manufacturing process of Monocrotophos.
33
2.15 Isoproturon
Cumene is nitrated with a mixture of nitric acid and sulphuric acid to produce
nitrocumenes. Nitrocumenes are reacted with sulphur and caustic soda to give
cumidine. Cumidine is reacted with urea and di-methyl amine in presence of
solvent to produce isoproturon. Isoproturon is isolated by filtration and dried then
pulverised and packed. The process flow diagram is given at Fig. 15
WASHING to ETP
Caustic Lye MAKE UP MAKE UP WATER
WATER
SULPHUR SULPHURIC ACID
SULPHUR
THIO SULPHUR
REDUCTION to ETP
SULPHATE RECOVERY
RESIDUES FOR
DISTILLATION
INCINERATION
UREA OFF GASES TWO STAGE
-NH3 WATER ABSORBER RECOVERED
NH3 Reuse /Sale
MAKE UP DMA
AQUEOUS STREAM
PURIFICATION
RAFFINATE to ETP
WATER
DMU MCB
RECOVERY RECOVERY
AQUEOUS MONOCHLORO PARACUMIDINE
SEPARATION RESIDUE ACID
BENZENE (MCB) FOR REUSE IN
RECOVERY CONDEN-STEP
ORGANIC HYDROLYSIS
LAYER
ORTHO NITRO
CUMENE FOR
PURIFICATION FROM STEAM DISTILLATION to ETP INCINERATION
34
2.15.1 Associated Air Pollutants
2.16. Phosalone
OH
O
NH2 - NH
+ H2N - C - NH2 + 2NH3
C=O
(HMCB) O
- NH - NH
+ Cl2 + HCl
C=O C=O
Cl
O O
- NH - N - CH2OH
+ HCHO
C=O C=O
Cl Cl
O O
- N - CH2Cl
+ HCl Gas +H2O
C=O C=O
Cl Cl
O O
(CMCB)
C2H5O SH
P2S5 + 4C2H5OH 2 P + H2S
C2H5O S
(DDPA)
35
C2H5O SH C2H5O SNa
P + NaOH P + H2O
C2H5O S C2H5O S
OC2H5
C2H5O SNa - N - CH2Cl - N - CH2 - S
+ + NaCl
P P
C=O C=O
C2H5O S Cl S OC2H5
O O
(Phosalone)
The process flow diagram for manufacture of Phosalone is shown in Fig. 16.
Ammonia (NH3), Hydrochloric Acid (HCl) and Hydrogen Sulphide (H2S) are the
identified air pollutants from the manufacturing process of Phosalone.
36
NH3 GAS HCl GAS
SOLVENT MAKE TO SOLVENT MAKE TO HCl
UP SCRUBBER UP SCRUBBER GAS
DA
P
URE REACTION REACTION AND CENTRIFUGE REACTION
CRYSTALLISATION
A
CHLORINE
MOTHER
FORMALDEHYDE LIQUOR
WATER SOLVENT
P2S H2S TO FURNACE
NaO
H
EFFLUENTS AQUEOUS
CONCENTRATION
LAYER
PHOSALONE
SOLVENT
RECOVERY
Fig. 16: Process Flow Diagram of Phosalone Manufacturing
37
2.17 Phorate
Phosphorus pentasulfide and ethyl alcohol are reacted slowly in the presence of
Diethyl thio phosphoric acid (DETA) heel at 60-65º C. Hydrogen sulphide
evolves from the reaction mixture. The gas is scrubbed with caustic lye. It gets
converted to Di- sodium sulphide and sodium hydrogen sulphide, which has a by
–product value. After the completion of reaction, the product is charged in
another reactor through a sparkler filter. The product of step one is reacted with
Formaldehyde and Ethyl Mercaptan at room temperature to produce crude
phorate. This is a condensation reaction. Crude Phorate thus obtained from
step I is washed using washing soda and steam stripped to remove volatile
organics and moisture. The process flow diagram of phorate manufacturing
process is show in Fig. 17.
S S
C2H5O S – CH 2 -SC 2 H 5
P + H20
C2H5O S
(Phorate)
Hydrogen Sulphide (H2S) and Ethyl Mercaptan (C2H5SH) are the identified air
pollutants from the manufacturing process of Phorate.
38
Phosphorous Penta Sulphide
Industrial Alcohol
Caustic lye
Hydrogen
DTA Reactor sulphide Reactor
Ethyl Mercaptan
Phorate Reactor
Soda Ash
Recycle
Washing Reactor
Water
Purification Reactor
Caustic lye
Phorate
Chlorine
39
2.18. Phosphamidon
O O O Cl O
CH3 -C -CH2 -C - N(C2H5)2 + Cl2 CH3 - C - C - C - N(C2H5)2 +2HCl
Cl
(DEA) (DDA)
O CH3 O
Chlorobenzene H3CO
DDA + (CH3O)3P P - O - C = C - C - N (C2H5)2
H3CO
Cl
(Phorphamidon)
(TMP)
Hydrochloric Acid (HCl) and Methyl Chloride (CH3Cl) are the identified air
pollutants from the manufacturing process of Phosphamidon
40
WATER
DEA 0.531
HCl GAS 0.244
CHLORINATION SCRUBBER
CHLORINE TO ETP
0.540 26.0
DEGASSING
DDA DRYING
METHYL CHLORIDE 0.168
TMP 0.599 TO STACK
NaOH
TOXIFICATION
SOLVENT
JET CONDENSATE
0.050
PRECONCENTRATION PURIFICATION DE-TOXIFICATION
41
CATALYST
769Kgs 231Kgs
ZINC PHOSPHORUS
WATER
DUST TANK/
TRANSFER
WATER TO ETP
1000
Kgs.
REACTOR
BALL MILL
GRINDING
SEIVING
PACKING
DESPATCH
Zinc Phosphide
42