Hazardous waste Treatment and Management
IN
Khaitan Chemical and fertilisers group
Presented By:
Kamesh Kumar
18CH60R39
Company
• KCFL began its operation in 1987 at Nimrani near Indore, West Madhya Pradesh.
The Company has India’s largest Single Super Phosphate (SSP) production capacity
of 11,13,500 MTPA in the states of Madhya Pradesh, Rajasthan, Uttar Pradesh,
Chattisgarh and Gujarat.
• Production of 2,70,600 MT of Sulphuric acid at four different locations in the states
of M.P., U.P. & Chhattisgarh.
• The Company’s main activities are Fertilizer, Sulphuric Acid, Soya Oil and Power
Generation for captive consumption.
SSP Production
The reactions occurring during the production of single superphosphate are
complex and are usually summarized as follows:
Ca5(PO4)3F + 5H2SO4 → 5CaSO4 + 3H3PO4 + HF
Ca5(PO4)3F + 7H3PO4 + 5H2O → 5Ca(H2PO4)2 .H2O + HF
These reactions can be combined to give the overall equation:
Ca5(PO4)3F + 7H2SO4 + 3H2O → 7CaSO4 + 3Ca(H2PO4)2 + H2O + 2HF
= 2CaF2+ O2
Minor 2CaO+2F2
Reactions 3CaO + P2O5 = Ca3(PO4) 2
CaO+SO3 = CaSO4
MgO+H2SO4 = MgSO4 + H2O
Fe2O3+3H2SO4 = Fe2(SO4) 3 +3H2O
CaF2+H2SO4 = CaSO4 +2HF
Pollution
4HF+ SiO2 = SiF4+H2O
Reactions
3SiF4+2H2O = 2H2SiF6+ SiO2
Process Flow Diagram :
Source of generation
• The evolution of fluorine containing gases is a major problem in the SSP Production
process.
• The arise from the fluoride and silicon contained as impurities in the rock.
• These elements combine with the water to form flurosilic acid (H2SiF6).
• Typical rock phosphate contains about 8% Silica and 3% Fluorine by weight and the
fluoride evolution is 25% of the fluoride in the rock, increasing with increased
sulphuric concentration.
Why Hazardous?
• Hexafluorosilicic acid can release toxic Hydrogen flouride gas when evaporated,
so it has similar risks.
• Inhalation of the vapors may cause lung edema.
• Disposal of such H2SiF6 solutions is difficult, since the materials therein, produce
stream contamination if the liquid .
The temperature condition in the den causes a partial dissociation of fluorosilic acid,
according to following chemical equation.
H2SiF6 SiF4 + 2 HF
Treatment Methods:
Fluoride Scrubbers:
The SiF4 is easily scrubbed with a 4 pass counter current water scrubber followed by a
2 pass alkaline Hypochlorite odour scrubber.
The Fluoride is converted to Fluorosilcic acid in the first 4 passes & is then consumed
as process liquor in the mixer.
Silica is precipitated during the first three passes & is kept in suspension using high
volume Warman centrifugal pumps.
Any remaining SiF4 is scrubbed out by the alkaline last two passes.
Utilization Process
• Process involves reaction of hydro fluoro-silicic acid with sodium chloride resulting
into precipitation of the Sodium SilicoFluoride salt
• Salt is then centrifuged and washed for recovery of Sodium silico fluoride precipitate
from mother liquor
• The centrifuged precipitate is dried in hot air oven dryer
H2SiF6 + 2NaCl Na2SiF6 + 2HCl
• The reaction proceeds at room temperature
Proposed Process
Hydro-fluoro-silicic acid
NaCl Solution
Reaction Vessel
Acidic Mother Liquor Centrifuging of precipitated SSF
Hot air oven dryer at 70 C
ETP
Multiple Effect Evaporator
Pulverization & Screening
Scrubber
Discharge with treated water
Product Na2SiF6
• The Spent mother liquor containing HCl collected in separate tank for treatment
with sodium hydroxide or calcium hydroxide followed by further treatment in MEE
• The MEE salt is sent to TSDF for encapsulation and secured landfilling
Efficiency of Utilisation:
• Produce 1.25 tonnes of sodium silico fluoride from 1 Tonne of hydro fluoro
silicic acid.
• Consumption of sodium chloride = 0.75 tonnes per tonne of spent hydro floro
silicic acid.
Product utilization
• In glass industry
• fluorinating agent in pharmaceuticals and drinking water
• As antiseptic in timber industry
• In Laundry and Dishwashing Products
• Hardening of cement
• solidifying agent in natural latex products
• Additive in plating with zinc, nickel, iron and filler in plastic
• To produce insecticide in pesticide industry and sodium fluoride in man-made cryolite
Discharge waste water
• pH – 5.5 – 9.0
• Fluoride – 2.0 mg/l
• COD – 250 mg/l
• Total Suspended Solids – 100 mg/l
• Total residual chlorine – 1 mg/l
Conclusion:
The Flouride gases and its related compound formed during
Superphosphate production was effectively treated and utilised in
different processes like water treatment as well as in Glass
industries,Aluminium industries,etc.
References :
• [Link]
• [Link]
• [Link]
• [Link]
