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Cyanides
Amarjit Singh
18201019
Mtech Environmental Engineering
Chromium
pigments in paints, inks, and lead chromate (chrome yellow, chrome green, molybdenum orange), zinc chromate, barium
plastics chromate, calcium chromate, potassium dichromate, sodium chromate
anti-corrosion coatings (chrome chromic trioxide (chromic acid), zinc chromate, barium chromate, calcium chromate, sodium
plating, spray coatings) chromate, strontium chromate
stainless steel and other high hexavalent chromium (when cast, welded, or torch cut)
chromium Alloys
textile dyes ammonium dichromate, potassium chromate, potassium dichromate, sodium chromate
• The pH is critical and should not be allowed to rise above pH 3. It may be necessary to arrange
for pH control to be included with acid addition to ensure satisfactory reduction.
• Hexavalent chromium levels of 0.1 mg per litre (0.1 PPM) may be consistently achieved .
• Typical flow diagrams are given in figure 7.9 for gaseous Sulphur dioxide and figure 7.10 for
aqueous solutions of sodium sulphite, bisulphite or metabisulphite.
• Generally Sulphur dioxide is preferred for larger treatment plants of above around 9 metre
cube per hour 2000 gallons per hour when the additional capital cost is outweighed by the
cheaper reagent
• Ferrous sulphate is the traditional alternative to Sulphur Dioxide . It has the advantages of lower toxicity
and lower cost, but the greater disadvantages of a significantly longer reaction time, great excess of
reagent, and the problem of subsequently removing iron by neutralization and precipitation
• The reaction is;
• Conditions for satisfactory reduction are well defined compared with Sulphur Dioxide;
residence time of at least 30 minutes is required but above pH 3 this increases as pH increases
to around an hour .
• Ferrous sulphate is not now widely used.
Removal of chromium
• Ion exchange is one of the more widely employed chromium and chromic acid
recovery process. Cation exchange although not widely practiced, may be
employed to recover trivalent chromium Ions. Anion exchange is employed for
hexavalent chromate ions. pH control is necessary to avoid degeneration of the
resin.
Ion Exchange
It is based on the exchange of cations or anions on synthetic resins with essential
characteristics of its regeneration after the elution of ions
• Resins are classified based on the type of functional group they contain:
• Cationic Exchangers:
-Strongly acidic –functional groups derived from strong acids e.g., R-SO3H
(sulfonic).
-Weakly acidic –functional groups derived from weak acids, e.g., R-COOH
(carboxylic).
• Anionic Exchangers:
-Strongly basic –functional groups derived from quaternary ammonia
compounds, R-N-OH.
-Weakly basic -functional groups derived from primary and secondary
amines, R-NH3OH or R-R’-NH2OH.
Cyanide
• Cyanide is probably the best known and the most ‘emotive’ pollutant.
• Cyanide (CN-) is a toxic species that is found predominantly in industrial effluents
generated by metallurgical operations.
• Here we are more interested in aqueous cyanide in alkaline solution.
• This can exist as sodium cyanide or a heavy metal cyanide such as nickel, copper,
zinc, cadmium or silver.
• It is the acid gas, hydrocyanic acid(HCN), that is particularly toxic, very small
concentrations rapidly causing death or inhalation.
• Thus acidification of any cyanide compound is highly dangerous.
• Wastewater from these processes that contains even trace amounts of cyanide
must be treated before discharge into sewage systems.
• Cyanide wastewater treatment is critical, because cyanide wastes are toxic to
living organisms. Specifically, cyanide may reduce or eliminate oxygen utilization
in organisms, including human beings, making cyanide poisoning potentially fatal.
• Aquatic life, including microorganisms involved in natural water purification
streams, is particularly susceptible to cyanide poisoning.
• Cyanide toxicity presents a direct human hazard if cyanide containing wastes
enter agricultural or municipal water supplies.
Treatment
• Most treatment methods are devoted to destruction of cyanide by oxidation either partially to
cyanate or preferably completely to carbon dioxide and nitrogen.
Oxidation by Chlorination
• This is the most popular and widely used method of oxidation.
• For small installations of upto 9m3 per hour (2000 gal/h) capacity, sodium hypochlorite solution
tends to be preferred, while larger plants tend to use gaseous chlorine which costs less but
requires a higher initial expenditure.
• Cyanide waste treatment is usually a two-stage process.
• Stage 1 oxidizes cyanide to cyanate using oxidizing agents such as sodium hypochlorite in the
presence of an alkali (pH = 10). This reaction is accomplished most completely and rapidly
under alkaline conditions at pH 10 or higher. An oxidation period of 10 to 15 minutes is usually
adequate however retention times up to 60 minutes are required to complete the reaction.
• The second stage oxidizes the cyanate (which is much less toxic than cyanide) to carbon dioxide
and nitrogen through the use of more sodium hypochlorite in the presence of Hydrogen
peroxide
• Conditions for successful oxidation are well defined,
pH is critical for both speed of reaction and extent of oxidation and for most
purposes oxidation at pH 10 or above is preferred.
Complete reaction should occur in 15 to 20 minutes.
The method is suitable for partial or complete oxidation, low or high cyanide concentrations,
and any metal cyanides with the possible exception of cobalt cyanide complex.