Treatment of Chromium and

Cyanides
Amarjit Singh
18201019
Mtech Environmental Engineering
Chromium

• Chromium is a metal that exists in several oxidation or valence states, ranging

from chromium (-II) to chromium (+VI).
• Chromium compounds are very stable in the trivalent state and occur naturally in
this state in ores such as ferrochromite, or chromite ore.
• Chrome III is an essential nutrient for maintaining blood glucose levels
• The hexavalent, Cr(VI) or chromate, is the second most stable state. It rarely
occurs naturally.
• Chromium occurs as both hexavalent and trivalent metal in aqueous solution.
• Most chromium giving rise to pollution is from the metal finishing industry where
it occurs in the hexavalent state as chromic acid.
• Hexavalent Chromium is used in many industrial applications primarily for its anti-
corrosive properties.
• Also used in electroplating (chrome plating).
Products that contain hexavalent chromium
Product Types of Hexavalent Chromium Chemicals

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

wood preservation chromium trioxide

leather tanning ammonium dichromate

 Sources of Chromium
• Aircraft Painting
• Pesticide Application (Wood Preservative)
• Leather tanning
• Electroplating
• Textile manufacturing
• dyeing, cement industry
• metal finishing
• photography industry etc
 Health Effects
• Ingestion Hazards
Erosive to stomach, Hemorrhaging and death are likely possible.
• Eyes
Direct eye contact with chromic acid or chromate dusts can cause
permanent eye damage.
• Respiratory Tract
Hexavalent chromium can irritate the nose, throat, and lungs.
Repeated or prolonged exposure can damage the mucous membranes
of the nasal passages and result in ulcers.
• Skin
Prolonged skin contact can result in dermatitis and skin ulcers.
Some workers develop an allergic sensitization to chromium. In sensitized
workers, contact with even small amounts can cause a serious skin rash.
• Cancer

• Chrome VI is classified as a known human carcinogen

• Hexavalent chromium is considered a potential lung carcinogen.
• Studies of workers in the chromate production, plating, and pigment
industries consistently show increase rates of lung cancer.
• Insoluble forms such as zinc chromate are the most potent 20 year cancer
latency
 Treatment
• The most common method of treating this material is by reduction to the
trivalent chromium, then precipitation of hydroxide by neutralization with alkali.

Reduction of Hexavalent Chromium

The extent of the reduction of hexavalent chromium to the trivalent state is

dependent on pH, time of reaction, and choice, concentration and degree of excess
of reducing agent.
• The most common reagents are based on gaseous Sulphur dioxide and aqueous
sodium salts according to following reactions;
• Conditions for satisfactory reduction are
pH - 2.5
Retention time of 10 to 15 minutes

• 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.

Oxidation by other methods

Ozonation
• This method of oxidizing has attracted much attention due to the low overall
cost, complete reaction and the convenience of the ozone being generated on
site.
• Reaction occur in two stages as for chlorine oxidation, with cyanate formed as an
intermediate.
• The method is suitable for effective oxidation because of ozone’s relative instability.

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.

Close pH control is unnecessary as reaction is very rapid between pH 9 and pH 12

• Electrolytic oxidation
• Oxidation by anodic oxidation is particularly suitable for high concentrations of
cyanide as the efficiency reduces at lower concentrations, when conventional
chlorination oxidation is needed
• The action is slow, requiring many hours or even days for adequate cyanide
oxidation but it is effective and valuable for complex cyanides such as nickel,
copper and ferro and ferricyanide complexes.
• This method is not widely used because of the cost of electricity and the
slowness of reaction.
• For difficult wastes and complex mixtures containing cyanide, such as oily
residues, incineration may be a convenient form of oxidation.
• Careful design and specification is essential to ensure sufficient residence time,
and excess air is necessary for complete oxidation.
Most chemical engineering unit operations have been applied to the problem of
cyanide treatment, particularly ion exchange, reverse osmosis and adsorption,
but none has proved viable to date.