Water pollution from smelters metal plating & metal finishing industry

Contents
i) Smelting Industry ii) Metal finishing & plating Industry

Smeltin g

The process of smelting

Smelting is the process of separating the metal from impurities by heating the concentrate to a high temperature to cause the metal to melt. Smelting the concentrate produces a metal or a high-grade metallic mixture along with a solid waste product called slag. Metal processing plants and smelters are facilities that extract various metals from ore to create more refined metal products. Smelting specifically involves heating the ore with a reducing agent such as coke, charcoal or other purifying agents.

Process of smelting is of two types Primary smelting processes mine ore and concentrates, process involves separating metal from ore using heat and reducing or purifying agents such as coke and charcoal. Once the ore is mined, it must undergo several different processes in order to be turned into usable or metallurgical material whereas in secondary smelting processes the metal is recovered by scrap .

Metals include
Aluminium Copper Iron Lead Nickel Zinc Silver Cobalt Gold Cadmium etc.

LOCATION

NAME OF COMPANY

PLANT CAPACITY PER YEAR(KT/YEAR) 345 14

Korba(Chhattisgarh) Alupuram

Bharat aluminium co. BALCO Hindustan aluminium co. HINDALCO Hindustan aluminium co. HINDALCO

Renukoot( UP )

345

Mettur
Hirakud

Madras aluminium co. MALCO

Hindustan aluminium co. HINDALCO

40
150

Angul

National aluminium co. 460

Introduction

Metal finishing processes involve treatment of a metal work-piece in order to modify its surface properties, impart a particular attribute to the surface, or produce a decoration. Plating is a subset of such finishing operations that involves putting a coating of metal over a base metal substrate to give various desirable properties to the object. Metal coating is another subset of such finishing operations and involves the application of a paint or powder coating to a metal work-piece. Products from metal finishing operations can range from structural steel to jewellery.

Metal finishing
The reason(s) for carrying out metal finishing can include: decoration, protection against corrosion, providing resistance to oxidation, high temperatures, or UV radiation, imparting mechanical properties, such as resistance to fatigue, improvement of ductile strength, or longevity, resistance to the use of abrasives, imparting electrical & thermal properties such as semi-conduction, thermal resistance, fire resistance, etc.

Metal finishing operations

The main operations that can occur in metal finishing are as follows: Cleaning: including solvent cleaning, aqueous cleaning, abrasive cleaning, and other types of cleaning such as ultrasonic cleaning, chemical polishing. Cleaning is usually carried out before the main metal finishing operation and sometimes between operations. Chemical and electrochemical conversion coatings: including chromating, phosphating, anodising, and colouring, Conversion refers to the fact that these processes involve changing or converting the surface layer to impart various properties to the surface. These processes are usually applied before painting to improve coating adhesion and provide corrosion protection.

Plating: electroplating of various types of metals onto metal surfaces. Other metallic coating: including hot dipping (such as galvanising) and mechanical plating (such as the peening process used for Dublins spire). Organic and other non-metallic coating: covers organic and other non-metallic coating and includes powder and liquid paints, resins and enamels. The coatings that have been applied are subsequently dried. This can be by leaving to dry in ambient air or assisted drying using an oven. Stripping: used to remove previous metallic coatings from parts or to remove coatings from articles that have to be reworked.

Industry description

Physical, chemical and electrochemical processes are all used to finish metal workplaces. The processes may simply polish the surface to provide a bright appearance or apply another metal to change the surface properties or appearance. Physical processes used in the metal finishing industry-such as buffing, abrasive blasting, grinding, tumbling, and polishing-do not generate as much waste as chemical and electrochemical processes. Physical processes involve the use of a solid material (or abrasive) to change the surface characteristics of workpiece, and the waste generated contains the abrasive and the material removed from the surface. The use of sand for paint stripping operations is an example of a physical finishing process

Metal plating process

Plating is a process of forming a thin coat of one metal over the surface of other metal or non-metal in order to Alter the surface properties of the other metal Improve its appearance Improve its resistance to corrosion & tarnishing, chemical attack etc. Increase hardness Coating of chromium, cadmium, copper, zinc, silver, gold etc. can be given by electroplating, in which these metals are made to form complexes with cyanide ion in order to increase their throwing power. Typically double cyanide bath are used, one containing cyanide of the metal to be plated & the other containing excess of alkaline cyanide.

Continued . . . . .

Cleaning :this is achieved by using org. solvents like trichloroethylene or perchloroethylene or an emulsion made from kerosene, a wetting agent & an alkali etc. the surface to be cleaned is made the anode. Rinsing :chemicals used in the cleaning operation are removed by rinsing with water. Chemical cleaning : for this the surface is dipped in acid or alkali, depending on whether the earlier step has used alkali/acid as a component of the cleaning solution. Rinsing : the surfaces are rinsed with water to remove reacting chemicals & products of the earlier reactions. Plating : the objects to be plated are made the cathode, while the metal, which is to plate the objects, is made the anode.

If the objects to be plated are small, they are placed in a barrel, which is dipped in the plating bath. This is called barrel plating. Draining : after the desired time period, the plated objects are lifted out of the plating bath & are held over the bath to allow draining of the bath contents. Rinsing & drying : the plating objects are then rinsed with good quality water(preferably demineralized water) & are dried with hot air. When the cleansing power of the rinse water is exhausted, it is topped up with the necessary plating chemicals & returned to the plating bath.

Waste characteristics
Most stripping baths are acidic in nature and consist of solutions of sulfuric, nitric, hydrochloric acid but alkaline baths containing sodium sulfide, cyanide & hydroxide may also be used. The total liquid wastes in the plating industry are not voluminous, but are extremely dangerous because of their toxic content. The character & the strength of plating wastes vary considerably, depending on plating requirements and type of rinsing used. So the contents of the plating bath must be destroyed(especially cyanides and other heavy metals such as chromium, cadmium etc.) or their concentrations must be reduced to safe limits.

PRETREATMENT STANDARDS FOR EXISTING SOURCES (PSES) ELECTROPLATING CATEGORY [courtesy EPA] Facilities Discharging ~ <38,000 liters (1.2,000 gallons) per day Pollutant ," Daily Maximum i) Cadmium (T) 1.2 ii) Lead (T) 0.6 Iii) Cyanide, A 5.0 Iv)Total Toxic Organics 4.57 (TTO) Maximum 4 Day Average 0.7 0.4 2.7 ---

Facilities Discharging >38,O00 liters (I0,000 gallons) per day

Pollutant Daily Maximum (mg/l) Cadmium (T) 1.2 Chromium (T) 7.0 Copper (T) 4.5 Lead (T) 0.6 Nickel (T) 4.1 Zinc (T) 4.2 Silver (T) 1.2 Total Metals 0.5 Cyanide, T 1.9 Total Toxic Organics 2.13 Maximum4 Day Average (mg/l) .7 4 2.7 0.4 2.6 2.6 0.7 6.8 1.0 ----

Treatment of waste
The methods used for disposal of waste from plating operations can be divided into two classes:[ Ohio River Valley Water S. C.] Modifications in design & operation within the manufacturing process to minimize or eliminate the waste problem1-Installing a gravity-fed, nonoverflowing emergency holding tank for toxic metals & their salts. 2-Eliminating breakable containers for concentrated material. 3-Designing special drip pans, spray rinses etc. 4-Reduce spillage, drag-out leak to the floor or other losses to a holding tank. 5-Using high pressure fog rinses rather than high-volume water washes. 6-Reclaiming valuable metals from concentrated plating-bath wastes. 7-evaporating reclaimed wastes to desired volume & returning to plating bath at rate equal to loss from bath. 8-Recirculating wet-washer wastes from fume scrubbers

Installation of a chemical(or physical) treatment plant to destroy or remove toxic & objectionable materials in the effluentSuch Treatment are designed primarily to accomplish 3 objectives: 1) Removal of cyanides 2) Removal of chromium 3) Removal of all other metals, oil and greases

Removal of cyanides
All acidic waste streams should be separated from cyanide bearing streams to avoid even accidental formation of HCN, a highly toxic chemical. Various method of cyanide bearing wastes are: Alkaline chlorination(most commonly used) Ozonation (costly) Acidification & natural aeration by lagooning (in remote areas like gold mine where HCN can be dissipated in air or absorbed in caustic soda) Acidification followed by forced aeration into a tall stack Treatment with ferrous sulphates Electrolytic oxidation in the presence of chloride ion Treatment with addition products

Alkaline chlorination (continuous & batch)

Reduction & precipitation of Cr.This involves reducing Cr(VI) as chromic acid & chromates in the waste to Cr(III) with reducing agents such as iron sulfate, sulfur dioxide or NaHSO3. Sufficient mineral acid should also be present to combine with the reduced Cr. And to maintain a pH of 3 or lower, which will ensure complete reaction. When the reduction is complete, an alkali (usually lime slurry) is added, to neutralize the acid and precipitate trivalent chromium.

Advanced techniques for Cr.

Combination of membrane bioreactor & ion exchange. Low cost adsorbents(coconut fibre etc. ) have also been used Rice husk, treated with sulfuric acid, followed by CO2 activation. Activated alumina For other heavy metals: Metals can be recovered from filter cake. Colloid flotation Electrolytic recovery Lead plating & cadmium plating is done in fluoborate bath which produces effluents having 100-250 mg/l of lead & 7-50 mg/l cadmium.it can be removed by coconut shell, treated with sulfuric acid in the presence of potassium persulphate /hydrogen peroxide.

Neutralization

Treatment of other metal, oil & grease bearing wastes by Neutralization & precipitation Usually involves recombining the Wastes with previously oxidised cyanide and reduced chromium wastes for subsequent and final treatment.

Recovery

Chrome acid recovery by vaccum evaporation

Current best practices to save water

Improve Operating Procedures -This section sets out improvements that can be made in operating practices. Reducing Drag-out -Drag-out is a term which refers to the removal of process solution from a bath as a result of its adherence to the work-pieces and the jig or barrel. If the amount of drag-out formed in the first place is reduced, this will consequently reduce rinsing requirements, effluent treatment requirements and prolong the life of process baths. There are a number of ways that drag-out can be reduced. Better positioning of work-pieces on racks: parts should be placed on the rack so that the largest surface or plane is nearly vertical and the longer dimensions are horizontal. The lower edge should be inclined, so that run-off will occur at a corner rather than the entire edge. Avoid positioning parts directly over one another where possible. Provide static rinses instead of running rinses to the plate surfaces.

Continued ..

Using countercurrent washing system, in which the plate object is passed through static rinsing tanks from left to right, while the rinse water is supplied only to the last rinsing tank.

References
Water.epa.gov.in Infohouse.p2ric.org www.envirocentre.ie

Thank you