Comprehensive Industry Document Series (COINDS)

COINDS /70/2007

COMPREHENSIVE INDUSTRY DOCUMENT ON ELECTROPLATING INDUSTRIES

OF CLEAN

CENTRAL POLLUTION CONTROL BOARD

MINISTRY OF ENVIRONMENT & FORESTS Website: www.cpcb.nic.in e-mail: cpcb@nic.in MAY 2007

Comprehensive Industry Documents Series (COINDS)

COINDS /70/2007

COMPREHENSIVE INDUSTRY DOCUMENT ON ELECTROPLATING INDUSTRIES

CENTRAL POLLUTION CONTROL BOARD

MINISTRY OF ENVIRONMENT & FORESTS

e-mail: cpcb@nic.in Website: www.cpcb.nic.in

May 2007

CPCB, 200 Copies, 2007

Published By : Dr. B. Sengupta, Member Secretary, Central Pollution Control Board, Delhi 32 Printing Supervision & Layout: P.K. Mahendru, and Anamika Sagar Composing & Laser Typesetting : Suresh Chander Sharma Printed at: DSIDC, New Dellhi:

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Central Pollution Control Board

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(A Govt. of India Organisation) Ministry of Environment & Forests

J. M. MAUSKAR, IAs
Chairman

Phone 22304948/22307233

FOREWORD
The Central Pollution Control Board (CPCB) brings out publications entitled "Compr::hensive Industry Document series (COINDS)" based on the industry-wise studies. These reports are intended to cover various aspects of different types of industrial units in the country with respect to their number, locations, capacities, types of product, usage of raw materials, process adopted, waste minimisation, pollution prevention and control measures. The Minimal National Standards (MINAS) have been evolved as a result of the COINDS. The present report entitled "Comprehensive Industry Document on Electroplating Industries" is latest one being published by the CPCB. The study for the report was conducted on behalf of the CPCB by ENC Consulting Engineers, Gurgaon. The help and assistance extended by the State Pollution Control Boards and by various electroplating units during the conduct of this study are gratefully acknowledged. Shri T Venugopal, Director, Shri R. C. Saxena, SEE and Ms. L.J. Pavithra AEE, has put keen efforts in preparing this volume under the able guidance of Dr. B. Sengupta, Member Secretary. I hope that this report would be useful to the electroplating units, regulatory agencies, consultants and others interested in pollution control in this sector.

(J. M. Manskar) May, 2007

'Parivesh Bhawan C.B.D.-cum-Office Complex, East Arun Nagar, Delhi-t 10 032 Fax : 22304948 t 22307078 email : cpcb@alpha.nic.in
Website : http://www.cpcb.nic in

Contents Chapter 1: Introduction Introduction 1. I Growth of Electroplating in India 1.1 Types and Location of Units 1.2 1.3 Future Potential Chapter 2: 2. I 2.2 2.3 2.4 2.5 Chapter 3 3.1 3.2 3.3 Chapter 4 4.1 4.2 4.3 4.4 4.5 Chapter 5 5.1 5.2 5.3 5.4 5.5 5.6 5.7 5.8 Chapter 6 6.1 6.2 6.3 6.4 Processes and Chemicals used Production Process Process Details Process Chemicals Some Theoritical Considerations in Electroplating Mass Balance for Plating Process In-depth Studies in Electroplating Industry General Analysis of Results Summary of Findings Recovery of Metals General Filtration and Centrifugation Evaporation Electrolytic Recovery and its Economics Reverse Osmosis Waste Minimisation and treatment to Control Pollution General Waste Minimisation and Process Modification Best Available Technology (BAT) Specific BAT Approach potential Initiatives and Cost Estimates Waste Treatment Options Hazardous Waste Rules House Keeping Guidelines Review of Existing Standards General Suggested Revisions in Existing Standards Recommendation for Monitoring of Revised Standard Safe Keeping of Data I 1 I 2 2

5 6 8 10 17

27 27 27 37

39 39 40 42 47

49 49 51 55 59 60 66 67

71 71 78 79

Chapter I

Introduction
1.1 Introduction
Electroplating is one of the varieties of several techniques of Metal Finishing. It is u technique of deposition of' a fine layer of one metal on another through elcctroI\ tic process to impart various properties and attributes, such as corrosion protection, enhanced surface hardness, lustre, colour, aesthetics, value addition etc. I:Icctroplatin operations form part, of large scale manufacturing plants (e.g. automobile. cycle. engineering and numerous other industries) or performed as job-work by small and tiny units. They are spread across the entire country with significant concentration in several states like Punjab. Haryana, part of U.P., Maharashtra, Karnataka,Andhra Pradesh, Tamil Nadu and West Bengal. Electroplating is considered a major polluting industry because it discharges toxic materials and heavy metals through wastewater (effluents), air emissions and solid wastes into the recipient environment. In order to regulate the quality of discharge of wastewater, the Central Pollution Control Board. in 1987, evolved Minimal National Standard (MINAS) flor discharge of effluent under the provision of the Environment (Protection) Act of 1986. This standard no\\ requires comprehensive review in view of the current body of' knowledge regarding discharge of pollutants, status of Industry, technology and implementation of regulatory mechanism.

1.2 Growth of Electroplating in India 1.2.1 Brief History & Present Scenario
Electroplating has a long history in India; like many industrial activities, it gained momentum after Independence. Modern day electroplating started in early sixties in Mumbai with dull Nickel. Bright Nickel followed soon after. Although official figures are not available, estimates (ref: 5) indicate that in 1970, electroplating industry was considered to be in the tune of Rs. 100 million. Since then, the industry has grown steadily without facing any recession. In 1976, the first semi-automatic plant was set up in Mumbai. Currently there are more than 600 automatic plants in the country. During the period 1970-85, the import restriction regulation in force led to high growth of this industry. It is estimated that electroplating industry is now worth Rs. I000 crores (Rs. 10,000 million; see Fig 1.1). This means that compounded average annual growth rate is about 16.6%. The sector employs about 1,30,000 people in approximately 12,000 organized units. No statistics is available for unorganized 'units.

1.2.2 Types and Location of Units

The Industry is widely spread out across the country. While there are primarily two varieties- (i) Primary User and Original Equipment (OE) manufacturer, who do electroplating as one of their overall manufacturing activity and (ii) Job work units, who do only plating for a large variety of components for both domestic and export purpose. Certain states have large number of units concentrated in some towns / cities, such as Andhra Pradesh -- Hyderabad Delhi Gujarat- Ahmedabad Haryana- Faridabad Karnataka- Bangalore Maharashtra - Mumbai, Pune, Nashik Punjab - Ludhiana Tamil Nadu - Chennai, Madurai Uttar Pradesh - NOIDA It is difficult to find out the distribution of production between the organized and small scale / tiny / unorganized sector. However, judging by the consumption of chemicals and additives, it is estimated that about 18,000 tons are consumed by organized sector, while tiny and unorganized sector consumes about 10,000 tons. Therefore, approximately 36 % of the industry is contributed by the unorganized sector.

Fig : 1.1 Growth of Electroplating Industry in India

Fig. 1.2 : Share of Chemicals as inputs to electroplating

Ut' the several varieties of Flectroplatine. Precious Metals (Gold, Silver etc.) rcquirc an input of Rs. 475 crores, whereas other metals (Ni, Cr. Cu, Zn, Sn etc.) require 27. crores - all principal bath chemicals only. The share of additives is estimated at Rs.250 .:rores (see Fig 1.2). Therefore value-wise, precious metals occupy highest position Nut industrial eflbrt and employment wise, conventional Cr. Ni and In plating occupies highest position. Of this sector. 2-wheeler industry (both hi-cycle and motorized units scooters. mopeds and motorbikes) is the single largest users. India is one of the largest producers of bi- cycles in the world, producing about 48,000 units per day. Motorized units production is estimated at 15,000 per day and is likely to grow very fast. 1.3 Future Potential
I hcrc are several sectors. which are at low key now but has high growth potential. One of this is electronic Industry and printed circuit hoards which is only worth Rs. 30 crores but has huge potential. Second is the automotive industry (both 2 and 4 wheelers), particularly plating on ABS. Similarly with Europe and North America gradually imposing very strict environmental regulation, there would be more outsourcing of components from industrialised countries to India. Thirdly, Indian chemical products are still the cheapest and of recognized quality. The export activity, which is now only 20 crores a year, can achieve 100% growth rate over the next ten years. The organic intermediates used in Ni and Zn plating are also well-established items for export. Considering that a concerted effort is undertaken by the industry, the projected growth rate is approx. 6%, which will not be difficult to achieve. Thus, the electroplating industry can acquire a size of Rs.2,000 crores in the year 2012 and can sustain this rate until 2015.

Chapter 2 Processes & Chemicals Used

2.1 Production Process The basic electroplating system consists of: I) A plating bath tilled with water containing a small amount of acid or alkali added to improve its conductivity. Thus baths used lor plating are either acid bath or alkaline bath. 2) An anode (positive electrode) - either the plating metal or an inert electrode: this is expended as the process goes on and replenished periodically 3) A cathode (negative electrode) - the item to be plated: these can he either hung inside the bath or placed in a barrel, which is rotated slowly to make the plating material deposited evenly Usually, the bath is contained in metal container, lined with acid/alkali resistant membrane e.g. pvc sheet to make it insulated trom electric circuit. The application of direct electric current across the bath solution causes the migration of Positively charged particles (anions) towards the negative electrode (cathode) and Negatively charged particles (cations) towards the positive electrodes (anode) The processes are often exothermic and this leads to elevated bath temperature compared to the ambient temperature. The process efficiency depends to some degree on the Concentration of acid and alkali in the solution "Temperature and Voltage applied across the electrodes The item to be coated is immersed in the bath solution as the cathode and the coating substance (the anode). However, if an inert electrode is used, the coating substance would be the metal salts in liquid form added to the solution. The metal salts subsequently dissociate into anions and cations, which then deposit onto the items to be plated. Apart from the bath chemicals and anode material, other chemical agents are used, such as: Brightener Wetter Booster Purifier These chemical agents help to provide desired attributes, such as bright surface finish, improved and even metal deposition, depolarization, faster reaction etc. etc. The chemicals vary according to the process variants and finishing requirements fr a particular metal plating.

By and large, most metal finishing operations typically involve 3 to 4 principal work steps or process operations, which may occur singly or in combination. These are: Surface preparation Pre-treatment Plating and Post-treatment
2.2 Process Details 2.2.1 Surface Preparation / Pre-treatment

The purpose is to prepare and clean the items for plating. The activities involved are as shown in Table 2.1 below
Table 2.1 Surface Preparation & Pre - treatment Main Activity Step Operation Function

Surface Preparation Pre-treatment

I 2

Buffing Cleaning

Smoothening of surface deficiencies bv s crapping Removal of oil, grease. dirt, scales from the surface of the items using solvents (often chlorinated
hydrocarbons)

Rinsing

Removal of adherent solvent/alkali/acid using water flow

2.2.2 Plating In the plating process, the items to be plated are placed as the cathode in an electrolytic bath containing metal salts. A Direct Current is passed (at low voltage) through the electrolyte, wherein metal ions are plated onto the cathode. The ions in solution are replenished by : The dissolution of metal from the anode (the plating substance) or Increasing the metal salt concentration of the solution (when using an inert electrode) or both After plating, the plated items are rinsed with water. After rinsing the items are dried either normal air drying or hot air drying or in an oven. The operations of plating. transfer from plating to rinsing tanks (in which bath solution drag-out occurs) and rinsing can either be manual or mechanized (automatic). 6

2.2.3 Post-treatment
Most F,lectroplating operations are completed by the plating operation, if the items do not require post-treatment (as in the case of Double Nickel Chrome Plating). The purpose of the post-treatment is: to enhance the physical appearance of the item to improve the corrosion resistance of the item for decorative purposes There are a varied number of post-treatments: conversion coatings chromating phosphating passivating metal colouring and sealing A brief description of these are given in the following paragraphs

(a) Conversion Coating: Conversion coating is provided to prevent corrosion and to limit the growth of salts, which may form due to corrosion. Many heavy metals, such as Chromium, Vanadium, Molybdenum and Tungsten in their high valence states have the ability to prevent such corrosion. The most commonly used conversion coating is hexavalent chromium using soluble chromate salt such as Potassium di-chromate, called chromate conversion coating or chromating. (b) Phosphating This is a process of coating a metal surface (usually galvanized iron & steel, aluminium etc.) with a layer of insoluble metal phosphates by treating it with an acidic phosphate containing solution. Zinc, iron and manganese phosphate coatings are common of which Zinc Phosphate is the most commonly used salt. Phosphating is done as an excellent base for receiving paints, oils and cold-forming lubricants (c) Sealing Anodic coatings are usually porous and are sealed and are sealed to improve colour durability and resistance to staining and corrosion. Sealing is done by immersion in hot water during which amorphous alumina surface of the anodic coating is converted to crystalline alpha alumina hydrate, which increases the volume and closes the pores. (d) Metal Colouring In this process a colour is formed on the surface of metals. This is quite an old process, which is not much used at present. However, Aluminium colouring is in vogue.

2.3 Process Chemicals A wide variety of chemicals and substances are used, depending upon the surface properties of the objects to be electroplated, plating and finishing requirement as well as the technology / facility offered by the platers. It is very difficult to provide full details of all those used, because there are more than one commonly used process for certain metals. I-fence a general description will be covered in this section. A summary is given in Annexure 3.

2.3.1 Brass Plating

In brass plating, generally a cyanide bath is used, which comprises, Cu(CN) 2 NaCN, Zn(CN) 2 and Na-, CO; . The anode is non-consuming conductor. 2.3.2 Bronze Plating Bronze being a combination of Copper and Tin, the bath salts comprise Cu(CN)2 , NaCN, Na, SnO-, and NaOH. Bath is therefore cyanide alkaline. Anode is non-consuming conductor like in brass plating. 2.3.3 Cadmium Plating Cadmium plating also uses an alkaline cyanide bath comprising bath salts like Cd(CN)2 NaCN, Na-, CO3 and NaOH.

2.3.4 Chromium Plating

There are variations of Chromium plating - ordinary chrome, hard chrome and bright chrome. Generally, chromic acid bath is used comprising bath salts like 1-I 2 r 0. 1 , I I,SO,, and Nal'. NaF is used to improve the conductivity of the electrolyte.
('

2.3.5 Copper Plating Three ") types of bath are used - (i) Cyanide Copper bath, (ii) Copper pyrophosphate bath and (iii) Acid Copper bath. As the name suggests, the bath in the third is acidic. while the. first two are alkaline. Bath constituents for Cyanide Copper bath are : Cu(CN), _ NaCN, Na CO; and NaOH. For Copper pyrophosphate, Cu2P" 07, NIS. OI-1 and K.iP2O7 are used. In acid copper process, a mix of CuSO. and 1-12SO.1 is used.
,

2.3.6 Gold Plating

Four processes are available - (i) Alkaline Cyanide f using KAu(CN)2, KCN, KON and K,C r O I I. (ii) Neutral Gold bath fusing KAu(CN) 2 , KCI and K21-IP0 3 J, Acid Cyanide f using KAu(CN) 2 , KCI and Citric Acids . It may be noted that the main constituent in all
-

three processes is Potassium Gold ('vanide. The l' urth is Mash Gold process using, AuCI and I ICI.

2.3.7 Nickel Plating

Three"' processes are commonly used - (i) Watts Nickel bath I using a mix of NiSO.j . NiCl2, 11,SO. and l -I;BO; ], (ii) Nickel Sulphamate Bath [ using Ni(NI l SO,)2 , I-INI-1-,SO; ], (iii) Wood's Nickel Bath ( using NiCI, and I lCl I. None of the processes use Cyanide.

2.3.8 Palladium
Being a precious metal, usage is somewhat restricted. Only one process using acid bath is commonly used. Bath constituents are:Pd(.'12 , NIi.,CI and IICI. Sometimes PalladiumNickel plating is used in which Palladium and Nickel is deposited in one bath. In this process, bath constituents are: Pd(NH3)2(NO,)2, Nickel Sulpharnate and Nl-I40FI.

2.3.9 Platinum
Two processes are available : (i) Alkaline Platinum and (ii) Acid Platinum. In the former. H2PtCl e,. (NH;a )3PO 4 and NH. 4 O(HI. In acid Platinum, bath constituents are: I l2l't(NO,.)2SO. 1 and 1-ISO.

2.3.10 Rhodium
Only one process using acid bath comprising Rhodium Sulphate and Sulphuric acid is used.

2.3.11 Silver
Two processes arc available, both using Silver Cyanide. Silver Cyanide bath comprises KAg(CN)2 , KCN and K2CO3 Acid bath uses KAg(CN)2 Nael -IPO.j and II;PO. .

2.3.12 Tin
There are three processes - (i) Alkaline, (ii) Acidic and (iii) Fluoroborate.. In alkaline Tin process, principal chemical used are Sodium Stannate and Caustic Soda, 'f'in Sulphate uses Stannous Sulphate and Sulphuric Acid. In Tin Fluoroborate process, Chemicals used are : Sn(BF4)2, HBF4, H3BO3and (IF.

2.3.13 Zinc
There are three processes available (i) Acid Cyanide. (ii) Alkaline Cyanide and (iii) Alkaline Cyanide Free. Acid Cyanide uses a bath comprising Zn(1 KC I. NI I. CI and I;BO; In Alkaline Cyanide, bath constituents are : ZnCN, NaCN. NaOI I and Na, ('O. In the Alkaline Cyanide Free (ACI") process. bath chemicals arc rather simpler. /,nO and NaOI l. The latter is gaining popularity as a Cyanide free process. 9

2.3.14 Anodising
Anodising is mainly used as a pre-cleaning operation but sometimes used as a metal finishing operation. In anodising, the object is made Anode, so that impurities and other metals are removed. Sulphuric acid is mainly used as electrolyte in the bath.

2.3.15 Phosphating
Phosphating is carried out mostly as post treatment of plating. However, it is often used as undercoat to receive paint on metal. .Bath constituents are Zinc-Calcium Phosphate and Na3PO 4 .

2.3.16 Chromating
This is also a post treatment to plating. Bath constituents are Na 2 CrO 4 and Na2 CO 3 .

2.3.17 Etching
This is used as a pre-treatment to plating and generally uses acidic bath Ferric Chloride etchant (Ferric Chloride and HC1), Acid etchant ( mix of CuCl2_ 1-ICI and 1-120 2 ). In Ammoniacal etchant, a mix of Ammonium Chloride, Ammonium Hydroxide and Sodium Hypochlorite) is used. A summary of chemicals is given in Table 3.2.

2.4

Some Theoretical Considerations in Electroplating

Electroplating is a complex chemical process and it is neither possible nor intended to deal with the theoretical aspects in this treatise. However, certain basic considerations and introductions would help in understanding the processes and factors influencing them. These would be dealt with briefly in this sub-section.

2.4.1 Calculation of coating, thickness, exposure time and current density

Faraday's laws form the basis of finding important values. Following are the parameters expressed in units customary in electroplating: E ei == Electrochemical equivalent, in g /ah F= Plated area in dm 2 1 = Current intensity, in amp i = Current intensity in amp/dm 2 t = Exposure time in minutes TI = Current efficiency in % d = Thickness of metal deposit, in microns (lt) y = Density in g/cm 2 V = Volume of the deposited metal G = Weight of the deposited metal

ELIJ

Faraday's first law in the form G = E el Q applies to a reaction which proceeds at 100% current efficiency. Because this is normally not the case, the current efficiency q must be introduced into the equation. We obtain G=E e 1Q1/100 (1) Introducing time in minutes and current density in amp/dm 2 we obtain G= E e l i Ftri / 6000 grams (2) The coating thickness d = V (cm 3 in t is then: F (dm'`) d= 100V microns () (3)

F
Substituting V = G , we obtain

Y
d = LOOG microns (pt) (4)

yF
According to this formula, we obtain the coating thickness on the plated surface F from the deposited weight G. For G we can introduce Eq.(2) and obtain d= 100 E el ii Ftri (g) 6000VF
or d= Eel ()

(5)

60 y F (6) Using this equation, the current density required to obtain the desired coating thickness, in a given time t is: i = 6 0 d y (amp/dm') (7)
Eel tl

And the time required, for a given current density, is: t= 60 d y (min)
Eel ill

(8)

If instead of the-coating thickness, the weight deposited is required, the formulae corresponding to equations (7) and (8) are obtained from Eq. (2): (9) i = 6000 G (amp/dm 2 ) Eel F tr1 And (10) t= 6000 G (min) Ee l F i 1^ These formulae apply equally to cathodic deposition and anodic dissolution of metal. The value of E e l are given in Table 2.2.

Table 2.2 Electrochemical equivalents, atomic weights, valencies, and densities of metals important in electroplating* Metal Ag Au Au Valency 1 1 3 Atomic Weight 107.870 196.967 196.967 Density (g/c ) at 200 C 10.50 19.29 19.29 8.64 8.83 6.95 8.93 8.93 7.86 7.31 8.90 11.34 11.97 21.45 12.44 7.28 7.28 7.13 Electrochemical equivalent E ei 4.024 7.348 2.4495 Electrolyte

2 Cd Co 2 Cr 6 Cu ! 1 2 Cu Fe 3 In Ni 2 Pb 2 Pd j2 4 Pt Rh 3 Sin 2 4 Sn T.n 2

112.40 58.9332 51.996 63.54 63.54 55.847 114.82 58.71 207.19 106.40 195.09 102.905 118.69 118.69 65.37

All silver baths Cyanide gold baths _ Ferro cyanide gold baths 2.097 All cadmium baths 1.099 All cobalt baths 0.323 Chromium baths 2.372 Cyanide copper baths Acid copper baths 1.186 1.042 All iron baths 1.428 All indium baths All nickel baths 1.095 3.865 All lead baths Palladium baths 1.984 1.819 All platinum baths All rhodium baths 1.2797 - - ----------- - 2.213 Acid tin baths Alkaline tin baths 1.106 - ------- ----- ---------------------1.219 All zinc baths

* Based on the international atomic weights of 1962 Source : Raub, K and K. Mueller, "Fundamantals of Metal Deposition" (ref: 8)

2.4.2 Electro-deposition of Chromium

Chromium occupies a special position with respect to the deposition mechanism. Although attempts to chromium from solutions of simple salts proved that chromium could he deposited, for example, from solutions of salts of trivalent chromium, the practical solution of the difficulties involved has not yet been achieved. Chromium, therel'ure, is always deposited from aqueous solutions of Chromic acid. These electrolytes differ in several respects from other plating baths. Eiere, we shall, only consider the deposition mechanism of chromium from chromic acid electrolyte - this has been the subject of numerous studies. Chromium occurs in the hexa, tri and divalent forms. While the [HCrO4] - ion predominates in dilute chromic acid solutions, mainly the [HCr2O7] - ion is formed at the concentrations usual in chromium baths. A certain quantity of trivalent chromium ions is also present. If such an aqueous solution is electrolyzed, a strong film forms on the cathode, and this prevents the formation of a metallic deposit because it is permeable 12

only to the small hydrogen ions and not to the large [HCr2O7] - ions. This coating consists of basic chromium (III) chromate, Cr (OH)CrO 4
.

In order to obtain deposition of metallic chromium, the electrolyte must contain a certain quantity of some other acid. This loosens the cathode film to such an extent through complex formation that chromium deposition is rendered possible. The effect of the Sulphuric acid present in a chromium acid electrolyte results from the fact that it forms an easily soluble complex with trivalent chromium, and hence tends to prevent the formation of a cathode film.

2.4.3 Co-deposition of foreign substances

All electrolyte components, thus not only the cations but also the anions and uncharged substances and particularly organic and inorganic colloids, can be included in the cathodic deposit in varying quantity, depending on the deposition conditions. Only in very rare cases is a metal deposited on the cathode in a highly pure form. Coatings from technical electrolytes nearly always contain foreign substances. The foreign substances arrive at the cathode owing to diffusion and convection. Only with positively charged substances is electrical transport involved. Most foreign substances are physically bound to the cathode surface by adsorption, and also partly (and more strongly) by chemisorption. Electrostatic binding can only occur when suitable charges are present. The adsorptive nature of the bond is indicated by the increase in the quantity of inclusions with increase in the concentration of the foreign substance up to a limit, the saturation limit of the surface, and by the relationships between incorporation and molecular size, the temperature and the adsorption capacity. The validity of the Freundlich adsorption isotherms has been demonstrated for some foreign substances. The direct co deposition of inorganic ions is relatively slight. When such anions are found in the deposit in appreciable quantities they are usually sparingly soluble decomposition products of other, often organic compounds. The incorporation of Sulphur in nickel and other metal deposits is due to the presence of Sulphur containing compounds such as thiosulpohate, thiourea, sulfonates etc. in the electrolyte. The incorporated sulphide is formed through hydrolysis of the added Sulphur compounds or by electrolyte reduction of quadrivalent Sulphur contained in the addition agents. Other foreign substances incorporated in the deposit are often formed in the cathodic diffusion layer likewise through likewise through chemical reactions or cathodic reduction. M. Schlotter and H Schmellenmeyer found maximum oxide contents of 3.5% in zinc deposits from a zinc sulphate electrolyte. The maximum oxide content of zinc coatings deposited from a cyanide electrolyte is generally only 3%, while that of deposits from an acid zinc bath is considerably lower. In metals deposited from a cyanide electrolyte is sometimes possible analytically to detect metal cyanide, which does not stem from inclusions of electrolyte. It is produced in the cathode film, adsorbed by the cathode and then incorporated into the deposit. Silver deposits from a cyanide electrolyte, produced under suitable working conditions, can contain upto 0.22 weight % of

13

cyanide.(e.g., Table 2.3) Various substances are intentionally added to the electrolytes used in practice in order to influence the properties of the deposits in certain ways. Organic additions are particularly widespread. However, not the additives but their decomposition products are often co deposited. Elucidation of the mechanism is thus difficult and relatively few studies have been carried out. The incorporation of these foreign substances is of special importance for the technological properties. The chemical composition of electrodeposited coatings is also clearly affected by incorporation of foreign substances. Thus, a measurable difference in the equilibrium rest potential as compared with that of the pure metal can often be found. The metal containing foreign substances usually has the less noble potential. The tarnishing rate is often increased, and chemical reagents also attack the metal more vigorously. Thus, for example, the induction period for the attack of dilute nitric acid on silver is shortened and sometimes reduced to zero. On the other hand, the lower corrosion resistance of bright nickel as compared with mat nickel is not due to the general affect of the foreign incorporations in bright nickel coatings, but to the specific effect of their Sulphur content.

2.4.4 Deposition of bright metals

The production of bright metal deposits is a relatively young branch of electroplating technology. The development of brightening electrolyte, which is credited to M Schlotter, began around 1930, when bright nickel coatings could for the first time be produced by adding organic compounds to simple nickel electrolytes. Although the deposition of bright metal coatings has made enormous progress since then, the chemical end energetic processes involved in it have not yet been fully elucidated. The development of brightening additives and brightening electrolytes has been carried out on an empirical basis. H Fischer distinguished two types of brightness, depending on the origin: reproduced and intrinsic brightness. Reproduced brightness is formed on a base material with a bright surface, and the corresponding electrolytes are also termed brightness preserving electrolytes. The brightness of the support is maintained only when thin coverings are applied and is lost when the thickness of the deposit exceeds certain limits. A bright effect is also achieved by means of the current-reversal technique. The cathodic current phase is maintained until the brightness begins to diminish. During the subsequent anodic phase, the surface is anodically polished. On this bright surface, another coating is deposited by the next cathodic phase: This technique can only be used if the electrolyte has a certain anodic polishing effect and provided that the anodic phase is short compared with the cathodic period. Intrinsic brightness is produced by brightening additives bright coatings can be deposited on mat surfaces from brightening electrolytes. The brightness is independent of coating thickness and may even increase with it.

14

Table 2.3 Effect of foreign substance addition on the properties of electrolytic silver (from 0.5 N AgNO3 solution) and copper (from 1 M CuSO4 solution) Foreign Substance Pure silver deposit from cyanide bath
Glycocoll 0.02

Quantity incorporated weight - %

Density G/cm3 10.502

-

Specific resistance at room temperature 10 -6 i2cm 1.59

1.9

Vickers hardness kp*/nm2 43-100

55

Metaphosphoric
acid

0.87
2.65

10.260
9.825

300
960

157-185
175

Citric acid or 2.4 citrate 3.5

5.8

9.214 -

1300
-

Tartaric acid or 0.7 tartrate 1.2 Asparagine 0.7

Boric acid Pure copper deposit Glycocoll 207 1.6 5.18

8.966 9.135 7.958 8.923 -_

62.6 270 17.2

1.7 1.7 1.8

143 175 178 50-70 63-70 -

0.01 0.06 0.19

Metaphosphoric acid
citrate

0.2 0.68
2.3

8.740
-

17 1350

Citric acid or 0.67

2.34 2.6 Aspartic acid --- 1.0 1.3

8.161 -t8.500

95.5
290 240 460 ----_

249
275-299 -^----265-268

Tartaric acid or 0.48

tartrate 0.49 0.87 0.97 1.24

233
219 220 249 195-278

15

Source : Raub, K and K. Mueller, "Fundamantals of Metal Deposition" (ref. 8) The units "pond" (p) and "kilopond" (kp) are units of force, whilst "gram" (g) and "kilogram" (kg) are units of weight

Carbohydrates give only a slight brightening effect and have little effect on the trend of the cathode potential-current density curves. The group of aliphatic compounds includes both strong and weak brightening agents. The first group increases polarization strongly, the second one only little or not at all. Aromatic compounds can also be divided into two groups with regard to brightening effect. Aromatic amines generally do not improve brightness appreciably but increase the polarization. Other aromatic compounds, particularly those containing Sulphur are strong brightening agents. Aromatic and heterocyclic sulfoacids are strong brighteners and invariably increase the polarization.

2.4.4 Explanatory notes on terms used in distribution of metal deposits on the cathode
Electrolytically deposited metal coatings are not distributed uniformly over the part serving as the cathode. The local thickness differences depend on a large number of factors, and are more pronounced when the profile of the part is irregular. Sometimes, no noticeable deposition takes place in recesses, the interior of tubes etc. Various terms, often not very clearly defined, have been introduced in electroplating technology in an attempt at characterization of the distribution of deposits on the surface of variously shaped objects. The term covering power is used to denote the depth to which metal deposition on a certain surface profile takes place. The depth of penetration of the deposit in centimeters into a certain surface recess can be taken as a measure of covering power. The term throtil'ing power is used to denote the local thickness differences in electrolytic coatings on an object. The throwing power of an electrolyte bath is good when the distribution of the deposit is uniform, and poor when it is not uniform. The great practical importance of throwing power is based on the fact, that the quality of an electrolytic coating depends greatly on its distribution on the metal to be protected. Not the mean thickness of the coating, but its minimum thickness at the 'critical' points is decisive. The critical points are those which are subjected to particularly intense mechanical or chemical stresses during use or which are particularly important for the functioning of the plated part. The customer must specify which points are critical'. In many cases, maximum uniformity of the deposit distribution is desirable, i.e. good throwing po'i of the electrolyte. The pertntage ratio of the smallest and greatest coating thickness at two particular points of the ob;cct may be used as a measure of the throwing power.

`Microti wing power' is given by the difference in deposit thickness at two particular points of a microprofile' (thus, in general, the differences in thickness at the grooves and
-

16

on the "flat" surface or the peaks of a surface profile). As the transition from the "macro" to the "micro" profile is continuous, it is important to know the factors, which determine the definition of these terms. With sufficient convection in the electrolyte, no effective differences in the thickn. ss of the cathodic diffusion layer are present within the range of the macro-throwing power. The cause of the macroscopic variation is the "primary current distribution". Inadequate convection at the micro level, however, can give rise to effective local differences in the thickness of the cathodic diffusion layer within the range of the micro -throwing power. This implies that the mass transport of the charged particles determines the discharge. A `primary current distribution" is not present within the range of the micro-throwing power. The borderline between macro and micro-throwing power is the point here diffusion becomes the decisive factor for the supply of charged complexes. By levelling is meant a decrease in the initial surface roughness of a part through deposition of the electrolytic coating. Levelling is not identical with micro-throwing power. Under certain conditions. however, leveling occurs within the range of the microthrowing power. The percentage ratio of the coating thickness on the profile.grooves and the peaks (or the "flat" surface) can also be taken as a measure of the micro-throwing power and leveling_ on a particular profile.

2.5 Mass Balance for Plating Process

As mentioned in the foregoing, the plating process could either involve anodic dissolution (e.g., Nickel, Zinc, etc.) or electrolytic dissolution (C'hromic acid). In either case, it is possible to calculate stbichiometric amount of metal deposition on cathode. In reality, no reaction is 100% complete, neither the assumptions valid in Fa adaY's las are wholly achievable. Due to these reasons, more inputs in the ferm of metal are needed. Secondly many substances are added to enhance. modify and alter the metal deposition process and properties of deposited metals. While some of these do not directly take part in mass transfer, others undergo a variety of complex processes like chemisorption. codeposition as oxides and various other forms. Generally. foreign substances arrive at the cathode owing to diffusion and convection and very little due to electrolytic transportation. As foreign substances, use of both inorganic and organic additions is widespread. For example, the induction period for the attack of dilute nitric acid on silver is shortened and sometimes reduced to zero. On the other hand. the lower corrosion resistance of bright nickel as compared with mat nickel is not dice to the general affrct of' the foreign incorporations in bright nickel coatings, but to the specific etTect of their Sulphur content. Thus, in many cases, not the additives but their decomposition products are often co deposited. Elucidation of the mechanism is thus difficult and relatively few studies have been carried out.

i7

In the case of deposition of bright metal coatings, enormous progress has been achieved since their inception, but the chemical and energetic processes involved in it have not yet been fully elucidated. The development of brightening additives and brightening electrolytes has been carried out on an empirical basis. In view of these constraints, the empirical nature and enormously large number of foreign substances and substances enhancing the bath electrolytes, the attempted mass balance would be restricted to principal constituents only, Two examples would be dealt with: Nickel and Chromium. It should also be remembered that apart from electrolytic inputs and metal deposition on substances (as cathode) as outputs, losses are to be considered. Here again, losses are principally due to dragouts and rinse. The mass (and related volumetric) rates depend on the (i) tecnique and handling practices and vary over a wide range. Well managed and properly handled plants may still get to achieve lower than I millilitre per sq. ft, while a range of I to 2 mllilitres per sq.ft of plated area or approximately I to 2 litres per 100 sq. m. of plated area is commonly encountered. (ii) rejection of bath when level of impurities reach certain pre-determined limits (iii) In addition, there are evaporation losses from bath but this is usually of acid /alkali mists and vapours. The mass emission rates of metals or metallic salts in vapours and mists are not yet well documented; it would be rather small compared to other two losses.

2.5.1 Nickel Plating

First, a calculation ofNi metal deposition is made using Faraday's law: E e g = 1.0995 y = 8.90 i = 4 amp /dm 2 ii =90(%) t = 20 min ( range 15 to 30 min) F = 100 sq. m. = 10,000 dm 2 G= 1.0995 x 4 x 10,000 x 20 x 90 6,000
= 13194 g

i.e., 0.132 kg per sq.m

For unit F, which carry out 14,00,000 sq.ft. of plating per year, they would need 17,174 kg. In reality they spend 1700 to 1800 kg of Ni anode per month i.e., 1750 x 12 kg per year on average. So, actual conversion is 17,174/ (1750 x 12) --- 84.2%. The industry average is 85 to 90 % . Therefore, 15 to 10% of Ni anode is lost/wasted. Estimate of dragout loss is calculated on the basis of Watts Nickel bath constituents : Nickel Sulphate = 240g/ Nickel Chloride = 40g/l 18

Boric acid

= 30 g/I

Total quantity lost in a year is calculated &, 1.0 litre of bath solution per 100 sq.m Nickel Sulphate (NiSO 4 . 7H 2 0) 31,226 kg Nickel Chloride (NiCl 2 6H20) = 5,204 kg Boric acid (H3B0 3 ) = 3,903 kg However, the entire dragout is not lost. First, they are recycled to bath; second, the unit may resort to metal recovery. In case of unit F, where Ni recovery is practiced, these figures reduce to 600, 102 and 96 kg respectively as net loss through wastewater. Part of Boric acid may be lost through evaporation, because the bath temperature is around 40 C and bath is agitated by blown air. The mass balance diagram is shown in Fig. 2.1.

2.5.2 Chrome Plating

Here also, a calculation of Cr metal deposition is made first, using Faraday's law: E ei = 0.323 y =-- 6.95 i = 9.5 amp /dm 2 n = 15(%) t = 3 min ( Average for decorative chrome) F = 100 sq. m. = 10,000 dm'

G = 0.323 x 9.5 x 10,000 x 3 x 15 6,000 - 230 g i.e., 2.3 g per sq.m of Cr Or correspondingly 2.30/0.52 = 4.42 g of anhydrous chromic acid per sq. m. of plated area of decorative chrome Using this figure in Unit H, plating area of 10 lakh sq. m. would need 4420 kg. In decorative plating, only about 10% of the chromic acid added to the bath is deposited on objects as plating. Unless recovered, the balance 90% would lead to losses. Also, there is dragout losses. Estimate of dragout loss is calculated on the basis of Chrome bath constituents Chromic acid = 280 - 320 g/l Sulphuric acid = 2.1 - 2.5 g/I Total quantity lost in a year is calculated @ 1.0 litre of bath solution per 100 sq.m. Chromic acid Sulphuric acid = 3000 kg = 23 kg

However, the entire dragout is not lost. First, content of dragout tank is often recycled to plating bath; second, the unit may resort to Chromium recovery. Part of sulphuric acid

19

Ni-deposition on Objects 17,174 kg

Spent Ni -anode 3826 kg

Ni -anode 21,000 kg

600 kg Dragout loss Tri- Bright

I
NISO4 31,226 kg NiCl2 5,204 kg
Tank

Ni -sulphate I SemiBright Ni -chloride

Drag out

Rinse Tanks

102k

Water

r')
Unreacted Ni 3826 kg

Ni-chloride Ni-sulphate 30,626.kg

5f02 k

Regeneration Unit Losses Ni -SO4 600 kg Ni -C12 102 kg

Regeneration chemicals /"acids

Fig 2.1 : Ni -Plating Mass Balance Diagram

(Showing metal recovery)

may be lost through evaporation. The mass balance diagram for a plant doing decorative Cr-plating @10 lakh sq. m. is shown in Fig. 2.2.

2.5.3 Silver Plating

First, a calculation of Ag metal deposition is made using Faraday's law: = 4.024 10.50 7 i 0.4 amp /dm 2 1 =99(%) t = 80 min ( range 75 to 90 min) F = 100 sq. m. = 10,000 dm 2 G=24.024x0.4x 10,000x80x99 6,000 - 19315.2 9

i.e., 0.193 kg per sq.m

For unit X, which carry out approximately 1800 sq. m.. of silver plating per year, they would need 347.4 kg. In reality they spend 350 to 360 k g of Ag anode per year on average. So. actual conversion is 97.8%. The industry average is 99 to 99.5 % Therefore, 0.5 to 1% of Ag is lost/wasted. Estimate of dragout loss is calculated on the basis of Potassium Silver Cyanide bath constituents Free Silver = 30g/I Free Cyanide = 30g/l Potassium Carbonate == 150 to 160 g/I Total quantity lost in a year is calculated = 540 g Free Silver 540 g Free Cyanide = 2790 g K2CO3 1.0 litre of bath solution per 100 sq.m

However, the entire dragout is not lost. First, they are recycled to bath; second, the unit resorts to metal recovery. In case of unit X. where Ag recovery is practised, the total of silver cyanide and potassium cyanide is 3000 g . Since the individual quantities are not known, the corresponding weight of K [Ag(CN) 2 is 996 g based on 80.5% silver content n, 100% purity. If recovery is considered as 99 %, 5.4 g of Ag is net l oss through wastewater. The mass balance diagram is shown in Fig. 2.3.

2.5.4 Zinc Plating

In alkaline non-cyanide (cyanide free) process, a calculation of Zn metal deposition is made using Faraday's Law: = 1.219 =7.13 p i

Deposition on Objects 4420 kg

Fresh Cr-acid Plating Bath Dragout Tank #1 #2 loss 3,000 kg Dragout Rinse Tank

Rinse Tank

3,000 kg

6,000 kg

U nreacted Water Chromic acid 36,580 kg

Regeneration 4 Regen. Chemicals Unit Chromic acid 38,000 kg Waste 1580 kg

Ii

Notes 1. Figures relate to plant doint 105 sq.m. p.a. 2.Waste with regeneration =1580 kg 3. Waste without regeneration = 36,580 to 39,580 kgs

Fig 2.2 : Chromium Plating Mass Balance Diagram

(Showing metal recovery)

Ag Deposition on Objects : 19.3 kg

Silver Anode 19.72

Silver Bath Free Ag 540g Free CN 540 g K2CO3 2790 g Unreacted Ag 0.42 kg Tank CN 108 g

Dragout loss Dragout

Ag 5.4 g

Potassium Silver

Cyanide

K2 CO 3 2790 g (as products of dissociation KOH, CO 2 . H)

CN 432 g Regene- Ag 534.6 g ration Tank Ag recovered in powder form 945 g 9.6 g Reaction products of K 2 CO 3 Silver loss CN432g

N w

NOTE : Figures relate to

100 sq. m. of plating

Fig 2.3 : Mass Balance Diagram of Silver Plating

T1
t F

= 14 amps per sq. ft. i.e., 1.506 amp/dm 2 = 75 (percent) = 40 min (average for auto component etc. corresponding to 12.5 micron thickness) 100 sq. m. = 10,000 dm 2

1.219 x 1.506 x 10,000 x 40 x 75 6000 = 9179.1 g = 0.092 kg per sq. m.

Now, 1000 sq.ft. (92.94 sq. m.) plated to 12.5 micron is mass eqivalent of 8.2 kg of Zn. The corresponding figure of G is 8.55 kg. For ACF process, Zinc platers use a range of 8.4 to 8.8 kg Zn anode corresponding to 12.5 micron thickness over 1000 sq. ft. ( 92.9 sq. m.) This means that the actual conversion may vary from 98 % to 94%. For a well-organised plater, the average is usually 98%. Therefore about 2 % Zn is lost / wasted. Estimate of drag-out loss is calculated on the basis of bath constituents @ 1.0 litre of bath solution per 100 sq. m. : FreeZn: NaOH: Organic Additive: 18g 190 g 15 ml.

Major part of the free Zn is recovered (about 90%) as hydroxides in the waste treatment unit and retrieved as sludge (non-hazardous). The sludge can be reused to manufacture zinc chloride, zinc sulphate etc. The two other processes, namely, Acid Zinc and Cyanide Zinc, have higher current efficiencies e.g., acid zinc 95% average (range : 92 to 98%) and cyanide zinc 80% (range : 60 to 85%). But they have unfavourable distribution ratios owing to reduced throwing power. This means that more metal is deposited in high current density areas as compared to low current density areas. In other words, for objects with high portion of high and medium current density areas, more metal has to be deposited to ensure minimum thickness specified, which is usually the areas of low current density. Correspondingly, the total amount of metal deposited will be higher in these two processes for same object as compared to ACF process. Obviously, the quantities of wasted metal and bath solutions (acids and/or cyanides) are higher in those processes.

2.5.5 Copper Plating

Copper plating is used in many situations, particularly as undercoat to receive precious metal coating. There are both cyanide and non-cyanide process. Acid Copper is one of the very commonly used processes. For this process, a calculation of Cu metal deposition is made using Faraday's Law:

24

Eei = 1.186 y =8.93 i 10 amps per sq. ft. i.e., 1.076 amp/dm tl - 100 (percent) = 55 min (average corresponding to 13.3 micron t thickness) F = 100 sq. m. 10,000 dm`
,

= 1.186x 1.076 x 10,000 x 55 x 100 6000 = 11697.9 g per 100 sq. m. = 0.1169.7 kg per sq. m.

2 Now, 100 sq. m. plated to 13.3 micron is mass eqivalent of 11.88 kg of Cu. The corresponding figure of G is 1 1.70 kg. So, the actual conversion process is about 98.5% or more. Therefore about 1.5 % cu remains in solution or wasted. Estimate of drag-out loss is calculated on the basis of bath constituents a 1.0 litre of bath solution per 100 sq. m. Drag-out losses: CuSO4 H" SO4

220 g 70 g

Major part of Cu is recovered (about 90%) as hydroxides in the waste treatment unit and retrieved as sludge (non-hazardous). The mass balance is shown in Fig.2.4.

25

H 2 504 2.925

CuSO 4 5.26:

Cu Anode 11.88 kg

Objects

Plated Objects Cu : 11.698 kg

H2SO4 2.855 kg Free Cu 0.182 kg

CuSO4 0.22 kg H 2 SO 4 0.070 kg

Fig 2.4: Mass Balance Diagram of Cu Plating Acid Copper Process

Chapter 3

In-depth Studies in Electroplating Industry

3.1 General

In order to carry out an in-depth study of a variety of electroplating units, considerations were given to various factors, such as - size of units (small, medium and large), location of industry (i.e., across the country), type of platers (i.e., primary users, who manufactures products in which electroplating is one of the manufacturing processes, such as bi -cycles, motorized two-wheelers, sanitary fixtures, etc and job work units, who render plating services to components manufactured by others), plating materials (Zinc, Chromium-several varieties, Nickel, Copper, Brass, Precious materials ( Silver, Gold etc.) and technology used, as some of them practice improved methods.

3.2

Analysis of Results

The results of the in-depth study have been analysed with respect to the following Type of units Quality of Raw (Untreated) Wastewater Quality of Treated wastewater Water Use and Cost of Wastewater Treatment Air Emission Status Noise Emission Status These are discussed in the subsequent paragraphs.

3.2.1 Type of Units

In the case of Electroplating, large units (with paid-up capital above Rs. 5 crore) are virtually non-existent. There are 'primary users', who manufactures complete products, such as bicycles, motorised two-wheelers and automobiles (4-wheelers), in which electroplating is one of the manufacturing operations. These units can also be called ' integrated units'. On the other hand, it is more convenient to classify these units on the basis of turnovers. In such a case, classification can be easier, irrespective of the fact whether they are primary users, outsourced units of OE manufacturers or job-work units. Table 3.1 shows the distribution of units in the in-depth study.

Table 3.1: Distribution of Units in the Study Gross Annual Turn-over > I crore Over 50 lakhs but under 1 crore Below 50 lakhs Percent of Total 54 14
32 27

Unit type Large Medium

Small

Consequently, all primary users and integrated units fall in the large category; these units generally tend to have mechanized and automatic handling and bath operation. They are more likely to have fume collection system too or are in a position to do so.

3.2.2 Quality of Raw (Untreated) Wastewater

The characteristic quality of raw (untreated wastewater observed during in-depth study is summarised in Table 3.2 for various types of plating.. The following observations may be noted: 1. Ni- Cr plating: In Ni -Cr plating wastewater, pH is usually acidic (mean pH being 2.9. TSS is not a concern but TDS is high (mean at 2754 mg/I; In several units it was noticed that alkaline rinse waste water are mixed with main wastewater from plating bath and rinsing tanks. In such cases, pH increases to near normal 7.41. This practice unnecessarily requires more acid to be added to lower the pH to around 2.5 for reduction ofCr(Vl) to Cr(lII). Both Cr(VI) and Cr (Total) are considerably high at 6.99 and 167.7 mg/L. Other metals (Ni = 91.2 mg/I and Pb = 2.8) also require alkaline precipitation. Oil & Grease and Total Residual Chlorine are not a matter of concern, because their values are within permissible limits of effluent for discharge. 2. Hard Chrome plating Although there is no fundamental difference in plating with respect to Chrome plating, the wastewater indicated very high TDS and Cr concentrations; this is partly due to the fact that rinse water volume is not as much as observed in decorative chrome plating and Ni -Cr plating. In other words, the wastewater is concentrated, having its own advantages and disadvantages. Removal of TDS is a serious requirement in final treatment of this kind of wastewater.

3. Blackening, Phosphating & Chromatting

The wastewater contains substantial concentration of Cr and Zn. pH is alkaline, because the sample was drawn from the neutralisation tank. Cyanide was rather low, because the effluent from cyanide oxidation is taken to neutralisation tank. Here too, TDS is high. 4. Zinc Plating This is the most common plating activity throughout the country, almost equal to NiCr plating. There are four processes which are in use. In Alkaline Cyanide Free process, the wastewater has alkaline pH (mean 8.2). substantially high Zn (mean 26.4 mg/1), some copper (probably coming from copper undercoat); Oil & Grease is not a concern. 28

In Acid Cyanide process, Zn concentration is high; pH is normal, because wastewater from Alkaline pre-cleaning is mixed with process bath and post-plating rinse water. The low cyanide concentration is inexplicable; perhaps large dilution water from other operations are mixed with bath and rinse wastewater. Wastewater from Alkaline Cyanide process has considerable concentration of Zn and cyanide, with high TDS. Other parameters are not of concern. 5. Acid Zinc (Cyanide Free) This process is widely used in Madurai, Tamil Nadu, where in tiny and small units, there is no treatment given to the wastewater. Zinc concentration is highest (mean 1675 mg/I and the range is very wide) among all the process variants; in fact it is incomparably high among others. Clearly, use of this requires immediate attention in regard to waste minimization as well as process modification.

3.2.3 Quali ty of Treated wastewater Table 3.3 summarises the quality of treated wastewater from the plants studied. The
following observations may be noted: a) five units out of 21 units impart no treatment to wastewater; these are tiny/small units, pointing to a serious problem nationwide; a) pH of treated wastewater is within desirable range. b) While the mean TSS is within acceptable limit, only in one unit, it is above limit. c) While there is no limit specified for TDS, in three units, it is above 2000 mg/I, a point of concern d) Cr(VI) is generally within limit and does not cause any concern e) Cr(T) range is wide and high exceedence in limit is observed in three cases indicating very clearly inadequate treatment. f) Ni- concentration meets standard in most cases; g) Zn concentration is within limit in most cases but exceeds in one, h) Cu conentration is within limit i) Oil & grease is not a matter of concern, generally within limit j) Cyanide is generally under limit k) Ammonia N is within limit; so is total residual Chlorine In summary, the main concern is inadequate removal of Cr(T) and Zn, indicating inadequate precipitation of metal sludge. Sludge handling and storage practices in many units are unsatisfactory, needs improvement. Conventional alkaline precipitation treatment does not remove dissolved solids. It is very interesting to note that one CETP (run privately) provides quite satisfactory treatment, meeting all parameters and also removing high TDS by reverse osmosis process.

29

3.2.4 Water Use and Cost of Wastewater Treatment

The water use and cost of wastewater treatment are summarized in Table 3.4. It is observed that water use varies widely among units owing to a large number of factors. Most units do not keep data on plating area due to the fact it is beyond industry practice and that where they do job-work, pricing is done on weight basis. Surface measurement is seldom done. However, data from large integrated primary user units indicate that water requirement varies from 68 to 230 litres per sq.m. of plated surface area of Ni-Cr plating. In smaller unorganised units this would still be more. On comparison, World Bank recommends a target of 1.3 litres per sq. m. of plated area for rack plating and 10 litres per sq. m of barrel plating where electroplating is routinely performed on objects with known surface area. Clearly, water use in the industry in the country is far higher than such targets. The of wastewater treatment varies rather widely. It is possible that accurate data may not have been furnished by the industry; even ignoring extreme cases, the reported range is as wide as Rs. 30 to Rs. 311 per kl. In the privately run CETP, the charge levied to customers vary from Rs. 0.50 to 1.25 for low TDS and Rs. 1.60 to 1.75 for high TDS . This makes sense that for medium, small and tiny units it would be genuinely economical to treat wastewater in a CETP, even by tankering. However, where the units treat their own wastewater, the cost of treatment is always below the generally accepted upper limit of 3% of total cost of production.

3.2.5 Air Emission Status

Electroplating give rise to fugitive emission from baths and pre-treatment tanks of elevated temperature. Vapours also emanate from baths at ambient temperature. Principal constituents of concern are acid fumes, gaseous pollutants and VOCs. Table 3.5 shows ambient air pollutants. It is observed that the fugitive emission levels are not high but acid fume levels can be reduced substantially by fume collection and scrubbing with water- rather simple techniques.

3.2.6 Noise Emission Status

Electroplating in itself does not involve any noise producing activity. The main cause is air blowers, used to supply air to tank agitation for pre-cleaning and some baths (e.g. Watts Nickel bath). In most cases, these are located close to plating tanks working area and workers are subjected to a sustained high noise level; predominant cause of higher noise level [higher than 75 and upto 84 dB(A)] is other industrial activity under same shed like machining, metal forming, stamping, forging etc. Table 3.6 summarizes the data.

30

Table 3.2 Summary of Raw Wastewater Quality

(mg/1, except pH) Parameters (Range & Mean) Zn Cd Pb 2.8 Cu 0+ G 2-14.6 (8.3) CN

Activity

3
see Note 3

Ni -Cr

Plating

H 2.2-3.5 (2.9) TSS 8-610 (12.3.7)

Cr(VI) 0.0153896

see Note 1

TDS 13584582 (2754) Ni 2.85376.5 (91.2) 14547

see Note 2 see Note 2

Cr (T) 2.0387.5 (167.7) 2.031592 (452) 21.5

Hard Chrome

2.2-4.3 (3.1)

388

(6.99) 1.01-14.0 (7.5)

7.8

Blackening, Phosphating

9.7 121 3944 BDL

21

7.8

0.05

Chromatting Cd plating Agplating Au _P1!!!!!L

10.17 8.5 115 2940

10.0 174

10.69

5830 1469

36.28 3.34

0.043 1.23 Cu =9.76

35.43

22.19

N. D. N.D.

0.109 0.06

7.2-9.2 (8.2) 134 3036

Cyanide Free Zn Acid Cyanide Zn

7.3-7.62

10.242:6 (26.4) 34.6

0.014

31

'7.62-9.7
(

I
7.62-9.7 35-121 (78) 21
i

1
I 5.6
(13.3)
-

i
39445178

Alkaline Cyanide Zn

0.01- 22.64
!

'

(4561)

0.0122.64 (7.57) i X7.57)

-

3.5
-

1
253325 (1675) J

Acid Zinc (Cyanide Free)

34-100 (67) 1914- 6008

(3961)

Notes

1. Where alkaline soak rinse wastewater is mixed with plating tank and rinse water, pH increases to a range of 6.58 7.90, with mean value at 7.41. Obviously such wastewater will require acid addition to lower pH for Chromium reduction 2. In one tiny hard chrome unit, there is no treatment given because of very small volume, increasing the concentration of pollutants to high level, shown here. 3. In one plating unit doing dull & bright Nickel on Chrome, wastewater is highly concentrated, showing Cr(VI) concentration at 53896 m4g/I 4. The large variation in concentration of Cr, Ni wastewater is mainly due to wide variation in quantum of water used for rinsing

Table 3.3 Summary of Treated Waste water Quality (mg/l. except pH) Parameters______
j 26.454 (40.1)
____ _______

Plant Activity
TSS 1100- 1 BDL0.06 7421 (3422) (0.024) 0.193.87 i (1.24) t 0.1-40 1 0.11- 1.76 (0.484) 2.50 1 (1.33) ( TDS I Cr (VI) Cr(T) Cu Zn 0& G 4.05.8 (4.9)

pH

Ni
Ag

I Cd

Cr, Ni -Cr & Zn plating

6.857.8 (7.41)

i CN 1 1 0.02i 0.21 (0.11

5)
4.0 BDL

NH3 -N 3.80

TRC <0.01

L
1.76. 3.87 7.93 -^ ; - j 1.723 0.20 0.173 - 2-21 xx

_____________

______ _____

BDL BDL 0.101 BDL ' BDL - 0.030.09 4 0.03 BDL BDL

<0.05 <0.05 <0.05

10.04 BDL Brass, Cr, Ni, 9.24 I 9.0 j 3150 i Cu plating. BDL 0.93; Cd Plating I 7.38 12.0 13404.0 - - - - Ag Plating ( 7.25 10.4 T 1438 8.2-8.5 1.8- 1026 -i; BDL BDL- - Phosphating. 148 2.2 Chromatting & 1637 Blackening ' ^ BDL BDL j 1.75 CETP - low 8.5 15 55 TDS stream BDL ! 0.13 i

<0.5

Table 3.4 Water Use & Cost of Wastewater Treatment (Selected units)
Water Use K1 per year Treatment Cost Rs. per ki 35 311 593* 0.008 69.2 6.648 94.44
-

Unit

Treatment Cost Rs.lakhs per year 2.10 2.10 4.45 1.0 2.45 10.97 17.0
i

Note

A B C 6000 675 750 12000 3540 165,006 18,000 16,500

-

Annual Turnover Rs. lakhs 1500 70 184 Treatment Cost as % of Turnover 0.14 2.90 2.42 0.007 0.39 0.15 1.73

E F G H

14400 624 7434 981

*Probably treatment cost includes other costs Very large primary user unit

n.a.

Does plating on 2.65 x 10' sq.m. annually CETP (Privately run)

0.03

K T 22,500 150,000 25 45

n.a. 14,000

LowTDS=0.40 H ighTDS= ] .60 to 1.75 111 30

V 3300 2.52

4500

76.36

0.06

X 240

141

0.5

208.33

0.45

Very high cost Does plating on 6.50 x 10' sq.m. annually (Zn-plating not included) High value products; does a variety of plating including cadmium, silver & gold Does silver plating on brass

Table 3.5

Air Emission Status

(Fugitive Emission, micrograms per Nm 3
)

Unit HCL mist NO,

H2 SO 4 mist

Type of Plating done by the Unit

SO2

B K
-

0.61 0.30 0.58

-

2.0 4.0 12.82

N P T -Do-

Ni, Cr, Cu, Precious metal Blackening/Chromating /Phosphating/Zn Ni/Cr Ni/Cr/Zn Ni/Cr/Zn/Phosphating 97 16.23
-

BDL BDL

r
0.30 0.61 0.5 2.0 12.82 6.3

Range Mean

26.64 22.10 80 74 16.23 97 5 2.3_

BDL BDL 17 5 BDL 17 negl igible

35

Table 3.6 Noise Emission Status

Ambient. dB(A)

Noise Level ! 42 (6) Air blower used for plating & pre-cleaning tanks rt Air blo er plus other sources like machining, polishing, metal forming, cutting etc: Nil

Noise Source

Note No noise producing activity Located within plating area

< 70

Per cent of plants observed (No. of units) 8(1)

70-75

>7^ upto 84

50 (7)

Generally contributed by activities not directly connected with plating

Note: Sustained, generally steady noise level exposure to workers over the 8-hr shift

36

3.3 Summary of Findings The findings of in-depth study is summarized as : Electroplating by itself may not constitute to he a large industry by conventional definition of paid-up capital. Big electroplating units are always a part of integrated industrial production (automobiles, cycles etc.), referred to in this study as primary users' These units arc usually mechanized, operated with semi-automated process control and better in pollution control, often employing metal recovery, rinse water recirculation and fume collection system. 2. Vast majority of units are small proprietary, partnership or private limited entities (turnover ranging from as low as 10 lakfis to 5 crores), these units vary widely in setup, plating process control, degree of mechanization, pollution control techniques and ability to modernize due to several reasons. These units with almost total manual operation and with little technical supervision need to be upgraded with various levels of BAT, as identified in Chapter 5. 3. Largest number of units are engaged in Ni -Cr and 7.n plating; wastewater characteristics vary widely mainly due to unorganized handling, wasteful rinsing, lack of process control. Large number of such units do not have any wastewater treatment t^icility, discharging their untreated wastewater into municipal drains Where treatment is dine, reduction of'Cr (VI) to Cr (I11) is generally satislactor\ but wastewater often contains high levels of Cr('l') and %n, indicating inadequate precipitation of metal sludge. This holds good for Cadmium and other plating too. No problem is found with respect to other pollutants. .!t is very interesting to note that one CETP (run privately) provides quite satisfactory treatment, meeting all parameters and also removing high TDS by reverse osmosis process 4. Sludge handling and storage practices in many units are unsatisfactory, needs improvement, particularly it contains hazardous materials. 5. Conventional alkaline precipitation treatment does not remove dissolved solids. Most effluents contain higher than 1800 mg/I, a figure often used as limit in other industrial wastewater. Even with sand filtration followed by activated carbon filtration. TDS as high as 3404 mg/I is noted. 6. Data from large integrated primary user units indicate that water requirement varies from 68 to 230 litres per sq.m. of plated surface area of Ni -Cr plating. In smaller unorganised units this would still be more. As comparison, World Bank recommends a target of' 1.3 litres per sq. m. of plated area for rack plating and 10 litres per sq. m of' barrel plating where electroplating is routinely performed on objects with known surface area. Clearly, water use in the industry in the country is far higher than such targets. 7. Cost of' wastewater treatment varies widely range being Rs. 30 to Rs. 311 per kl. Scale of operation is one of the main reasons - larger the plant, lesser is the cost per kl. In the privately run CETP, the charge levied to customers vary from Rs. 0.50 to 1.25 for low TDS and Rs.1.60 to 1.75 for high i'DS . This makes sense that for medium, small and tiny units it would be genuinely economical to treat wastewater in a CETP, even by tankering their wastewater. 8. Where the units treat their own wastewater, the cost of treatment is always below the generally accepted upper limit of 3% of total cost of production. 37

9. As far as air pollutant emission is concerned, the fugitive emission levels are not high but acid fume levels can be reduced substantially by fume collection and scrubbing with water- rather simple techniques. 10. In most cases, worker exposure to average noise level is upto 75 dB(A). Where workers are subjected to a sustained high noise level; predominant cause of higher noise level [higher than 75 and upto 84 dB(A)] is found to be other industrial activity close by and under same shed such as machining, metal forming, stamping, forging etc Ambient air quality due to fugitive emission of filmes and vapours were studied. It was found that the oxides of Sulphur and Nitrogen are quite within the limits of concentration of ambient air. As far as acid mist concentrations are concerned, the average concentration of H2 SO 4 is 6.0 mg/ Nm 3 . The 1-ICI mist concentrations are negligible. However, this is to be viewed with respect to international standard because there is no standard for this parameter in India.

Chapter 4
Recovery of Metals 4.1 General.
During electroplating operations, metal salts are used partly by electro-deposition of metals and partly by rinsing and washing. While the first part goes into plating, the second part is lost and actually poses a problem in wastewater treatment. Even in plating baths, solutions often needs to be discarded because of presence and build-up of impurities that either hinder the efficiency of plating process or cause deterioration in quality of plating. Either way, the baths are to be discarded before fresh bath is made. This is indeed a waste both in monetary terms and environmental considerations. Bath regeneration is therefore done to counter discarding it entirely. Various methods are used for regeneration of baths and contents of pre-treatment, rinse and wash tanks. These methods are briefly described below with their specific advantages and constraints of use. Of these methods, metal recovery through ion-exchange presents highest potential and serves the dual purpose of resource (metal) recovery and waste minimisation (by re-use of water of regenerated bath solutions). Hence this process would be discussed in more detail.

4.2 Filtration & Centrifugation

Filtration with or without centrifugation is one of the widely used and effective methods for prolonging and improving the life of bath. Although it does not directly recover metals, it enhances the use of metal salts thus controlling and reducing the wastage of metal salts. Activated carbon filter is widely used to remove dissolved organic impurities (example: Nickel Baths) in addition to its action in removing solids. Such filters are used continuously or intermittently during plating. The removal of oils from alkaline cleaners by ultrafiltration considerably prolongs the life of treatment baths and reduces interference by oils with flocculation and settling steps during clarification. Separation of the grease film from degreasing baths is another example of the use of centrifugation or filtration. However, these are not generally used in small-scale operations. The advantages of these techniques are: Fast regeneration of treatment baths with high efficiency; Production work does not have to be interrupted; Wastes resulting from these are highly concentrated and thus could be recovered; Disposal of residues is easier due to low volumes and more convenient with sludge disposal operations of the ETP Newer methods and technologies have come up such as hydro-cyclones, packed-media filters and electrolytically enhanced cross-flow membrane etc. 39

4.3 Evaporation 4.3.1 General

Evaporation losses are considerable in hot baths, such water losses can be compensated by recycling cascade rinsing (last tank of cascade). In theory, if the if the effluent rate equals the evaporation rate, a complete recovery of bath chemicals can he achieved. Even if complete recovery is not achieved, substantial recovery can easily be obtained.

4.3.2 Simple Measures

As the simplest example, the direct recovery of plating baths is realised with a static dragout tank. Rinse water from this tank is used for the replenishment of volume losses of the process bath due to the evaporation. Periodic water transfer from dragout into the process tank is made manually or better by a small pump. Practical recovery ratio realised by this method is not usually higher than 50 -- 60 %. Many platers in the small scale sector in India employs this technique. As an improvement to above, in case of cold bath, the dragouts and contents of first static rinse tanks can be concentrated by forced evaporation. However, application will depend on the trade-off between energy and operating cost versus cost of recovered chemicals (such as metal salts). Clearly, this technique is used in case of expensive chemicals. A more desirable method would be to use condenser, which would enable to recirculate the condensate (water) to rinse tanks and chemicals to bath.

4.3.3 Advanced Techniques Tin, Copper, Zinc etc.

Efficiency of direct recovery can be significantly improved by the introduction of several drag-out/rinse tanks arranged in series. Such a technique has been developed in Poland and applied in Poland and several countries with encouraging results. Air lift pumps (made of PVC) are used for rinse water transfer from tank to tank and from the first rinse tank to the plating tank.(Fig 4.1.). The return rates and opening and closing of valves are automated (controlled by electronic level controller and conductometric probes). Depending upon the plating line output, the evaporation losses of the bath and the space available in the shop, 4 dragout tanks in a series can be introduced. The tanks can work in closed loop system with zero discharge. This technique has been successfully used for Nickel, Tin and Copper plating baths and other hot baths recovery with an efficiency of 85 -- 95%. It has also been used for recovery of cold baths such as Zinc, wherein a small evaporator is used. Such a system for Zinc barrel plating line has been quite successful. Recovery ratio of Zn plating bath was 98% (about 300kg Zn per year). Average water consumption for rinsing was reduced from 200 1/ sq.m. to 18 I/sq.m., i.e., achieving a rinse-water reduction of 91%. Other savings included: 1. Reduction of Energy cost in plating shop 2. Reduction of consumption of anode and plating salts 3. Reduction in cost of waste water treatment 4. Reduction of sludge volume 40

LEVEL INDICATOR

I
t-----------. ........

COMPRESSED AIR WATER

'TI9_flF1E'1
PLATING BATH RINSE TANK # I RINSE TANK #2 RINSE TANK # 3 * AIR LIFT PUMPS

Fig 4.1 : Schematic Diagram of Direct Recovery System (WCCK)

4.4 Electrolytic Recovery & its Economics 4.4.1 General

This technique is now well developed and used in both large and small scale electroplating units. One major constraint of this method is that complete recovery of the metal from dilute solutions can not be achieved. As the metal salt concentration reduces, due to the metal extraction, the voltage must be increased in order to continue with the cathodic deposition. Voltage enhancement is ultimately limited by secondary reactions. Hence in practice, electrolytic recovery is used in conjunction with other methods. For example, electrolytic recovery of Copper from pickling baths has been successfully used. Electro-dialysis is one of the techniques in this group. In this technique, rinse water is pumped through a stack of ion-selective membranes that allow metal ions (for example in Nickel recovery, Nickel, Sodium and other cations) to pass through when an electrical current is applied. Nickel passes into an acid solution, which must then be neutralised for re-use. Over 99%, of Nickel can be recovered and treating relatively large volumes (of rinse water) is possible. However, since Nickel passes into an acid solution, it needs to be neutralised for re-use. Moreover, membrane life and serviceability can be a concern with Electro-dialysis systems. The most common and effective means of recovery from dilute solutions is by ion exchange method. Two most common metals Nickel and Chromium recovery and recycling would be dealt with. The technique and its economic viability would be discussed in the following paragraphs in more detail.

4.4.2 Nickel Recovery / Recycling by Ion - exchange

Nickel baths are followed by several counter current flowing water rinse tanks to prevent carry over and contamination of subsequent chrome plating baths. Typically, Nickel bath solutions of around 0.1 litre per sq. m. of plated area is lost as dragout to the rinse tanks. There are two options to deal with the waste water (a) Treat the waste water by alkaline precipitation and dispose of the waste water and put the sludge in secure landfill; (b) Recover Nickel and recycle to Nickel plating bath (recovery rate >97%) and treat the balance 3% or so. A plater would choose the more economical between the two desired alternatives. There are conventional ion exchange units as well as advanced ion-exchange units. In a conventional unit, the rinse water is pumped to ion-exchange column containing strong acidic cation exchange resin characterised by high capacity, good chemical resistance and'stability. The resins exchange hydrogen ions and Nickel ions are retained on resin which gets saturated with Nickel Salts after sometime. Then passing of Nickel solutions are stopped and resin regenerated with 55 pure Sulphuric or Hydrochloric acid. The regenerated solution contains Nickel ions in the form of NiSO.z or NiCl2 . All brightener and products of its breakdown are also removed leaving regenerated solution

42

free from organic contamination. The solution can now be returned to plating tanks semi-bright Nickel and/or tri -Nickel. The comparative economic comparison of a small plant is given in Table 4.1 Table 4.1: Economic Comparison of Waste Treatment vs. Nickel Recovery
(Basis: 2.5 kg of NiSO 4 per day)

Component

_
Nickel Salta 165 per kg Sulphuric Acid Rs. 6 per

Waste Disposal cost pey 2.5 kg 412.50 3 12 50 2 476.5 1,42,950

Operating Cost (Rs) of Recover System _ -_ 3 kg 18 __ 12^__

kg
Electricity 4 per kWh

Labour
Chemical for Sludge handling Total per day Total per year @ 300 working days/yr Net Saving_per r

LS
LS

LS
-

50
80 24,000 1,18,950

Clearly, recovery/recycling presents a very encouraging case in favour of its adoption, even in small plants. However, the capital investment and cost of replacement of resin must also he considered for net gain. For a good quality control on plating and consequently on the bath constituents, the following are to be considered. I. Contaminants that have accumulated in the rinse tanks should be removed before the Ni solution is recycled to the plating baths; If not, the recycled contaminants would build-up in the bath and cause an adverse effect on the plating quality and bath life. Carbon filters are used for this purpose. 2. Brighteners are usually Sodium salts of organic compounds and they are consumed / degraded in the plating process or lost to dragout. Dragout actually provides an important outlet for degraded brighteners and Sodium. Recycling presents following problems - degraded brighteners increase the load on Carbon filters - some decanting of the tank may be required to control Sodium levels - Brightener control is difficult when a portion is recycled - recycling to semi-bright tanks require absence of brighteners of the bright baths 3. Recovered solution should be sufficiently concentrated a Ni- concentration of 35-40 g/1 is acceptable for direct recycling 4. Recycled mix of Ni salts (Sulphate and Chloride in a particular ratio) should be same as original mix ratio

43

5. pH of the recycled solution should be in correct range 6. In some Ni- plating baths, the Ni concentration builds up beyond the required limits. This occurs due to the the difference of the current efficiencies of the cathode and anode. The anode efficiency does in fact approach 100% butr the cathode efficiency usually falls in the range 90-96%; this causes more Ni anode dissolution into the bath solution than what is being plated and the Ni concentration and pH in the bath will increase. This problem can be controlled with the use of specially designed insoluble anodes. In the advanced recovery system using ion-exchange process, some of these problems have been tackled to provide better efficiency and performance. This type of system uses to sh ort packed resin columns (i.e., cation and acid sorption) with fully automated operation. l;conomic comparison is shown on Table 4.2.

Table 4.2 Economic comparison of Advanced Ion-exchange Nickel Recovery vs. Waste Treatment
(Basis: 2.5 to 3.0 kg /hr dragout operation)

- ------- Component

Nickel Salt Sulphate + chloride 1 65 perkT 32% Hydrochloric Acid @ Rs 4,00 0/tonne 93% Sulphuric Acid Rs. 6 , 000 per tonne 100% Caustic Soda Rs. l 5 ,000 per tonne 10% sludge + handling , R s.50 0 p er tonn e Plant water (; Rs. 15 per cu.m. D.M. Water (1 Rs.25 per cu. m . Tot al per year j Net Saving per ye ar
-- ---

-- ---- ---Waste Disposal cost Rs. p er d --20,000 kg Rs 3,300,000

Operating Cost (Rs) of Recove System Rs.33,000 200 kg

6.3 tonne 75 tonne 45,000 cu. m. 2,000kg

_
Rs. 8,000 Rs.54,000 Rs.1 12,500 Rs. 375

Rs.94,500 Rs. 37,500 Rs. 6,75,000

9,000 kg 7.5 tonne 0.75 tonne

5,400 cu.m.

Rs.l 35,000 3,42,875 37,64,125

------

41,07 ,000

--

-----

---

---

i he operating advantages are;

Very dilute rinse feed solution (<0.5 to 1.0 g/1 as Nickel) resulting in high concentration purified product (>35 40 g/l as Nickel) Organic brighteners are rejected allowing direct recycle to semi-bright baths Prevents Sodium build-up in plating bath Regeneration of resin with a mixture of Sulphuric and Hydrochloric acid produces a mix of Nickel Sulphate and Chloride that matches bath chemistry

44

 Excess regenerant acids from the initial product of the first resin bed are sorbed out in the second resin bed resulting in the final Nickel products having a pH suitable for direct recycle.

4.4.3 Chrome Recovery / Recycling by Ion -exchange

In decorative plating, only about 15% of Chromic Acid added to the bath actually gets plated on the objects. The balance is lost as dragout to rinses and fume scrubbers. Clearly this indicates a huge waste of metal, which is also very hazardous. Moreover, decorative as well as hard chrome plating baths become contaminated over a period of time due to dissolution of metals from the plated components and other operational factors. These dissolved cationic contaminants (trivalent Cr, Fe, Ni, Cu, Zn etc.) lower the throwing power of the bath and lower current densities. This results in slower plating operation, consuming more energy, Plating quality is also adversely affected. All these factors together (i.e., defects in surface coating, material loss and costs of treatment and disposal to comply with pollution control regulations) lead to purification and recycling of Chromic Acid. Conventional ion-exchange based recovery system comprises cation and anion exchange columns. The first column, containing cation exchange resin, removes trivalent Cr, Ni, Fe, Cu etc. The effluent, then containing only hexavalent Cr is passed through anion exchange resin. This removes hexavalent Cr, leaving the effluent free from all metal ions. When the resins get saturated, they are regenerated and recovered Chromic Acid is recycled to baths. The economic comparison is shown in Table 4.3 The cost of a typical locally manufactured plant (of 2.5 kg Chromic Acid recovery costs about Rs. 1,00,000 with a resin volume of 50 litres. The cost of resin is Rs. 600 per litre with minimum life of 1 year (average life is between 2 to 3 years). The depreciation available on the investment is 100 %. Therefore pay back period is about a year.

Table 4.3: Economic Comparison of Waste Treatment vs. Chrome Recovery

(Basis: 2.5 kg of Chromic Acid from static Rinse Water per day)

Component
Chromic Acid @110 per k Sodium Metabisulphite @ Rs. 12 per kg Caustic Soda @ Rs. 14 per

Waste Disposal cost Rs. er da _ 275 2.5 kg

7.5 kg 4 kg 2 kg 3 LS 90 56 6 12 50

Operating Cost (Rs) of Recovery System

4 kg 3 kg 10 LS

56 12 40 50

kg Saving on Sulphuric Acid Rs. 3 per kg Electricit a, 4 er kWh L abour

45

Chemical for Sludge handling Saving on plant water (after recycling) Total per day Total per year @ 300 working days/yr Ne t Saving per y r

LS LS

_
158 47,400

_
496 1,48,800

--- --

--

---

--------1,01,400

Despite such encouraging results, conventional ion exchange recovery systems have one problem. Direct recycle of the dragout solution to the plating bath will also recycle the metal contaminants and lead to build-up of contaminants as recycling goes on. An effective recycling system has to incorporate both recovery and purification. However, dragout solution after purification could be too dilute for direct recycle to the chrome bath .A good arrangement would be to use an atmospheric evaporator for the purified recycled solution. The availability of two or three counter flowing rinse tanks in the plating line could ensure a high degree of recovery with such a system (over 90 - 96% of dragout losses) with the possibility of also reducing rinse water requirements by 70 80% . The economic comparison of larger capacity plants is given in Table 4.4.

Table 4.4:Economic Comparison of Chrome Bath Recovery with Treatment

(based on 3,785 litres bath volume; 240 g/l chrome; 15 g/l metals)

Itemn
Bath replacement Chemicals Solids Disposal Liquid Disposal Total Costs

Advanced Ionexch. System

On-site Treatment
Rs. 1,50,500 Rs.74,605 Rs57,663

Rs.23,177

Off-site Treatment Rs. 1,50,500 -_

Rs.3,44,000 Rs.4,94,500

Rs.29,154

Rs 2,82.768

Typical recovery efficiencies of various techniques and methods, including simple static recovery rinse used by most of the small scale platers, are summarised in Table 4.5. However, it may be noted that the recovery efficiencies reported here are only general indicators. Proprietary processes and techniques using same method can achieve higher efficiencies. Also, adoption of a particular technique depends not only on metal and/or chemical recovery efficiency but also on effect on plating quality, overall economy and availability of operational skill. Whatever the variant, metal recovery means (i) a straightforward pollution abatement at source, (ii) a cleaner production process and (iii) substantial saving of water.

46

4.5 Reverse Osmosis Reverse Osmosis is one of the membrane filtration techniques, in which the pore size of the membrane varies from I to 15 Angstrom and the liquid is filtered through a semipermeable membrane, which allows only water molecules since the pressure is more than the osmotic pressure. Application of this process is based on the fact that since the RO membrane normally rejects compounds and ions above a molecular weight of 150. most of the ions will be rejected. When rinse water is subjected to RO, water (with some compounds) will conic out as permeate and the rest of the chemicals will remain in the concentrate or rejects. The concentrate can be recycled to bath. This is possible when rinses from various processes are segregated. ff they are mixed, the concentrate will contain a variety of chemicals and obviously, it will need to be evaporated (with solar energy) and sludge disposed as hazardous sludge. The major limiting factor for use of RO system is the presence of Iron and free chlorine, which the membranes are not ai HIe to withstand, causing fouling of membrane. If sufficient pre-treatment precedes R(?. t henn it is a viable alternative to conventional system.
-

The process has been in use in BIEL, Trichy since the last four years for Chromium plating rinse-water with a capacity of 50 litre per hour (permeate). The savings achicv cd by lower consumption of water and chemicals pay for the plant in about two ycar^.:Morc facilities like this are successfully being built in Madurai Electroplatcrs' park in Madurai. and other parts of Tamil Nadu

47

Table 4.5: Selected Metal Recovery Techniques & Methods for Types of Plating Acid Copper Plating Nickel Plating Acid Zinc Plating Cadmium Plating (Cyanide) ` y y. y
y y y
ve)

Method T Cv<"1nide [cchnignc ilver Plating. Cyanide Zinc Plating y y y

Cyanide Copper Plating

Chrome Plating (Decorati

Thick Chromium Plating

Chromic Passivati on Y

Copper Pickling

Acid Picklin g Y Y

^ !on

Eacha

-n-c laectrc,l: is

Y
Y

Eiectro Dials' iS

SIIOC Stat

.__

i
y )'

v^;,

Recd' N\ Rinse T^ pical^ > 99/o Reco\ e'

80)

98%

98% -70-

95%

70%

80%

70%

98%

98%

80%

98%

98%

Ef lcICnc\

Source: I. NEP. "Environmental Aspects of the Metal Finishing Industry. A Technical Guide`. Paris. 1993

Chapter 5
Waste Minimisation & Treatment to Control Pollution 5.1 General
Electroplating generates all three forms of waste -- liquid, gaseous and solid. Of these. liquid wastes are predominant. Such liquid wastes include : (i) spent chemicals and solutions such as acids, alkalies, cleaning agents, bath chemicals comprising platinoo chemicals as well as additives such as brighteners. levellers etc. and rinse waters. which may contain some or all of these depending upon sources, method of plating and housekeeping practices. Gaseous wastes include solvents and vapours from hot pre-treatment and process bath;. They include acid alkali mist, Volatile Organic Compounds (VOCs). In some cases. mists and VOCs may contain metals in addition to process chemicals. Accordino to one estimate, approximately 30% of the solvents and degreasing agents used can he released as VOCs when baths are not regenerated. Solid wastes include, sludges generated from wastewater treatment. diidge,., frc w cleaning and bath tanks and various residues like, cleaning powder. buffin ' compound s . spent anodes and various scraps. Unused chemicals, spent resins frons icon-exchange metal recovery systems also contribute to solid waste. Much of the solid vvaste contain hazardous and toxic substances. Waste minimisation therefore occupies the most important position in the ,oll ros i ! pollution from electroplating and overall protection of the recipient environment \a h air and land (soil).

5.2 Waste Minimisation & Process Modification

Waste minimisation in an Electroplating unit may include any one. combination or all of the following: 1. Minimisation of Wastewater Generation This is the single most significant step towards waste minimisation. The results of the indepth study points to an immediate need towards this objective. While the large and organised units practice full or partial wastewater minimisation. small scale and tiny units do not do anything at all. Numerous studies reported in literature also point out to se' cral approaches, which can be briefly stated as; Introduction of rinse water recirculationwith automatic benefit of chemical recovery and reuse Static rinse water recovery Avoiding and controlling spillage single largest cause of high wastewater generation in the unorganised sector. By using troughs between tanks and using well defined linear configuration in place of barrels and avoiding haphazard rinsing and washing will ensure very significant reduction in quantum of wastewater generated.

49

 Introduction of cascade and/or counter- current rinsing Use of fogging and spraying on objects (rack plating) Introduction of metal recovery by electrolytic method (ion-exchange and its advanced application leading to high recovery ratio of water (upto 80%). Analyses of cost saving by metal recovery using ion-exchange process indicate that for a small scale plant @ 2.5 kg Chromic acid per day and 2.5 kg Nickel Sulphate per day, gross saving would be Rs. 1.01 lakh and 1.20 lakh per year. For large plants @ 2.5 kg Nickel Sulphate per hour, the saving by advanced ionexchange would be Rs.37.64 lakhs per year.

2. Minimisation of Gaseous Emission

Except a few states (e.g., Karnataka and Maharashtra), State Pollution Control Boards do not generally require electroplating units to provide any measure for elimination or control of gaseous emission. As discussed earlier, gaseous emission takes place as vapours from hot baths, normal evaporation from cold baths do not constitute significant source of such emission and VOCs from organic cleaning baths. Use of collecting hoods and scrubbers can significantly control or eliminate vapours from baths. Collecting arrangements have improved substantially but older plants either have no collecting hoods or only side suction arrangement, which are not effective at all. Completely covered baths are ideal solution but they are useful in completely automated plants as used in Europe and parts of North America. However use of top suction hoods with properly designed scrubber system certainly controls much of the gaseous emission. As far as emission of VOCs are concerned, ideal solution is not to use those with high environmental concerns (discussed in Section 4); even if they are used, the best practice is to keep the tanks fully covered at all times and using vapour arresting devices.

3. Minimisation of Solid Waste

Major part of solid waste (that too, hazardous) is sludge from waste water treatment plant. Therefore, if measures are taken to minimise waste water generation by adopting methods stated in sub -para I above, waste water sludge generation is minimised. Other constituents of solid waste are: (1) spent anodes, (ii) tank sludges, (iii) spent carbon filters and (iv) empty containers of chemicals etc.. The last-named one is usually sold to scrap dealers. Tank sludges and spent carbon filters may contain hazardous metal salts. While the quantity depends on production, disposal practices should conform to regulatory requirements pertaining to hazardous substances. Therefore using non-hazardous chemicals will lead to minimisation of hazard in solid waste from process chemicals. Use of Cyanide free process (e.g. Alkaline Cyanide Free Zinc plating), use of trivalent Chromium in place of hexavalent Chromium are examples of such hazard minimisation.

50

4. Minimisation of Noise Emission Plating activity by itself does not produce significant noise, except barrel plating of small obhects. Major source of noise is operation of air blowers used for blowing air in plating (for Nickel Plating) and in pre-cleaning operations . Such noise is minimised by putting the air blower in a separate room with noise muffling arrangements. In many plants and factories, it was observed that high ambient noise level in plating areas is caused by activities other than electroplating such as machining, stamping, .metal forming, forging, etc. etc. Noise reduction in such activities is however, outside the purview of this study.

5.3 Best available Technology (BAT) 5 .3.1 General The Best Available Technique (BAT) means the most effective and advanced stage in the development of' activities and their methods of operation, which indicate the practical suitability of particular techniques for providing in principle the basis for minimum emission values designed to prevent and, where it is not practicable, generally to reduce emissions and the impact on the environment as a whole.
Techn quel include both the technology used and the way in which the installation is designed, built, maintained, operated and decommissioned, including also training. Available techniques means those developed on a scale which allows implementation in industrial sector under economically and technically viable conditions, taking into consideration the costs and advantages. Best means most effective in achieving a high general level of protection of the environment as a whole. The objective of the BAT Guidelines is to provide a list of techniques. including technologies, which will provide guidance to the local regulatory bodies and the industries when determining BAT for an activity. 'i'he BAL' identified in this Report is intended to control and/or minimise pollution and improve the environmental performance by incorporating the technological advances as they occur. In the identification of BAT, emphasis is placed on pollution prevention techniques, including cleaner technologies and waste minimisation, rather than end-of-pipe treatment. Consideration should be given to energy efficient technologies and practices and to efficient use of raw materials, chemicals and water. Whenever economically and technically feasible, dangerous substances should be substituted by less dangerous or non-dangerous substances. Measures such as in-plant changes, process recycling and improved material handling and storage practices may also be employed to eftcct reduction in emissions. "l'he guidance issued in this note in respect of the use of' any technology, technique or standard does not preclude the use of any other similar technology, technique or standard, which may achieve the same emission. The entire range would not necessarily be

51

appropriate in specific cases. The specific choice depends on a wide range of circumstances but the crucial factor is that the selected regime achieves BAT. When deciding the technology, local Ambient Quality Norms must he taken into consideration. In addition to providing for the installation of equipment and the operation of procedures for the reduction of possible emissions, BAT will also necessitate the adoption of an ongoing programme of environmental management and control, which will focus on continuing improvements aimed at prevention, elimination and/or progressive reduction of emissions. When determining best available techniques generally or in specific cases, bearing in mind the likely costs and benefits of a measure and the principles of precaution and prevention, account must be taken of: 1) the use of low-waste technology, 2) the use of less hazardous substances, 3) introduction of recovery and recycling of substances generated and used in the process and of waste, where appropriate, 4) comparable processes, facilities or methods of operation which have been tried with success on an industrial scale, 5) technological advances and changes in scientific knowledge and understanding, 6) the nature, effects and volume of the emissions concerned, 7) the commissioning dates for new or existing installations, 8) the length of time needed to introduce the best available technique, 9) the consumption and nature of raw materials (including water) used in the process and their energy efficiency, 10) the need to prevent or reduce to a minimum the overall impact of the emissions on the environment and the risks to it, 11) the need to prevent accidents and tominimise the consequences for the environment; The techniques are regarded as representing BAT for a new activity. However, it is also generally intended that existing facilities will progress towards attainment of similar emission standards (ES). but the specific ELV requirements and associated time frames will be identified on a case by case basis when the consent application is being processed. Furthermore, for all facilities, additional and more stringent requirements may be specified on a site-specific basis whenever environmental protection so requires. Hence the BAT guidelines are not the sole basis on which consents are to he granted, since information from other sources and legal Acts will also be considered. including sitespecific environmental and technical data. and other relevant information.

5.3.2 Best Available Technique-Solutions (BATs)

52

In order to avoid unwanted adverse impact on the environment from the plating activities, various abatement measures can he adopted. While many industrial units may have already implemented various solutions. To a large extent these solutions can be referred to as conventional solution. The fundamental approach in achieving BAT involves following important considerations. all wastes are to be considered as unused raw materials although a complete non-waste solution is not realistic BAT might be applied in the three key areas - good housekeeping practices involving working habits and attitudes - technical modification involving modifications on existing machinery, - process modification involving substitution of' chemicals and alternative processes BAT might be applied at different levels of sophistication: Immediate application : applying low-tech measures : applying medium-tech measures Intermediate application Advanced application : applying high tech measures BAT measure(s) might he applied progressively i.e. singly or in combination as some measures require: - no significant or little investment but need more organised working. cleaning and better supervision with maintenance while - other measures needing considerable investment in the form of additional equipment BAT might result in: reduction in resource consumption of: - water - chemicals - energy (electricity) reduced amount/emission of: - wastewater containing, chemicals. sludge and other waste types air emission
-

improved bottom line in terms ot - reduced production costs - improved product quality - credibility and competitiveness

53

4.3.3 BAT benefits The following benefits might be expected: Minimised risk of pollution in event of accidents Minimised chemical exposure of employees Minimised consumption of chemicals and water Improved personnel morale due to healthier and safer work environment Production-downtime prevention or reduced scrap production caused by improper choice of materials, insufficient programming facilities, bad maintenance of equipment or bad configuration of the processes

5.3.4

General BAT approach Some general BAT measures, which are relatively simple and easy to adopt are summarized below. Table 4.1: Examples on general BAT measures within electroplating
General (P Measures Method Benefit

Cleaning and maintenance

Improve cleaning and Maintenance

Reduce consumption of chemicals and energy (heat and electricity)

----------------------------------------------------Have paved and sheltered storage Minimise risk of Appropriate storage of ch mical drums with drums stacked not more than - chemical contamination 0) soil 3 tiers and to allow free movement - spillage onto floor of the fork lifl
-----------------------------------------------------

Insulate hot process tanks including piping Maintain chemical concentration in plating baths at optimum level Introduce drip guard between adjacent tanks

Use chemical resistant material

Reduce heat losses

-----------------------------------------------------

Use conductivity meters to know when to top up chemicals due to Depletion

- Avoid chemical depletion - Prevent overdose of chemicals

-----------------------------------------------------

Use chevron shaped deflectors to return drag-out of chemicals/liquid hack to the relevant tanks

- Avoid spillage onto the floor - Recovery of chemical drips back into relevant tanks

Replace worn-out - - - - Use plastic tanks which are - - - - - - Prevent chemical leakage - - - - - resistant to corrosion tanks and leaky pipes - Reduce water consumption Increase Iii span of'tanks ----------------------------------------------------Install water pipe with spray - Reduce consumption of water Spray rinsing in small nozzles over the rinsing tanks - Reduce metal drag-out pulses wherein work pieces are sprayed during hoisting
---- -----------------------------,-------------------

Rotate plating barrels at top position Adopt multiple counter-flow rinsing and back-filling to plating bath

Use auto controller to effect the Rotation

Shake oil drag-out

-----------------------------------------------------

Use, for instance. air-lift pumps for hack-filling to previous rinsing tank with : - inlet at the top and - outlet at the bottom Pre-condition for back-filling is use of

- Reduce drag-out of chemicals/liquid - Save use of fresh water - Less cross contamination between tanks

54

General CP Measures

Method
de-ionised water

Benefit

-----------------------------------------------------

Use tenside or polypropylene halls in hot process tanks Clean contact points

Place sufficient plastic balls to cover the whole water surface Area

Reduce chemical evaporation loss - Minimise heat loss - Prevent mist formation - Ensure good electrical

-------------------------------------------------

-----^

Manually clean by use of steel

and

busbars

Brush

connections
Keep busbars free from "chemical cake"' and unwanted coatings Reduce electricity consumption Improve plating quality

------------------------------------------------------

Maintain rack Insulation

Coat all parts .except the electrical contact points, with chemical resistant polymer. The coating shall be non-porous and without Cracks

Avoid unnecessary - consumption of plating metal - plating of the racks - usage of electricity for surplus plating

Note: CP indicates Cleaner Production

Figures 4.1, 4.2 and 4.3 schematically depict the application of BAT techniques. 5.4 Specific BAT approach Ideas to implement some specific BAT measures are summarized herewith under the heading of: pre-treatment activity plating activity

5.4.1 Specific CP Approach in Pre-Treatment Table 4.2: BAT approaches in pre-treatment

Application in Pretreatment Pre-cleaning of small size Work pieces Method Use a centrifuge to remove all dirt prior to degreasing or to impose
cleanliness requirement onto the client (medium tech)

Benefit - Reduce lengthy pre-treatment - Reduce electricity consumption in

surface preparation

---------------------------------------------------------

Removal of accumulated oil and grease

Use centrifuge (medium tech)

- Reduce infiltration of impurities (undesirable salts and organics including oil and grease) in
degreaser tank

Prolong life span of degreaser bath

---------------------------------------------------------

Ultra-filtration of alkaline Degreaser bath for inlet water Ultrasonic degreasing

Self-explanatory (high tech)

As above

---------------------------------------------------------

Selt. explanatory (high tech)

As above

55

Electroplating Work Step 1:

Fig. 4.1

Electroplating Pre-treatment - BAT approach

Electroplating Work Step 2:

Fig. 4.2

Plating Operation - BAT approach for Nickel & Chromium Plating

.r,

bQ

E
0 U

ca
N fl.

C: iV

0
D V

(
W

Q
C

0
I-

0
C

C) C.

0
i7

58

For visualisation of some of the applications, see same illustration in Drawings 1,2 and 3 at end of this Section.

5.4.2 Specific BAT Approach in Plating

Table 5.3 summarises BAT approach in plating.

Table 5.3: BAT approaches in plating lines

Application in Plating Water flow meter and Conductivity meter Method Introduce on-line flow meter in water intake pipe Introduce on-line conductivity meter-in process tank Benefit Water savings trom correct adjustment of - water flow into last rinse tank - plating chemical replenishment

---------------------------------------------------------Reverse osmosis (RO) on last RO is not recommended for use in Reduce infiltration of impurities Rinse water for inlet water systems where : (undesirable salts and organics) into pH is 12-14 or pH is 0-2 rinsing tanks organics in influent water> 5 gIl ---------------------------------------------------------Place evaporator next to the Reduce consumption of zinc Zinc plating plating bath. The inlet pipe and back-filling pipe is installed in the process tank ---------------------------------------------------------- Saving of raw materials Recover heavy metals from used Nickel, chrome, copper and rinsing water for reuse in plating - Reduce amount of sludge tin plating - Reduce concentrations of heavy baths by means ofelectrolysis cell or ion exchanger (and evaporation metals in wastewater - Recover heavy metals for re-use or unit, if required) secondary raw materials to be sold off

5.5

Potential initiatives and cost estimates The below tabulation gives an idea of the different cost range relating to the various initiatives. It is to be noted that the costs are broad estimates only.

Table 5.4:Potential solutions and cost estimates

Applicability
Low-tech measures

Initiatives / Actions
Cleaning + maintenance Drip guard (polypropylene plastic material)

Cost Range in Rs
Negligible Negligible

-------------------------------------------

between tanks
-------------------------------------------

Replace leaky tanks and repair leaky pipes

Negligible

------------------------------------------Negligible Sheltered storage for chemical drums with secondary containment but without drainage
-------------------------------------------

Insulation ol'hot process tanks and piping

Negligible

............................................................. Put air blovaer in separate enclosure Medium-tech measures

Water flow meter and conductivity meter * Multiple counter flow rinsing / sequence

R. 10.000 - Rs. 50.000 Rs. 5.000 Rs. 10.000 - 50.000

-------------------------------------------

-------------------------------------------Rs. 15.0011 25.000 Barrel rotation * (at top position) * ------------------------------------------Rs. 10.000 - 35. 00O Sprak rinsing, ------------------------------------------Rs. 70.000-- 1.00.000 Centrifuge (pre-treatment)
Introduce / improve vapour collection hoods

And scrubber system High-tech measures Reverse osmosis or ion exchanger Ultra filtration / Ultrasonic (pre-treatment) Back filling to plating baths Evaporator bath and activated carbon filter Electrolysis cell

Rs. 50.000 - 1.50,000 Rs. 50.000 - 3.00.000 Rs. 1.00.000

-------------------------------------------

-------------------------------------------

Rs. 15.000 -- 50.00O Rs. 30.000 -- 1.00.000

Includes construction and installation of electrical contacts for operation mechanisms Note : In view of the availability of different designs and systems, the details of costs can vary. The industry is encouraged to acquire the latest cost information from the equipment supplier if any cleaner production initiative in the above is taken up.

5.6 Waste Treatment Options 5.6.1 General

An electroplating unit generates various streams of liquid waste, which require different treatment techniques. Such separate treatment (often pre-treatment) avoids the possibility

60

of mixing incompatible wastes, which makes treatment difficult, expensive and less reliable. Often such mixing can be a hazard to personnel or formation of complexes that are difficult to treat, such as mixing of Nickel plating wastewater with Cyanide bearing wastewater leading to formation of Nickel Cyanide. Therefore, segregation of wastewater streams is of paramount importance. During the in-depth study, it has been noted that in majority of small-scale and tiny units, this is just not done , indicating an urgent need to introduce this basic requirement. As a general rule, waste streams and characteristics must be carefully evaluated before selecting a treatment scheme. It was found during the study that units in large and medium scale have opted for treatment schemes that cater for their particular wastes, although there is a commonality of treatment methods and/or processes used. In some circumstances, (e.g., in Bangalore),. it is found to be economical, practical and much better managed to have a centralized vaste treatment facility operated by a separate entity. In fact it is a welcome development that in many states, industrial estates and parks are coming up to shift existing units and accommodate in a properly organised group of electroplating units with a Clfl'P (example Faridabad in Haryana; Madurai in Tamil Nadu, Anand Parbat area in Delhi etc.) 5.6.2 Principles of Treatment For most heavy metals, precipitation as insoluble hydroxy or sulphite compounds is achieved by addition of simple reagents followed by pli adjustment and sedimentation. In the case of hexavalent Chromium, it is necessary to First chemically reduce the metal to trivalent state and then form insoluble precipitates. However for certain very hazardous heavy metals such as Cadmium, a totally separate system may be advantageous, including separate disposal procedures. Where the wastewater contain cyanides, removal of' cyanides is achieved by oxidation to harmless residues, followed by a precipitation step to remove accompanying soluble metal ions. It is important. to distinguish between treatment of' rinse water (high flow and low concentration) and discarded strong process solutions (cleaners, acid dips, plating solutions etc.) of low volume and only occasional discharge but of high concentration. Clearly, a batch treatment system would cope with two types of wastewater rather than a continuous flow system which is likely to be upset by shock loads. The guiding principle is to store such strong wastes and release them gradually into treatment system. Thus flow equalisation is animportant operation to integrate into the treatment system.

5.6.3 Treatment Processes 5.6.3.1 Treatment of Hexavalent Chromium bearing wastewater. Hexavalent chromium compounds come from processes such as polishing and brightening, pickling, passivation, chrome plating and plastic metallisation. Reduction of

om

Cr(Vl) to the more easily precipitated trivalent state ( rather non-toxic) can be achieved in many ways. Sulphur compounds are commonly employed for the reduction of hexavalent chromates. Advantages include short reaction times, the simple observation of the reactions by measuring redox potential and a low yield of sludge after neutralisation with Sodium hydroxide. The sulphur compound include (i) Sulhur-di-oxide gas, dissolved in solution, (ii) metabisulphite (Na2S2O5) or normal sulphite (Na2SO3 ). These compounds, in acid solution (pH range 2 to 3), dissociate and the bisulphite anion (1-I SO; ^) reduces the Cr to the trivalent state. Stoichiometrically, for the reduction of 1 g of Cr (VI), 0.92 g of S is required. From this, the quantities of the appropriate reagents can be computed, assuming the reaction quickly goes to completion. Iron salts can also be used because they are sometimes cheaply available. The theoretical requirement is 3.22 g Fe (11) and 6.60 g H2SO 4 Or 4.91 g of 1-ICI for reduction of 1 g of Cr (VI). Table 5.4 shows the yield of hydroxide precipitation and of dissolved Sulphur salt (contributing to raised TDS) indicating the burden on the environment in other forms. The high amount of sludge produced is one of the discouraging factors against use of Fe salts and not normally used in India.

Table 5.4:Precipitation of Hydroxides and Neutral salts from reduction of Cr (VI)

Precipitated hydroxides Yield of Na2SO4 as dry matter (kg) From neutralization (kg) Sulphur di-oxide 4.1 1.98 Sodium bi-sul hite 1.98 8.2 8.34__ Ferrous Sul hate 16.4 Source: UNEP, :"Environmental Aspects of the Metal Finishing Industry, A Technical Guide". Paris, 1993 Reducing Agent

5.6.3.2 Treatment of Cyanide bearing wastewater

The Chemistry of Cyanide detoxification is relatively complicated and in most cases, degradation needs more than one reaction step. Degadation with Chlorine Cyanides can be oxidized by chlorine; both chlorine gas and Sodium hypochiorite can be used. Except in very large plants, where use of Chlorine gas is more economical, most plants use Sodium Hypochiorite. In case of use of Chlorine gas, the hydrochloride generated together with hypochlorite requires further neutralisation chemicals. This technique is suitable if the Cyanide concentration ranges between 0.1 and 1.0 g/l. A distadvantage of using chlorine gas is the high production of salts from the subsequent neutralisation.

62

When Sodium Hypochlorite is used, there is a two step process. In the first step, cyanides are oxidised by hypochlorite to cyanogen chloride, which is an extremely toxic gas. The second step, which takes place almost simultaneously, involves hydrolysis of cyanogen chloride to cyanate. The latter is highly soluble in water but care should be taken to ensure that the temperature does not exceed 40 0 C, so that degassing does not take place. Hazards are best minimized by ensuring as rapid a hydrolysis as possible. This is achieved at a high pH of around 1 1.5 with a detention time of upto I hour to guarantee complete reaction. Good mixing is essential. In some countries the retention time may be set by regulation. In most cases found during the in-depth study, further oxidation from Cyanate to Nitrogen and Carbon is not carried out and the effluent is sent to an equalisation tank for neutralisation. Where further oxidation is required, it is carried out by using Sodium Hypochlorite again at a pH of 8.0 to 8.5. It is very important to have correct and reliable pH control to prevent toxic gas formation under acidic conditions. Degradation with Active or Activated Oxygen Oxidation of Cyanides directly using oxygen leads to a great benefit that no salts are produced and no neutralisation of solution is required. This can be done by using (i) Hydrogen Peroxide, (ii) Persulphuric Acid and (iii) catalytic oxidation. Theoretically, 1.3 kg 11202 is sufficient per kg of cyanide. However, in practice. (a) excess 1-1,0 2 is required to ensure complete reaction and (b) this process is not recommended with low initial cyanide concentration i.e., less than 500 mg/l.. Addition of catalysts or Formic acid accelerates the reaction, enabling the method suitable for use in the concentration range of 100 to 1000mg/I. Persulphuric acid is often used as Oxygen delivering substance. It hydrolyses to I (,O and sulphuric acid in aqueous solution. Direct ozonation is another available method. Conentrated peroxides and persulphates are hazardous substances and should be dealt with accordingly.
,

Electrolytic Process When the cyanide waste is concentrated, an economical solution for degradation is electrolysis in presence of chlorides. Cyanides can be oxidised by electrolytic splitting of oxygen from hydroxides. Precipitation of Cyanides Iron ions form highly stable complexes with cyanides. A precipitation of divalent or trivalent hexacyanoferrates is possible as a detoxification step within the final wastewater treatment. But the resulting sediment is not fit for disposal to a landfill site , because acids or photolytic reactions may, under certain circumstances, release cyanides from the residue. Such sediments can be subjected to thermal destruction.

b3

Comparison of Methods
The popular detoxification method for cyanides in small metal finishing plants is still oxidation by chlorine. Advantages are the speed of reaction, easier process control, low costs and a relatively long experience in handling. For concentrated wastes, precipitation as hexacyanoferrates is suitable but must be followed by thermal degradation. Peroxy- compounds have the general disadvantage of long retention times. These processes are useful only where small quantities of cyanide bearing wastewaters are to be treated. The content of salts in the effluent is low. in summary, if cyanides are destroyed in in a continuous flow stream, hypochlorite treatment may be the best choice because of its simple handling and other advantages as mentioned before. if concentrated or small volumes are to be treated, techniques should be chosen which yield a minimum of waste even if'performance and maintenance is more complex.

5.6.3.3 Neutralisation and Precipitation

This principal operation in the wastewater treatment is intended to convert dissolved metals to insoluble hydroxides and removed from the effluent. The operation is preceded by flow equalisation as an essential step. The precipitation chemicals used are Sodium Hydroxide, Lime and Soda. Magnesium hydroxide is sometimes used but the reaction is slower and pH range is limited. Alkaline wastewaters are neutralized by sulphuric acid but it has a constraint for sulphate limits, if set as effluent standard. Smaller facilities use Sodium Hydroxide solution (450 g/I). 1-Iowever. if the wastewater contains fluorides. Lime solution should be used. Lime solution is cheaper and used by larger units. A lime solution preparation unit is required in the latter case. The maintenance of correct pH is essential for efficient precipitation of metal hydroxides. Fig 5.4 shows the pH ranges for precipitation of several metal hydroxides. For most cases, pH would be in the range of 8.5 to 1 1. Unnecessary high pil may interfere with the formation of a good settleable sludge. Therefore, the best practice is to maintain a Pl ' slightly above minimum pH value. Further adjustment may be required in case of specific effluent standard.
-

5.6.3.4 Design & Costing of a Typical Wastewater Treatment Plant

Based on the treatment techniques discussed above, a typical wastewater treatment plant for a unit doing Cr/Ni plating and a little Zn plating using Cyanide Zn process can be designed and cost estimates made. The capital cost of such a unit is estimated at Rs. 2.16 lakhs. The operation & maintenance cost is estimated at Rs. 1618 per day or

64

C vi

Figure 8.4 : Range of pH for Precipitation of Metal Hydroxides

approximately at Rs. 4.85 lakhs. The cost per kl comes to about Rs. 46 per kl, which is considered rather high as compared to Unit J, privately run CETP. It is interesting to note that cost of chemicals alone accounts for 86 -- 88% of total operating cost. Clearly, this points out to the need to minimise water and chemical consumption and introduce metal recovery. 5.7

Hazardous Wastes Rules

According to the Hazardous Waste (Management and Handling) Rules, 2002 and as amended vide S.O. 593 (E) dated 2oth May, 2003, the following wastes from Electroplating Industry are identified and listed in Schedule 1 of the said rules I. Acid Residues 2. Alkali Residues 3. Spent bath/sludge containing sulphide, cyanide and toxic metals 4. Sludge from bath containing organic solvents 5. Phosphate Sludge 6. Sludge from staining bath 7. Copper etching residues 8. Plating metal sludge 9. Chemical Sludge from wastewater treatment In the following paragraphs, salient features of the rules are mentioned. For complete information, the reader may refer to the original rules and amendments vide the Gazette of India (extraordinary) part II, section 3 (ii), in which the notification dated 20` x ' May 2003 has been published.

5.7.1 Responsibility of Waste Generator (occupier)

According to the provisions of the rules, every occupier of an industrial unit or waste generator shall obtain authorization from the concerned State Pollution Control Board or Committee to handle, treat, store and dispose off such hazardous wastes. For this purpose, the occupier (industrial unit generating waste) shall submit information in a designated Form No. 1 to seek authorization. The authorization would be valid for stipulated period and renewal must be sought. Furthermore, the unit shall also submit an annual return to the concerned State Pollution Control Board or Committee in the designated Form 4. The occupier shall take all practical steps to ensure that such wastes are properly handled and disposed off without any adverse effects which may result from such wastes. Ile shall also be responsible for proper collection, reception, treatment, storage and disposal of these wastes either himself or through the operator of a facility.

5.7.2 Transport of Hazardous Waste

In case of transport of hazardous wastes to a facility for treatment, storage and disposal, the rule also provides for procedures to be followed by the waste generator, transporter, operator of the facility and the State Pollution Control Board/ Committee. "Storage".

66

however means storing hazardous wastes for a temporary period, at the end of which the hazardous waste is treated and disposed off.

5.7.3 Disposal of Hazardous Waste

As far as the Disposal facility is concerned, the industrial unit not having a hazardous waste treatment and disposal facility of his own, shall send wastes to a common Treatment. Storage and Disposal Facility (TSDF). He shall also become a member of such facility. The onus of setting up of a common TSDF rests with the State Pollution Control Boards, although the rule stipulates that " the occupier or operator of a facility or any association of occupiers shall be jointly and severally responsible for identifying sites for establishing the facility for treatment, storage and disposal of hazardous wastes". Procedures are clearly laid down how to identify a site and set up a facility. To ensure transparency and accountability of the State Pollution Control Board (s)/Committees, the rule stipulates that such boards or committees shall prepare an inventory of hazardous wastes and compile information related to treatment & disposal. Furthermore, every State Pollution Control Board (s)/Committee shall maintain a register providing particulars of disposal on any land or premises and such register shall be open for inspection to any person interested or affected.

5.8 Housekeeping Guidelines

Although good housekeeping is a matter of attitude, particularly the attitude of management and shared by the workforce, it is more of a necessity than an option in an industry like electroplating. Many of the chemicals used are hazardous and toxic, there is good potential of accidents to occur and the industry poses threats of adverse impacts on the natural environment. These factors lead to a great need for good housekeeping. in order to ensure health and safety of all working personnel as well as the public at large. The housekeeping can be subdivided into three main topics: (a) storage and handling of chemicals (b) housekeeping in production shop floor i.e., pre-cleaning and plating operations and (c) housekeeping of rejects and wastes. In order for housekeeping to be effective and routinely carried out, the following are essential: Management accepting its lead role in providing safe working conditions and procedures. Participation by the workforce in ensuring safety at work Clear allocation of responsibilities for safety and health services Safety training and instruction, on induction and on-going Reporting, investigation and analysis of accidents and working conditions Dissemination of information on hazards and risks Co-operation with labour and safety instructions and reviews

67

In the following paragraphs, brief guidelines are given for better housekeeping;

5.8.1 Storage and Handling of Process Chemicals

Process chemicals consist generally of (a) acids, (h) alkalies (c) cleaning agents (d) metal salts for preparation of bath solutions (e) additives and (f) anodes. The basic guidelines are: I. Acids and alkalies should be stored separately 2. Containment bonds should be provided on floor to containn accidental leakage or spills 3. Volatile organic compounds should be stored in gas tight containers and kept under lockable covered sheds 4. Only authorized personnel shall have access to these materials. These personnel should be made aware of material characteristics through training; Material Safety Data Sheets (MSDS) should be displayed at a prominent location. 5. Training to provide aid during accidents and spills should be given to designated personnel, whose names and contact details should he displaced at prominent locations Wherever possible, solution preparation should he done in lined tanks/containers 6. and transferred to process baths by pumps only.

5.8.2 Housekeeping in Production Shop Floor

This aspect is by far the most important activity in the day-to-day running of an electroplating plant. Good housekeeping will ensure smooth production. encouragement to personnel and developing a positive :ittitude among all. These can he generally summarised as: 1. Avoid clutter and untidy working condition. Introduce floor marking to designate areas for material storage, movement of personnel and handling equipment such as pallet trucks and worker stations, control panels and so on. 2. F;nsure that floor should always be dry, non-slippery and clean ;. Provide curbing and channels to accommodate valve gland leaks and overfow-s, condensates and drainage and lead them to designated holding and/or equalisation tanks for treatment and/or recovery 4. No rinse-water or drag-outs should spill on the floor the most important item totally ignored in small and tiny units across the country 5. A holding pit should be provided to arrest accidental spills or leakages on shop floor, sloped towards it. 6. Floor should be kept clean and free of obstacles for unhindered movement of personnel. 7. While filling or topping up tanks/ baths, care should he taken to prevent overtlowsusc following techniques: Fit hoses with spring loaded nozzles Use metering pumps to accurately translcr required quantities, where feasible Where water is added directly from piping, use float level controls Install backflow- preventers, where water is discharged below solution surface

68

 Supervise regularly and keep records of all such operations, indicating overflows, and losses, spills etc, whatever occurs. 8. Regularly check all alarms, control devices and meters/recorders as per manufacturer's advice 9. Check all metal protection such as tank lining, painting on railings, piping. chains and hoists and electrical/piping racks against signs of corrosion. A timely intervention saves lot of expensive repairs, shutdowns and avoidable accidents. 5.8.3 Housekeeping of Rejects and Wastes Rejects and Wastes generated in Electroplating wastes include the following: Process waters of various kinds Spent process solutions and electrolytes Surplus chemicals Empty containers, packing materials Scraps of various kinds Sludges and filter cakes Process Water, Spent Process Solutions and Surplus Chemicals The detailed considerations for the first three have been discussed in Chapter 4 and Subsections 5.1 through 5.4. However, general guidelines can be summarised as under: 1. All process wastewater should be segregated according to their characteristics 2. Wherever feasible, recovery of metals and other chemicals should he recovered care being taken to ensure undesirable salt content do not rise in recycled solutions 3. Flow equalisation tanks must be provided before treatment of various streams and in each unit operations 4. For very small wastewater flow, it is advisable to haul wastewater to a common treatment facility, 5. Tanks, piping, valves, filters shall be of corrosion resistant materials and leakproof. Arrangement should be provided to arrest leakages by channels and curbings and brought to holding tanks/equalisation tanks lor further treatment/disposal. 6. Surplus chemicals not meant for use or return to vendor, should be diluted and discharged slowly into appropriate stream of' wastewater; they should not he disposed of by discarding them into general waste bins or ri'ashing lhenr down the drain unless speel lical permitted_by regulatory authorities 7. l la ardour chemicals and wastes shall be disposed through licensed contractor

69

Empty Containers, Packing Materials e tc. Since many chemicals used in electroplating are toxic, there is good chance that virtually anything coming in contact with operations can be contaminated. Good housekeeping will ensure that this will not be the case and if contamination occurs, they should be decontaminated or disposed properly. The following may be noted: 1. Tools and equipments should be kept only in designated area and not left elsewhere 2. Separate waste bins for different kinds of waste should be used with clear labelling and workers trained to use them 3. If empty containers are used as waste bins, it should be first thoroughly cleaned and all previous markings pbliterated and /or painted over 4. Containers of toxic and hazardous chemicals should not be used for other storage; they should be disposed as per manufacturer's instructions 5. All materials that are contaminated with chemicals can be considered to be toxic as safety measure and treated accordingly.
Sludges an d Filter Cakes

Disposal of sludges is now one of the major environmental concerns for the electroplating industry. Because of heavy metal content, sludges from wastewater treatment plants are considered hazardous. Many countries including India have regulations concerning handling, storage and disposal of such hazardous materials. Based on the findings of the in-depth study, it was noted that in many areas irrespective of the state, centralised sludge disposal facility has not been built by the State Pollution Control Boards. In such cases, the industry has been asked to organise safe storage for a specified period. The following guidelines may be useful in this regard: I. Sludges should be compressed and dewatered to reduce volume as much as practicable 2. They then should be poured in PE bags, sealed and labelled or tagged with date, quantity and description of content 3. These bags should be kept in a watertight compartment, preferably concrete chanbers with lockable covers 4. Manual handling and/or carrying as headload by manual labour should be strictly prohibited 5. Most units simply store them on roof tops or in "godowns" with leaky tin roofs; such practice allows sufficient wetting and eventual run-off of such sludges entering soil and groundwater. This practice is against the spirit of environmental protection. 6. Formation of leachate must be avoided at all times to prevent remobilisation of toxic and hazardous substances in the sludge. 7. Pre-treatment and chemical stabilisation of the sludge by the generator himself may be done, particularly by large units. 8. Only properly designed, constructed and certified/authorized landfill sites should be used for final disposal.

70

Chapter 6 Review of Existing Standards

6.1 General

Currently there exists an industryspecific standard for discharge of effluent from electroplating industry. This standard was promulgated under the Environment (Protection) Rules, 1986 and meant to be observed by all electroplating units as a niini/niin acceptable quality of effluent. The state pollution control boards or the local regulatory authority are empowered to form stricter or more stringent requirements depending on the requirement of the recipient environment. However, in actual practice, most of the SPCBs follow these standards, while granting consent for discharge of effluent. There is no industry-specific standard for air emission for electroplating industry. During the in-depth study, it was observed that for large and medium units, there could be significant emission of acid mist from bath (pre-treatment and platin),'particularly from hot baths. While, many units voluntarily provide vapour collection and treatment through scrubber, not everyone does so. This is more a matter of in-plant .sir quality than discharge to ambient air. Measurements reveal that concentrations are not high enough to cause alarm; but monitoring over a sufficiently long period can only provide a more complete picture. As far as regulatory standard for acid mist is concerned, Karnataka State Pollution Control Board (KSPCB) stipulates a post-scrubber limit of 50 mg/Nm 3 and a minimum stack height of 9 m above highest floor level or 3 m abo\ c ground level, whichever is higher. Maharashtra SPCB stipulates a limit of 35 mg/Nm' . SO2 and NO., concentrations even inside the plant and near worker positions are well within limits of ambient air quality. The electroplating operations do not include any significant noise generating activity. The main source of noise is air blower, which is used for pre-cleaning and in Baths like Nickel for gentle air agitation. During the in-depth study, it was found that other mechanical operations in an integrated plant give rise to significant noise within the plant. In no case, high ambient noise was observed outside the plant.
6.2 Suggested Revisions in Existing Standards. 6.2.1 Need for Revision & Present Scenario

In view of the foregoing, it is clear that revisions are required in the existing standards to make it more appropriate to the state of the industry in the country and also to act as a driving force for protection to the recipient environment. At the same time it is to be borne in mind that majority of units are in tiny and small scale, who are not immediately able to upgrade the technology to achieve cleaner production. f lowever, it is not possible to protect the environment in a significant manner, unless cleaner production is achieved. Consequently, there is a need to adopt a balanced and practical approach so that goal is achieved over a period of time.

71

Before making suggestions / recommendations, the following facts and constraints are to he kept in view: I. Emission standards with respect to Industrial activities in general and Electroplating in particular are based primarily on health considerations worldwide. Such considerations relate to health effects of pollutants such as metals, toxic organic compounds and acids/alkalies. Effects on workers (i.e., exposure to ambient environment) as well as the recipient environment are taken into consideration while formulating standards. As more knowledge through research become available, more pollutants are identified and brought under regulatory standards and standards are made more stringent. 2. The means of achieving standards are chiefly based on waste minimisation, and restricting use of hazardous and toxic materials and processes. Examples include (a) strict limits on Cadmium use, (b) development and use of non-cyanide processes (c) use of Chromium (Ill) in the place of Cr(Vl) and stricter control of use of toxic organic cleaning solvents are some of the examples. Improvement on capture and treatment of gaseous emissions, are results of' regulatory controls and environmental awareness, not the other way round. Cost effectiveness of treatment processes are results of industrial competitiveness to meet environmental goals for common good for the public at large. In India, the medium and large units, particularly "primary users", carry out electroplating as one of the operations in a chain of industrial production. They are able to comply with existing standards and they have the ability and means to further improve the operation, thereby reducing wastes both qualitatively and quantitatively. Also, more reliable records of material use, quantum of electroplating and waste management are available, which arc useful in achieving load-based standard in future. This fact is also reflected in the US federal regulations, which allow such "integrated facilities to adopt load based standard, i.e., pollutants per sq. m. of plated surface area. In tiny and small scale operations, doing mainly job-work, it is nearly impossible to have any reliable record of 'area of plated surface'. Introduction of load based standard does not appear to be feasible for this sector. The small and tiny units carry out both job-work and also work of dedicated customers (manufacturing and/or plating of Original Equipment - 0E). While some of them do both, others do only one of them. Also they tend to switch between the two, depending on the market forces. Many of these units do a mix of plating of common as well as precious metals. Therefore, for these units, it is difficult to classify them as "common metals" category or "precious metals" category, as used in IJS federal regulation. That kind of distinction does not appear to be feasible in India, at least in the foreseeable future. The most common problem observed during in-depth study is the highly disorganised practice of rinsing and washing by tiny and small-scale units all across

3.

4.

5.

6.

72

the country. There is substantial scope for improvement in pollution control by way of waste minimisation, metal and chemical recovery. 7. Furthermore. these small and tiny units neither have the capacity - technical. financial and managerial to adopt full-scale wastewater treatment technology. It is more appropriate for them to collect their wastewater and treat in a CET P. Where industrial estates are not in existence or difficult to set-up, this would he a practicable and better managed option by using tankers. Plating on plastic and Aluminium has gained popularity and many units do this type of plating. Any revision in Standard should include such metallic pollutants like Aluminium. Despite introduction of more environment-friendly processes like Cyanide Free Zinc Plating, Cyanide based Zinc plating is still being used. Sufficient discouragement seems to be necessary against use of' such processes, eventually banning such processes. Metal recovery and Chemical recovery by ion exchange techniques may cause build up of sulphate and sulphite ions in the wastewater. Since such recovery ought to be encouraged, thereby leading to a distinct and consequent possibility of raised concentration of such ions in the wastewater. The existing standard does not include such parameters. As far as control of air pollution at source is concerned, the medium and large units. particularly "primary users", provide a collection system of vapours and gases. followed by wet scrubbing; Units in Karnataka are able to comply with existing standards and they have the ability and means to further improve the operation. The technology required to comply with better and improved standards are not only available but also affordable to most industrial units. The underlying principle is to organise small-scale and tiny units, introduce non-waste method of working and treating their waste collectively. Where introduction of metal recovery and related waste minimisation are primary considerations, the technologies and processes are adequately available and they are cost effctive too. These aspects have heen amply and elaborately covered in Chapters 7 and 8. The Best Available Techniques (see Section 8.4) do not require excessive cost. In fact, they are quite affordable to both small and medium operations.

8.

9.

10.

11.

12.

6.2.2 Recommendation for Revision in Existing Standard

Based on the findings of the study, following recommendations arc made to revise the existing wastewater discharge standard: Load based or concentration based? In case of medium and large units, particularly "primary users", more reliable records of material use, quantum of electroplating and waste management are available, which are useful in achieving load-based standards in future. This fact is also reflected in the US federal regulations, which

73

ii.

iii.

iv.

allow such "integrated facilities to adopt load based standards, i.e., pollutants/m 2 . of plated surface area. In tiny and small scale operations, doing mainly job-work, it is nearly impossible to have any reliable record of `plated surface area'. Introduction of load based standards does not appear to be feasible for this sector. Therefore, it is not advisable to introduce load based standards. Point of discharge? Since electroplating wastewater contains highly toxic constituents and considering enough scope for undetected discharge with high levels of pollutants, it is proposed to restrict discharge to public sewers only. The standards are to be commensurate with dilution available but to withstand adverse effect on biota responsible for biological treatment" of wastewater in sewage treatment plants. Differentiation between common metals & precious metals? Many of electroplating units carry out a mix of plating of common as well as precious metals. Therefore, for these units, it is difficult to classify them as ``common metals" category or "precious metals" category, as used in US federal regulation. That kind of distinction does not appear to be feasible in India, at least in the foreseeable future. Differentiation between small and large wastewater production? All across the country, a clear and common picture of dismal situation in wastewater management is observed in the study. Despite existence of standards for the last several years, these units have continued to operate with impunity, violating discharge standards, even with consent orders. The small and tiny units do not have the technical, financial and managerial capacities to adopt full-scale waste water treatment technologies. It is more appropriate for such units to collect their wastewater and treat in a CETP. These units, discharging upto 10,000 kilolitre/annum or correspondingly 33 kilolitre daily must exercise an option of either (a) maintaining and operating their own wastewater treatment plants individually or (b) transporting their wastewater to a CETP through tankers. This stipulation may be waived in cases where action is already under way to shift and regroup such units in an organized industrial estate in a new location. This must be the responsibility of State Pollution Control Boards. Large and medium units may either continue to operate their own wastewater treatment facilities (but with more effective monitoring) or voluntarily to opt for transporting their wastewater to CETP through tankers.

v.

Inclusion of additional parameters? Judging by the present trends in electroplating and considering standards being adopted in other countries, it is evident that the existing list of parameters (refer Annexure -II) needs to be expanded. Plating on plastic and Aluminium has gained popularity and many units do this type of plating. Any revision in standards should include such metallic pollutants like Aluminium.

74

Metal recovery and chemical recovery by ion exchange techniques may cause build up of sulphate and sulphite ions in the wastewater. Since such recovery ought to be encouraged, thereby leading to a distinct and consequent possibility of raised concentration of such ions in the wastewater. The existing standard does not include such parameters. The additional parameters along with their limit values are proposed in Table-6.1.

Table-6.1: Suggested List of Additional Parameters Sl. No. Pa r amete rs Limit value (mg/1) T 10 be implemented in Aluminium 5.0Phase 1 1 Tin 2 2.0 Phase I Phase I 3 Silver 1.2 4 15.0 Phase I Fluorides (as F) Sul hides (as S) 2.0 Phase I 5 6 Sulphates (as S)* 400.0 Phase 2 0.5 7 Trichloroethane Phase 2 0.5 Phase 2 Trichloroethylene 8 Phase 2 9 5.0 Phosphates (as P) Note: * This parameter may be introduced in Phase-1, provided the local unit of the State Pollution Control Board feels that a higher value is likely to disrupt the operation of local sewage treatment plant and also cause sulphide corrosion in sewers. ** It is proposed that the revision be implemented in two phases. Implementation of Phase-I should commence on the date of notification of standards and for the implementation of Phase-2, a 2-year tinne period may be allowed for the industry to organise themselves.
------- ----

vi.

Environmental friendly processes? Despite introduction of more environmentfriendly processes like Cyanide Free Zinc Plating, Cyanide based Zinc plating is still being used. Sufficient discouragement seems to be necessary against use of such processes, eventually banning such processes. Air pollution? At present there is no regulatory standards for air borne pollutants specific to the electroplating industry. At least, large and medium electroplating units are required to provide effective collection system of gases and vapours from all hot baths and treat the gases and vapours with a water scrubber in Eirest phase. The scrubbed gases should conform to the standards as proposed in Table-6.2. Phased implementation is suggested, considering present state of the industry and facilities for reliable testing and analyses.

vii.

75

"Fable-6.2: Proposed Standards for Air Emission from Electroplating Baths

i. No.

Parameter
Acid Mist (HC1 &
H2SO4
)

El nission Limit mg/Nm 3 50

To be implemented in Phase-I

2 -- ---

Phase- I Phase-2 5 4 (_V I) Phase-2 5 5 Chromium (Othe rs) Phase-2 - -------- ----------5 Pha se-2 Note: Existing standards for SO2 and NO, shall continue to be applicable. Lead

Nickel

--- -_. --- ---- -

viii. M onitoring? Due to the very nature of the wastewater of electroplating industry, it is not practical to do the monitoring quite frequently, say, every week. This would be rather expensive and less likely to be followed in practice. On the other hand, if monitoring is done at longer intervals, say once a month or once every two months, the real picture about compliance would not be available, leading to defeat of the very purpose of monitoring. Flence a middle path seems to be reasonable, practical and implementable. It is therefore proposed that Some selected parameters (Cadmium, Chromium [Cr (VI) and Cr (Total)], Cyanides, Copper, Silver and Nickel) be monitored more frequently, while other parameters be monitored at longer intervals. In case of tiny and small units, the selected parameters need to be monitored at least once a week, generating 50 to 52 sets of values in a year. The other parameters need to be monitored at least once a month, generating 12 sets of values in a year. If 95% compliance is ensured, the performance may be considered satisfactory. In case of medium and large units, the selected parameters need to be monitored daily and the other parameters need to be monitored once a fortnight. Wherever it is possible, flow based grab sampling is to he done to get representative sample. Source pollution for air emission (stack monitoring) should be carried out monthly under normal operating conditions. The proposed standards are given in Table 6.3

76

Table 6.3 Proposed Wastewater Discharge Standards for Electroplating

Industry

Concentration not to exceed

Co be

SI. Parameters No ' I 2 pH Temperature

(mg/1, except pH & temperature) 6.0 to 9.0

implemented in** Same Existing

Shall not exceed 5 c above the

ambient temperature of the receivin., body

Same Existing

Oil & Grease

10

Same Existing

4 5 6 7 8 9 10

Suspended Solids Cyanides (as CN) Ammonia ca l Nitrogen (as N) Total Residual Chlorine (as Cl) J Cadmium (as Cd) 1 Nickel (as Ni) Zinc (as 1_n)

100 0.2 50 1.0 2.0 3.0 5.0 j 0.1 2.0 3.0 0.1 3.0 10.0
5.0

Same Existin g Same Existing Same Existing Same Existing Same Existing Same Existing Same Existing Same Existing Same Existing Same Existing Same Existing Same Existing Same Existing Phase

--- -- - - --

11
12 i3 14

Hckavalr.nt Chromium (as Cr) total Chromium (as Cr) Copper (as Cu) 1 ,ead (as Ph)

15 , Iron (as Fe)

16 , Total Metal
17 Aluminium
i i:

-------

Phase
2.0 Phase 19 ^lver 1.2

-/x

 20 ( Flourides (asF)

Phase 1 15.0

21

Phase
Sulphides (as S) 2.0

Phase 2
Sulphates (S)* 400

Phase 2 Trichloroethane Trichloroethylene Phosphates (as P} 6.3 Recommendation for Monitoring of Revised Standard During the in-depth study, it was observed that monitoring of wastewater quality from electroplating units were neither uniform nor regular and well defined. In order for the standards to be meaningfully utilised for protection of environment, monitoring should be carried out at regular interval and a clear understanding of compliance requirement is necessary by both the monitoring agency (State Pollution Control Boards) and the industry. Due to the very natrwre of the wastewater of electroplating industry, it is not practical to do the monitoring quite frequently, say, every week. This would be rather expensive and less likely to be followed in practice. On the other hand. if monitoring is done at longer intervals, say once monthly or once every two months, the real picture about compliance would not be available, leading to defeat of the %cry purpose of monitoring. I fence a middle path seems to be reasonable, practical and implernentable. Considering the above, it is suggested that some selected parameters be monitored more frequently. while other parameters be monitored at longer intervals. Parameters like Cadmium. Chromium. [Cr(VI) and Cr ("f)). Cyanides, Copper, Silver and Nickel need to be monitored once every week. That would provide a data ot' S0 to 52 sets every year. If 95% compliance is ensured, the performance should he considered satisihctory. Other parameters should be monitored ai least once a 11 owh. generating 12 sets of values every year. lor these parameters also. 90 compliance must be niet. This should be applicable to all tins and small units. For medium and large units. c%/ili' ntoniloring of selected parameters should be carried out. Other parameters can he monitored evei lorini^hi. It is very important to note that for each unit. the style of functioning and operation of treatment facilities should be known to the monitoring agency. This ir,ctor should be taken into consideration and a monitoring, programme should he written down and agreed between the industry and the agency (SPCI3s) while granting and/or renewing consent orders. Monitoring should follow such agreed programme. If the industry is nonfunctional due to commercial or any other reason. the unit must inform the agency in due time to accommodate any deviation. which also must be recorded.

79

Source Pollution for air emission (stack monitoring) should be carried out monthly under normal operating conditions. 6.4 Safe keeping of Data Keeping data and records safely and in a manner that data can be retrieved at ease is of great importance. Such data form a reliable base over which to build and modify from time to tinne regulatory or other suitable mechanism for - pollution control and environment protection measures. It is recommended that data should be kept in computerised data-base for aperiod of at least 5 years. Data ledgers co-signed by industrial unit and monitoring, agency should he kept, similar to audited accounts record.

(S t)