Surya Narayan Satapathy, Nitesh kumar Bhoi

ABSTRACT
One of the basic requirements of a human being is Water. Globalization, un-
controlled population and other factors are creating shortage of pure water and
the issue is a concern for many countries. Thus, it becomes imperative to think
about water purification using effective and inexpensive techniques and its
reusability. A wide range of wastewater treatments are currently known to
people. With the recent technology development in, a new technique has been
introduced in the industry, named as electrolytic water treatment. The main
objective of this project is focusing on electrolytic waste water treatment process
and its methodology , its applications.

INTRODUCTION

The classical physicochemical treatment processes that are used for the
wastewater treatment is filtration, air stripping, ion-exchange, chemical
precipitation, chemical oxidation, carbon adsorption, ultrafiltration, reverse
osmosis, volatilization and gas stripping and Biological process(both aerobic and
an-aerobic) such as activated sludge, constructed wetlands etc. One of the
advance technology is the electrolytic waste water treatment process.

Electrolytic treatment process involves the passing of electric

current through water, which has proven very effective in the removal of
contaminants from water. Electrolytic waste water treatment have been in
existence for few years ,using a variety of anode and cathode geometries,
including plates, balls, fluidized bed spheres, wire mesh, rods and tubes.

Electrolytic waste water treatment includes processes like- Electro

Coagulation, Electro Oxidation, Electro Chlorination, Filtration. Electrolytic
treatment process can be one of the affordable wastewater treatment processes
 around the world by reducing electricity consumption and miniaturization of the
needed power supplies.

STATEMENT OF PROBLEM -
Numerous effluent treatment methods / techniques are being in practice for
industrial waste water and effluent treatment all over the world but in mining and
mineral processing area, these technologies are yet to make their way. One of the
challenges among the emerging technologies is its compatibility with existing
processes and its affordability and process time and requirement of an
alternative, which can be directly applied to resolve above problems.

WASTE PRODUCED IN MINING AND METALLURGICAL OPERATIONS-

The types of waste materials generated are dependent upon the type of mining
activity. There are three main types of mining activity: (1) the recovery of
cassiterite from the river sediments (so called tin streaming or placer mining);
(2) the underground and opencast mining for metal (hard rock mining); and (3)
opencast mining for aggregates and industrial minerals, most important of which
is the mining for china clay(kaolin).

TYPES OF MINING

HARD ROCK MINING TIN STREAMING OPEN CAST MINING

WASTE PRODUCED DURING HARD ROCK WASTE PRODUCED DURING OPEN CAST
MINING ARE- MINING ARE-

(1) SPOIL HEAPS(LARGE BLOCK OF (1)CHINA CLAY CONTAINS CLAY,FINE

ROCKS,METAL CONTAMINATION) SAND,MICA.
(2) ACID MINE DRAINAGE
(AMD)(PRODUCED DUE TO (2)ALSO CONTAIN HEAVY MINERALS
OXIDIZATION OF SULPHIDE TO PRESENT WITH IN GRANITE.
SULPHATE) (3)MINERALS INCLUDE ZIRCON
(3) HIGHLY ASSOCIATED WITH AMD Fe & ,MONAZITE,XENOTIME WHICH INCREASE
Mn, ALSO INCLUDE Pb,Zn,Cu,As. THE ABUNDANCE OF Zr,Ce,La AND Y.
(4) MINUTE PARTICELS OF ORE
MINERALS.
REACTION INVOLVED IN WASTE PRODUCTION-

(1)FORMATION OF ACID MINE DRAINAGE-

For example-Pyrite(FeS2) and Chalcopyrite (CuFeS2 - the main ore mineral for
copper )are sulphides, which can oxidise. In a wet oxygenated environment pyrite
will oxidise to produce sulphuric acid and iron hydroxide as follows:
2FeS2 + 7O2 + 2H2O 2FeSO4 + 2H2SO4

Bacteria (e.g. Thiobacillus ferroxidans) can speed up this chemical process by as

much as 100 times:

4FeSO4 + O2 + 2H2SO4 2Fe(SO4)3 + 2H2O

At pH values of between 4 and 7 the ferric ions produced in this reaction will tend
to precipitate out as ochres. Additionally, the sulphuric acid and ferric sulphate
produced from pyrite can then oxidise other metal sulphides such as chalcopyrite:

CuFeS2 + Fe(SO4)3 CuSO4 + 2FeSO4 + 2S

(2) OPEN CAST MINING-

CHINA CLAY CLAY+FINE SAND+MICA+HEAVY MINERALS

CLASSICAL METHODS USED FOR WASTE WATER TREATMENT-

CLASSICAL METHODS METHODOLOGY DISADVANTAGES

(1) STANDARD REMOVES SOLIDS FROM TIME CONSUMING,HIGH

FILTRATION LIQUID USING FILTRATE LABOUR COST,PRESENCE
(INVOLVES BIOFILTER, OF MICRO ORGANISMS,
MAGNETIC, RESIN ETC.) HARD METALS
(2) AIR STRIPPING INVOLVES INTIMATE CONTACT
WITH GAS(AIR) TO REMOVE
VOLATILE SUBTANCES PRESENT
IN LIQUID PHASE.
(3) CHEMICAL PRECIPITION USES CHEMICAL PRECIPINANT
TO REMOVE SOLID FROM LIQUID.
(4)CHEMICAL OXIDATION OXIDIES ORGANIC POLLUTANT TO
CO2 ,H2O BY USING OXIDATION
REACTOR, UV-RAY.
(5)CARBON ABSORPTION USES ACTIVATED CARBON TO
TREAT WASTE WATER.
* BIOLOGICAL PROCESES*
(6) ACTIVATED SLUDGE USES AIR AND BIOLOGICAL FLOC
COMPOSED OF BACTERIA AND
PROTOZOA TO REMOVE WASTE
ORGANIC PRODUCT.
IT CAN ONLY TAKE OUT
CHEMICALS THAT CAN
EVAPORATE,BULK ITEMS
POLUTANT CAN NOT
TAKEN OUT.
TIME CONSUMING, CAN
NOT STOP GROWTH OF
MICRO ORGANISMS.
TIME CONSUMING,HIGH
COST,PRODUCTION OF
BIOLOGICAL WASTE.
HIGH COST ,CAN NOT
REMOVE HARD MATERIALS
MORE GROUND AREA.
TIME CONSUMING,
LARGE GROUND AREA
REQUIRED,CAN NOT
REMOVE HARDMETALS.
(7)CONSTRUCTED WETLANDS
AN ARTIFICIAL WETLAND IS REQUIRED MORE GROUND
CREATED TO TREAT AREA, PERFORMANCE VARY
WASTE WATER. ACCORDING TO CLIMATE,
NOT USEFUL FOR HEAVLY
POLLUTED WATER.

ELECTROLYTIC WASTE WATER TREATMENT-

Electrolytic water treatment is an electrochemical water and wastewater
treatment technology that, in its simplest form uses an electrochemical cell where
a dc voltage is applied to electrodes, usually made of iron or aluminum, and water
or wastewater is the electrolyte. It involves the generation of coagulant in situ by
dissolution of metal from the anode with simultaneous formation of hydroxyl ions
and hydrogen gas at the cathode. This process produces the corresponding
aluminum or iron hydroxides and/or poly-hydroxides. The generated gas also
helps to float the flocculated particles at the water surface.

Wastewater by Electrolytic water treatment was practiced for recent decades

with limited success and popularity. However, in the later years its usage has
increased as evidenced with a larger number of companies selling these units.
This is because the technology has been optimized to minimize electrical power
consumption and maximize effluent throughput rates. It has also proven to be
competitive and effective in the treatment of water and wastewater to remove
heavy metals such as Pb, Cd, Cr, and As, metals such as Mn, Cu, Zn, Ni, Al, Fe, Co,
Sn, Mg, Se, Mo, Ca, and Pt. It has also seen applications in removing anions such
as CN- , PO4 -3, SO4 -2, NO3 - , F- and Cl- , non -metals such as P, organic
compounds such as total petroleum hydrocarbons (TPH), toluene, benzene and
xylenes (TBX), methyl tert-butyl ether (MTBE), COD, BOD, suspended solids, clay
minerals, organic dyes, and oil and greases from a variety of industrial effluents .

It generally involves four important processes such as Coagulation, Oxidation

, Chlorination, Filtration etc.

THEORITICAL BACKGROUND-
(A) ELECTRO COAGULATION (EC)-

EC has several successive stages-

(1) Generation of metal ions-

Anode:

Fe Fe+2 + 2e-

Fe Fe+3 + 3e-

(2) Hydrolysis of metal ions and generation of metal hydroxides and

polyhydroxides -

This has been studied and explained repeatedly for coagulation processes in
water treatment.

Fe + 6H2O Fe(H2O)4(OH)2 (aq) + 2H+1 + 2e-1

Fe + 6H2O Fe(H2O)3(OH) 3(aq)+ 3H+1 + 3e-1

(3)Electrolysis of water-

Water is also electrolyzed in a parallel reaction, producing small bubbles of

oxygen at the anode and hydrogen at the cathode, and as a result, flotation of the
coagulated particles occurs

Anode: 2H2O(l) O2(g) + 4H+ + 4 e-

Cathode: 2H+ + 2 e- H2(g)

(4) Destabilization and aggregation-

Destabilization of the contaminants, particulate suspension, breaking of

emulsions, and aggregation of the destabilized phases to form flocs through
compression of the diffuse double layer and charge neutralization of the ionic
species present. Therefore, suspended solids and colloids in small quantities are
easily removed by EC.

(5) Physicochemical reactions-

The following physicochemical reactions may also take place in the EC cell:
chemical reaction and precipitation of metal hydroxides with pollutants, cathodic
reduction of impurities or metal ions present, electrophoretic migration of ions,
oxidation of pollutants to less toxic species, and other electrochemical and
chemical processes.

(B) ELECTRO OXIDATION-

Electro-oxidation is affected by generation of hydroxyl free radicals by

electrolysis of water.

H2O OH

Hydroxyl free radicals are powerful oxidizing agent and oxidizing agent and
oxidize tough to treat organics present in the effluent. Direct oxidation of
organics at the high surface catalytic electrodes leads to complete mineralization
of organics to carbon dioxide and water.

C6H6 CO2 +H2O

This method consists of carrying out the oxidation reaction at the anode where
pollutants are transferred into non-toxic substances, by decomposition into
simpler compounds or transferring into oxidation form. It is used mostly for
organic substances. Wastewater treatment by this procedure can be: direct or
indirect electrochemical oxidation.

The first application of the electro-oxidation (EO) was cyanide destruction. The EO
is mainly used for degradation: aromatic compounds, pesticides, paints, industrial
pollutants, pharmaceuticals waste and other organic. The advantage of this
method is that finally products are mainly CO2 and H2O. This is the case for some
organic as aliphatic, depending on stoichiometry. Even chlorine is not the problem
since it is converted in the form of chloride ion.

(1) Indirect electrochemical oxidation-

Strong oxidants are produced on anode and then chemical oxidation take place.
The most effective type of the indirect electro-oxidation is creation of hydroxyl
radicals via Fenton reagent. In Fenton reaction, highly reactive hydroxyl radicals
(-OH) are generated

H2O OH abs + H++e-

Fe+2+ H2O Fe+3 + OH + OH-

The indirect electro-oxidation rate is dependent on the diffusion rate of strong

oxidants electroformed into solution which are able to completely convert all
organic into water and carbon dioxide. The electrochemical method of
depollution presents many important advantages because it does not need
auxiliary chemicals; it is applicable on a large range of pollutants and does not
need high pressures and temperatures.

Further improvement could be achieved by using of UVA radiation. UV lights

(=365 nm) was successfully used to accelerate the mineralization process. This is
the photo-electro-Phenton process.

(2) Direct electrochemical oxidation-

The Direct electro-oxidation takes place directly at the anode through the
generation of physically adsorbed "active oxygen" (adsorbed hydroxyl radical,
-OH). Direct EO process is also called electrochemical mineralization (EM) of
organic contaminants. It is a relatively new technology for wastewater treatment
with moderate concentrations of organic pollutants, the chemical oxygen demand
(COD) up to 5 g/l.
The main advantage of technology is that it does not consume chemicals, but just
electrical energy. EO does not produce secondary pollution and requiring
relatively little additional equipment and maintenance. These advantages make it
attractive compared to most other waste water processes.

Example of complete (electro) mineralization is a direct electrochemical oxidation

of the herbicide 2,4,5-Trichlorophenoxyacetic acid, also known as 2,4,5-T and
Silvex (trade name). The whole process can be represented by the following
reaction:

C8H5Cl3O3 +13O2 8CO2+31H++3Cl-+28e-

Or by COD during electrochemical decomposition, the theoretical reaction of

mineralization 2,4,5-T can be written as:

C8H5Cl3O3+7O2 8CO2+3HCl+H2O

Oxidation potential of the anode is directly dependent on the over potential for
oxygen separation and adsorption enthalpy of hydroxyl radicals on the anode
surface. It follows that for an anode material: the higher the over potential for
oxygen, the greater the oxidizing power of the anode material.

(C) ELECTRO CHLORINATION-

Electro-chlorination is the process of producing hypochlorite by running an

electric current through salt water. This is used to disinfect water and make it safe
for human use such as drinking water.

The main idea involved in this process, is the electrolysis of water to produce a
chlorinated solution. This happens when water is inserted into electrolyzer cells.
The first step is removing the solid excess from the water. As the water flows
through the anode/cathode channel, a low voltage DC currents applied. When
this happens, the electrolysis is triggered and sodium hypochlorite is instantly
produced as well as hydrogen gas (H2). The hydrogen rich sodium hypochlorite
then travels to a tank that removes the hydrogen gas.

It can be simply represented by the following equation:

 NaCl + H2O +ENERGY NaOCl +H2

In words this reads, energy is added to sodium chloride (table salt) in water,
resulting in sodium hypochlorite and hydrogen gas.
The product of this process, sodium hypochlorite, contains 0.7% to 1% chlorine.
Anything below the concentration of 1% chlorine is considered a non-hazardous
chemical although still a very effective disinfectant. In addition, the sodium
hypochlorite produced is in the pH range of 6-7.5. This means that the chemical is
relatively neutral in regards to acidity or baseness. Also, at that pH range, the
sodium hypochlorite is extremely stable and the electro-chlorination extremely
effective.
(D) FILTRATION-
Filtration is a process where a contaminated fluid is passed through a special
pore-sized membrane to separate microorganisms and suspended particles from
process liquid.

The principle of micro filtration is physical separation. The extent to which

dissolved solids, turbidity and micro-organisms are removed is determined by the
size of the pores in the membranes. Substances that are larger than the pores in
the membranes are fully removed. Substances that are smaller than the pores of
the membranes are partially removed, depending on the construction of a refuse
layer on the membrane.
Micro filtration is pressure-dependent process, which remove dissolved solids and
other substances from water to a lesser extent than nano-filtration and Reverse
Osmosis.
Membranes with a pore size of 0.1 10 m perform micro filtration which is made
up of Polyethylene porous hollow fiber microfiltration membrane
(hydrophilic). Microfiltration membranes remove all micro-organisms. Only part
of the viral contamination is caught up in the process, even though viruses are
smaller than the pores of a micro filtration membrane. This is because viruses can
attach themselves to bacterial biofilm.
Micro filtration can be implemented in many different water treatment processes
when particles with a diameter greater than 0.1 mm need to be removed from a
liquid.
For this process the effective membrane area is about- 8m2 to 20m2.
And the filter flow volume varies from - 0.4-1.0 m3/hour.
Maximum operational pressure is about 2kg/cm2 and temperature about 450C.
IMPLIMENTATION OF ELECTROLYTIC WATER TREATMENT PROCESS IN
MINING AND METALLURGICAL OPERATION-

Different operation like Blasting, Quarrying, Crushing, Forth flotation(mining)and

smelting, Calcination, Hoopes process, Leaching, Liquation(metallurgical) uses
most amount of water, which leads to the formation of-
(a) solid solution of heavy metals
(b)increase in pH
(c) insoluble particles(0.1-3 m)
(d) oils, chemicals, ash
(e)increase in micro- organisms( if water is stagnant)
(f)Heavy rocks within water body.
METHODOLOGY-
(1) At first all the waste water produced in different operations are collected in a
Tank (specifications)