TECHNOLOGY AND INDIAN MARKET SCENARIO MINING CHEMICAL

BHARAT CHEMTECH, CHENNAI

EXECUTIVE SUMMARY ........................................................................................6 SECTION I INDIAN MINING INDUSTRY STATUS ..................................................10

1.1. 1.2. 1.3. 1.4. 1.5. 1.6. 1.7. 1.8. 1.9. Dominant minerals in India and its rank in world mining industry............................................. 10 Indian production of selected minerals ......................................................................................11 Indian production of minerals of all type....................................................................................11 Pattern of production of Indian mineral.....................................................................................12 Indian production, import and export ........................................................................................13 Number of Reporting mines in India...........................................................................................13 Number of minerals produced in India.......................................................................................14 Statewise production pattern of minerals..................................................................................14 Major mining units in India ......................................................................................................... 14

SECTION II OVERVIEW ON MINING PROCESS ....................................................15

2.1. 2.2. 2.3. 2.4. 2.5. 2.6. 2.7. Metals and its ore .......................................................................................................................15 Type of ores and the metal extracted from the ores................................................................. 15 Flow diagram for ores and the group metals.............................................................................. 16 Need for mining chemicals ......................................................................................................... 17 Main functions of mineral processing ........................................................................................17 Sequences of mining process - Outline.......................................................................................17 Detailed description of concentration process in mining...........................................................18

2.7.1. Hydraulic washing process (Gravity separation)....................................................................... 18 2.7.2.. Magnetic separation process................................................................................................... 18 2.7.3. Chemical separation .................................................................................................................18 2.7.4. Froth floatation process............................................................................................................ 19

SECTION III INDUSTRY STATUS ON MAJOR MINES IN INDIA ..............................22 I COPPER...........................................................................................................22

1.1. 1.2. Processing of copper ore ............................................................................................................ 22 Status of Indian copper mining industry.....................................................................................23 Import dependent on copper ore .......................................................................................23 Indian major players ........................................................................................................... 23 Indian production................................................................................................................23 Indian demand copper metal..............................................................................................24 Profile of major players....................................................................................................... 25

1.2.1. 1.2.2. 1.2.3. 1.2.4. 1.2.5.

II ALUMINIUM ..................................................................................................28
2.1. 2.2. Processing of aluminium ore ...................................................................................................... 28 Status of Indian aluminium mining industry...............................................................................31

III RON ..............................................................................................................38

2.1. 2.2. Processing of iron ore .................................................................................................................38 Status of Indian iron mining industry..........................................................................................40

IV LEAD AND ZINC.............................................................................................47 V COAL..............................................................................................................50

Need for washing non-coking coal.......................................................................................................... 50 Advantages of washing non-coking coal................................................................................................. 50 Major players in coal mining...................................................................................................................51 Current status of coal washeries ............................................................................................................ 52

VI MICA ............................................................................................................53

SECTION IV INDIAN SUPPLY DEMAND SCENARIO ON MINING CHEMICAL.........54 I. FLOCCULANT / COAGULANT...........................................................................55

1.1. 1.2. 1.3. 1.4. 1.5. 1.6. 1.7. 1.8. 1.9. 1.10. 1.11. 1.12. 1.13. General details ............................................................................................................................55 Role of flocculant in Mineral processing.....................................................................................55 Selective flocculation .................................................................................................................56 Difference between coagulant and flocculant............................................................................ 56 Classification of flocculant .......................................................................................................... 58 Advantages of polymeric floccs over inorganic flocs .................................................................. 60 Usage of flocculants in metallic minerals ...................................................................................61 Coagulant Aids ............................................................................................................................64 Polyacrylamide............................................................................................................................68 Polyaluminium chloride .......................................................................................................... 76 Other flocculants including specialty flocculant ..................................................................... 77 All India market for flocculants in water treatment sector ....................................................78 All India market for flocculants in mining sector .................................................................... 78

II COLLECTORS ..................................................................................................79
2.1. 2.2. 2.3. 2.4. 2.5. 2.6. General details ............................................................................................................................79 Major Collectors used in Indian mining industry ........................................................................ 84 Indian manufacturers..................................................................................................................85 Indian import / export level ........................................................................................................ 85 Indian demand for xanthates...................................................................................................... 86 All Indian demand for collectors................................................................................................. 86

III FROTHERS.....................................................................................................87
3.1. 3.2. 3.3. 3.4. 3.5. General details ............................................................................................................................87 MIBK (Methyl isobutyl ketone) ................................................................................................... 95 Glycol ethers ...............................................................................................................................97 Others including MIBC (Methyl isobutyl carbinol), 2-EH, diacetone alcohol..............................98 All Indian demand for frothers in mining industry ..................................................................... 99

IV OTHER MINING CHEMICALS........................................................................100

4.1. 4.2. 4.3. 4.4. 4.5. Depressants...............................................................................................................................100 Activators .................................................................................................................................. 101 Dispersant / Grinding Aid.......................................................................................................... 102 Others including Modifying agent ............................................................................................103 All India demand for other miscellaneous mining chemicals ...................................................104

V CONSOLIDATED ALL INDIA DEMAND FOR MINING CHEMICALS ....................105

Productwise demand ............................................................................................................................105 Sectorwise demand pattern..................................................................................................................105

EXECUTIVE SUMMARY
Dominant minerals in India and its rank in world mining industry

Dominant minerals
Bauxite, Copper, Lead Limestone Chromite, Iron, manganese zinc

Indias rank
1st 3rd 4th 5th 6th Mica (alumino silicate); Barite, chromite, coal & lignite; Iron ore; Bauxite Manganese.

Statewise production pattern of minerals

Need for mining chemicals

Minimizing water consumption Maximizing recovery Reducing land areas consumed by tailings disposal Minimizing the costs and time required to rehabilitate such land. Reduce the complexity of processing low quality ores Aim to ease the accessibility from remote source

Type of chemical used in mineral processing

Flocculant / coagulant Collectors Frothers Depressants Activators Scale inhibitor Dispersant / Grinding aid Modifying agent (pH modifier, cationic modifier, ionic modifier, organic modifier) Agglomeration aid Rheology modifier Dust suppressor

Flocculants / coagulants
Conversion of stable state dispersion to the unstable state is termed destabilisation and the processes of destabilisation is termed as coagulation / flocculation. Coagulation: If destabilisation is induced through charge neutralisation the process is called coagulation. Flocculation: The process of forming larger agglomerates of particles through high molecular weight polymeric materials is called flocculation. Mostly used coagulants / flocculants compounds include Polyacrylamide polyaluminium chloride. Rs. 108 crores

All India market for flocculants in mining sector

Collectors
Basis of froth flotation is the difference in wettabilities of minerals. Most minerals in nature are hydrophilic. They do not readily float in froth flotation. Even some of the minerals which are hydrophobic in nature require supporting reagents to increase the hydrophobicity and some chemical reagents are added to float to the surface. The recovery is often improved when a collector is used. Chemicals that promote hydrophobicity of a mineral are called that mineral's promoter or collector. Collectors get adsorbed on the mineral surfaces rendering the particles hydrophobic and floatable. Major collectors used in Indian mining industry is sodium isopropyl xanthate. All India market for collectors in water treatment sector Rs. 25 crores

Frothers
Frothers are liquids that produce the froth on which the flotation process depends. The froth resembles soap suds and provides the physical separation between the mineral(s) floated and the pulp containing the waste. The froth must be strong enough to support the weight of the mineral floated and yet not be tenacious. It should have the tendency to break down when removed from the flotation cell. The frother should not enhance the flotation of unwanted material. When the mineral surface has been rendered hydrophobic by the use of a collector, stability of bubble attachment especially at the pulp surface depends to a considerable extent on the efficiency of the frother Mostly used frothers in Indian mining industry are pine oil, MIBK and glycol based formulatory compounds. All India market for frothers in water treatment sector Rs. 60 crores

All India demand for other miscellaneous mining chemicals

Indian demand for other miscellaneous chemicals including scale inhibitor, dust depressant, pH modifier, activators etc Rs. 157 crores

All India Productwise demand for mining chemicals

Mining chemicals Flocculant Collectors Frothers Others including scale inhibitor, dust depressant, pH modifier, activators etc Total Market value in Rs. Crores 108 25 60 157 350

Sectorwise demand pattern for mining chemicals

SECTION I INDIAN MINING INDUSTRY STATUS

1.1. Dominant minerals in India and its rank in world mining industry

Dominant minerals
Bauxite, Copper, Lead Limestone Chromite, Iron, manganese zinc

Indias rank
1st 3rd 4th 5th 6th Mica (alumino silicate); Barite, chromite, coal & lignite; Iron ore; Bauxite Manganese.

1.2.

Indian production of selected minerals

950 million tonnes 14 million tonnes 245 million tonnes (Fe content: 157 mil ton) 92 million tonnes (Pb content) 31 million tonnes (Cu content) 5000 tonnes

Coal ore Bauxite ore Iron ore Lead ore Copper ore Mica

1.3.

Indian production of minerals of all type

1.4.

Pattern of production of Indian mineral

Metallic minerals 18%

Non metallic minerals 12%

Fuel minerals 70%

1.5.

Indian production, import and export

1.6.

Number of Reporting mines in India

1.7.

Number of minerals produced in India

Fuel Minerals Metallic Minerals Non-metallic Minerals Minor minerals Total Type Number of minerals 4 11 52 22 89

1.8.

Statewise production pattern of minerals

1.9.

Major mining units in India

Bharat Aluminium Company Bharat Gold Mines Limited Bunder Project Coal India Ltd Dempo Gujarat Mineral Development Corporation Limited Hindalco Industries Hindustan Copper Limited Hindustan Zinc Limited Hutti Gold Mines Limited Indian Rare Earths Limited Kudremukh Iron Ore Company Ltd. MOIL Limited MSPL Limited National Aluminium Company National Mineral Development Corporation Neyveli Lignite Corporation Obulapuram Mining Company Rajasthan State Mines and Minerals Limited Sesa Goa Singareni Collieries Company Sterlite Industries Uranium Corporation of India Vedanta Resources

2.1.

Metals and its ore

Metal Aluminum Chromium Cobalt Copper Iron Lead Magnesium Manganese Mercury Nickel Tin Titanium Tungsten Uranium Zinc

SECTION II OVERVIEW ON MINING PROCESS

Ore Mineral Bauxite Chromite Skutterudite Chalcopyrite Chalcocite Bornite Hematite Magnetite Galena Cerusite Dolomite Magnesite Pyrolusite Cinnabar Pentlandite Cassiterite Ilmenite Rutile Scheelite Wolframite Uraninite Sphalerite Chemical Formula Al2O33H20 FeCr2O4 (Co,Ni,Fe)As3 CuFeS2 Cu2S Cu5FeS4 Fe2O3 Fe3O4 PbS PbCO3 (Ca,Mg)CO3 MgCO3 MnO2 HgS (Fe,Ni)9S8 SnO2 FeTiO3 TiO2 CaWO4 (Fe,Mn)WO4 UO2 ZnS

2.2.

Type of ores and the metal extracted from the ores

Type of ore Metals Aluminium Copper Iron Iron

Compound (in the ore) Bauxite - Al2O3, 2H2O Cuprite - Cu O

2 2 3

Oxide Ores

Haematite - Fe O Magnetite - Fe O Iron Pyrite - FeS Copper Glance - Cu S, Copper Pyrites - CuFeS Zinc Blende - ZnS Limestone - CaCO Rock Salt - NaCl Fluorspar - CaF
3 2 2 3

Sulphide Ores

Copper Zinc Calcium Zinc Sodium Calcium Silver Aluminium

Carbonate Ores

Calamine - ZnCO3
2

Halide Ores

Horn Silver - AgCl Cryolite - Na3AlF6

2.3.

Flow diagram for ores and the group metals

2.4.

Need for mining chemicals

Minimizing water consumption Maximizing recovery Reducing land areas consumed by tailings disposal Minimizing the costs and time required to rehabilitate such land. Reduce the complexity of processing low quality ores Aim to ease the accessibility from remote source

2.5.
* *

Main functions of mineral processing

Preparation of the valuable minerals from waste minerals . Separation of valuable minerals into two or more products

2.6.

Sequences of mining process - Outline

Main process 1.Hydraulic washing. 2. Gravity separation. 3. Magnetic separation. 4. Chemical separation. 5. Froth floatation. 1. Calcination for carbonate ore. 2. Roasting for sulphide ore. 1. Roasting - mercury (Hg) is produced by roasting Cinnabar (HgS) in air. 2. Reduction - using highly reactive elements. Example: aluminium reduces manganese dioxide to manganese. 3. Electrolytic reduction - highly reactive elements, such as sodium and mercury, are obtained by electrolytic reduction when the metal is deposited at cathode. 1. Electrolytic refining - of copper, gold, tin, lead, chromium, nickel, etc. 2. Liquation process - for tin, lead and bismuth. 3. Distillation process - for zinc, mercury. 4. Oxidation process - for iron. Sub process

Concentration of the ore (removal of unwanted purify the ore). Conversion into metal oxide

Reduction of metal oxide to metal

Refining of impure metal into pure metal

2.7.

Detailed description of concentration process in mining

2.7.1. Hydraulic washing process (Gravity separation)

This process separates the heavier ore particles from the lighter gangue particles. This is done by washing them in a stream (jet) of water over a vibrating, sloped table with grooves. Denser ore particles settle in grooves. Lighter gangue particles are washed away.

2.7.2.. Magnetic separation process

This process is used in the extraction of metals which exhibit magnetic properties. For example, in the extraction of iron, crushed magnetite ore (iron) particles are separated using their magnetic property. The pulverized ore is moved on a conveyor belt. Electro-magnetic wheel of the conveyor attracts only the magnetic particles into a separate heap. Only the magnetic particles are attracted by the mag. Wheel.

2.7.3. Chemical separation

This process utilises the difference in some chemical properties of the metal and gangue particles for their separation. For example, in the Bayer's process of aluminium extraction, the bauxite ore is treated with hot sodium hydroxide solution. Water soluble sodium aluminate formed is filtered to separate the undissolved gangue particles. Sodium aluminate (NaAlO2) is further processed to get aluminium oxide (Al2O3).

2.7.4. Froth floatation process

Flotation is a process in which valuable minerals are separated from worthless material or other valuable minerals by inducing them to gather in and on the surface of a froth layer. This process is based on the ability of certain chemicals to modify the surface properties of the mineral(s). Some chemicals are used to generate the froth and still others are used to adjust the pH. Certain chemicals are even capable of depressing the flotation of minerals that are either to be recovered at a later time or are not to be recovered. Sulfide and non-sulfide minerals as well as native metals are recovered by froth flotation. Normal flotation- The economic minerals are floated with respect to the gangue minerals present. Ex. For normal flotation Coal

Reverse flotation- Gangue mineral matter is floated with respect to the economic mineral. Reverse flotation is generally applied when the impurity content of the feed material is high. Ex. For reverse flotation Iron ore

2.7.4.1.

General details

Basis of froth flotation is the difference in wettabilities of minerals. Most minerals in nature are hydrophilic. They do not readily float in froth flotation. Without reagents there would be no flotation and without flotation, the mining industry would not exist. Even some of the minerals which are hydrophobic in nature require supporting reagents to increase the hydrophobicity and some chemical reagents are added to float to the surface. The finely powdered ore is mixed with water and suitable collecting and frothing chemical in a large tank. A current of compressed air agitates the mixture. The ore particles are wetted by oil and forms a froth at the top, which is removed. The gangue particles wetted by water settle down. Ore preferentially wetted by oil is removed as froth. Gangue wetted by water is removed after it settles down

2.7.4.2.

Mechanism of froth flotation

If a mixture of hydrophobic and hydrophilic particles are suspended in water, and air is bubbled through the suspension, then the hydrophobic particles will tend to attach to the air bubbles and float to the surface. The froth layer that forms on the surface will then be heavily loaded with the hydrophobic mineral, and can be removed as a separated product. The hydrophilic particles will have much less tendency to attach to air bubbles, and so it will remain in suspension and be flushed away.

SECTION III INDUSTRY STATUS ON MAJOR MINES IN INDIA

1.1. Processing of copper ore

COPPER

Types of copper ore Oxide ores (simple leaching process) Sulfide ores (Beneficiation in flotation cells) Processing method First the copper ore from open pit mine is blasted, loaded and transported to the primary crushers. The ore is crushed and ground to liberate the copper-bearing mineral from the waste material or gangue. The reduced product is then subjected to secondary crushing which typically involves a series of rod or ball mills. The final material particle size will normally be less than 100 microns. During the final milling stage collectors are added to the slurry which render the sulphide particles hydrophobic. These copper minerals are then concentrated by flotation when air bubbles are introduced into the slurry. Frothers are normally added to the slurry to stabilise the copper particle. Flocculant is added to the tailings from the flotation cells to promote rapid sedimentation, which returns to the process water circuit. The thickened tailings are normally further dewatered by using flocculant.

The copper concentrate is removed and is then thickened and dewatered where flocculants are used to improve the sedimentation and filtration rates.

1.2.

Status of Indian copper mining industry

1.2.1. Import dependent on copper ore

India is not a major producer of copper ore but it produces the refined form of copper. It contributes to about 3.5 to 4% of the worlds total production of copper that sums up to a figure of 6 lakh tons. India has always been an importer of copper ore to satisfy the domestic consumption demand. The countries from the ore is imported into India are *Chile *Indonesia *Australia *Canada

India is indulged in importing copper ores from the ore exporting countries of the world and extract copper out of them as there is a shortage of copper mines in the country. The production of copper in India is dependent on these imports only.

1.2.2. Indian major players

The following companies in India largely handle production of copper from its ore. * * * * Birla Copper (Hindalco) Sterlite Industries Hindustan Copper M/s Jagadia Copper Ltd. (formerly SWIL Ltd.) Has started operating its 50,000 tonnes plant based on secondary route.

1.2.3. Indian production

Production during the period 1997 Present production capacity Present production level 47,500 tonnes Around 10 lakh tonnes Around 5 lakh tonnes

Plantwise installed capacity of copper

1.2.4. Indian demand copper metal

Domestic demand for copper Major consumers of copper A major percentage i.e. 10% of the total consumption in India is contributed by the following two major tele-communication providers BSNL MTNL Around 5 lakh tonnes.

The rest of the demand is contributed by the construction and automobile sector.

1.2.5. Profile of major players

i. Hindustan Copper Ltd

Activity details Hindustan Copper Limited (HCL), a Govt. of India Enterprise under the administrative control of the Ministry of Mines, is the only vertically integrated multi unit copper producer in India engaged in wide spectrum of the following activities Mining Beneficiation Smelting Refining Manufacturing of copper cathodes & continuous cast copper wire rods

Ore Reserves including resources: Additional mining reserves (old mines): Rakha mine 47.19 million tonnes @ 0.97% copper Kendadih Mine 12.85 million tonnes @1.73% copper Chapri Block 63.50 million tonnes @1.14% Cu

Khetri Copper Complex (KCC), Khetri Nagar, Rajasthan, Khetri Nagar- 333504 Jhunjhunu (Rajasthan) Tel No.: 91(0) 1593 220065/220305 01593-22305 (Chemical Purchase department) Fax No.: 91(0) 1593 220038/220002 E-Mail kcc@hindustancopper.com Activity Ore processing 31000 tonnes per annum

Production capacity of metal Malanjkhand Copper Project (MCP)

Malanjkhand Copper Project P.O.- Malanjkhand Dist. Balaghat Madhya Pradesh Ph.- (07637) 257-072/042/040/032/016 / Fax (07637) 257038 / 032 E-Mail hcl_mcp@hindustancopper.com, hclmcp@sancharnet.in, hclmcp1@sancharnet.in Activity Open pit mine with a capacity of 2 million TPA of ore with a matching concentrator plant, Tailing Disposal System and other auxiliary facilities.

Taloja Copper Project (TCP), Taloja, Maharashtra. PLOT NO:E-33 TO E-36 M.I.D.C. AREA P.O. TALOJA-410 208, RAIGAD, MAHARASHTRA Phone (022) 2740-2679 Fax (022) 2741-2468 Activity Continuous Cast Copper Rods (CCR) with a capacity of producing 60,000 TPA , Using copper metal produced by other units of its parent company and converts it into copper rods. Indian Copper Complex P.O. Ghatsila Dist. Singhbhum(E) Jharkhand Phone (06585) 225-768/492/873/869 400 Fax (06585) 225-806 Activity Established in 1930 Operating Mine: Surda~26 MT @ 1.20% Cu Process plants to produce 19,000 TPA of refined copper 20500 tonnes per annum

Production capacity of metal

ii

Sterlite Industries (I) Ltd

Contact details SIPCOT Industrial Complex, Madurai Bypass Road, TV Puram P.O Tuticorin- 628 002, Tamil Nadu Phone No.: +91 461 4242591(10 lines) Fax: +91 461 2340203 Production details on metal Period 2010 Copper Zinc and lead Aluminium 3.34 lakh tonnes 7.68 lakh tonnes 2.68 lakh tonnes

2.1.

Processing of aluminium ore

II

ALUMINIUM

After crushing and grinding the ore to less than 1mm, it is then subjected to high temperature and pressure after the addition of concentrated sodium hydroxide. The alumina dissolves in the highly caustic liquor and of the many impurities only silica is soluble. After digestion the sand particles are removed with the slurry being settled in primary thickeners where the flocculant is added. The aluminum industry relies on the Bayer process to produce alumina from bauxite. It remains the most economic means of extracting alumina, which in turn is vital for the production of aluminum metal - two to three tonnes of alumina are required to produce one tonne of aluminum, depending upon the content of alumina in the bauxite.

2.1.1. Production of alumina from bauxite

Bauxite is crushed, ground and digested in caustic soda (sodium hydroxide) at high pressure and temperature. The resulting liquor contains a solution of sodium aluminate and undissolved bauxite residues containing iron, silicon, and titanium. These residues, known as red mud, settle gradually to the bottom of the settling tank and are filtered and removed. The clear sodium aluminate solution, which is called aluminate liquor, is pumped into a huge tank called a precipitator. Fine particles of alumina are added to seed the precipitation of pure alumina particles as the liquor cools. The precipitation process is a batch as well as continuous. The solid particles concentration increases, which are removed, filtered and washed, and are then passed through a rotary or fluidized calciner at 1100C to drive off the chemically combined water. The result is a white powder, pure alumina. The caustic soda, which is called, spent liquor is recycled and returned to the start of the process and used again.

The Bayer Process : Today all the alumina produced from bauxite uses the Bayer Process -an economical method of producing aluminium oxide which was discovered by an Austrian chemist Karl Bayer and patented in 1887. The process dissolves the aluminium component of bauxite ore in sodium hydroxide (caustic soda), removes impurities from the solution; and precipitates alumina trihydrate, which is then calcined to aluminium oxide High-pressure digestion technology is adopted for the production of Alumina. The Bauxite received from mines is stored in the open bauxite yard. It is blended and crushed. The crushed bauxite is then conveyed to Ball Mill section where the bauxite along with the recycled caustic soda solution called digestion liquor is ground. The slurry after grinding is stored in tanks and pumped to Desilication units after preheating. The desilicated slurry is digested in the series of digesters by steam at high pressure. The digested slurry is flashed and diluted before going to settling tanks. Flocculants are added for faster sedimentation of the mud. The settled mud (called Red Mud) is subsequently washed before going to red mud disposal area. Hydrocyclone : Under modernization programme with installation of Hydro cyclone which has pivot role for hydrate filtration. Raw and fine crystals of alumina hydrate are separated through hydrostatic process from hydrate liquor. Fine crystals are resent to precipitation for seeding whereas raw crystals are sent as product to calcinations through filtration process where finally it is turned into alumina powder. By way of using the hydro cyclone in alumina plant, the production and productivity is supposed to be improved 30 to 40%. The clear supernatant liquor (called aluminate liquor) is filtered and cooled in heat exchangers. The cooled aluminate liquor is then pumped to precipitation unit. The precipitated hydrate is filtered, washed and stored in hydrate godown. The product hydrate is fed to kiln where it is calcined at a temperature of 1200C. The Calcined alumina is stored in silos.

Smelting Process : Bharat Aluminium Co. Ltd. (BALCO) uses VSS (Vertical Stud Soderberg) technology to produce Aluminium from Alumina. Alumina is dissolved in an electrolytic bath of molten cryolite (Sodium Aluminium Fluoride) within a large carbon or graphite lined steel container known as a "pot". An electric current is passed through the electrolyte at low voltage, but very high current. The electric current flows between a carbon anode (positive), made of petroleum coke and pitch, and a cathode (negative), formed by the thick carbon or graphite lining of the pot. Molten Aluminium is deposited at the bottom of the pot and is siphoned off periodically. It is then taken to a holding furnace, cleaned and then cast.

2.2.

Status of Indian aluminium mining industry

2.2.1. Indian major players

Major players Though there are more than 200 mines operating in the country, most of these are small open cast and manually operated. Industry is dominated by following five integrated players which are in the manufacture of alumina/ aluminium, Bharat Aluminium Company Limited (BALCO) National Aluminium Company Limited (NALCO), Hindustan Aluminium Corporation Limited (HINDALCO) Indian Aluminium Comp-any Limited (INDAL) Madras Aluminium Company Limited (MALCO)

Among these, the Panchpatmali bauxite mine of NALCO in Orissa accounts for about 40% of the countrys production.

Production capacity of Indian players

2.2.2. Indian availability of bauxite

India is self-sufficient in bauxite, the chief raw material for the manufacture of aluminium. Indian available resources of bauxite Indian production of bauxite Around 3 billion tonnes Around 14 million tonnes

Indian place in the world in bauxite availability 5th Major state which have bauxite deposit Other major bauxite reserves containing states Orissa and Andhra Pradesh (Around 90%) Jharkand, Andhra Pradesh, Maharashtra.

2.2.3. Profile of major players

BALCO The public sector company BALCO was the first company in which the Government of India has disinvested its stakes to M/s Sterlite after liberalization. The third largest Aluminium Company in India is held by Sterlite Industries which has 51% share holding and by GOI, which holds the remaining 49%. Activity and product range Calcined alumina Aluminium metal Power plant 200,000 tonnes per annum 100,000 tonnes per annum 270 MW

Capacity status on individual mining units Proved and Probable reserves million MT 6.6 7.1 13.7

Aluminium Mines Mainpat Bodai Daldali Pandrapat Jamirapat Total BALCO

Inferred reserves million MT 5.0 2.0 8.0 15.7 30.7

Aluminium Oxide % 48.0 48.0 48.0 51.0 49.0

Aluminium Oxide % 48.0 48.0 48.0

NALCO Activity Bauxite mining Alumina refining, Aluminium smelting and casting Panchpatmali hills of Koraput district in Orissa

Location

Availability Resource Capacity Quality 310 million tones 4.8 million tonnes per annum The quality of ore is Alumina 45% and Silica 2%.

HINDALCO and INDAL Both is flagship of Aditya Birla Group, are vertically integrated through all stages of the aluminium business. Hindalco Hindalco is the market leader in aluminium production followed by Nalco. Business Market share Primary aluminium, extrusions, rolled products, foils, and alloy wheels In the value-added segment, Hindalco, along with its subsidiary Indal, has around 50 per cent market share. 345,000 tonnes 660,000 tonnes 779 MW

Smelting capacity Alumina refining capacity Captive power plant Indal, Hirakud (Orissa) Capacity Captive Power Plant

65,000 tonnes per annum 67.5 MW

Mining division Muri Alumina Post Chotamuri-835 101 Dist: Ranchi, Jharkhand Phone: (06522) 244253/334 Fax: (06522) 244342 MALCO Contact details Post Box. 4, Mettur Dam Salem District. - 636 402 Tamilnadu, South India Phone : 4298 - 222061 - 64 Fax : 4298 - 222069, 222215 E-mail : masec@vedanta.co.in Activity MALCO is the only integrated primary Aluminium Metal complex in the entire South India. MALCO was taken over by the Sterlite group, a subsidiary of Vedanta resources in 1995. Captive mining, refining, smelting Coal based Captive power generation

Method of mining Method of mining used is open cast semi-mechanized. Overburden, which is in the form of soil & moorum, is first excavated by a combination of shovel/excavator and dumper in order to expose orezone. Then the ore zone is drilled and blasted. The blasted ore is subject to sorting in order to upgrade the ROM Grade to Plant Feed Grade i.e. 34% Al2O3. Sorting is carried out at the mine-face and the rejects associated in the ore zone are back-filled concurrently. The area is then levelled and afforested. The sorted ore is then trucked to the Mettur Dam Complex for further processing.

Location of Bauxite Mines Yercaud , Salem district Kolli hills, Namakkal district Smelting and refining unit - Mettur Smelting capacity Refinery capacity

Reserves capacity 0.8 million tonnes 0.9 million tonnes

40,000 tonnes per annum 80,000 tonnes per annum

2.1.

Processing of iron ore

III IRON

2.1.1. Type or iron ore

Haematite Magnetite

India is currently producing all the possible marketable products of iron ore, namely iron ore lumps, ore concentrates, pellets, iron oxide powder and iron ore sinter. One of the most immediate technological challenges facing the industry is to deal with the problem of processing alumina rich iron ore fines and slimes. During the wet processing of iron ores, substantial amount of fine particles/slimes is generated in downstream which need to be recovered effectively for their usage and beneficiation. The slime sample from Karnataka had a feed grade of 63.84% total Fe, 2.64% Silica and 3.98% alumina. The dispersion of the fine iron ore particles were carried out with sodium hexa meta phosphate (SHMP), tetra sodium pyrophosphate (STPP) and Dispersant N6, a low molecular weight anionic poly-acrylamide polymer. The effect of process parameters pulp density, types of reagents and their dosage on the separation index following dispersion was studied The selective flocculation studies were carried out on fully dispersed slime sample using modified starch and polyethylene oxide as selective flocculant. The results show that about 95% recovery could be achieved through the separation following dispersion with the enhancement of Fe grade from 1.5 wt. % to 2 wt. %.

2.2.

Status of Indian iron mining industry

2.2.1. Indian Availability

2.2.4. Production of iron ore (lumps and fines) by principal states

In million tonnes

2.2.5. Major regions with haematite resources

Jharkhand-4036 million tonnes (28%), Orissa-4761 million tonnes (33%), Chattisgarh-2731 million tonnes (19%) Karnataka-1676 million tonnes (11%) Goa-713 million tonnes (5%).

The balance resources are spread over in the state of Maharashtra, Madhya Pradesh, Andhra Pradesh, Rajasthan, Uttar Pradesh and Assam together contain around 4% of haematite.

2.2.6. Major regions with magnetite resources

Karnataka-7812 million tonnes (74%), Andhra Pradesh-1464 million tonnes (14%)

Rajasthan-527 million tonnes (5% each), Tamil Nadu-482 million tonnes (5% each), Goa-214 million tonnes (2%).

Assam, Jharkhand, Nagaland, Bihar, Madhya Pradesh and Maharashtra together account for a meager share of magnetite resources. The most important magnetite deposits are located in Babubadan, Kudremukh, Bellary, Anadurga and Bangarkal areas of Karnataka, Goa region, Ongole and Guntur districts of Andhra Pradesh etc. Other deposits are also located in Jharkhand, Bihar, Tamilnadu, Kerala and Assam etc.

2.2.7. Major iron ore mines in India

SAIL
SAIL has the second largest mining outfit in the country. YEAR OF COMMISSIONING RATED CAPACITY ( IN MT) 4.25 4.30 4.20 2.01 1.10 2.4 0.7 1.10 0.80 0.34

SL. NO

MINES

STATE Iron ore

1. 2. 3. 4. 5. 6. 7. 6. 7. 8.

KIRIBURU MEGHAHATUBURU BOLANI BARSUA KALTA GUA MANOHARPUR (Chiria) Kuteshwar (Limestone) Bhawanathpur (Limestone) Tulsidamar (Dolomite)

JHARKHAND JHARKHAND ORISSA ORISSA ORISSA JHARKHAND JHARKHAND Flux MADHYA PRADESH JHARKHAND JHARKHAND

1964 1985 1960 1960 1966 1919 1907 1974 1979 1970

IV LEAD AND ZINC

1.Gravity separation: After the coal is mined, it is ground down by ball mills and is subjected gravity separation to remove the waste. 2.Flotation process: Further purification is done by adding flotation agent 3. Sedimentation process: Fine coal is recovered by sedimentation process by adding flocculant. 4. Filtration / centrifugation: Fine grade coal end product is obtained by filtration / centrifugation process by adding flocculant to enhance the separation. In the case of brown coal or coal with high clay content, prior to flocculant addition, there is the requirement to add coagulant to achieve efficient solids capture.

COAL

Need for washing non-coking coal

Freight saving owing to reduced ash Consistency in the feed coal for better performance of end user Problems in disposable of bottom ash and slag Environmental pollution due to fly ash and trace elements Power Plant equipments would be protected from high wear & tear on coal and ash flow paths, combustion chambers, mills, crushers etc.

Advantages of washing non-coking coal

High output for the thermal power plant Plant utilisation factor increased from 73 to 96% Specific consumption reduced from 770 gm to 530 gm per kwh Auxiliary fuel consumption was reduced practically to nil Auxiliary power consumption reduced by 1.5% Minimization of deposits, clinker formation and leakage development in the boiler

Major players in coal mining

Current status of coal washeries

20 coal washeries ( 32.37 MTPA) for coking coal 28 coal washeries (70.35 MTPA) for Thermal coal Three more (Approx 21 MTPA) under various stages of construction/approvals.

India produces about 62% of worlds mica. Bihar (60%), Andhra Pradesh (20%) and Rajasthan (10%) are the major mica mining states in India. Mica is a natural valuable mineral product applied to a group of a complex aluminosilicate minerals having a sheet or plate like structure with different chemical compositions and physical properties. The ordinary mica crystals as they come out of a mine is in form of rough books or lumps of irregular shape, size and thickness, associated with impurities and structural imperfections. They have to undergo a long operation of cutting, sorting and processing from crude to commercial quality. The operations performed consists of cobbing or cleaning the crude crystals as extracted from the mine with its associated impurities; rifting or splitting the cobbed mica into usable sheets by sickle and then by sharp knife removing major flaws and structural imperfections, such as cracks, holes, reeves, crossgrains and other physical defects to obtain the maximum usable area with minimum wastage.

VI MICA

SECTION IV INDIAN SUPPLY DEMAND SCENARIO ON MINING CHEMICAL

Mining chemicals form a crucial part of the chain, and are absolutely fundamental to maximising recovery. The industry has both commodity and specialised chemicals. The type of chemical used in mineral processing include the following. Flocculant / coagulant Collectors Frothers Depressants Activators Scale inhibitor Dispersant / Grinding aid Modifying agent (pH modifier, cationic modifier, ionic modifier, organic modifier) Agglomeration aid Rheology modifier Dust suppressor

1.1.

General details

I.

FLOCCULANT / COAGULANT

Mineral slurries which contains colloidal particles in nature normally carry charges on their surface, and hence they are stable and not separable. The surface property of such colloidal particles can be changed by addition of some chemicals (coagulants / flocculants) so as to facilitate the separation of solids. Conversion of stable state dispersion to the unstable state is termed destabilisation and the processes of destabilisation is termed as coagulation / flocculation. A wide variety of chemicals exist for use in clearing raw water of suspended solids in coagulation/ flocculation processes. It is typically found that combinations of coagulants can be used to achieve much higher performance and process efficiency. Coagulation: If destabilisation is induced through charge neutralisation the process is called coagulation. Flocculation: The process of forming larger agglomerates of particles through high molecular weight polymeric materials is called flocculation. No substantial change of surface charge is accomplished in flocculation. Now-a-days inorganic flocculants such as ferric chloride and aluminium chloride are replaced by polymeric compounds. Mostly used coagulants / flocculants compounds include Polyacrylamide polyaluminium chloride.

1.2.

Role of flocculant in Mineral processing

In all mining operations, solids and liquids must be separated which can be facilitated by flocculants in the thickening of froth flotation concentration and clarification steps. In most mineral processing, the suspended fines are impurities arising from crushing and grinding. They are separated as the solid phase rather than the mineral of interest, which remains in solution, coal being an exception. The mining industries requiring flocculants include coal, iron ore, bauxite and uranium etc. The coal industry is the largest user. Both cationic and anionic flocculants are used including some natural polymers. Cationic polymers are of quaternary ammonium type, e.g. poly (DADMAC) or polyamine especially in the recovery of coal. The principal anionic synthetic flocculants are poly (acrylamide-acrylate) copolymers although nonionic polyacrylamide is also utilized. Among natural polymers used are starch, guar gum, animal glue, lignin (sulfonate) etc.

1.3.

Selective flocculation

One of the applications that have shown considerable promise in the beneficiation of mineral fines is selective flocculation. This process involves flocculating particles of one type from a well dispersed suspension of the ore or mixture, followed by separating the flocs by either froth flotation or sedimentation. Selective flocculation, like flotation, takes advantages of the differences in the physico-chemical properties, but unlike flotation, does not depend entirely on the wettability characteristics of the particle surfaces. The selective flocculation involves three steps: dispersing the fine particles, selectively adsorbing the polymer on the active component (flocculating particles of interest) and forming flocs, and separating the flocs. The major applications of selective flocculation have been in mineral processing, but many potential uses exist in biological and other colloidal systems. These include purification of ceramic powders, separating hazardous solids from chemical wastes and removal of deleterious components from paper pulp. Industrial applicability of this process has so far been limited, e.g. processing of taconite and potash ores, because results obtained by selectively flocculating natural ores or complex synthetic mixtures often do not correlate with the selectivity observed in single component systems. Selective flocculation of desired fraction has become an active area of research in the field of flocculation. A critical review on iron oxide/quartz separation using starch and polyacrylic acid (PAA) indicates starch to be a more selective reagent. The presence of clays, particularly Montmorillonite, is known to have a detrimental effect on the selectivity of separation. To achieve the desired selectivity ( <10% flocculation of clay ), Sodium silicate is to be added. The primary objective of adding sodium silicate is to prevent hetero coagulation. It was observed that selective flocculation of iron oxide-kaolin mixtures using a modified polyacrylamide flocculant containing hydroxamate functional groups. Flour apatite, the phosphate fertilizer mineral, occurs in nature. In association with silicate and carbonate minerals. During flotation separation of apetite a significant proportion of P2O5 values is lost in the form of slimes.

1.4.

Difference between coagulant and flocculant

Coagulation Inorganic compounds ex. FeCl3, FeSO4 , al. sulphate etc Flocculation Polymeric material namely polyacrylic acid, polyacrylamide etc More of thickening More of clumping together of substances or encapsulation of substances Neutralization of charged colloid. No change in charge due to the Due to charge neutralization, it addition of polymeric often assists in turbidity and compound. No physical change colour removal. takes place such as colour or turbidity removal.

Properties Compounds used

Physical change

Charge of the colloid

Type of usage Stability Usage

Water treatment Compact and loosely bound Coal, Soda ash, taconite and some extent to uranium industry

Waste water treatment Large size, strongly bound and porus Major mineral industries including coal, copper, gold, silver, zinc etc

http://wecleanwater.com/html/floccin/flocculation-vs-coagulation.htm Discussion with Mr. S.K. Sharma, Scientist, R & D department, NMDC Tel: 040-27170224 Mob: 8500667302 Flocculant and coagulant There is no need to use both coagulant and flocculant. It depends upon the type mineral, contents of minerals. Some of the flocculant can initiate the coagulation itself and therefore no need to add coagulant. Discussion with Mr. Venkataraman Mob: 09820232243 Flocculants and coagulant More than 90% of the mining industry use flocculant only. Coagulant is used rarely. No need to use both coagulant and flocculant. Coagulant is cheaper than flocculant. Coagulant is used mainly in water treatment industry. Flocculant is used in waste and industrial water treatment. Where-ever, froth flotation is used, flocculant and collectors should be used. Polyelectrolytes with low molecular weight are used as coagulant whereas high molecular weight are used as flocculant.

1.5.

Classification of flocculant

Synthetic polymer
Synthetic flocculants have advantages of possibility of tailor made in terms of molecular weight and composition and therefore efficient at very low dose levels when compared to natural flocculant such as starch. More over, synthetic flocculants are easily dissolved and do not require cooking. Cationic flocculant Quaternary type such as poly DADMAC or polyamine, phosphonium, sulphonium compounds, Polyacrylamide (acrylamide and acryloyl oxyethyl trimethyl ammonium chloride, formed by quaternization of dimethyl aminoethyl acrylate with methyl chloride) polyamines, polyimines, polyvinyl pyridine etc Anionic flocculants Homopoly acrylic acid, polyacrylic acid co acrylamide and hydrolyzed polyacrylamide. Polyvinyl sulphonic acid, polystyrene sulphonic acid , 2-Acrylamide-2-methyl propyl sulfonic acid (AMPS) Non-ionic flocculants Acrylamide monomer polymerised to give polyacrylamide, Polyethylene oxide

Natural polymer
Starch, guar gum, animal glue, lignin (sulfonate) , Chitin and chitosan deri. Sodium CMC etc. The vast categories of materials used as flocculating agents can be classified broadly into two categories

1.6.

Advantages of polymeric floccs over inorganic flocs

The flocs are larger and stronger and are more rapidly formed. The salt concentration is not increased and much less sludge is generated. The dosage requirement is quite low (typically 1% on a dry weight basis) whereas that of inorganic flocculants may be as high as 20%. The inorganic flocculants frequently require pH adjustment, which is not necessary with polymeric flocculants. The polymeric flocculants are more convenient and easier to use. However, inorganic flocculants are inexpensive and often used for economic reasons.

1.7.

Usage of flocculants in metallic minerals

Common inorganic flocculant Disadvantages Fast mixing is critical to proper functioning. Nonoptimal pH leads to excessive dosage A standard in requirements, should be used between pH 5.5 Alum coagulation/flocculation. and 7.5, typically requiring alkaline additives to (Aluminum Attracts inorganic suspended achieve optimum pH. Performance substantially Sulphate) solids very effectively. degrades at lower temperatures. Poor efficiency for attracting organic suspended solids. Relatively large dosage required when used alone. Alternative to Alum. Ferric Lower efficiency for removing organic suspended chloride is good at attracting solids than alum. Fast mixing is critical to proper Ferric Chloride inorganic SS. Gives more functioning. Should be used between pH 5.5 and ferric compact sludge. pH sensitivity is 8.5, typically requiring alkaline additives to sulphate somewhat less than alum. achieve optimum pH. Generally large dosage Suitable for usage in the limerequired. softening process (pH 9). Polyhydrolysed metal salt Chemical PACl / PAC (Polyaluminum Chloride) Polyaluminum Sulfate Polyiron chloride Advantages Does not require addition of alkali to raw water for coagulation, and is much less sensitive to pH, operating withing pH 4.5 9.5. Mixing time not critical. Floc is tougher, and if substituted for hydrolyzing metallic salts, may be possible to reduce dose and avoid using coagulant aid. Suitable for high colour applications. Specific chemical composition depends on preparation. Disadvantages Generally requires an onsite production process to prepare pre-hydrolyzed metallic salts from alum. Generally requires an onsite production process to prepare pre-hydrolyzed metallic salts from alum. Chemical Advantages

Synthetic cationic polymer Chemical Epichlorohydrin dimethylamine (epi-DAM) Amino methyl polyacrylamide Polyalkylene Polyamines Polyethylenimine Advantages Lower dosages required, producing denser sludge. When used in combination with metal salts, greatly reduces their dosage requirement, resulting in substantial economic benefits . Disadvantages Determining correct proportion for mixing with inorganic coagulants and other additives has been challenging due to a historical lack of instrumentation for determining relative amounts of inorganic, organic, and biological suspended solids in raw water.

The flotation tests were performed using 1.0 lb. of Tall Oil A plus either 0.4 lb. or 0.6 lb. of froth modifier per ton of feed, using the 11 different hydrocarbon "oil" type reagents (0.4:1.0 froth modifier/tall oil mixture was used). Additional froth modifier was added separately to obtain a ratio of 0.6:1.0. Tap water was used for all tests. The P2O5 recovery results are presented for each reagent as bar graphs for easier visualization .

1.8.

Coagulant Aids

In addition, various additives can be used to aid in the coagulation and flocculation process. These may accelerate the flocculation process or strengthen the floc to make it easier to filter. Coagulant aids can be roughly broken into two classes based on their mechanism of action. Some coagulant aids, generally the synthetic polymers, bind to particles much like coagulants themselves. Others, generally the inorganic and also natural polymers, act as sites of nucleation to speed the formation of floc. Nucleating agents typically also increase the density of floc, and so speed settling. In the case of synthetic polymer coagulant aids there is a blurring between coagulant proper and coagulant aid. The distinction is that synthetic polymer coagulant aids are added mainly for how they improve sludge properties (density, strenth, floc-size), easing separation and speeding flocculation, and that they may not be efficient when used alone as primary coagulants. Synthetic Cationic Polymers Polydiallyldimethyl ammonium chloride (poly-DADMAC) Polydimethyl aminomethyl polyacrylamide Polyvinylbenzyl trimethyl ammonium chloride Polyacrylamides polyethylene oxide Anionic Polymer A110 Produce larger shear(Kemira) resistant flocs by Hydrolyzed promoting bridging. Polyacrylamides Polyacrylic acid Polystyrene sulfonate Polyacrylates Increases complexity of coagulation/flocculation stage but improves process performance and economy when used properly Produce denser more shear-resistant sludge. For use with metallic coagulants.

Synthetic Neutral Polymers Synthetic Anionic Polymer

Natural polymers

Sodium alginate

Particularly suited for use with ferric salts, but if used properly can be effective when used with alum Inexpensive additives for increasing settling velocity, and reducing coagulant dosage. For use with organic polymer coagulants Inexpensive additives for increasing settling velocity, reducing dosage.

Chitosan Starch Aluminum Chloride Inorganic Coagulant Aids Activated Silica Bentonite, kaolinite Calcium Carbonate

These less expensive polymers are somewhat less efficient than synthetic polymers

Increases complexity of coagulation/flocculation, but improves process performance and economy when used properly

Substitution of Magnafloc for ferric chloride

Ferric chloride is a Class 8 dangerous goods and requires appropriate storage and handling. It is an extremely aggressive corrosive. Ferric chloride is introduced into the sludge stream just prior to dewatering. As a result of the atomised mists produced through the filter belt operation a perfect mechanism existed for the dispersal of this corrosive substance. All equipment within the filter belt press room was severely effected by corrosion. All valves, steel pipe work, walkway gratings, pumps and associated fittings exhibited extensive corrosion to the point where some pieces of equipment were inoperable and access to the area unsafe. The main entry doors were corroded to the point that they would no longer close.

Product Safety A detailed assessment of the properties of both products indicated that Magnafloc was able to deliver on first performance criteria. The outcome of a product comparison is detailed in Table 1.

De-watering Characteristics Both agents were good sludge conditioners, producing a sludge cake in the order of 18- 23% dry solids. Only one adverse difference was seen in using the two chemicals. Significant quality differences were seen within the centrate.

As outlined in Table 2 centrate quality varied significantly with three parameters only. The pH of the centrate when using ferric chloride was in the range of 4.0-5.0 compared to 8.0-9.0 for Magnafloc 1597. This pH shift in using the new product benefited two areas of operation, less corrosive and more effective centrate treatment. The second parameter of significance was iron. The iron content of the centrate produced using Magnafloc 1597 was in the order of 100 times less. Concentrations of iron in the sludge were reduced by six fold when using Magnafloc 1597. This allowed for a significant reduction in the iron content of the end product biosolids. This reduction was seen as a future advantage in maintaining a commercially viable agricultural product when minimal research has been conducted on the impacts of iron within soils.

The third parameter of significance was phosphorus. The phosphorus content of the centrate produced using Magnafloc 1597 was in the order of 10 times more. This was a result of ferric chloride having a significantly greater binding capacity of phosphorus within the sludge. During the course of the trial it was decided that to effectively treat the centrate this flow would be redirected from the off site treatment area to the head of works. As the Bendigo WRP process is BNR the treatment of phosphorus levels within the centrate had to achievable. It was found during the course of the trial that the biological process removed a proportion of this phosphorus. Residual phosphorus moving through the plant Cost It was found that significantly less Magnafloc 1597 is required to achieve the same cake solids when using ferric chloride. The equivalent dose rates for ferric chloride and Magnafloc 1597 are detailed in Table 3. Table 3: Dose Rates for Ferric Chloride Compared to Magnafloc 1597

However Magnafloc 1597 is around six times the cost of ferric chloride. During the course of the trial it was found that the change over to Magnafloc 1597 was cost neutral. Any financial gains in flocculant/coagulant savings have been absorbed by additional alum dosing to remove phosphorus in the centrate treatment.

1.9.

Polyacrylamide

1.9.1.

General details

Polyacrylamides are water-soluble polyelectrolytes, i.e. they carry ionic charge as well as the polymer chain. Polyacrylamides are available in a wide range of molecular weights which formed from acrylamide subunits. It can be synthesized as a simple linear-chain structure or cross-linked, typically using N,N'methylenebisacrylamide. Polyacrylamide is not toxic. However, unpolymerized acrylamide, which is a neurotoxin, can be present in very small amounts in the polymerized acrylamide, therefore it is recommended to handle it with caution. Depending upon the charge, these polymers are anionic or cationic. Homo polymers of acrylamide are also included in the family of polyelectrolytes though they do not carry any charge. These are called nonionic. Important application sectors include the following Treatment of raw water for potable purpose Treatment of waste water/industrial effluent / sewage water Treatment of water for industrial use Oil exploration Brine clarification in caustic chlorine unit Metal and mineral processing Paper industry Sugar juice clarification Coal washeries

1.9.2.

Indian trade analysis

In India, requirement of polyacrylamide is partly met by imports and partly by domestic producers. Indian producers of polyacrylamide, import acrylamide monomer and polymerise the product by dissolving in water to produce polyacrylamide. Acrylamide monomer is not presently produced in India. Indian import of polyacrylamide / acrylamide

Imported acrylamide monomer is mostly used in the production of polyacrylamide for water treatment application.

Portwise import details of polyacrylamide- Period 2009-2010

Chennai 2% Mumbai 7%

Delhi 1%

JNPT 90%

Countrywise import details of polyacrylamide Period 2009-2010

Belgium 1% S. Africa 1% China 26% Italy 1% Australia 4% Germany 5% U.S. 5% Japan 5%

U.K. 12%

France 25%

Korea S. 15%

Sample of individual import Product name Flomin 4956 Modified polyacrylamide Flomin 4995 Modified polyacrylamide Flomin 4956 Modified polyacrylamide Flomin 4995 Modified polyacrylamide Flomin ALD 60 HAZY dispersion of polyacrylamide in mineral oil Quantity in tonnes 9 9 6 6 21.6 Vizag port Shipment value in USD 26361 25906 17574 17271 17863 Value per quantity in USD 2929 2878 2929 2878 827

Nhav Sheva

51.6

104975 Neg.

Export of polyacrylamide and acrylamide monomer

1.9.3.

Indian supply scenario

Acrylamide monomer Presently acrylamide monomer is not produced in India. Black Rose Industries Ltd , Mumbai proposed to set up the plant for acrylamide monomer . Installed capacity of the new project Schedule Polyacrylamide Polyacrylamide is produced by number of units in the country. Such organisations import acrylamide monomer and polymerise the product for use as flocculant. Major players SNF Indian Ltd, Anhdra Pradesh Dai Ichi Karkaria Ltd., Maharashtra Kimberlite Chemical, Karnataka Onedo Nalco Ltd Thermax Ltd, Maharashtra Kaushal Aromatic Chemicals Pvt. Ltd Suyog Chemicals Pvt. Ltd. / Star Orechem International Ltd Rubamac Rishab Metals & Chemicals Pvt. Ltd April 2012 10000 tonnes. Proposes to increase 20000 tonnes to 2013 and further to 40000 in 2015.

Indian production of polyacrylamide Consumption norm for production of polyacrylamide Chemical raw material Acrylamide Acrylic acid Paraffinic solvent

9700 tonnes

Requirement per tonne of polyacrylamide in tonnes 0.251 0.136 0.286

1.9.4. Indian demand for polyacrylamide

Indian demand for polyacrylamide in water treatment sector including mining sector 11250 tonnes Indian market for polyacrylamide in value terms Around Rs. 190 crores

Sample of consumers of polyacryalmide in water treatment sector Karur Sukkaliyur Common Effluent Treatment, Karuru Jeedimetla Effluent Treatment Co., Hyderabad Vapi Waste & Effluent Management Company, Gujarat Pallavaram Tannery Ltd Effluent treatment co Chrompet Ambur Tannery Effluent Treatment Plant, Ambur Ranipet Tannery Effluent Treatment, Ranipet Haldia Petrochemicals, Kolkata Sample of consumers of polyacryalmide in mining sector Details provided separately under section

1.9.5.

Recent developments in technology

Flocculation properties of polyacrylamide grafted carboxymethyl guar gum (CMG-g-PAM) synthesised by conventional and microwave assisted method. Pal S, Ghorai S, Dash MK, Ghosh S, Udayabhanu G. Source : Polymer Chemistry Laboratory, Department of Applied Chemistry, Indian School of Mines, Dhanbad 826 004, India. sagarpal1@hotmail.com J Hazard Mater. 2011 Sep 15;192(3):1580-8. Epub 2011 Jul 2. A novel polymeric flocculant based on polyacrylamide grafted carboxymethyl guar gum (CMG-gPAM) has been synthesised by grafting polyacrylamide chains onto CMG backbone using conventional redox grafting and microwave assisted grafting methods. Under optimum grafting conditions, 82% and 96% grafting efficiencies have been observed in case of conventional and microwave assisted methods respectively. The optimum sample has been characterized using viscometry, spectroscopic analysis, elemental analysis, molecular weight and radius of gyration determination. The flocculation characteristics of grafted and ungrafted polysaccharides have been evaluated in kaolin suspension, municipal sewage wastewater and decolourization efficiency of a dye solution (methylene blue). It is evident from results that CMG-g-PAM synthesised by microwave assisted grafting method is showing best flocculation characteristics.

Microwave assisted synthesis of polyacrylamide grafted dextrin (Dxt-g-PAM): Development and application of a novel polymeric flocculant. Pal S, Nasim T, Patra A, Ghosh S, Panda AB. Source: Polymer Chemistry Laboratory, Department of Applied Chemistry, Indian School of Mines, Dhanbad 826 004, Jharkhand, India. sagarpal1@hotmail.com Int J Biol Macromol. 2010 Dec 1;47(5):623-31. Epub 2010 Aug 20. An efficient polymeric flocculant was synthesized by microwave assisted grafting of polyacrylamide to dextrin. By varying the reaction conditions, various grades of graft copolymers were synthesized to obtain the optimized one. The flocculation efficiency of the grafted products in kaolin suspension was dependent on the molecular weight, radius of gyration and length of the grafted polyacrylamide chains. The flocculant obtained by microwave assisted grafting method was superior to dextrin and polyacrylamide-based commercial flocculant (Rishfloc 226 LV) in flocculation tests. Novel biodegradable polymeric flocculant based on polyacrylamide-grafted tamarind kernel polysaccharide. Ghosh S, Sen G, Jha U, Pal S. Source: Department of Applied Chemistry, Birla Institute of Technology, Mesra, Ranchi 835 215, Jharkhand, India. Bioresour Technol. 2010 Dec;101(24):9638-44. Epub 2010 Jul 18. Novel biodegradable polymeric flocculants were produced by conventional redox grafting, microwave-initiated and microwave-assisted grafting of acrylamide to tamarind kernel polysaccharide (TKP). The flocculation efficiency of the grafting products in kaolin suspension, municipal sewage wastewater and textile industry wastewater was primarily dependent on the length of the grafted polyacrylamide chain. The flocculant obtained by microwave-assisted grafting method was superior to TKP and polyacrylamide-based commercial flocculant (Rishfloc 226 LV) in flocculation tests.

1.10. Polyaluminium chloride

Polyaluminium chloride is used as coagulation/flocculation agent for water purification and as a substitute for alum. PAC is reputed to provide faster flocculation and stronger flocs than alum in some applications. PAC is produced in concentration ranging from 10 to 30%. It is largely used in India for drinking water purification in cooling towers, industrial wastewater treatment and as a process chemical in the paper industry. Purification of river water, lake water and underground water Purification of industry water and industry recycling water Purification of waste water Reclaiming coal from coal-washing waste water and kaolin in ceramic industry Purification of the waste water in printing and dyeing industry, leather industry, beverage industry, meat-processing industry, coal-washing, metallurgy industry, mine, pharmacy, paper-making, and purification of the waste water containing fluorine, oil and heavy metals Tann-age and cloth cockling-prevent Cement solidifying and molding Refining of pharmaceuticals, glycerin and sugar Catalyzer carrier Paper-making glue

1.10.1.

Indian trade analysis

Neg.

Indian import / export of polyaluminium chloride

1.10.2.

Indian supply scenario

Major players of polyalumium chloride include the following Aditya Agro Chemicals, Gujarat Amines Biotech Private Limited, Gujarat Andhra Sugars Ltd Andhra Pradesh Anus Laboratories, Andhra Pradesh Grasim industries, MP Gujarat Alkalies & Chemicals, Gujarat Kanoria Chemicals, New Delhi Neel Chem India Ltd. Gujarat Neel chem. (India) Ltd, Gujarat Premier Minerals & Chemical Industries, Gujarat Rubmach, Gujarat Synergy Multichem, Gujarat

Indian production of PAC solution with the concentration ranging from 10 to 30% 130,000 tonnes

1.10.3.

Indian demand for polyaluminium chloride

Indian demand for polyaluminium chloride (10 to 30%) including water treatment and mining industries 130,000 tonnes Indian market in value Around Rs 260 cores

1.11. Other flocculants including specialty flocculant

There other major flocculants used in water treatment sector include the following Ferric alum Ferric sulphate Lime Sodium acrylate, Dimethyl aminoethyl acrylate, Polyethylene imines Indian market for the flocculants of above type in water treatment sector Rs. 250 crores

1.12. All India market for flocculants in water treatment sector

Polyacrylamide Polyaluminium chloride Other flocculants including alum, ferric chloride , lime etc Total Product Market value in Rs. Crores 190 260 250 700

1.13. All India market for flocculants in mining sector

Mining sector holds around 15% of all India water treatment sector. All India market for flocculants / coagulants in mining sector Rs. 108 crores

2.1.

General details

II

COLLECTORS

Basis of froth flotation is the difference in wettabilities of minerals. Most minerals in nature are hydrophilic. They do not readily float in froth flotation. Even some of the minerals which are hydrophobic in nature require supporting reagents to increase the hydrophobicity and some chemical reagents are added to float to the surface. The recovery is often improved when a collector is used. Chemicals that promote hydrophobicity of a mineral are called that mineral's promoter or collector. Collectors get adsorbed on the mineral surfaces rendering the particles hydrophobic and floatable.

Classification of collectors
Many different chemicals are used as collectors. Collectors can be generally classed depending on their ionic charge as follows *Cationic *Anionic *Nonionic The cationic and anionic collectors consist of a polar part that selectively attaches to the mineral surfaces, and a non-polar part that projects out into the solution and makes the surface hydrophobic. The nonionic collectors are simple hydrocarbon oils which are naturally hydrophobic.

Cationic collectors Cationic collectors use a positively-charged amine group which it can attach to negatively-charged mineral surfaces. Cationic collectors are mainly used for flotation of oxides, carbonates, silicates and alkaline earth metal mineral such as barite, carnallite, and sylvite, certain rare-metal oxides, and for separation of potassium chloride (sylvite) from sodium chloride (halite).

Primary Anionic collector

Secondary

Tertiary

Anionic collectors has a negatively-charged end that will attach to the +ve part of mineral surfaces, and a hydrocarbon chain that extends out into the liquid make the hold hydrophobic.

The functional group or ligand comprises one or more of the important donar atoms N, O, S attached to a central atom of C, P, S or N. The donar atoms are involved in bonding with metal or other active sites on the mineral via chemical or physical interactions. Sulphide mineral In general, collector for sulphide mineral and precious metal minerals should contain atleast one sulphur atom which are more selective Sulphide collector families o o o o o o o Dithiocarbamate, dialkyl Dithiophosphate, dialkyl or diaryl Dithiophosphinate, dialkyl Mercaptan, alkyl Mercapto benzothiazole Monothiophosphate, dialkyl / diaryl Xanthate ester, allyl, alkyl

Non sulphide minerals Non sulphide minerals should contain atleast one oxygen, or nitrogen atoms which are mostly non selective. Fatty acids Primary amines Petroleum sulfonates Alkyl hydroxamates Alklyl phosphonates

A typical anionic collector for oxide mineral flotation is sodium oleate, the sodium salt of oleic acid. The anionic group responsible for attaching it to the mineral surface is the carboxyl group, which dissociates in water to develop a negative charge. The negatively-charged group is then attracted to positively-charged mineral surfaces. Structure of oleic acid, a very commonly used anionic collector

Since particles that are immersed in water develop a net charge due to exchanging ions with the liquid, it is often possible to manipulate the chemistry of the solution so that one mineral has a strong positive charge while other minerals have a charge that is either only weakly positive, or negative. In these conditions, the anionic collector will preferentially adsorb onto the surface with the strongest positive charge and render them hydrophobic. Non ionic collectors Hydrocarbon oils, and similar compounds, have an affinity for surfaces that are already partially hydrophobic. They selectively adsorb on these surfaces, and increase their hydrophobicity. The most commonly-floated naturally-hydrophobic material is coal. Addition of collectors such as #2 fuel oil and kerosene significantly enhances the hydrophobicity of the coal particles without affecting the surfaces of the associated ash-forming minerals. This improves the recovery of the coal, and increases the selectivity between coal particles and mineral matter. Fuel oil and kerosene have the following advantages over specialized collectors for froth flotation: 1) they have low enough viscosity to disperse in the slurry and spread over the coal particles easily 2) they are very low-cost compared to other compounds which can be used as coal collectors. In addition to coal, it is also possible to float naturally-hydrophobic minerals such as

molybdenite, elemental sulfur, and talc with nonionic collectors. If another, more-expensive collector makes a surface partially hydrophobic, adding a nonpolar oil will often increase the hydrophobicity further at low cost. Straight hydrocarbons : Straight hydrocarbons such as fuel oil, diesel, kerosene are also used extensively as auxillary or secondary collectors or even as primary collectors for coal and molybdenum ore. Anionic collectors for sulphide minerals The most common collectors for sulfide minerals are the sulfhydryl collectors, such as the various xanthates and dithiophosphates. Xanthates are most commonly used and are highly selective collectors for sulfide minerals, as they chemically react with the sulfide surfaces and do not have any affinity for the common non-sulfide gangue minerals. Other highly-selective collectors for use with sulfide minerals, such as dithiophosphates, have somewhat different adsorption behavior and so can be used for some separations that are difficult using xanthates.

2.2.

Major Collectors used in Indian mining industry

The collectors used in practice include the following * * * Sodium or potassium salt of alkyl xanthate (Ex. Ethyl, propyl, butyl, and amyl xanthates of sodium or potassium. Diethyl and dicresyl dithiophosphates. Oleic and palmitic acid and their sodium soaps.

The first two groups are used for the flotation of sulphide minerals, of oxidized minerals of copper and lead, and for native metals. The third group is used for the flotation of oxide minerals, oxygen-salt minerals, halogen minerals, and silicates.

Xanthate type collectors

The most widely used collectors for sulphide flotation are xanthates (sulphydryl type) which have polar bivalent sulphur. The reaction of xanthate with oxidation product of sulphide surface through ion exchange process is considered to be a major adsorption mechanism for flotation of sulphides. As the metal xanthates so formed scale off the mineral surface, the solubility of copper, lead, silver and mercury in xanthate is very low whereas solubility of iron and zinc xanthates is much higher. There fore sphalerite activation by copper sulphate is necessary. The alkali earth metal xanthates (Ca, Ba, Mg) are very soluble and they have no collector action on the minerals of such metals nor on oxides, silicates or alumino-silicates. This phenomenon permits extremely selective flotation of sulphides from gangue minerals. Xanthates are normally used in weakly alkaline pulps, since they decompose in acid media and at high pH hydroxyl ions can displace xanthate ions from the mineral surface. Sodium isopropyl xanthate is the universal collector used in the copper flotation plants. Sodium isopropyl xanthate is often replaced by amyl xanathate as it yields pyrite-rich copper concentrate suitable for flash smelting. The performance of combination of two or more xanthates/collectors has been found much superior to those of individual collectors and therefore copper flotation plants are employing combination of two to four collectors.

Other type of collectors

The other sulphur- bearing collectors are thiono carbonates, dithiophosphates (Aerofloat) and phthilocarbonitrides. The dithiophosphates are not as widely used as xanthates, but are still important reagents in sulphide flotation.

2.3.

Indian manufacturers

Star Oreochem/ Suyog Chemicals, Nagpur

Amruta Industries, Mumbai Rishi Chemical Works Pvt.Ltd., Kolkata

Indian production capacity all type of xanthate Indian production of all type of xanthate

2700 tonnes per annum 2400 tonnes per annum

Highlights of discussion with Star Orechem International Ltd / Suyog Chemicals, Nagpur Person contacted Mr. Rajesh Tel: 0712-2558323, 24 Email: suyogchemicals@gmail.com

The company produces Xanthate - Collectors The company supplies xanthate to copper, nickel, zinc and gold processing. Highlights of discussion with Amruta Industries 10, Shree Maya Apartments, 5, College Street, Off. Ash Lane, Dadar Mumbai, Maharashtra PIN: 400 028 Phone: +(91)-(22)-24224776 Fax: +(91)-(22)-24222248 Contact person: Mr. Menon , Tel: 022-27689020 Mr. Krishnan, Marketing 022-24314951

Produces only xanthate type chemicals for non ferrous minerals such as zinc and copper. Production quantity 1200 tonnes per annum

2.4.

Indian import / export level

Around 800 tonnes per annum Small quantity of the order of around 50 tonnes

Indian import of all type of xanthates Indian export of all type of xanthates

2.5.

Indian demand for xanthates

Indian demand for xanthate of all type in application sectors including mining, rubber, herbicide 3200 tonnes per annum Indian demand for xanthate of all type in mining sector in volume term Indian demand for xanthate of all type in mining sector in value term 2600 tonnes per annum Rs. 18 crores

Amongst the xanthate, sodium isopropyl xanthate is the major chemical used in mining sector Discussion with Mr. Venkataraman Mob: 09820232243 In iron ore, the content of iron is 58%, and that of impurity is 3 to 4%. Collectors are used to separate the impurity to float away and then separated. In the case of copper or zinc or lead ore, the content of required mineral part is around 10 to 20% and that of impurity holds around higher share. So collectors are used to adsorb the specific mineral parts rather than impurities. Frothers are just to enhance the flotation. Both collectors and frothers work based on hydrophilic / hydrophobic nature. Chemicals that promote hydrophobicity of a mineral are called that mineral's promoter or collector. Collectors get adsorbed on the mineral surfaces rendering the particles hydrophobic and floatable.

2.6.

All Indian demand for collectors

Rs. 25 crores

Indian demand for collectors of all type in mining sector in value term

III FROTHERS
3.1. General details
Frothers are liquids that produce the froth on which the flotation process depends. The froth resembles soap suds and provides the physical separation between the mineral(s) floated and the pulp containing the waste. The froth must be strong enough to support the weight of the mineral floated and yet not be tenacious. It should have the tendency to break down when removed from the flotation cell. The frother should not enhance the flotation of unwanted material. When the mineral surface has been rendered hydrophobic by the use of a collector, stability of bubble attachment especially at the pulp surface depends to a considerable extent on the efficiency of the frother Pine oil which contains aromatic alcohols has been widely used as frother in copper ore flotation plants. Cresol (cresylic acid: CH3C6 H4OH) is also widely used. Major other frothers used in India include the following MIBK MIBC Glycol blend Others including pine oil, 2-EH , Diacetone alcohol

Frothers are heteropolar surface-active compounds containing both hydrophilic head and hydrophobic tail part, capable of adsorbing in the air-water interface. The frother molecules are arranged at the airwater interface such that the hydrophilic head is oriented into the water phase and the hydrophobic chain in the air phase. When two bubbles come in contact with each other, the liquid film between them becomes thin and breaks, causing bubbles to coalesce. When coalescence of bubbles does not take place in fractions of seconds, the bubbles rise to the surface and aggregate, forming a foam or a froth. Hydrophilic head or polar groups oriented towards water phase and hydrophobic tail oriented towards air phase.

Difference between foam and froth

Foam: Imperfectly drained unstable liquid-bubble systems Froth: More stable, better drained bubble systems. a. A non-drained spherical bubble foam FOAM b. A partially drained foam showing distortion of bubbles c. After further drainage, the borders continue to thin d. A well drained froth FROTH

Characteristics of frothers
Hetero-polarity (Hydrophilic and hydrophobic) Preferentially adsorbs and orients at water / air interface Does not form stable bonds.

Branching Less branching -More selective for finer particle sizes. More branch for larger particles

Smaller bubble: Straightens out the moving path of the small particles Increase the probability of a mineral particle to collide with bubble More bubbles to attach to a particle, reducing the chance of detachment.

Molecular weight The performance of frother improves as its molecular weight increases until it reaches a max. With further increases in mol. wt, the performance becomes worse. Study was carried out with polyethylene glycol frothers on flotation of coal. PEG with mol. wt 400, 600, 1000 and 1500 were tested. Product PEG with mol. wt 1000 and more PEG with mol. wt 600 PEG with mol. wt 400 Flotation recovery Worse results Best results In between 600 and 1000

The best performance of PEG 600 was attributed to its greater surface activity over all other tested frothers Coal recovery Vs frothers

Diesel acts as collector

Coal recovery Vs flotation time

Selectivity Yield ash relationship

Classification of frothers based pH

Acidic Phenols Alkyl sulfonates Neutral Aliphatic alcohol Aromatic alcohol Alkoxy paraffin Synthetic / proprietary Basic Pyridine

Acidic frothers Acidic frothers perform well only in acidic pH. Used extensively till 1960, but the usage get diminished later because of environmental consideration. Ex. Aromatic alcohols including Cresols, phenol, naphthalin, xylenol. Basic frother These are used in flotation of base metals. These frothers are represented by pyridine and homologs. Ex. Pyridine oxychlorides and pyridine sulfotrioxide Neutral This is the most important group of frothers widely used in flotation of base metal ores, oxide minerals and industrial minerals. They are functional in both acidic and alkaline pulp. Aromatic alcohol Aliphatic alcohol Alkoxy Synthetic Cresol, xylenol MIBC, terpinol, 2-EH, Diacetone alochol TEB (Triethoxy butane) Poly glycol ethers, PPO, PEO,

Aliphatic alcohol frothers Aliphatic alcohol frothers are used as mixtures of different carbon lengths and as a mixture of hydrocarbon oils. The following mixtures are common in mineral flotation Mixture of C6-C9 alcohols - Highly selective. Mixtures of C4-C7 alcohols and hydrocarbon oil - livelier froth than MIBC. Can be used for copper molybdenum or molybdenum flotation, talc, graphite, sulfur and coal. Mixtures of C5-C8 carbon alcohols - Less persistent froth than the other alcohol mixtures

Cycli aliphatic alcohols and natural oils These frothers are basically mixtures of different cyclic alcohols, ethers, terpineols, and ketones, which can be produced as synthetic mixture or from the pine resins. Less sensitive Composition not always constant and consequently frothing properties are variable. Alkoxy propanes Selective and in many cases Improve rates of flotation of copper and zinc minerals

Polyglycol ethers There are several variations of polyglycol ethers produced by different manufacturers o Dow Chemical - Dowfroths (Polypropylene glycol methyl ether) Dowfroth 200, 250 and 1012. DF 250 is the mostly used one. Based on methanol and propylene glycol Cyanamid - Aerofroths : Based on PO and PG. Union Carbide - Ucon frothers : Based on PPG and PEG

o o

Salient features of frothers commercially used

3.2.

MIBK (Methyl isobutyl ketone)

Methyl isobutyl ketone is highly flammable. Its vapour can readily form an explosive mixture of air

Application
As a solvent for inks, coatings, and adhesives, As an extraction agent in the metallurgical / dewaxing/deoiling of petroleum products As solvent in pharmaceuticals As a raw material for rubber antiozonants.

Advantages of MIBK
Has quite low solubility in water, making it useful for liquid-liquid extraction Has a similar polarity to ethyl acetate, but greater stability towards aqueous acid and base. It can be used to extract gold, silver and other precious metals from cyanide solutions, such as those found at gold mines, to determine the levels of those dissolved metals.

Indian trade analysis

Import

Indian demand for MIBK

All India demand for MIBK including mining industry Indian demand for MIBK in mining industry in volume term Indian demand for MIBK in mining industry in value term Around 17000 tonnes 2200 tonnes Rs. 26 crores

3.3.

Glycol ethers

A wide range of synthetic frothers, based mainly on high molecular weight alcohols is now in use in many plants. Polypropylene glycol Polyglycol ethers Polypropylene glycol ethers Polyglycol glycerol ethers

Combination of two or more frothers is also reported to give better performance. Sample of import Product name Autofroth B5 B Side DPE 1604 Autofroth B5 A Side isocyanate Total Quantity in tonnes 4 4 8 Shipment value in USD 17170 17170 34340 Value per quantity in USD 4292.5 4292.5

Mumbai Sea

Indian supply
Presently there is no production of polyglycol based frother in India. The requirement is met by import either directly by the end user or by the distributing organizations. Vimal Agencies Ltd C-310, Shyamkamal, Agrawal Market, Vile Parle (East), Mumbai- 400057, India Tel :91-22-42551100 / 2612 7281 Fax : 91-22-2612 7382 Email ID : info@vimalagencies.net, coating@vimalagencies.et Vimal Agency imports glycol based frother of Dow Chemical and supplies in India

Indian demand for glycol ethers

Around 12000 tonnes of polypropylene glycol and glycol ethers are imported into India. Indian demand for glycol ethers in mining industry in volume term Indian demand for glycol in mining industry in value term 1800 tonnes Rs. 22 crores

3.4.

Others including MIBC (Methyl isobutyl carbinol), 2-EH, diacetone alcohol

MIBC
MIBC is a transparent colourless liquid with a sweet odour Use in mining industry In Natural Graphite beneficiation plant Finds use as a hydraulic fluid component, as a frothing agent in ore flotation Demand for MIBC in mining sector MIBC is primarily used in the production of lube oil additives and for antiwear and corrosion inhibitors. The second largest use of MIBC is as a flotation frother for treating copper ores, coal and tar sand mining. In mining frother applications, MIBC is used in the ppm range, with usual concentrations less than 1000 ppm and in many cases in the hundreds of ppm range (100 - 600 ppm). MIBC is not produced in India Around 700 tonnes of MIBC is imported. Indian demand for MIBC including mining industry Indian demand for MIBC in mining industry in volume term 700 tonnes 80 tonnes

2-EH and diacetone alcohol

2-ethylhexanol is a clear, colorless liquid with a mild odor. Because of its low volatility, 2ethylhexanol is not considered a Hazardous Air Pollutant (HAP) solvent by the United States Environmental Protection Agency (U.S. EPA). Both 2-EH and diacetone alsochol can be used as frothing solvent in extraction of metal in mining industry. Demand for 2-EH and diacetone alcohol in mining industry Small quantity

Indian demand for other miscellaneous frothers including pine oil

Indian demand for MIBC in mining industry in value term Rs. 12 crores

3.5.

All Indian demand for frothers in mining industry

Demand in value (Rs. In crores) 26 22 12 60

Frother MIBK Glycol ethers Others including MIBC, pine oil etc Total

IV OTHER MINING CHEMICALS

4.1. Depressants
The problem in froth flotation is that certain gangue minerals have hydrophobic surfaces and undesirably float contaminating the precious mineral concentrate. To negate the hydrophobic minerals tendencies to float, depressants are used. Depressants - physically adsorb on the surface of gangue minerals rendering the particles hydrophilic and non-floatable. The use of depressants allows for higher precious metal recovery and grades and can improve the economics of downstream processing (e.g. smelting costs)

Natural
Name of the depressant Quebracho & Lignin sulfonates Dextrin and starch CMC and guar gum Carbohydrate colloid (Aero 633) Usage Iron sulphide minerals Silicates and carbonaceous matter Magnesium silicates such as talc and pyroxene. Especially useful in the flotation of PGM and Ni ores Carbonaceous minerals in the flotation of base metal surfide ores

Synthetic
Name of the depressant Cyanide Ferrocyanide 0Sulfoxy species Usage Depression of Iron sulphide such as pyrite, pyrrhotite and arsenopyrite. Depression of zinc minerals during Pb flotation from Pb/Zn ores Depression of Cu and Fe sulphide in Cu/Mo separation Depression of Zn and Fe sulphides during flotation of Cu and Pb minerals, and depression of Pb minerals in selective flotation of copper minerals. Also used in conjunction with starch for the depression of Pb minerals during Cu/Pb separation Used alone or in combination with cyanide for depression of Zn minerals in the flotation of Pb/Zn, Cu/Zn and Cu/Pb/Zn ores Depression of Pb minerals during Cu/Pb separation Depression of Cu and Fe sulphides minerals in Cu/Mo separation Used for the depression of pyrrhotite in Cu/Ni ores Used in the separation of pyrite from arsenopyrite

Zn sulphate Dichromates Sodium sulphide and hydrosulphide DETA (Diethylene triamine) Permanganate and other oxidizing agents

4.2.

Activators

Certain minerals do not float well with the use of only a collector, but require prior activation. The most commonly used activators are: CuSO4 PbNO3 or Pb acetate NaHS NaCN Activation of Zn sulfide and Fe sulfide minerals such as pyrite and pyrrhotite when the latter contain values such as Au, Ni and PGM elements. Used for the activation of antimony sulfide minerals or such as stibnite. Commonly used prior to collector addition for the activation of Cu, Pb, and Zn minerals. Acts as a surface cleaning agent

4.3.

Dispersant / Grinding Aid

Many ores contain significant quantities of clay minerals and other "primary slimes". These can have an adverse effect on flotation metallurgy due to increasing pulp viscosity and slimes can form a coating on the surface of valuable minerals thereby inhibiting their flotation. Dispersants have the synergistic effects in grinding and dispersion of minerals. These products reduce the viscosity of clay and carbonate allowing for easier transport and processing. Where a reduction in particle size is needed, these acts as effective grinding aid. Ex. sodium silicate, soda ash, various polyphosphates, and low molecular weight polyacrylates and sodium polycarboxylate.

4.4.

Others including Modifying agent

A large number of other reagents usually referred to as "Modifying agents" are used in the flotation of sulfide ores. This is especially true in the case of complex ores, where two or more valuable minerals have to be separated from each other, e.g. Pb/Zn ores, Cu/Zn ores Cu/Pb/Zn ores, Cu/Mo ores, Cu/Ni ores etc.

pH Modifier
Most minerals exhibit an optimum pH range for a given collector. While some minerals can often be floated at the natural pH of the ores, in most cases the pH has to be adjusted for maximum recovery and selectivity. The most commonly used reagents for alkaline circuits are lime and soda ash. For acid circuit flotation, the most commonly used reagent is sulfuric acid. These three modifiers are generally the most cost effective. Other pH modifiers are also used occasionally when difficult separations are involved. pH modifiers : Cationic modifiers Anionic modifiers Organic modifers Classification Examples CaO, Na2CO3, NaOH, H2SO4, HCl Ba2+, Ca2+, Cu+, Pb2+, Zn2+, Ag+ SiO32-, PO43-, CN-, CO32-, S2Dextrin, starch, glue, CMC

Scale Inhibitor
Used to prevent calcium carbonate and calcium sulphate scale formation in process lines and equipment. Ex. Organo phosphonate, sulphonated copolymer, carboxylic terpolymer.

Agglomeration Aid
Binders are used for agglomeration to result fired pellets with more uniform size, increased porosity and improved reducibility. Ex. Bentonite, CMC

Rheology Modifier
Used in viscosity modification of tailing and thinning and dispersing of concentrated mineral slurries. Ex. Mineral oil, vegetable oil, oil esters, triglycerides

Dust Suppressor
Chemical binder/encrusting agent which has been specially formulated to provide an adherent film to the surface of a variety of minerals. Ex. Calcium chloride, magnesium chloride

4.5.

All India demand for other miscellaneous mining chemicals

Indian demand for other miscellaneous chemicals including scale inhibitor, dust depressant, pH modifier, activators etc Rs. 157 crores

Productwise demand

CONSOLIDATED ALL INDIA DEMAND FOR MINING CHEMICALS

Mining chemicals Market value in Rs. Crores 108 25 60 157 350

Flocculant Collectors Frothers Others including scale inhibitor, dust depressant, pH modifier, activators etc Total

Sectorwise demand pattern