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Nickel Ore ProcessingPrepared By- Mukesh Ranjan Behera

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CONTENTS- What is Nickel Nickel Physical and Chemical Properties Nickel History and Indian Nickel Market Formation of Nickel and its Types Processing Options relative to deposit type Laterite Ore Processing Sulfide Ore Processing Sukinda COB Analysis World Nickel Reserve and Production Nickel Uses

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WHAT IS NICKEL- Nickel is a strong, lustrous, silvery-white metal. Nickel is a chemical element with symbol Ni and Atomic number

28, atomic mass 58 amu (one nickel atom contains 28 protons, 28 electrons, and 30–36 neutrons depending on the isotope).

Isotopes: Five stable isotopes: Nickel-58, nickel-60, nickel-62, nickel-61, nickel-64.

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Nickel

Crystal of Nickel Face-centered cubic(FCC) structure. In fact, about 65 per cent of nickel is used to manufacture stainless steels, and 20 per cent in other steel and non-ferrous (including "super") alloys, often for highly specialized industrial, aerospace and military application.The most common ores of Nickel include Pentaldite, Pyrrhotite, Garnierite.

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NICKEL PHYSICAL PROPERTIES Color-Silvery White Metal Phase-Solid Melting Point-1455 degree centigrade Boiling Point-2730 degree centigrade Density- 7.81 g/cm3

Conductivity- Fairly good conductor of heat and electricity Malleability- It’s capable of being shaped or bent Luster-  Exhibits a shine or glow Hardness- Harder than iron Ferromagnetic- Nickel is easily magnetized Ductility- It can be beaten into extremely thin sheets. It is more resistant corrosion and oxidation.

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CHEMICAL PROPERTIES- Nickel is relatively un reactive, but react with strong acids. It does not react with alkalis.

Nickel History-The elements name come from German mythology, Nickel. In 1824 People thought that Nickel as a by product of cobalt. The introduction of nickel in steel production 1889 was increased because the demand of nickel increased.The main deposits in world are New Caledonia in Pacific,Sudbury Region in Canada, and Norilsk in Russia.In 1922 -1981 Canada is the largest Nickel Producer in World.In that time Canada use 99.9% of nickel, in coin producing.Nickel Occurs nature Principally as Oxides, Sulphides, and Silicates.Ores of Nickel are mined in Over 23 Countries and are smelted or refined in 25 Contries.

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Indian nickel market India does not have any history related to the metal nickel.In India nickel is vary law grade deposit and there is no processing plant. But as one of the fastest developing nations of the world, Indian demand for stainless steel and consequently nickel has been rising at a high rate.A rising demand and no production makes the country a total importer of nickel. The country imports around 50000 MT of nickel annually. This demand is expected to rise in future with the increase in the demand of stainless steel. The government has implied import duties in the import of the metal @ 15%.

Primary nickel is produced and used in the form of Ferro-nickel, nickel oxides and other chemicals, and as more or less pure nickel metal. Nickel is also readily recycled from many of its applications, and large tonnages of secondary or "scrap" nickel are used to supplement newly mined metal

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FORMATION OF NICKEL ORE- Pure nickel shows a significant chemical activity that can

be observed when nickel is powdered to maximize the exposed surface area on which reactions can occur.

Even then, nickel is reactive enough with oxygen that native nickel is rarely found on Earth's surface, being mostly confined to the interiors of larger nickel–iron.

On Earth, such native nickel is found in combination with iron, Earth's inner core.

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Primary nickel is produced from two very different Ores 1. Laterites 2. SulphidesLaterites ores are normally found in tropical climates where weathering, with time, extracts and deposits the ore in layers at varying depths below the surface. Laterites ores are excavated using large earth-moving equipment and are screened to remove boulders. Sulphides ores, found in conjunction with copper-bearing ores, are mined from underground..

Laterite Ore SulphidesOre

Characterestics of ore

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CLASSIFICATION OF NICKEL LATERITES ORE-A: Hydrous Mg-Ni silicate deposits (~35% of total resource) serpentines, Nepouite, Garnierite in saprolite High grade: global mean 1.53% Ni

B: Semecite silicate deposits (~15% of total resource) Clays content with saprolite and pedolith Low grade: global mean 1.21% Ni

C: Oxide deposits (~50% of total resource) Fe and minor Mn oxides, in form of saprolite and pedolith Low grade: global mean 1.06% Ni

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Laterites include limonites, saprolites and their mixtures (laterites contain max. 3-4% Ni). Limonite reserves are greater than saprolites.About 35-40% of world primary nickel production comes from laterites( but difficult processing, upgrading, high capital and operating cost compared to Sulphides).

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East Pinares, Cuba, Oxide Goro New Caldonia,Oxide CAWSE Western Australia ,Oxide

PLATEUA,New Caledonia,Silicate

Murrin Murrin Australia

Hydrous Silicate

Bulong Western Australia Semisite Silicate

CIRCE New Caldonia Hydrous Silicate

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Lateritic Ore Processing Nickel laterite is a complex ore containing several kinds of

metal elements. Nickel present as a minor constituents of other minerals, therefore, it is not easy to concentration.

Lateritic ores have a high percentage of free and combined moisture, which must be removed.

Drying removes free moisture; chemically bound water is removed by a reduction furnace, which also reduces the nickel oxide.

Ni atoms

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PROCESS ORE PRODUCT COMMENTSmelting1859, New Caledonia

Hydrous silicate Ferro-nickelmatte

Energy intensive; (smelting ~1600ºC)

Caron processReduction & ammoniacal leach1944, Cuba

Oxide; hydrous silicate

Ni oxide; Ni briquettes Energy intensive (reduction ~700ºC) low Co recovery

High pressure acid leach (HPAL)1959, Moa Bay, Cuba

Oxide; smectite Ni briquettes; electronickel; oxide, sulphide, carbonate

Less energy intensive. Plant & process problems

Atmospheric Leaching

Hydrous silicate Ni-Co hydroxide Atmospheric leach after HPAL

Acid heap leach H2SO4 Atmospheric leachH2SO4 HCl/MgCl2

Oxide; smectite

Oxide; smectitehydrous silicate

Ni-Co hydroxide Lower capital cost;Lower recoveries

PROCESSING OPTIONS FOR NICKEL LATERITES-

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PROCESSING OPTIONS RELATIVE TO DEPOSIT TYPE

Oxide(or smectite)

Transition

Hydrous silicate

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Hydrous silicate ore(“garnierite”; serpentine)Too costly for smectite

e.g., tumbling of boulder ore

1400 - >1600ºC; high energy cost

SiO2/MgO <2 or >2.5= ferronickel

SiO2/MgO 1.8-2.2= matte

~77% of total production in 2000 33% or less of new capacity NICKEL LATERITE PROCESSING

Smelting

FEED

P ROCEESS

Drying

Upgrading

Reduction roast

Smelting

Converting

P RODUCT

Fe-Ni or Ni matte90% recovery

Ni: >2.0%Co: 0.04%Fe: 20%MgO: 25%

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High grade oxide ore, some hydrous silicate; tolerates more Mg than HPAL. Too costly for smectite.

~700ºC; high energy cost

Complex pyrometallurgical - hydrometallurgical process; high energy cost with lower recoveries than smelting and PAL.

No new plants anticipated

NICKEL LATERITE PROCESSINGCaron process

FEED

P ROCEESS

Reduction roast

Grinding, drying

Leach ammonia cal CO3

Cobalt separationNi carbonate precipitation

P RODUCT

Ni:94% recovery

Ni: 1.8%Co: 0.1%Fe: 25-40%MgO: <12.0%

Co:90% recovery

Calcining

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Oxide or smectite ore, low Mg and Al to reduce acid consumption

Upgrade oxide by screening to remove barren silica

High capital costs, with new plants having numerous teething problems in plant and process.

Product options include sulphides: Murrin2, Halmahera hydroxide: Ravensthorpe, Vermelhocarbonate: Cawse

NICKEL LATERITE PROCESSING

High pressure acid leaching

FEED

P ROCEESS

Leach H2SO4

Ore preparation

Acid plant

S

Energy

Wash/neutralizeSX-EW or precipitate

P RODUCT

Ni:94% recovery

Ni: 1.3%Co: 0.13%MgO: <5.0%

Co:90% recovery

240-270ºC; lower energy cost Caron process

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NICKEL LATERITE PROCESSINGAtmospheric leaching

FEED

Oxide ore (but, potentially, any ore type, including low grade hydrous silicate)

P ROCEESS

Heat and leach H2SO4

Ore preparation

Acid plant or excess from HPAL

S

EnergyWash/neutralize

SX-EW or precipitate

P RODUCT

Ni (Co) hydroxide~80-90% recovery

Ravensthorpe, Gag Island: oxide, serpentine saprolite (hydrous silicate)Sechol: oxide, saprolite

Enhanced high pressure acid leaching (EPAL); 80-105ºC

Sechol/Jaguar tested HCl/MgCl2 leach at 80-105ºC. Process could also yield MgO and magnetite concentrate as products. Trial discontinued

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NICKEL LATERITE PROCESSINGHeap leaching

FEED

Potentially, any ore type, including low grade hydrous silicate and rejects

P ROCEESS

Heap, leach for 12-18 months

Ore preparation

Acid plant or excess from HPAL

S

EnergyWash/neutralize

P RODUCT

Ni (Co) hydroxide ~80% recovery

SX-EW or precipitate

Caldag, Nornico - oxide; Murrin Murrin - smectite

Crush; upgrade by screening to remove barren silica

Neutralize using low grade saprolite ore

Suitable for smaller deposits; low capex and opex

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PROCESSING OPTIONS FOR NICKEL LATERITES

HPAL Atmospheric leach

Heap leach

Capital expenditure $17-22 $13-16 $8-12

Operating expenditure $2.50 $2.50 $2.50

$US/lb Ni

Traditional processing (smelting, Caron) is generally very energy intensive. HPAL plants use less energy but require high capital expenditure and are yet to be fully optimized best suited to large deposits. Acid leaching at lower temperatures and ambient pressures offer lower capital expenditure (but lower recovery). Better mineralogical characterization is needed to optimize grade control, beneficiation and processing.

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FERRO NICKEL ORE-

A recent development in the extraction of nickel laterite ores is a particular grade of tropical deposits, typified by examples at Acoje in the Philippines.

This ore is so rich in limonite (generally grading 47% to 59% iron, 0.8 to 1.5% nickel and trace cobalt) that it is essentially similar to low-grade iron ore.

Fe –Ni Ores Processing-

1. Pyro-metallurgy(Rk-EF-75%)2. Hydro-metallurgy(HPAL-15%) 3. Combined(Caron Process, Rather Obsolete) 4. Nickel Smelting Technology

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Nickel Project Owner Country % Ni KT Ni Process

Cerro matoso BHP-B Colombia 2.3 41.6 RKEF

Codemin Anglo Brazil 2.1 9.1 RKEF

Doniambo SLN/Eramet New Caledonia 2 51.1 RKEF

Falcondo Falcon Bridge Dominican Rip 1.14 18.8 RKEF

Larymna Larco SA Greece 1.10 19 RKEF

Loma d NIquel Anglo Venezulea 1.6 10.9 RKEF

Pomala PT ANTAM Indonesia 1.58 17.6 RKEF

Kavadarci Cunico F.Y.R.O.M 2 15 RKEF

Sorowako Vale Inco Indonesia 2.10 72.4 RKEF

Murrin Murrin Mineral Resources Australia 1.43 30.5Moa Bay Cuba 1.5 31.5

Fe –Nickel Production in world-

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FE –NI PRODUCTION IN GREECE- Larco is the Fe-Ni producer in Europe. 13th Largest Nickel

production in world. Covers more than 6% of the annual demand in Europe. Ni production is 19000 tons per year(Avg Ni content Fe-Ni 20%).

Laterite ore Production in Greece(tonnes)-

2010 2011 2012 2013 Total Production

2200000 2600000 2300000 2200000 85000000

Mines Annual Production(tonnes)

Average Ni Content (%)

Evia Mine 1.2-1.5 million 1-1.03

Ag. Ioannis mine 700,00 1.05-1.1

Kastoria Mine 250,000-300,000 1.3

Servia Lignite mine 350,000 1.2

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KEY FACTS OF RESOURCES-

Sample Evia mine(55% w/w) Ag . Ioannis mine(30% w/w)

Kastoria mine(15% w/w)

SiO2 28.2 18.6 32.2

Al2O3 7 10.9 2.9

Fe2O3 47.5 45 24.8

Fe Total 33.2 31.4 7.2

Cr2O3 3.1 2.7 1.4

MnO 0.04 0.04 0.01

MgO 3.2 4 15.4

Ni 1.03 1.05 1.3

Co 0.05 0.06 0.06

S 0.4 0.45 0.45

Cao 3 6.6 1.45

LOI 5 7.5 12.5

Mineralogical and chemical composition of Larco Laterite Ores(% wt)

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Fe-Ni Production Process

Handling Of Raw Materials

Pre-heating and Pre Reduction in Rotary Kilns

Electric Furnace Reductive Smelting

Enrichment-Refining in OBM type Converters

Fe Ni SpecificationsChemical Element Content

Ni 17-25%Co 0.75-1.00%As 0.15% maxP 0.02% maxS 0.15% maxCu 0.10% maxC,Mn,Si,Cr Traces

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Flow Chart of FeNi Production in Larco

Oxygen Bottom Maxhuette-Oxgen bottom Blow Process

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Material and Energy supply (Disel,electricity,electrodes,coke,Pellet,etc)

Waste Management Utilization

Field Operations

•Ore Mining and Beneficiation

Plant Operations

•Feed Operation

Plant Operations

•Smelting and Refining

Rotary Kilns

EF Furnace OBM Converter

Raw Materials Stockpiles

PelletDust Collector

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Stage Input Unit

Value

Ore Mining and Mineral Beneficiation

Electricity

Disel

kWh/t ore Litre/t ore

4.8

2.4

Ore preparation Electricity

Cement

kWh/t ore

T/t Fe Ni

21.8

0.25

Smelting and Refining

Lignite

Coal

Carbon Electrodes Lime

Oxygen

Electricity

T/t Fe Ni

T/t Fe Ni

Kg/t Fe Ni

Kg/t Fe Ni

Litre/t Fe Ni

kWh/t Fe Ni

2.84

2.63

63

74

210

10286

Input Inventory Data-

Functional Unit: 1 t of FeNi product (20% Ni)

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THE EFFECT OF GANGUE MINERALOGY ON THE DENSITY SEPARATION OF LOW GRADE NICKEL ORE

Density separation is widely used to pre concentrate minerals and reject unwanted gangue. For base metal sulfide ores, dense medium separation(DMS) is used to separate the sulfide minerals, which are relatively dense.

After DMS it is treated in Flotation . Overall upgrade of Ni from 0.4 to 0.7% Ni in the flotation sample as a recovery of 87%.

The efficiency of DMS according to the characteristics of the ore .For low grade ores with complex mineralogy, the properties of the gangue minerals are important factor that determine the behavior of the ore during the separation.

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The sink-float analysis results on the head sample indicate that, at a density cut-point of 3.0, 48 mass % of the ore reported to the sinks and 52% to the floats(Figure-1) . For Pentaldite Ore

Figure 1 Washability curve

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The Ni grade was measured at 0.4% and the cumulative grade achieved at Pentalandite a cut-point SG of 3.0 is 0.74% at a recovery of 83%. This density cut-point was chosen for the DMS test work in order to maximise the waste rejection while obtaining a low Ni grade in the overflow(Figure-2) .

Figure 2 Cumulative grade and recovery curves calculated for pyrrhotite and pentlandite from the sink-float analysis

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In Nkomati mine where initial mining activity was centered on the Ore. More recently the mining has been focused on lower grades ores. Average Ni and Cu ores grade are 0.66 to 0.68% and 0.22 to 0.44% respectively.

The flow sheet of Nickel Production. A pentlandite grade of approximately 2% should be present in

the underflow, with a recovery of 83%. The pyrrhotite grade is estimated at 12%, with an 88% recovery.

Grinding 300 micron

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DMS TEST WORK AT A CUT POINT OF 3The nickel Grade and Recoveries, as well as mass distribution of the bulk sample calculated

Stream No Stream Name

Mass(%) Ni Grade(%)

Ni Recovery (%)

1 ROM 100 0.43 1002 -12mm+1mm 84 0.39 763 -1mm 16 0.62 244 DMC

Overflow44 0.13 13

5 DMC Underflow

50 0.67 63

6 Flotation feed

46 0.67 87

Mass,Grde,Recovery Information at different Point of the Flow Sheet-

Fraction Mass(%) Grade (%) Recovery( %)SSs Cc

Sinks 48 5.63 0.23 0.67 85 68 83Float 52 0.95 0.10 0.13 15 32 17Total Feed

100 3.20 0.16 0.39 100 100 100

S Cu Ni NiCuS

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Nickel Resources

Source Ni Fe Cu SiO2 Al2O3 MgO Others

Nickel FerrousSerpentine

MoreahAssam

0.51 7.86 ------ 33.84 ----- 33.14 --------

Do RanakpurRajasthan

0.26 5.75 38.45 1.83 37.18 16.19LOI

Nickel FerrousLaterite

BadampharOdisha

0.34 29.4 15.5 22.4 3.4 Cr2O30,27 V2O5

Do (Dense) SukindaOdisha

0.62 39.5 0.02 16.5 14 1.2 1.85Mn

Do(light) SukindaOdisha

1.41 47.04 6.8 12.36 1.1 2.9 MnO

CopperTailings

I.C.C.Ghatsila

0.073 9.33 0.17 59.7 13.94 ------- 1.45 S1.27 P2O5

Nickel Resources and Their Chemical Analysis in India-

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Sukinda Chromites Over Burden Analysis By NML-The average nickel concentration in the COB ore of Sukinda lies in the range of 0.4-0.7%. The existing deposit of COB ore in the Sukinda valley has been estimated to he around 140 million tonnes.

Process for Nickel Enrichment- COB ore of Sukinda valley is a high silica matrix. Present nickel enrichment process consists of primarily three stages.

Neutralisation

Stage I : Digestion with acid/ Combination of acids, HCI, HNO3 and H2SO4.Stage lI Neutralisation with alkali. Na2CO3 and NaOH.Stage III : Calcination at 900°C

Oxides of Ni,Co,Cr,Fe

Hydroxides of NiCo,Cr, and Fe

Leach liquor of Ni,Co,Cr, and FeRaw Nickel Ore

Ni-0.4-0.7%I

Digestion

II

III Calcination 900 degree centigrade

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Parameters Optimized Value

COB ore 500 mg

Fineness -44 mesh

Hcl Concentration 50ml 12N

HNO3 Concentration 50 ml 14 N

H2SO4 Concentration 100 ml 36 N

H20 500 ml

Digestion time 3 hr

Temperature 100 degree Centigrade

Optimized Parameter with reference to extraction of Nickel-

Final product :-The final product after the calcination was essentially a mixed oxide of Fe, Ni, Cr, Co and other trace elements like, Al, Mn,Zn, Na. Ca etc. Complete analysis of a typical final product is given in Table .

Element/Radical Content(%)

LOI 0.11

SiO2 0.13

Fe2O3 92.12

NiO 2.54

Cr2O3 1.75

CoO 0.14

Al2O3 1.21

MnO 1.42

ZnO 0.38

Na2O 0.67X-ray diffraction of the final product indicated that it consisted of two phases Fe2O3and nickel ferrite,NiFe2O4. It could be possible that the final product consisted of a magnetic and a non magnetic phase

Complete Analysis Of Final Product-

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Fe2O3 constituted the nonmagnetic fraction while NiFe2O4 made for the magnetic fraction. This opened up the possibility of further nickel enrichment by separating the magnetic and non-magnetic fraction through magnetic separation. It was calculated from chemical analysis assuming all the nickel were converted into NiFe2O4 the percentage is 9.37% . The process is not energy intensive and generates valuable by-products that have ready market in the country. The process is environment friendly and does not waste and effluent disposal problems.

Sukinda Chromite Ore Mines

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30

15

117

7

6

5

54

4 2 2 2

World Nickel ReserveAusraliaNew CaledoniaBrazilRusiaCubaOtherIndonesiaSouth AfricaCanadaChinaMadagascarPhilipinesDominan Republic

422007 2008 2009 2010 2011 20120

100

200

300

400

500

600

700

800

Africa

Asia

Oceania

America

Europe

Global Nickel Production in MT

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34

20

13

7

7

5

55

1.2

Nickel Uses in Different SectorTransport/Defence

Fabricated Metal

Electric Equipment

Petroleum Industry

Chemical Industry

Construction

household Ap-pliances

Industrial Ma-chinery

Other

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653.90.8

7.3

8.3 5.3

2.72.9

0.5 0.92.4

Estimate Use of Nickel 2014Stainless steel

Super alloys

Coinage

Other nickel alloy

Plating

Other steel alloys

Foundry

Batteries

Catalyst

Other Chemical

Other

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Nickel Uses

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