By:

Behzad Vaziri Hassasvazirihassas@itu.edu.trbehzadvaziri@hotmail.comMineral Processing Eng. B.Sc. Student

Flotation and FlocculationProf. Dr . Mehmet Sabri ÇELIKAssoc. Prof. Dr. Gülay BULUT

COPPER FLOTATIONand related plants in Turkey

Spring 2011-2012

Approximately:35 Minutes

Symbol of Element : Cu Atomic Number : 29 Atomic Mass : 63.546 amu Melting Point : 1083.0 °C - 1356.15 °KBoiling Point : 2567.0 °C - 2840.15 °KNumber of Protons/Electrons : 29Number of Neutrons : 35Crystal Structure : Cubic Density @ 293 K : 8.96 g/cm3 

Color : red / orange / brown

Conductivity : %99.95

Electron Configuration Exception

1s2 2s2 2p6 3s2 3p6 3d10 4s1

COPPER (Cu29)...

Retrieved from:www.periodic-table.org.uk

WORLD DEPOSITS

Retrieved from: www.mapsofworld.com

World most useful metals:Iron Aluminum ⇒ ⇒ Copper

Deposit: 340 million Tons

Chile %19 USA %18

Russia %7 Zambia %7

Congo %6 Canada %5

Others %38

United States Geological Survey (USGS):All the copper deposits in the world is estimated to be about 6.1

billion Tons

COPPER İN THE WORLD

ایران در مس کانسار

- قربانی- خوئیتاجبخش1999

TURKEY DEPOSITS

Probable + Proved:

1.462.580 tonsRetrieved from:MTA Genel Müdürlüğühttp://www.mta.gov.tr

Location Reserve (t)       % Cu Cu (t)

1. Rize / Çayeli /  Madenköy 16.511.040 5,5 908.107

2. Trabzon / Maçka / Güzelyayla 154.700.000 0,3464.100

3. Siirt / Şirvan / Madenköy 14.515.000 3,0 435.450

4. Erzurum / İspir / Ulutaş 73.600.000 0,31 228.160

5. Kırklareli / - / Dereköy 65.209.000  0,31 208.668

6. Artvin / Murgul / Damar 15.238.000 1,18 179.808

7. Kastamonu / Küre / Aşıköy 1.229.208  1,56175.176

8. Artvin / Murgul / Çakmakkaya 16.618.000  0,99164.518

9. Artvin / Kafkasör / Cerrattepe 1.200.000 10,0120.000

10. Artvin / Kafkasör / Cerrattepe 3.800.000 2,179.800

11. Giresun / Espiye / Lahanos 1.529.000 4,2364.676

12. Kırklareli/Demirköy/İkiztepe 12.700.000  0,3949.539

RESERVES’ LOCATION IN TURKEY

BAKIR RAPORU TMMOB METALURJİ MÜHENDİSLERİ ODASI - 2003

A Agardite Aikinite Ajoite Aktashite Algodonite Anthonyite Antlerite Apachite Arcubisite Arthurite Atacamite Athabascaite Aubertite Aurichalcite Azurite

COPPER MINERALS

B Bayldonite Berryite Blossite Boleite Bornite Botallackite Bournonite Briartite Brochantite Bukovite

C Calciovolborthite Caledonite Calumetite Carrollite Cesbronite Chalcanthite Chalcocite Chalcophyllite Chalcopyrite Chrysocolla Clinoclase Connellite Cornubite Covellite Crookesite Cubanite Cupalite Cuprite Cyanotrichite

D Devilline Dicopper chloride

trihydroxide Digenite Dioptase Djurleite Domeykite Dragon Bone Stone Duftite

E Enargite Euchroite

F Fornacite Frankhawthorneite Freibergite Fukuchilite

G Gabrielite Geerite Germanite Gilalite

H User:Hankster713

/Sandbox Herbertsmithite

I Icosahedrite

J Jalpaite Johannite

Retrieved from: www.mindat.org

K Kesterite Keyite Khatyrkite Kinoite Kobellite Kröhnkite

L Langite Lavendulan Leightonite Libethenite Linarite Liroconite Lyonsite

COPPER MINERALS M Malachite Marthozite Melaconite Meneghinite Metatorbernite Metazeunerite Mohite Mooihoekite M cont. Moolooite Mottramite Murdochite

N Nekrasovite Niedermayrite

O Olivenite

P Papagoite Pearceite Penroseite Plancheite Polybasite Pseudomalachite

R Rickardite Rosasite

S Sabatierite Salzburgite Sampleite Schmiederite Seligmannite Shattuckite Skaergaardite Stannite Stromeyerite

T Talnakhite Tennantite Tenorite Tetrahedrite Torbernite Tsumebite Turquoise Tyrolite Tyrrellite

U Ulrichite Umangite Utahite

V Vauquelinite Volborthite

W Weissite

X Xocomecatlite

Z Zeunerite Zhanghengite Ziesite Zincmelanterite

131 minerals!!!

Retrieved from: Mindat.org

MAIN COPPER MINERALSMineral Formulation %Cu by Weight Density

Bornite Cu5FeS4 63.3 5.1

Chalcopyrite CuFeS2 34.5 4.5

1. Native copper Cu 100 8.9

2. Cuprite Cu2O 88.8 6.1

3. Chalcocite Cu2S 79.8 5.9

4. Tenorite CuO 79.8 6.5

5. Covellite CuS 66.4 4.7

6. Atacamite CuCl2 .3Cu(OH)2 59.4 3.8

7. Malachite CuCO3 .Cu(OH)2 57.3 4.0

8. Tennantite Cu8As2S7 57.0 4.7

9. Brochantite Cu4SO4(OH)6 56.2 4.0

10. Azurite 2CuCO3 . Cu(OH)2 55.1 3.8

11. Antlerite Cu3SO4(OH)4 54.0 3.9

12. Enargite Cu3AsS4 48.3 4.4

13. Luzonite Cu3(As,Sb)S4 48.1 4.3

14. Chrysocolla CuSiO3.2H2O 36.0 2.2

Bornite

Chalcopyrite

EXTRACTION OF COPPER

80

20

concentration / flotation / Smelting / refiningleaching / solvent extraction / electrowinning of ‘oxide’ and chalcocite ores

G.W. DavenportExtractive Metallurgy of Copper - 2000

The ease of floatability of minerals decreases as the ionic character of the chemical bonding increases. The gradation between covalent and ionic bonding

is simply presented by the illustration below

Fuerstenau (1962 )

% ionic Character

Covalentbonding

Ionicbonding

Flotability

Sample from Ergani contains◦ 2.03% copper,◦ 0.15% cobalt◦ 3.73% sulfur

Recovery of copper and cobalt from this ore with hydrometallurgical treatment is not economical

The flotation of samples is done through a sulphurized medium containing sodium hydrosulphide as a sulphidising agent

pH 8.7

New Application for Flotation of Oxidized Copper Ore

Firat AydinRecep ZiyadanogullariA New App. For Flotation Of Oxidized Copper Ore - 2005

Generalized flowsheet for producing ~%30Cu Concentrate from Cu-Fe-S and Cu-S Ores

G.W. DavenportExtractive Metallurgy of Copper - 2000

Size

Reductio

n~

%0,5Cu

Rougher

~%19Cu

Cleaner

and

Scaveng

er

~%30Cu

a) too large a grind size (+100µm) causes Cu minerals to remain combined with or hidden in non-Cu minerals - preventing their flotation

b) too fine a grind size (-10µm) causes ‘slime’ formation. This slime coats the Cu minerals and prevents some of them from being floated.

Required size for Flotation: ~50-80µm

G.W. DavenportExtractive Metallurgy of Copper - 2000

EFFECT OF ROUGHNESS ON FLOTATİON

T.G.Vizcarra et alinfluence of particle shape properties and associated surface chemistry on the flotation kinetics of chalcopyrite - 2011

Angularity

Selective Sulphide Flotation Floting a specific mineral

Differential Sulphide Flotation Floting minerals step by step

Bulk Flotation Floting all minerals but one (reverse flotation)

Sulfide Minerals Flotation Methods

COLLECTORS...

S. Komar KawatraFlotation fundamentals

Xanthate Adsorption Mechanism

G.W. DavenportExtractive Metallurgy of Copper - 2000

Sulfure groups on the polar head of collectores attaches to the Sulfide

Minerals while ignores oxides (Gang Minerals)

AGGRESSİON OF COLLECTORS

Gaudin et. al. Flotation of galena with alkyl xanthate 1928

Carbon Chain:Amyl => 5Buthyl => 4Propyl => 3Ethyl => 2Methyl => 1

Depressant effect of H+/OH- ions

G.W. DavenportExtractive Metallurgy of Copper - 2000

((Sulphide/Oxide)) flotation

Lee, K. et al. (2008)Flotation of mixed copperoxide and sulphide minerals

Doses: (PAX = 14 g/t) , (AM28 = 420 g/t) , (MIBC = 48 g/t)

Flotation of the blended Sulphide/Oxide Cu ores at the same timePotassium Amyl Xanthate (PAX) was used to float the sulphide copperPotassium n-octyl hydroxamate (AM28) to float oxide copperMethyl Iso Butyl Carbinol (MIBC) as a frother

pH of the pulp for flotation was the natural pH of the ground ore, at approximately pH 8.1

PAX

Arsenic (As) bearing minerals: Enargite (Cu3AsS4)

Tennantite (Cu12As4S13) In association minerals

Chalcocite (Cu2S) Covellite (CuS) Chalcopyrite (CuFeS2)

Separation Method Addition of sodium thiosulphate in alkaline conditions

Order of th Oxidation of Copper Minerals:Chalcocite > Tennantite > Enargite > Bornite > Covellite > Chalcopyrite.

Arsenic-bearing minerals in copper ores

D.Fullston, et al.Zeta potential study of the oxidation of copper sulfide Minerals (1998)

Contact Angle of Both MineralsContact angle of ChalcopyriteContact angle of Tennartite

a) Fresh sample; after conditioning usingb) Diethyl dithiophosphate (AEROFLOAT 208) Collectorc) Sodium thiosulphate Na2S2O3. 5H2O Surface Modifierd) Both chemicals, at certain concentration

(100kg/ton of Na2S2O3; 6×10−5M of DTP)H.T.B.M.Petrus et al. Effects of sodium thiosulphate on chalcopyrite and tennantite - (2011)

Diethyl dithiophosphate (DTP) was the preferred

collector rather than xanthate due to its better selectivity

for pyrite rejection in complex sulfide ores

Oxidation of Surface increase the recovery of Chalcocite yet not affect Chalcopyrite recovery in presence of clays.

The zeta potential of many gangue minerals in flotation including quartz, dolomite and clay minerals are negative in alkaline solutions.

Surface Oxidation of Copper Sulfide Minerals and Being Coated With Slimes

Y.J.Peng, Sh.ZhaoThe effect of surface oxidation ofcopper sulfide minerals on clay slime (2011)

Fresh Surface Oxidized Surface

A. Kastamonu Küre (Aşiköy-Bakibaba) Eti Bakır

B. Elazığ Ergani Bakır

C. Artvin Murgul (Çakmakkaya)

D. Rize Çayeli (Madenköy) Bakır

E. Giresun Espiye (Lahanos) Bakır

SOME PLANTS FROM TURKEY

KASTAMONU KÜRE(AŞİKÖY-BAKİBABA) ETİ BAKIR

Collector:Z-200 - xanthateIsopropyl ethyl thionocarbamate

Remember...

ELAZIĞ ERGANİBAKIR İŞLETMESİ

Copper Ore

Crashing

Rod Mill

Ball Mill

Hydrocyclone

Thickener

CollectiveFlotation

ScavengerFloatation

Tailing

Hydrocyclone

Ball Mill

CopperFlotation

PyriteConcentrate

Cleaning 1

Cleaning 2

CopperConcentrate

ARTVİN MURGUL(ÇAKMAKKAYA )İŞLETMESİ

Copper Ore

Comminution

Thichener

CollectiveFlotation

Comminution

CopperFlotation

Cleaning 1

Cleaning 2

CopperConcentrate

PyriteConcentrate

ScavengerFloatation

Tailing

Plant capacity: 1 Million Tons / Year

Raw Ore Purity: %4 Cu %6 Zn

Products: 150,000 tons %25 Cu 70,000 tons %50 Zn

RİZE ÇAYELİ(MADENKÖY) BAKIR İŞLETMELERİ

T.C. ÇAYELİ KAYMAKAMLIĞIwww.cayeli.gov.tr

Erkan YILDIRIM ÇAYELI BAKIR ISLETMESI VE EKONOMIK

COGRAFYA BAKIMINDAN ÖNEMI - 2006

Collector: AEROPHINE 3418ApH regulator: CaCO3

RİZE ÇAYELİ(MADENKÖY) BAKIR İŞLETMELERİ

Flotation of by product (Zn) in Rize Çayeli

Activator: CuSO4

pH: 11.8 – 12

Collector: Sodium IsoPropyl Xanthate (SIPX)Erkan YILDIRIM ÇAYELI BAKIR ISLETMESI VE EKONOMIK

COGRAFYA BAKIMINDAN ÖNEMI - 2006

Tenor : % 3.5 Cu, % 2.38 Zn,

Rezerv:◦ 2.408.380 tons proved Cu reserves◦ 2.312.000 tons proved Zn reserves

Produced copper concentrate is sold overseas

GİRESUN ESPİYE(LAHANOS) BAKIR İŞLETMELERİ

Demir Export A.Şwww.demirexport.com

INNOVATİONS...

Current practice uses slurry pHs in excess of 10, achieved by adding burnt lime (CaO)

Lime production is an energy-intensive process that releases large quantities of carbon dioxide into the atmosphere

Lime produces scaling in piping and equipment, requiring the use of descaling reagents.

Lime flocculates fine material and may occlude fine copper-sulfide particles.

Lime increases the viscosity of the mineral slurry and tends to hinder aeration, slowing flotation kinetics.

LOWER-PH COPPER FLOTATİON REAGENT

www.oit.doe.gov/inventionsU.S. DEPARTMENT OF ENERGY

MİCRO BUBBLES İN FLOTATİON

MİCRO BUBBLES İN FLOTATİON

MİCRO BUBBLES İN FLOTATİON

[1] Davenport, W.G. (2002), Extractive Metallurgy of Copper – fourth edition

[2] Ziyadanogullari R., Aydin F., (2005), A New Application For Flotation of Oxidized Copper Ore, Journal of Minerals & Materials Characterization & Engineering

[3] H.T.B.M Petrus et al, (2011), Effects of Sodium Thiosulphate on Chalcopyrite and Tennantite: an Insight For Alternative Separation Technique, Elsevier Ltd

[4] TMMOB Metalurji Mühendisleri Odası (2003), - Bakır Raporu

[5] Peng Y., Zhao Sh., (2011), The effect of surface oxidation of copper sulfide minerals on clay slime coating in flotation, Elsevier Ltd

[6] Kawatra S.K. , Flotation Fundamentals

[7] Lee K. et al, (2008), Flotation of mixed copper oxide and sulphide minerals with xanthate and hydroxamate collectors, Elsevier Ltd

[8] DEVELOPMENT OF A LOWER-PH COPPER FLOTATION REAGENT SYSTEM, (2001), Office of Industrial Technologies Energy Efficiency and Renewable Energy, U.S. Department of Energy Washington, DC

[9] Yıldırım E., (2006), ÇAYELI BAKIR ISLETMESI VE EKONOMIK COGRAFYA BAKIMINDAN ÖNEMI, University of ATATÜRK

[10] Vizcarra T.G. et al, (2011), The influence of particle shape properties and associated surface chemistry on the flotation kinetics of chalcopyrite, Elsevier Ltd

[11] Fullston D. et al, (1999), Zeta potential study of the oxidation of copper sulfide minerals, Elsevier Science B.V.

REFERENCES...