Interactions in multi-component mineral systems

Interactions in

Multi-Component Mineral Systems

Component Mineral Systems

Oleg N Antzutkin (coordinator)

Oleg N. Antzutkin (coordinator)

,

Hanumantha Rao

_{, Fatai Ikumapaiy}

_,

Björn Johansson

_j

_{, Andreas Berggren}

_gg

_{, Allan Holmgren}

_g

_,

Anna-Carin Larsson

_{, Sven Öberg}

_,

Jonas Hedlund

_{, Johanne Mouzon}

_{, Iftekhar Uddin Bhuiyan}

_,

S ij F

Seija Forsmo

1_{Division of Chemical Engineering,Division of Chemical Engineering, Division of Mineral Processing} 2_{Division of Mineral Processing}

and Metallurgy, Department of Chemical Engineering and Geosciences; 3_{Department of Mathematics, Luleå University of}

Technology; 4_{New Boliden AB;} 5_LKAB

Technology; New Boliden AB; LKAB.

Agricola Research Center - Multicomponent Mineral Systems ARC-MMS (2008 - 2012)

Bergforskdagarna, 4-5 May 2010, Luleå 7.3 Mkr 2.8 Mkr (20.7 %) 2.5 Mkr (18.5 %) 0.920 Mkr (6.8 %) Total: 13.52 Mkr

Interactions in Multi-Component Mineral Systems

Justification: Understanding on these interactions is important for optimizing processes and quality of products Knowledge of surface speciation and chemistry of interfaces is

quality of products. Knowledge of surface speciation and chemistry of interfaces is essential. MODELS FOR SPECIATION Ores: ZnS, PbS, SPECIATION OF/ON SURFACES ARE CuFeS₂, FeS₂, gang minerals ARE NEEDED! FROTH FLOTATION (for separation AGGLOMERATION -magnetite ( p of minerals) Reagents: collectors, -olivine -dolomite -bentonite frothers, depressants Recycled process (binder) recycled process t ith C 2+ y p water with Ca2+_, SO_x2-_{, reagents, etc} water with Ca2+_, Na₂SiO₃, flotation reagent (ATRAC)

Lars Gunneriusson Allan Holmgren F t i Ik i Hanumantha Rao Andreas Berggren j h

ARC-MMS-1

Effects of ions in

the process water

Fatai Ikumapayi Björn Johansson

(

)

STRUCTURE

the process water

on flotation

ARC-MMS-2

(

)

ARC-MMS-2

Structure of

collectors on MeS

Anna-Carin Oleg Antzutkin

Larsson

(NMR, ab-initio quantum mechanical

calculations)

Sven Öberg Lena Svendsen

Larsson

ARC-MMS-3

3D-distrib. in iron

oxide pellets

oxide pellets

(

)

)

Objective 1: To provide remedies t l ti l Lars Gunneriusson Allan Holmgren F t i Ik i Hanumantha Rao Andreas Berggren j h to selectively regulate surface properties of sulphides, which Fatai Ikumapayi Björn Johansson

(

)

(

)

Anna Carin Larsson

Oleg Antzutkin

collectors in improving selectivity and recovery of the

Sven Öberg Lena Svendsen

Objective 3:

To supply a new type

f f

recovery of the valuable sulphide

minerals

of 3-D data for water, air bubbles, flotation reagents and particles

in wet iron ore pellets

Jonas Hedlund

Seija Forsmo

in wet iron ore pellets. To create remedies for controlling of air-bubble

inclusions in iron oxide ll t hi h ff t

Johanne Mouzon Jonas Hedlund Iftekhar Uddin Bhuniyan

pellets, which affect their mechanical

•

ARC-MMS SUBPROJECT 1

Flotation chemistry of complex sulphide

ores-Flotation chemistry of complex sulphide ores

Recycling of process water

Ikumapayi Fatai Kolawole (Ph.D student) Prof. Kota Hanumantha Rao (coordinator)

The effects of major components of calcium (Ca

_j

_p

₍

_{) and}

₎

sulphate (SO

_{) ions in process water on sulphide mineral}

flotation have been investigated through:

1. Hallimond flotation of single pure sulphide minerals using

tapwater and water containing SO

_{and Ca}

tapwater and water containing SO

and Ca

2. Bench scale flotation of complex sulphide ores using

tapwater and process water and with tapwater in the

tapwater and process water and with tapwater in the

presence of Ca

_{and SO}

4

2-3 Zeta-potential measurements

3. Zeta potential measurements

Influence of Ca

and SO

ions in solution

on recovery of PbS, ZnS and CuFeS

Influence of Ca

and SO

ions in solution

on recovery of PbS, ZnS and CuFeS

Effect of sulphate and calcium ions on sulphide mineral flotation

P Risks of undesired activation of FeS₂ at 70 80 Process water: [SO₄2-_{] ≈ 60 mg/L} [Ca2+_{] ≈ 130 mg/L} 2 elevated [SO₄2-_], which may accumulate in the 50 60 70 % PbS accumulate in the process water with

time! 30 40 50 R ec o v er y % PbS ZnS FeS2 CuFeS2 10 20 30 R [Ca2+_{] = 128 mg/L} 0 0 200 400 600 800 1000 1200 1400 1600 1800 l h t t ti i l ti /l

F. Ikumapayi, B. Johansson, H. Rao, Recycling of Process Water: Effect of calcium and sulphate ions in sulphide flotation. Conference, Mineral Engineering, Luleå, 2-3 February 2010 & POSTER

Zeta-potential measurements

Zeta-potential measurements

The variation of zeta-potential in the

Effect of Ca2+ and fixed SO42- concs. on zeta potential of

sulphide minerals

Effect of SO₄2- _{and fixed Ca}2+ _c 20.00 Process water: presence of Ca2+ _and SO₄2- _{at different} concentration 20 00 30.00 10.00 [Ca2+_{] ≈ 130 mg/L} [SO₄2-_{] ≈ 60 mg/L}

suggests their strong influence on the mineral-collector i t ti ! 10.00 20.00 V FeS2 0.00 0 500 1000 m V interaction! 10 00 0.00 0 200 400 600 800 p ot ent ia l m V CuFeS2 PbS FeS2+700mg/lSO4 -10.00 a pot ent ia l i n m Future work: To -20.00 -10.00 Ze ta p _{CuFeS2+700mg/lSO4} PbS+700mg/lSO4 -20.00 Ze ta Future work: To study speciation at mineral surfaces i ATR FTIR 40 00 -30.00 40 00 -30.00 using ATR-FTIR Spectroscopy and Potentiometric -40.00 Ca2+ _{concentration mg/l} -40.00 SO₄2- _concentrat

F. Ikumapayi, H. Rao, UNPUBLISHED RESULTS

•

ARC-MMS SUBPROJECT 2

Molecular scale approach towards behaviour

Molecular scale approach towards behaviour

of collectors on sulphide surfaces

Dr Anna-Carin Larsson (coordinator)( ) Prof. Sven Öberg

What happens to a collector when it adsorbs to a

What happens to a collector when it adsorbs to a

mineral surface?

13

_{C CP/MAS NMR combined with}

Quantum Mechanical DFT

Q

calculations can provide an

answer on a molecular level

Different carbons give signals in different positions

depending on the electronic environment

( h

i l hif )

(chemical shifts)

Potassium iso-propylxanthate Potassium iso propylxanthate Shape of spinning sidebands give sidebands give additional information which can be used to can be used to identify different species on a i l f mineral surface Spinning sidebands = “s” s δ_iso= (δ_xx+ δ_yy + δ_zz)/3 δ_aniso= δ_zz-δ_iso η = (δ - δ ) / δ _i s s s s s _s s s _s η (δ_yy δ_xx) / δ_aniso Ω= |δ_zz-δ_xx|

Data for relevant xanthate species and products of their decomposition, which can form in a flotation

pulp or on a mineral surface pulp or on a mineral surface

A few examples of data for the most interesting carbon -CS₂ K iso-propylxanthate exp DFT δ_iso 231.6 231.6 Dixanthogen exp DFT δ_i 206.8 205.3 δ_aniso 154.4±4.6 164.3 η 0.60±0.05 0 60 δ_iso 206.8 205.3 δ_aniso 140.6±4.2 161.8 η 0.15±0.15 0 06 0.60 Ω 278.2±8.2 295.7Pb iso-propylxanthate_{exp DFT} δ_iso 226.4 224.7 0.06 Ω 222±12 237.4 iso δ_aniso 142.8±4.1 154.4 η 0.73±0.04 0 76

There is a good agreement between experimental and calculated data 0.76

Ω 266.0±7.0 290.1

Substitution K → Pb/Cu/Zn decreases δ_iso

It is possible to distinguish different

f i i 13_{C CP/MAS NMR!}

Xanthate adsorption/decomposition on PbS

(Larsson, Öberg, Lindberg, Sun, unpublished)

Decomposition products CS₂-carbon 13_{C-enriched to provide stronger NMR signals}

3 mM Heptylxanthate (HX)p y ( ) pH 8p

3 A l h (A ) 8 3 mM Amylxanthate (AX) pH 8

3 mM Ethylxanthate (EX) pH 7.5

+ S

Surface adsorbed xanthate

O₂ +

OH-₊

Eventually, the alkyl chain decomposes into hydrophilic PbCO₃ through intermediate steps Surface adsorbed xanthate

stays more stable the longer the alkyl chain is

ARC-MMS SUBPROJECT 3

ARC-MMS SUBPROJECT 3

Iftekhar Uddin Bhuiyan (PhD student)

3D Data for Iron Ore Pellets

3D Data for Iron Ore Pellets

Dr Johanne Mouzon

Prof. Jonas Hedlund (coordinator)

LKAB’ ll t l t f

LKAB’s green pellets are complex arrangements of: • iron ore particles with a broad size distribution

• a binder (e g bentonite)a binder (e.g. bentonite) • additives (e.g. olivine) • water

• porosity

It is this complex arrangement and interactions

b diff h d i h

between different components that determine the wet and dry strengths of the pellets and

subsequently the final porosity for oxidization and reaction in blast furnaces ⇒ 3D data are valuable!

Extreme High Resolution Scanning electron microscope (XHR-SEM)

Cryogenic-SEM Images of Green

Iron Ore Pellets (with and without

Cryogenic-SEM Images of Green

Iron Ore Pellets (with and without

Iron Ore Pellets (with and without

flotation reagent ATRAC)

Iron Ore Pellets (with and without

flotation reagent ATRAC)

AFRA R f

AFRA Reference

With ATRAC

With ATRAC

_{Without ATRAC}

Image analysis

Spherical Porosity Distribution

Image analysis

Spherical Porosity Distribution

Spherical Porosity Distribution

Spherical Porosity Distribution

Image analysis

Spherical Porosity Distribution

Image analysis

Spherical Porosity Distribution

Spherical Porosity Distribution

Spherical Porosity Distribution

According to analysis f SEM i

of SEM images

flotation reagent (Atrac) entrapped more air

bubbles and the size fraction between10 and 150 µm is increased by µ y the flotation reagent.

Lars Gunneriusson Allan Holmgren F t i Ik i Hanumantha Rao Andreas Berggren j h

ARC-MMS-1

Effects of ions in

the process water

Fatai Ikumapayi Björn Johansson

(

)

the process water

on flotation

ARC MMS 2

(

)

ARC-MMS-2

Structure of

collectors on MeS

Anna Carin Larsson

Oleg Antzutkin

collectors on MeS

(NMR, ab-initio calculations)

Sven Öberg Lena Svendsen

NEW

_ARC-MMS-3

3D-distrib. in iron

oxide pellets

?

FORMAS

NEW

oxide pellets

(

Microscopy

)

Mkr) Novel titanium phosphate ion-exchangers for water

treatment”_{“in-kind” + 0.4 Mkr}

)

Johanne MouzonJonas Hedlund

ACKNOWLEDGEMENTS

ALL FELLOWS AND SPONSORS OF ARC MMS ALL FELLOWS AND SPONSORS OF ARC-MMS:

Prof. Hanumantha Rao; Fatai Ikumapaiy; Björn

Johansson; Andreas Berggren; Assoc. Prof. Allan

Holmgren; Assoc Prof Lars Gunneriusson; Dr

Holmgren; Assoc. Prof. Lars Gunneriusson; Dr

Anna-Carin Larsson; Prof. Sven Öberg; Prof. Jonas

Hedlund; Dr Johanne Mouzon; Dr Seija Forsmo;

SUSTAINABLE USE OF NATURAL RESOURCES

THINK ABOUT FUTURE GENERATIONS!

Bergforskdagarna, 4-5 May 2010, Luleå