Prof. Oleg N. Antzutkin (coordinator)



Agricola Research Center –

Multicomponent Mineral Systems

(ARC-MMS, “ARC-2”):

Partikelteknologi inom gruvindustriella

processer – växelverkan i mineralsystem

med flera komponenter

Prof. Oleg N. Antzutkin (coordinator)

Division of Chemical Engineering, Luleå University of Technology, Luleå, SE-97187, Sweden

Historisk backgrund:

ARC-”1”

(finansierer: SSF, STINT och gruvföretag, 2002-2007

Koordinator:

Prof. Willis Forsling

)



Sustainability is the issue of survival!

- China commissions two new coal-fired power stations each week!

- China overtakes US as leading CO₂(g) emitter: (In 2006 China emitted 6.2 billion tonnes of CO₂(g) compared to 5.8 billion tonnes emitted by the US)

- Atmospheric CO₂(g) increased from 284 ppm (in

1832) to 383 ppm (in 2007) => Climate change!

- Only the UK alone discards 27 million tonnes of waste a year => severe ecological issues!

OUR COMMON TASKS:

- ALTERNATIVE ENERGY SOURCES

- IMPROVING OF PROCESSES (to minimize CO₂(g) emission)

- NEW TECHNOLOGIES (to minimize CO₂(g) emission)



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

Total: 14.6 Mkr

VINNOVA: 7.3 Mkr (50%)

New Boliden AB: 2.8 Mkr (19.2 %) LKAB: 2.5 Mkr (17.1 %)

Lundin Mining: 2.0 Mkr (13.7 %)

ARC-MMS program coordinator:

Prof. O.N. Antzutkin,

The Division of Chemiical Eng.

New Boliden and Lundin Mining LKAB

Project I

Recycling of process water and influence of its chemistry on sulphide flotation and flotation selectivity

Objectives: To provide remedies

to selectively regulate surface properties of sulfides, which are affected by recycled process water

Research coordinator:

Prof. H. Rao, The Division of Mineral Processing

Project II

Molecular scale approach towards dithiophosphate (DTP) behaviour on sulphide surfaces Objectives: To utilize understanding of adsorption mechanisms of collectors in improving selectivity and recovery of the valuable sulfide minerals

Research coordinator:

Dr A.-C. Larsson,

The Division of Chemical Eng.

Project III

3D data for iron ore pellets

Objectives: To supply a new type

of 3-D data for water, air bubbles, flotation reagents and particles in wet iron ore pellets. Remedies for air-bubble inclusion

Research coordinator:

Prof. J. Hedlund, The Division of Chemical Engineering

The central goal of the program: Understanding of mineral-aqueous interface chemistry and affinities within multi-component mineral systems for development of new surface related mineral processing technologies



ARC-MMS-1

Ions in

the process

water

ARC-MMS-3

3D-distrib.

in iron oxide

pellets

ARC-MMS-2

DTP,xan on

MeS

Johanne Mouzon Jonas Hedlund Anna-Carin Larsson Lars Gunneriusson Allan Holmgren Fatai Ikumapayi

Iftekhar Uddin Bhuniyan

Hanumantha Rao Sven Öberg

New

Boliden

Björn Johansson

Lunding Mining

Mikael Schauman

Zinkgruvan AB

Bengt-Arne Bergström

LKAB

Seija Forsmo

New Boliden

VINNOVA

Oleg Antzutkin Lena Svendsen





ARC-MMS-1 Ions in the process water ARC-MMS-3 3D-distrib. in iron oxide pellets ARC-MMS-2 DTP,xan on MeS Tribochemistry B,Mo-DTP, DTC on steel and non-steel surfaces

HLRC

Iron oxides fluorapatite, waterglass, bentonite, dolomite, olivine, ssNMR/DNP on TiPSi adsorbents Nanoparticles with modified surfaces Collaboration:

Yinan University, China IWRI, Australia

Aarhus University, Denmark The University of Warwick, UK Kola Science center, Russia

Blagoveszhensk University, Russia Budapest University, Hungary Kazan’ University, Russia Umeå University

At LTU:

Mathematics Dept. Dept. Mechanical Eng. Div. of Physics

Dept. Of Health Sc.

Payman Roonasi Anuttam Patra Faiz Ullah Shah

Mattias Gran Allan Holmgren

Oleg Antzutkin

Marina Maslova, Daniela RusanovaOleg Antzutkin, Allan Holmgren

As adsorption on Fe_xO_y Ivan Carabante

S

urface

Mats Lindberg Allan Holmgren

C

hemistry

G

roup

Oleg Antzutkin VR09 appl. VINNOVA 2008-2011 VR09 appl. Kempe 2009



•

Project I

Recycling of process water and influence of its

chemistry on sulphide flotation and flotation

selectivity

Ikumapayi Fatai Kolawole (Ph.D student)

Prof. Kota Hanumantha Rao (coordinator)

Collector-mineral interaction in the presence of flotation effluent components: adsorption, zeta potential and spectroscopic studies.

Influence of Ca2+ _{and SO}

42- species: Bench scale flotation tests of complex

sulphide ore.

Influence of RSC species: Hallimond flotation response of pure minerals and bench scale flotation tests of complex sulphide ore.

Collective influence of process water components: Hallimond flotation response of pure minerals and bench scale flotation tests of complex sulphide ore.

Influence of pulp redox potential (controlled chemically and potentiometrically) on surface speciation and flotation selectivity.



Influence of Ca

2+

ions in solution

Effect of calcium ions on sulphide flotation

0 10 20 30 40 50 60 70 80 90 0 100 200 300 400 500 600 700

Concentration of calcium ions mg/l

R eco ver y % PbS ZnS FeS2 CuFeS2



Influence of SO

₄2-

_{ions in solution}

Effects of sulphate ions on sulfide mineral flotation

0 10 20 30 40 50 60 70 80 90 100 0 200 400 600 800 1000 1200 1400 1600 1800

Concentration of sulphate ions mg/l

R eco ver y % PbS ZnS FeS2 CuFeS2



Some Conclusions (Project I)

•

Activation of pyrite is obvious at high calcium ion and

low to high sulphate ions concentrations in solution.

•

Depression of galena and chalcopyrite at low to high

concentration of sulphate in solution

•

Depression of galena and chalcopyrite at averagely low

concentration of sulphate and calcium ions combined in

solution.

•

Depression of sphalerite at low to high concentration of

sulphate and calcium ions combined in solution.



Flotation reagents behavior on

sulphide surfaces

Molecular scale approach towards DTP

behaviour on sulphide surfaces

Sub project II ARC-MMS

Dr Anna-Carin Larsson (project coordinator)

Prof. Sven Öberg



A.-C. Larsson, Z. Sun, M. Lindberg (UNPUBLISHED RESULTS)

Adsorption of Na-Amyl-Xanthate on ZnS

228 ppm: Precipitate CuX or CuX₂ 166 ppm: ? 226 ppm: Precipitate PbX₂ 150 ppm: Artifact 185 ppm: Monothiocarbonate? X₂ca 210 ppm?

13_C

enriched xanthates

Some interesting results -

13

_{C solid state}

NMR: A powerful tool to study surface

adsorbed species

ZnS activated by 3 mM Pb2+ ZnS activated by 3 mM Cu2+ ZnS activated by 0.3 mM Pb2+ _{or Cu}2+ (same result in both cases) No activation



Quantum Mechanical Calculations

(DFT)

•

ZnS+Xan

•

•

Computer simulations show how Heptyl-Xanthate

•

binds to clean ZnS surfaces

•

Adsorption energies, tilt angles and IR-data were

calculated.

•

Simulation of Cu-activation shows a stronger bond.

•

KBuDTP

A more refined interpretation of experimental data could be made due to the combination of experiment and computer simulations

Hellström, Larsson, Fredriksson, Holmgren, Öberg, J Phys Chem, 2008



Prof. Jonas Hedlund

Dr Johanne Mouzon

Iftekhar Uddin Bhuiyan

3D Data for Iron Ore Pellets

ARC-MMS Project 3

LKAB’s green pellets are complex arrangements of: • iron ore particles with a broad size distribution • a binder (e.g. bentonite)

• additives (e.g. olivine) • water

• porosity

It is this complex arrangement that determines the wet and dry strengths of the pellets and subsequently the final porosity for oxidization and reaction in blast furnaces ⇒ 3D data are valuable!



Bentonite bridges between iron oxide (and olivine) particles in pellets

SEM

Dr Johanne Mouzon and

Iftekhar U. Bhuiyan



Image Processing



Image analysis

Spherical Porosity Distribution



ARC-MMS-1 Ions in the process water ARC-MMS-3 3D-distrib. in iron oxide pellets ARC-MMS-2 DTP,xan on MeS Tribochemistry B,Mo-DTP, DTC on steel and non-steel surfaces

HLRC

Iron oxides fluorapatite, waterglass, bentonite, dolomite, olivine, ssNMR/DNP on TiPSi adsorbents Nanoparticles with modified surfaces Collaboration:

Yinan University, China IWRI, Australia

Aarhus University, Denmark The University of Warwick, UK Kola Science center, Russia

Blagoveszhensk University, Russia Budapest University, Hungary Kazan’ University, Russia Umeå University

At LTU:

Mathematics Dept. Dept. Mechanical Eng. Div. of Physics

Dept. Of Health Sc.

Payman Roonasi Anuttam Patra Faiz Ullah Shah

Mattias Gran Allan Holmgren

Oleg Antzutkin

Marina Maslova, Daniela RusanovaOleg Antzutkin, Allan Holmgren

As adsorption on Fe_xO_y Ivan Carabante

S

urface

Mats Lindberg Allan Holmgren

C

hemistry

G

roup

Oleg Antzutkin VR09 appl. VINNOVA 2008-2011 VR09 appl. Kempe 2009



1. RF patent 2235685. A method for sphene concentrate processing. Maslova M.V, Gerasimova L.G BI 25 2004.

2. RF patent 2207980 A method for titanium-containing concentrate processing. Maslova M.V, Gerasimova L.G BI 19, 2003.

Adsorption of Metal Ions on Titanium Phosphate

> 800 million tonnes of apatite tailings (Kola Region, Russia), ca 5 % of tailings is sphene, CaTiSiO₅

- Titanium Phosphate adsorbents are produced from sphene by decomposition with H₂SO₄ and treatment with H₃PO₄



SEM

sphene

Ref. 2: Maslova et.al, J. S. S. Chem. 2008

sphene

Ti(HPO₄)₂.H₂O Ti(HPO₄)₂.H₂O

TiP + sphene

Ti(OH)_1.36(HPO₄)_1.32.2.3H₂O



ssNMR/DNP on TiPSi

adsorbents

Co-applicant:

Prof. Mark E. Smith (University of Warwick) Oleg Antzutkin (10%) Allan Holmgren (10%) (Marina Maslova 15%) a PhD student (80%) “Vetenskapsrådet” 2009 application Applicants:

“Development of novel solid-state NMR

methods for studies of surface and metal ion

adsorption on new types of sorbents”

Fig. left: 145.72 MHz 31_{P MAS NMR spectra of polycrystalline titanium phosphates (TiP) before}

(bottom) and after (top) of adsorption of 50 mL 0.4 g/L Cu+2_{(aq) on 0.25 g of the sorbent. Assignment of} P-resonances is suggested in the figure. right: inversion recovery profiles, which point at the differential T₁ of different P-sites in the sorbent: Those with directly bound Cu(II) have T₁ ca. 7 ms (fast recovery of the signals), while the free P-sites have T₁ ca. 70 ms (slower recovery). UNPUBLISHED RESULTS.



ARC-MMS-1

Ions in

the process

water

ARC-MMS-3

3D-distrib.

in iron oxide

pellets

ARC-MMS-2

DTP,xan on

MeS

Johanne Mouzon Jonas Hedlund Anna-Carin Larsson Lars Gunneriusson Allan Holmgren Fatai Ikumapayi

Iftekhar Uddin Bhuniyan

Hanumantha Rao Sven Öberg

New

Boliden

Björn Johansson

(Lunding Mining)

Mikael Schauman

(Zinkgruvan AB)

Bengt-Arne Bergström

LKAB

Seija Forsmo

New Boliden

VINNOVA

Oleg Antzutkin Lena Svendsen Unfortunately, leaving ARC-MMS from Sep.09

WELCOME to join ARC-MMS!