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)
- RECYCLING
Agricola Research Center - Multicomponent Mineral Systems
ARC-MMS (2008 - 2012)
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
New Boliden and Lundin Mining
Project I
LKAB
Project II
Project III
Recycling of process water and
influence of its chemistry on
sulphide flotation and flotation
selectivity
Molecular scale approach
towards dithiophosphate (DTP)
behaviour on sulphide
surfaces
Objectives: To provide remedies
to selectively regulate surface
properties of sulfides, which are
affected by recycled process
water
Objectives: To utilize
understanding of adsorption
mechanisms of collectors in
improving selectivity and recovery
of the valuable sulfide minerals
Research coordinator:
Prof. H. Rao, The Division of
Mineral Processing
Research coordinator:
Dr A.-C. Larsson,
The Division of Chemical Eng.
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 %)
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
ARC-MMS program coordinator:
Prof. O.N. Antzutkin,
The Division of Chemiical Eng.
New Boliden
Hanumantha Rao
Allan Holmgren
Lars Gunneriusson
Fatai Ikumapayi
Björn Johansson
Lunding Mining
Mikael Schauman
Zinkgruvan AB
Bengt-Arne Bergström
ARC-MMS-1
Ions in
the process
water
Anna-Carin Larsson
Sven Öberg
ARC-MMS-2
DTP,xan on
MeS
Oleg Antzutkin
VINNOVA
Lena Svendsen
ARC-MMS-3
3D-distrib.
in iron oxide
pellets
Jonas Hedlund
Johanne Mouzon
Iftekhar Uddin Bhuniyan
LKAB
Seija Forsmo
New Boliden
Chemistry of Interfaces
Collaboration:
Surface
Chemistry
Group
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
VINNOVA
Umeå University
Oleg Antzutkin, Allan Holmgren
Marina Maslova, Daniela Rusanova Ivan Carabante
ssNMR/DNP on
TiPSi
adsorbents
ARC-MMS-1
2008-2011
Ions in
At LTU:
the process
Mathematics Dept.
water
ARC-MMS-2
Dept. Mechanical Eng. DTP,xan on
Div. of Physics
MeS
Dept. Of Health Sc.
ARC-MMS-3
3D-distrib.
in iron oxide
pellets
Allan Holmgren
Mattias Gran
VR09 appl.
Tribochemistry
B,Mo-DTP, DTC
on steel and
non-steel
Faiz Ullah Shah
surfaces
Oleg Antzutkin
Mats Lindberg
As adsorption on
FexOy
VR09 appl.
HLRC
Iron oxides
fluorapatite,
waterglass,
bentonite,
dolomite,
olivine,
Kempe 2009
Anuttam Patra
Oleg Antzutkin
Nanoparticles with
Allan Holmgren
modified surfaces
Payman Roonasi
• 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 SO42- 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 Ca2+ ions in solution
Effect of calcium ions on sulphide flotation
90
80
Recovery %
70
60
PbS
50
ZnS
40
FeS2
CuFeS2
30
20
10
0
0
100
200
300
400
500
600
700
Concentration of calcium ions mg/l
F. Ikumapayi, H. Rao, UNPUBLISHED RESULTS
Influence of SO42- ions in solution
Effects of sulphate ions on sulfide mineral flotation
100
90
80
Recovery %
70
PbS
60
ZnS
50
FeS2
40
CuFeS2
30
20
10
0
0
200
400
600
800
1000
1200
1400
1600
1800
Concentration of sulphate ions mg/l
F. Ikumapayi, H. Rao, UNPUBLISHED RESULTS
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
Dept of Chemcial Engineering and Geosciences / Dept of Mathematics
Some interesting results - 13C solid state
NMR: A powerful tool to study surface
adsorbed species
Adsorption of Na-Amyl-Xanthate on ZnS
13C
enriched
xanthates
228 ppm: Precipitate CuX or CuX2
166 ppm: ?
226 ppm: Precipitate PbX2
150 ppm: Artifact
185 ppm: Monothiocarbonate?
X2 ca 210 ppm?
ZnS activated by 3 mM Pb2+
ZnS activated by 3 mM Cu2+
ZnS activated by 0.3 mM Pb2+ or Cu2+
(same result in both cases)
No activation
A.-C. Larsson, Z. Sun, M. Lindberg (UNPUBLISHED RESULTS)
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
ARC-MMS Project 3
3D Data for Iron Ore Pellets
Prof. Jonas Hedlund
Dr Johanne Mouzon
Iftekhar Uddin Bhuiyan
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
Swelling properties of bentonite and mobility of H2O is important for binding capacity?
Image Processing
Binary Image with appropriate threshold value
Image analysis
Spherical Porosity Distribution
3D Porosity Mechanical strength of pellets?
Collaboration:
Surface
Chemistry
Group
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
VINNOVA
Umeå University
Oleg Antzutkin, Allan Holmgren
Marina Maslova, Daniela Rusanova Ivan Carabante
ssNMR/DNP on
TiPSi
adsorbents
ARC-MMS-1
2008-2011
Ions in
At LTU:
the process
Mathematics Dept.
water
ARC-MMS-2
Dept. Mechanical Eng. DTP,xan on
Div. of Physics
MeS
Dept. Of Health Sc.
ARC-MMS-3
3D-distrib.
in iron oxide
pellets
Allan Holmgren
Mattias Gran
VR09 appl.
Tribochemistry
B,Mo-DTP, DTC
on steel and
non-steel
Faiz Ullah Shah
surfaces
Oleg Antzutkin
Mats Lindberg
As adsorption on
FexOy
VR09 appl.
HLRC
Iron oxides
fluorapatite,
waterglass,
bentonite,
dolomite,
olivine,
Kempe 2009
Anuttam Patra
Oleg Antzutkin
Nanoparticles with
Allan Holmgren
modified surfaces
Payman Roonasi
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
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.
SEM
Ti(OH)1.36(HPO4)1.32.2.3H2O
sphene
TiP + sphene
sphene
Ref. 1: Maslova et.al, Inorg. Chem. 2008
Ti(HPO4)2.H2O
Ti(HPO4)2.H2O
Ref. 2: Maslova et.al, J. S. S. Chem. 2008
“Development of novel solid-state NMR
methods for studies of surface and metal ion
adsorption on new types of sorbents”
ssNMR/DNP on
TiPSi
adsorbents
Applicants:
“Vetenskapsrådet” 2009 application
Oleg Antzutkin (10%)
Allan Holmgren (10%)
(Marina Maslova 15%)
a PhD student (80%)
Co-applicant:
Prof. Mark E. Smith
(University of Warwick)
Fig. left: 145.72 MHz 31P 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.
New Boliden
Hanumantha Rao
Allan Holmgren
Lars Gunneriusson
Fatai Ikumapayi
Björn Johansson
(Lunding Mining)
Mikael Schauman
(Zinkgruvan AB)
Unfortunately,
Bengt-Arne Bergström
leaving
ARC-MMS
from Sep.09
Sven Öberg
ARC-MMS-2
DTP,xan on
MeS
ARC-MMS-1
Ions in
the process
water
Oleg Antzutkin
VINNOVA
Lena Svendsen
Anna-Carin Larsson
ARC-MMS-3
?
WELCOME to join ARC-MMS!
3D-distrib.
in iron oxide
pellets
Jonas Hedlund
Johanne Mouzon
Iftekhar Uddin Bhuniyan
LKAB
Seija Forsmo
New Boliden
