Limestones and solid wastes as
adsorbents for mining waste
and process waters treatment
Adsmat
1.1.2012 – 30.6.2014
Professor Mika Sillanpää
Head of Laboratory of Green Chemistry
Professor Marjatta Louhi-Kultanen
PhD student Evgenia Iakovleva
Laboratory of Green Chemistry
Tampere
Vesi ja emissioseminaari
20-21.05.2015
Low-cost andsorbents for mining waters treatment
User need
• Cheaper methods for mining waters treatment
Solution
• Search adsorbents based on the low-cost materials
• Improve the efficiency of the water treatment with lower cost
Users
• Mining and ore processing industries
Laboratory of Green Chemistry
Benefits
• To optimize the mine-industries water treatment by increasing
the purification efficiency while decreasing its cost
Solutions
Acid Mine Drainage
treatment
• AMD neutralization
• Metal ions removal
Usage of solid wastes and limestones
for mine waters treatment
Laboratory of Green Chemistry
Solid wastes
• Aproximately 100
billion tones per year
of ore mined in the
world
• About 30-40% of ore is
Process water treatment
used
• Removal of anions,
• The remaining 60-70%
metal ions, radioactive
of ore is waste
substances
Benefits
• Reuse of solid wastes
• Saving energy and facilities
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• Development of low-cost method for
waste- and process water treatment
Approach
CaFeCake
SuFe
Nordkalk
Norlsk
Nickel
Harjavalta
Ca – 37; 21%
Si – 10; 42%
Ca – 12%
Fe – 10%
AMD and
process
water
treatment
and
removal
RH
DI-60
Norilsk
Nickel
Harjavalta
Ekokem
Metsä
Tissue
Corporation
Fe – 39%
Si – 3%
Ca – 15%
Fe – 10%
Ca – 12%
Si – 5%
Metal ions
and
removal
Process
water
treatment
removal
Laboratory of Green Chemistry
FF, FS limestone
The particle size distribution, specific surface area
and zeta-potential results of unmodified and
modified limestones*, **
* Industrial products and wastes as adsorbents for sulphate and chloride removal from synthetic alkaline solution and
mine process water; Chemical Engineering Journal; 02/2015
** ACID MINE DRAINAGE (AMD) treatment: neutralization and toxic elements removal with unmodified and modified
limestone; Ecological Engineering Journal 08/2015
Laboratory of Green Chemistry
The particle size distribution, m Specific zeta-potential,
<90 <75 <50 <25 <10 surface
mV
%,
%,
%,
%,
%, area, m2
pH 11
g-1
FS
451
420 318
228 156
1.35
0
FS_NaCl 589
568 450
282
270
1.46
-15
FS_ww
273
134 131
91
90
1.29
-6
FF
599 567 354
185 177
1.82
-25
FF_NaCl 872
798 535
494
487
1.63
-20
FF_ww
492
421 188
87
88
1.58
-6
RH
180
165 154
130
98
62.5
-7
DI-60
1390 1265 1200 1020 990
3.3
-14
Elemental composition of mining water from copper
mine of Finland and process water (MPW) from
Norilsk Nickel Harjavalta
RSDs at 3 times the detection limit were less than 3%
Ni(II),
ppm
13
Zn(II),
ppm
2080
Fe(III),
ppm
911
Cl-,
ppm
-
Na+,
ppm
-
level 500 2.3
76
1.7
5900
3400
-
-
level 720 3.2
4.4
0.3
242
52
-
-
NorNikel 12
0.11
2.13
0.18
0.60
954
11570
* Industrial products and wastes as adsorbents for sulphate and chloride removal from synthetic alkaline solution and
mine process water; Chemical Engineering Journal; 02/2015
** ACID MINE DRAINAGE (AMD) treatment: neutralization and toxic elements removal with unmodified and modified
limestone; Ecological Engineering Journal 08/2015
Laboratory of Green Chemistry
level 270 2.6
Cu(II),
ppm
108
pH
Pretreatment of limestones
1. Crushing
2. Grinding
3. Classification by size
2 mm
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0.3 mm
Approach
Batch methods to find the optimal conditions of
adsorption
• With various concentration of pollutants and amount of sorbents
• With various of contact time and pH
• Ions competition study
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Nordkalk materias
Removal of Zn(II), Fe(III), Cu(II), Ni(II) ions from AMD and SO42-, Cl- anions from mine process
water with FS, FF. Initial concentration of metal ions is 20 mg L-1, sulphate is 30 g L-1, and chloride
is 2.5 g L-1
100
90
80
60
50
40
30
20
10
0
FS
FF
Zn
83
99
Fe
93
86
Cu
46
97
FS
Ni
11
62
FF
SO4
73
68
Cl
52
45
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Removal, %
70
Norilsk Nickel materias
100
90
80
70
60
50
40
30
20
10
0
CaFe-Cake
SuFe
As(III)
72
As(V)
93
CaFe-Cake
SuFe
CN
97
97
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Removal, %
Removal of As(III), As(V) and CN with CaFe-Cake and CN with SuFe. Initial concentration of As(III)
and As(V) is 20 ppm, cyanides is 100 ppm
Ekokem materias
Removal of As(III), As(V), Zn(II), Fe(III), Cu(II), Ni(II), SO42-, Cl- with RH AMD and process water.
Initial concentration of As(III) and As(V) is 20 ppm. Initial concentration of metal ions is 20 mg L-1,
sulphate is 30 g L-1, and chloride is 2.5 g L-1
100
90
80
60
50
40
30
20
10
0
RH
As(III)
100
As(V)
100
Zn
83
Fe
56
Cu
49
Ni
11
SO4
75
Cl
82
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Removal, %
70
Metsä Tissue materials
Removal of SO42-, Cl-, Zn(II), Fe(III), Cu(II) from process water and AMD with DI-60. Initial
concentration of metal ions is 20 mg L-1, sulphate is 30 g L-1, and chloride is 2.5 g L-1.
100
90
80
60
50
40
30
20
10
0
DI-60
SO4
54
Cl
80
Zn
85
Fe
98
Cu
23
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Removal, %
70
Summary table
%
FS_ww FF_ww
RH
DI-60
93
86
56
98
46
97
49
23
83
99
83
85
SuFe
CaFeCake
(
52
45
82
80
73
68
75
54
)
( )
pH 1.5
~100
72
~100
93
97
6
6.8
4.5
97
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62
Removal mechanism of metal ions with
unmodified and modified limestones
2=
+2
(
should be exchanged with
attached to the surface of the adsorbent to form a complex compound)
=
and
+
+
=
+
, while pH of the solution increased)
+
and
(Ion exchange between
• Complexation
b)
Iron compounds are kmown to be effective sorbents for various ion
metals. Iron compound are components of FF, FS, RH and DI-60. Metal
ions could be removed by complexation onto surface area of sorbents
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• Precipitation
• Sorption
• Ion-exchange
a)
2
+
Collaboration with School of Chemistry and
Chemical Engineering of Queen’s
University Belfast (UK)
• Co-granules of limestone and coffee
waste
•
•
Acidity neutralization
Anions and metal ions removal
• Co-granules of sulphate tailings,
limestone and cofee waste
•
Complex purification of mine waters
from cyanides and metal ions
7th International Granulation Workshop in Sheffield
Laboratory of Green Chemistry
•
Why coffee waste?
• Coffee waste consists of a higher C/N ratio, including carboxylic
groups, which exhibited high efficiency for Ni ions removal to
chelates forms by ion-exchange mechanism
world for the consumption of coffee. Finland produced about
50.000 tons coffee wastes per year
Laboratory of Green Chemistry
• According to Coffee Institute of Paulig, Finland is the first in the
Commercialization measures
• FF_ww – limestone (Nordkalk)
• AMD treatment (pH from 1.5 to 6.5; removal of Zn-99%, Fe-86%,
Cu-97%, Ni-62%, SO4-68%)
• RH – iron sand (EKOKEM)
• As(III) and As(V) removal (~100%)
• CaFe-Cake and SuFe – sulphate tailings (Norilsk Nickel)
• Cyanides (97%) and As(III) (72%), As(V) (93%) removal
• Co-granules of coffee wastes and limestones for AMD treatment
• Co-granules of coffee wastes, limestones and sulphate tailings for cyanides,
arsenic, and metal ions removal
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• DI-60 – paper and pulp wastes (Metsä-Tissue)
• Process water treatment from anions (removal of SO4-54%, Cl-80%, Zn85%, Fe-98%)
Candidate, Bachelour and Master defense
Candidate
• Jenni Tervaportti, Kaivannaisteollisuuden vedenkäsittelyn tarpeet,
2014, LUT
Master Theses
• Heini Rytkönen, Adsorption of arsenic from ammonia containing
waste water by ferrous hydroxide waste, 2015, LUT
• Maria Nikitenko, Treatment of Ni-containing acidic mine waters with
calcite side-stones, 2013, LUT
• Ghali El Oumari, Treatment of Fe-containing acid mine waters in
fixed bed adsorption column with calcite side-stone, 2014, LUT
Laboratory of Green Chemistry
Bachelour
• Eduard Musin, Adsorption Modeling, 2013, MAMK
• Aleksandr Murzin, Adsorption modeling for As(III) and As(V) removal
from synthetic wastewater by low-cost adsorbents, 2015, MAMK
Publications
Reviews
• The use of low-cost adsorbents for wastewater purification in mining
industries
Environmental Science and Pollution Research; 02/2013
• Low-cost adsorbents for arsenic separation from wastewaters
•
Eco-efficient water and solid wastes usage in mining and ore processing in
Finland, preparation
Laboratory of Green Chemistry
Book: Innovative Materials and Methods for Water Treatment: Solutions for Arsenic and
Chromium Removal, CRC Press; 08/2015
Publications
Research works
• Industrial products and wastes as adsorbents for sulphate and chloride
removal from synthetic alkaline solution and mine process water
Chemical Engineering Journal; 02/2015
Ecological Engineering Journal 08/2015
• Solid wastes as adsorbents for efficient As(III) and As(V) removal from
mine waters, Chemical Engineering Journal; under reviewing
• Manufacturing of novel low-cost adsorbents: co-granulation of limestones
and coffee waste, Bioresource Technology Journal; under preparation
• Removal of cyanides from mine waters by column with granulated
sulphate tailigs, Powder Technology Journal; under preparation
• Novel low-cost adsorbents for acid mine drainage treatment, Powder
Technology Journal; under preparation
Laboratory of Green Chemistry
• ACID MINE DRAINAGE (AMD) treatment: neutralization and toxic
elements removal with unmodified and modified limestone
Thank you for your attention!