ProMine 23.-25. April 2013, Levi 1

ProMine - Nano-particle products from new mineral resources in Europe

Products from schwertmannite

G.E.O.S. Ingenieurgesellschaft mbH

WOLA Chemisch-technische Erzeugnisse GmbH Bangor University

Vattenfall Europe Mining AG

UBIG GmbH

ProMine 23.-25. April 2013, Levi 2

Pigments from schwertmannite

G.E.O.S. Ingenieurgesellschaft mbH

WOLA Chemisch-technische Erzeugnisse GmbH

Vattenfall Europe Mining AG

Iron in mine water - a resource?

River „Kleine Spree „, (29.09.2008)

Iron in mine water – a resource?

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Nochten – modelsite for schwertmannite products

• Open cast mine Nochten: 18 Mio t/year lignite • Waterlift: ~ 120 Mio. m³/year

Watertreatment plant Tzschelln: 20 Mio. m³/a mine water

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Flowsheet - pilot scale schwertmannite production

Schwertmannite

Microbial iron oxidation

25-35 g/m3*h

Mine water

Air

Fe2+ + MO + O2 + CO2 → Fe 3+ + biomass

16Fe3+ + 3,5 SO42- + 25 H2O → Fe16O16(OH)9(SO4)3,5 + 41 H+

Fe3+ + 3 H2O → Fe(OH)3 + 3 H+

Max. throughput

Amount of recovered Schwertmannite

Reactor volume

5 m³/h 5 t/year 10.5 m³

Schwertmannite from Lignite mine water

Parameter Unit Mean

Analysis-water (106°C) % by wt 9.8

Fe % by wt 48.8

SO42- (acid-soluble) % by wt 16.6

Aluminium % by wt 0.1

Silicium % by wt 0.5

NH4+ (CaCI2-extract) mg/kg 6.6

Potassium mg/kg 118

Sodium mg/kg 46

Calcium mg/kg 506

Magnesium mg/kg 180

Arsenic mg/kg 106

Nickel mg/kg <2

Zinc mg/kg 11

Manganese mg/kg 10

Phosphorous mg/kg 228

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Pigment production from schwertmannite

Laboratory scale optimization of pigment production: - optimization of drying, calcination and sieving conditions - testing of various mechanical and chemical pelletizing processes

Mechanical drainage of schwertmannite

Pre-shredding of the dried sludge

Thermal drying

Grinding Screen and stream grading

high temperature

roasting

Solid separation Washing water, H2SO4

Filter

water water

Red Pigment

gas treatment

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Pigment specification…

Parameter Requirements with regard to group and category

Red pigment Yellow pigment

A B C D A B C D

Total content of Fe2O3 determined after drying at 105°C [min. % by wt] 95 70 50 10 83 70 50 10

Volatile matter at 105°C [max % by wt] 1 1.5 2.5 2.5 1 2.5 2.5 2.5

Water soluble fraction [% by wt] (hot extraction)

Type I ≤ 0.3 -

Type II ≥ 0.3 and ≤ 1 ≤ 1

Type III > 1 and ≤ 5

Water soluble chloride and sulfate as Cl- and SO42-

[% by wt] Type 1 ≤ 0.1 -

Sieve residue (45 µm) [% by wt] Grade 1 ≤0.01

Grade 2 >0.01 and ≤0.1

Grade 3 >0.1 and ≤1

Acidity or Alcalinity of the aqueous extract [max. ml 0.1 mol/l solution] 20

Presence of lead chromate unverifiable

Total content of CaO, after drying at 105°C [max. % by wt] class a 0.3

class b, c 5

class d as agreed between contracting parties

Presence of organic colourants unverifiable

Technical scale production tests

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Calcination Grinding

Result: • 300 kg iron

oxide after calcination

• 120 kg pigment

Technical quality of developed iron oxide pigments

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Iron oxide pigment (IOP) DIN-Norm Nochten Ochre Nochten Red (33) Bayferrox Rot Bayferrox Rot Rudner IOP Yellow pigment Red pigment type 130 type 222

Application in concrete stones coatins, stains,

ceramics, engobes concrete stones stains, engobes, glazes ferrite

Colour ochre brick-red brick-red brick-red brick-red

Volatile matter, 105°C % EN ISO 787-2 <1 <0.5 <0.5 <0.5 <0.5

Fe2O3 % EN ISO 1248 75-80 99 95-97 90...96 > 99

SiO2+Al2O3 % 55913 0.1 0.1 3 max. 4.0 <0.20 Water-soluble percentage, hot extraction % EN ISO 787-3 ~10 <0.1 0.3 0.5 <0.15 pH EN ISO 787-9 2…3 3...5 6.0 4...8

Tapped density g/cm³ EN ISO 787-

11 0.9-1.1 0.6 0.9 1.4...1.8

Theoretical density g/cm³ EN ISO 787-

10 ~5 5.22 5.0 5

oil adsorption g/100

g EN ISO 787-5 50-55 24-33 26 15 Sieve residue <45 µm % EN ISO 787-7 <0.1 <0.1 0.05 max. 0.1 Specific surface m²/g 12…15 12...15 3.8-4.8

ProMine 23.-25. April 2013, Levi

Application of pigments in coatings

Investigation Description Scale Result Partner

Specific pigment tests

Analysis of pigments for application in coatings

L Pigments are suitable for application in colour and coatings

WOLA

Production of base coatings

Primer coats with different organic binding agents

L & T Coats applied on metallic test panels

WOLA

Test of the coatings Salt spray test, weather resistence

T Nochten pigments can be used in anticorrosive primer coats

WOLA

ProMine 23.-25. April 2013, Levi 12

Corrosion resistant coatings

ProMine 23.-25. April 2013, Levi 13

Large scale application test

ProMine 23.-25. April 2013, Levi 14

Adsorbents from schwertmannite

G.E.O.S. Ingenieurgesellschaft mbH

and UBIG mbH

Adsorbent production from schwertmannite

• produced from the mineral schwertmannite

• adsorption of oxo anions (e. g. Arsenate) in industrial effluents, mine water

• very high sorption capacity for Arsenic and good sorption kinetics (similar or better than commercial products)

• maximum sorption capacity in unbuffered surroundings

• filterstable agglomerates for application in passive water treatment systems

• very low elution of As from the loaded material (Requirements for landfilling)

• cheaper than commercial products

• Patent was submitted in May 2012 (EP12167884.1)

15 15

Based on the results of the national project:

Technical quality of SHM agglomerates

16

adsorbent/ binder

test series

SHM-sorpX SHM-49 SHM-sorpP SHM-57

Organic

binder Organic binder Compaction

Organic binder and compaction

As(III) mg/g

buffered (pH qmax)

29.8 (pH 7.5)

35.7 (pH 7.5)

27.5 (pH 7.5)

36.8 (pH 7.5)

unbuffered (pH qmax)

64.8 (pH 6.6)

56.8 (pH 6.6)

42.0 (pH 6.7)

16.5 (pH 4.8)

As(V) mg/g

buffered (pH qmax)

50.7 (pH 7.5)

37.5 (pH 7.5)

25.6 (pH 7.5)

16.7 (pH 7.5)

unbuffered (pH qmax)

60.3 (pH 6.8)

55.8 (pH 6.7)

37.6 (pH 6.8)

21.4 (pH 5.9)

adsorbent

test series

Fe(OH)3 sludge

FerroSorp® Plus GEH® 104 Bayoxide®

E33 HCF

As(III) mg/g buffered to pH 7.5

22.6 28.9 18.6 18.3

As(V) mg/g − 40.1 33.2 21.1

Adsorption capacity for SHM granules

Comparison with commercial products 1 mm

Granula produced with organic binder

Adsorption kinetics: - better adsorption kinetics for

As(V) compared to commercial products:

Sorption

product SHM-Sorp

FerroSorp Plus GEH® 104 Bayoxide®

E33 HCF

Elimination of As(V) in days

5-8 17 6 9

Pilot plant for adsorbent production

chamber filter press

screw conveyor

ploughshare mixer

roll crusher

sieving plant

chamber dryer 1

chamber dryer 2

dissolver

conveyor belt

weighing /packaging

weighing machine

conveyor belt

stirrer tank

piston diaphragm pump

water water, binder

water, binder

air

M

M

Flow sheet: pilot plant for adsorbent production from schwertmannite

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Individual processing steps

Mixing with binding agent Drying of the material Crushing and sieving

Products: filterstable schwertmannite pellets

1 cm

Testing the technically produced products

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0

2

4

6

8

10

12

14

16

18

20

0 0.5 1 1.5 2 2.5 3 3.5 4 4.5

As-

sorp

tion

cap

acit

y [m

g/g]

equilibrium As-concenration in the liquid phase [mg/l]

experimental data

Langmuir

0

5

10

15

20

25

30

0 0.5 1 1.5 2 2.5 3A

s-so

rpti

on c

apac

ity

[mg/

g]

equilibrium As-concentration in the liquid phase [mg/l]

experimental data

Langmuir

Filterstable adsorbents with a maximum equilibrium sorption capacity of 35 mg/g As were produced

After ProMine: Pilot scale application tests in passive water treatment plants supported by various industrial partners and laboratory scale tests concerning further oxo anions and different water qualities

Estimation of the profitability of an industrial scale production

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Production amount: 10,000 t SHM/a

Cost category Biosynthesis of SHM from mine watermine water

Capital costs 3,672,540 €Depreciation (10 years) 367,254 €/aOperating costs(energy, maintanace) 155,000 €/aTotal annual cost 522,254 €/a

Pigment production Adsorbent productionCapital costs 6,443,250 € 3,993,250 €Depreciation (10 years) 644,325 €/a 399,325 €/aOperating costs

Man power 108,000 €/a 108,000 €/aEnergy 900,000 €/a 300,000 €/aChemicals 500,000 €/aMaintenance 644,000 €/a 399,000 €/a

Total annual cost 2,818,579 €/a 2,228,579 €/a

Revenues from sales 3,410,000 €/a 5,600,000 €/a

Profit / loss 591,421 €/a 3,371,421 €/a

ProMine 23.-25. April 2013, Levi 21

Thank you! WOLA Chemisch-technische Erzeugnisse GmbH Bangor University

Vattenfall Europe Mining AG

UBIG GmbH