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

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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 1 ProMine April 2013, Levi

2 Pigments from schwertmannite G.E.O.S. Ingenieurgesellschaft mbh WOLA Chemisch-technische Erzeugnisse GmbH Vattenfall Europe Mining AG 2 ProMine April 2013, Levi

3 Iron in mine water a resource? Iron in mine water - a resource? River Kleine Spree, ( )

4 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 4

5 Flowsheet - pilot scale schwertmannite production Air Mine water Microbial iron oxidation g/m 3 *h Fe 2+ + MO + O 2 + CO 2 Fe 3+ + biomass 16Fe ,5 SO H 2 O Fe 16 O 16 (OH) 9 (SO 4 ) 3, H + Fe H 2 O Fe(OH) H + Schwertmannite Max. throughput Amount of recovered Schwertmannite Reactor volume 5 m³/h 5 t/year 10.5 m³ 5

6 Schwertmannite from Lignite mine water Parameter Unit Mean Analysis-water (106 C) % by wt 9.8 Fe % by wt 48.8 SO 2-4 (acid-soluble) % by wt 16.6 Aluminium % by wt 0.1 Silicium % by wt 0.5 NH + 4 (CaCI 2 -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

7 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 water water Mechanical drainage of schwertmannite Thermal drying Pre-shredding of the dried sludge gas treatment high temperature roasting Solid separation Washing water, H 2 SO 4 Filter Red Pigment Grinding Screen and stream grading 7

8 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 Fe 2 O 3 determined after drying at 105 C [min. % by wt] Volatile matter at 105 C [max % by wt] Water soluble fraction [% by wt] (hot extraction) Water soluble chloride and sulfate as Cl - and SO 4 2- [% by wt] Type I Type II 0.3 and 1 1 Type III > 1 and 5 Type Sieve residue (45 µm) [% by wt] Grade 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 Presence of organic colourants class d as agreed between contracting parties unverifiable 8

9 Technical scale production tests Calcination Grinding Result: 300 kg iron oxide after calcination 120 kg pigment 9

10 Technical quality of developed iron oxide pigments 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, stains, engobes, concrete stones ceramics, engobes glazes ferrite Colour ochre brick-red brick-red brick-red brick-red Volatile matter, 105 C % EN ISO <1 <0.5 <0.5 <0.5 <0.5 Fe 2 O 3 % EN ISO > 99 SiO 2 +Al 2 O 3 % max. 4.0 <0.20 Water-soluble percentage, hot extraction % EN ISO ~10 < <0.15 ph EN ISO EN ISO 787- Tapped density g/cm³ Theoretical density EN ISO 787- g/cm³ 10 ~ g/100 oil adsorption g EN ISO Sieve residue <45 µm % EN ISO <0.1 < max. 0.1 Specific surface m²/g

11 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 April 2013, Levi

12 Corrosion resistant coatings 12 ProMine April 2013, Levi

13 Large scale application test 13 ProMine April 2013, Levi

14 Adsorbents from schwertmannite G.E.O.S. Ingenieurgesellschaft mbh and UBIG mbh 14 ProMine April 2013, Levi

15 Adsorbent production from schwertmannite Based on the results of the national project: 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 (EP ) 15 15

16 Technical quality of SHM agglomerates Adsorption capacity for SHM granules test series As(III) mg/g adsorbent/ binder buffered (ph q max ) unbuffered (ph q max ) SHM-sorpX SHM-49 SHM-sorpP SHM-57 Organic binder 29.8 (ph 7.5) 64.8 (ph 6.6) Organic binder 35.7 (ph 7.5) 56.8 (ph 6.6) Compaction 27.5 (ph 7.5) 42.0 (ph 6.7) Organic binder and compaction 36.8 (ph 7.5) 16.5 (ph 4.8) Adsorption kinetics: - better adsorption kinetics for As(V) compared to commercial products: Sorption product Elimination of As(V) in days SHM- Sorp FerroSorp Plus GEH 104 Bayoxide E33 HCF As(V) mg/g buffered (ph q max ) unbuffered (ph q max ) 50.7 (ph 7.5) 60.3 (ph 6.8) 37.5 (ph 7.5) 55.8 (ph 6.7) 25.6 (ph 7.5) 37.6 (ph 6.8) 16.7 (ph 7.5) 21.4 (ph 5.9) Comparison with commercial products test series adsorbent Fe(OH) 3 sludge FerroSorp Plus GEH 104 Bayoxide E33 HCF 1 mm As(III) mg/g buffered to ph 7.5 As(V) mg/g Granula produced with organic binder 16

17 Pilot plant for adsorbent production Flow sheet: pilot plant for adsorbent production from schwertmannite stirrer tank water water, binder conveyor belt M chamberfilter press roll crusher weighing machine screw conveyor sieving plant water, binder ploughshare mixer conveyor belt M air chamber dryer 1 piston diaphragm pump weighing /packaging dissolver chamber dryer 2

18 Individual processing steps Mixing with binding agent Drying of the material Crushing and sieving Products: filterstable schwertmannite pellets 1 cm 18

19 Testing the technically produced products Filterstable adsorbents with a maximum equilibrium sorption capacity of 35 mg/g As were produced As-sorption capacity [mg/g] experimental data Langmuir As-sorption capacity [mg/g] experimental data Langmuir equilibrium As-concenration in the liquid phase [mg/l] equilibrium As-concentration in the liquid phase [mg/l] 19 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

20 20 Estimation of the profitability of an industrial scale production Production amount: 10,000 t SHM/a Cost category Biosynthesis of SHM from mine water mine water Capital costs 3,672,540 Depreciation (10 years) 367,254 /a Operating costs (energy, maintanace) 155,000 /a Total annual cost 522,254 /a Pigment production Adsorbent production Capital costs 6,443,250 3,993,250 Depreciation (10 years) 644,325 /a 399,325 /a Operating costs Man power 108,000 /a 108,000 /a Energy 900,000 /a 300,000 /a Chemicals 500,000 /a Maintenance 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

21 Thank you! WOLA Chemisch-technische Erzeugnisse GmbH Bangor University Vattenfall Europe Mining AG UBIG GmbH 21 ProMine April 2013, Levi