BREF MetClean TM proces. MetClean TM anlæg i blok 5 på KARANOVERENS anlæg i Roskilde

Transkript

1 BREF MetClean TM proces MetClean TM anlæg i blok 5 på KARANOVERENS anlæg i Roskilde Date:

2 BREF og MetClean TM processen Marina Snowmann bad i slut aug om input til BREF for LCP om vandrenseteknikker. I BREF en var nævnt som BAT processer : Filtrering granular filter (sand, GAC), roterende m/u vakuum båndfiltre, filterpresser ph neutralisering, Koagulering, flockulering, fældning (kalk, Fe(III), Al(III), polymer Flotering (vakuum. IAF, DAF) Krystallisation i fluid bed Inddampning ionbytning Biologisk behandling 2

3 Ion exchange resin Photo of a solid waste incineration ion exchange resin after 2 years of operation. This ion exchange polishing step is located after a precipitation process and before a GAC filter. The ion exchange filter is regenerated twice a day with acid and base. This resin can t be regenerated any longer and must be renewed. Cost 100,000 + manpower and end deposit The chrystals seen in the picture is gypsum, and if you look carefylly on the background you can se the same chrystal deep inside 3

4 BREF MetClean TM Primo sep indsendtes beskrivelse af MetClean TM processen samt en beskrivelse af Actiflo TM processen. Actiflo TM processen er i LCP sammenhænge en fældeproces og derfor en BAT proces. MetClean TM er hverken repræsenteret ved at være en fældeproces (co-precipitation) eller en krystallisation Processen kan derfor ikke puttes ind under de eksisterende BAT processer. Den er derfor indoptaget som en potentiel eller kandidat BAT proces. 4

5 Actiflo TM processen generelt

6 Actiflo TM i hovedtræk 6

7 MetClean TM processen generelt

8 Principperne bag MetClean TM Processen Oxidations middel Fe ++ eller Mn ++ ph kontrol Restprodukt Granulat Ikke farligt affald Kolonne Rent vand Til jernprocessen anvendes: FeSO 4 x 7H 2 O Til manganat processen: MnSO 4 x 4H 2 O Iltningsmidler: NaMnO 4, H 2 O 2, O 2, NaClO Spildevand med Tungmetaller 8

9 Det kemiske princip bag MetClean TM Processen Reaktion og adsorption af tungmetaller MetClean TM processen er en kombination ar adsorption og co-precipitation 1. Frie overflader af FeOOH eller MnO 2 2. Adsorption af Fe ++ eller Mn ++ samt metaller/metalloider til overfladerne af O og OH 3. Iltning af Fe ++ eller Mn ++ til henholdsvis FeOOH eller MnO 2 overfladen retableret Heavy metal O x agent Fe ++ /Mn ++ FeOOH or MnO 2 Sand Surface layer Water flow 9

10 Principperne i MetClean TM Process De kemiske reaktioner Iron process 4 Fe ++ + O 2 + 6H 2 O 4FeOOH + 8H + 2 Fe ++ + H 2 O 2 + 2H 2 O 2FeOOH + 4H + 2 Fe ++ + ClO + 3H 2 O 2FeOOH + Cl + 4H + Chromate process CrO 4 + 3Fe H 2 O 3FeOOH + Cr(OH) 3 + 4H + Fotografi af et stærkt tørret granulatkorn. Det lyse i forgrunden er overflader af FeOOH og As medens det mørke i baggrunden er et sandkorn Manganese process Mn ++ + ClO + H 2 O MnO 2 + Cl + 2H + 3Mn MnO 4 + 2H 2 O 5MnO 2 + 4H + 10

11 Principperne i MetClean TM Processen De metaller og metalloider der er eftervist fjernet i en MetClean proces Iron process Arsenic (III & V) Chrom (III & VI) Molybdenum (VI) Antimon (V) Selenite (IV) Silisium Uran (VI) Vanadium (V) ph 5 7,5 Manganese process Aluminium Barium Cadmium Cobalt Kobber Kviksølv Nikkel Bly Radium Strontium Zinc ph 7,5-9 11

12 Andre forhold i MetClean TM Process o o Anlægget kan køres 24/7, men kræver specialuddannet personale Processen er bedst til efterpolering. Mindst suspenderet material I form af aske, gips og kalk osv. skal fjernes o Utilstrækkelig beluftning og reaktionstid i svovl absorber vil medføre utilstrækkelig oxidation af SO 2. Dette vil medføre slamdannelse og driftsforstyrrelser I MetClean TM processen. Vil kræve øjeblikkelig forøgelse af iltningsmiddel og reduction i fjernelse af anioner. o Restproduktet er et ikke farligt affald I henhold til EU s klassifikation af affald 12

13 Udvalgte referencer a) Wastewater from solid waste incineration, KARA, L90, Renonord *), Boliden *), PKN Orlen *) b) Wastewater from FGD, Avedøre power station c) Leachate from slag wach, flyash and APC landfill, Renonord, Robdrup, Koge Harbour *), Tarong *), AV d) Mining, Dragon Mining, Cogema Uranium mine *) Talison *), Boroo *) e) Groundwater pollution, Stenholtvang *), Gørding f) Drinking water, Brøndbyøster, Tucson *) *) Pilot test 13

14 KARA/noveren MetClean Manganese process Polishing step, removing Cd, Hg and Pb The existing precipitation plant from Alstom could not fulfill discharge limits for Cd and Pb From Dec to May 2006 a temporary handheld plant was operated to fulfill the limits May 2006 a new automatic full scale plan was taking in operation, and have been operated since. Quench and absorber MetClean Flue gas Ca(OH) 2 TMT15 poloy NaOH FeCL 3 Traditional precipitation

15 Energnist/L90 Iron process Polishing step, removing Mo and Sb The traditional gypsum and precipitation plant can t fulfill the discharge limits for antimony and molybdate. A full scale plant was established. Reduce content of Mo and Sb from approx µg/l To less than 30 µg/l The columns at L90 Quench and absorber MetClean Flue gas Ca(OH) 2 TMT15 poloy NaOH FeCL 3 Traditional precipitation 15

16 Column, ø1200 Column, ø500 Avedøreværket - power Station Demonstration Wastewater treatment Polymer ph 7,5-8,5 Settling tank Na 2 S Precipi tation Out Buffer tank Lamella separator NaOH KMnO 4 MnSO 4 Sludge 16

17 AV leachate from APC landfill Manganese process Removing Cd and Pb The plant at AV 2000 to 2006 AV is a landfill for special waste and until cells of this landfill contains semidry residual from Amager solid waste incinerations. Part of temporary plant In 1997 a temporary pilot plant was established and until 2000 this plant was in operation. Hereafter a new full scale plant was installed, and operated until 2006 when the waste was send to NOAH in Norway. In out Ba µg/l Cd µg/l 75 1,3 Co µg/l 0,834 <0,198 Cu µg/l 3,38 2,31 Hg µg/l 0,0653 0,033 Ni µg/l 8,82 1,72 Pb µg/l 172 5,72 Zn µg/l 48,9 4,