TREATMENT AND DISPOSAL OF RESIDUES

FROM ALUMINIUM DROSS RECOVERY

K.E. Lorber

Institute for Sustainable Waste Management and Technology (IAE),

Montan University Leoben

A-8700 Leoben Franz-Josef-Strae 18

Tel. +43 (0) 3842 402-5101 Fax +43 (0) 3842 402-5102
iae.unileoben.ac.at iae@unileoben.ac.at
 Contents
1. INTRODUCTION
1.1 Dross Formation & Characterization
1.2 Metal Recovery from Dross
1.3 Dross is Hazardous Waste
2. LANDFILLING of FINE DROSS-RESIDUES
2.1 Gas-Formation Potential & Gas Migration
2.2 Site-Investigation Results
2.3 Groundwater Pollution
3. PYROMETALLURGICAL TREATMENT
3.1 Salt Cake Leaching & Crystallization Process
3.2 Calcination & REFINING of OXIDIC RESIDUES
4. CONCLUSIONS

DepoTech 2012 O.Univ.Prof.Dipl.-Ing.Dr.techn. Karl E. Lorber, 20.12.2012, Folie 2

 1. INTRODUCTION
1.1 Dross Formation & Characterization

Al-DROSS: Residue from Al-Industry, formed during REFINING

and by AIR OXIDATION of liquid metal during
MELTING, SKIMMING, HOLDING & CASTING
OPERATIONS

ALUMINIUM DROSS: Unwanted Residue

Complex Mixture of:
Metallic Oxides
Nitrides
Carbides
Sulfides
Salts from Fluxing Process (NaCl, KCl, Na3AlF6, etc.)
Dirt
Impurities
Metallic Aluminium Recovery

DepoTech 2012 O.Univ.Prof.Dipl.-Ing.Dr.techn. Karl E. Lorber, 20.12.2012, Folie 3

 DROSS COMPOSITION

R COMPOSITION of DROSS
E
TYPE of DROSS METALLIC Al RESIDUAL
C COMPOUNDS
[%]
O
Untreated DROSS < 80% Al2O3, Al2O3 * MgO,
V
Flatcake & Crumbs 90-70% AlO3 * SiO2,
E Al2O3 * FeO, etc.
R Concentrate 70-50% Al2O3, AlCl3, NaCl, KCl
Y
Coarse Residue 50-20% CaF2, NaF, AlF3, etc.

Fine Residue 20-5% Al2O3, AlN, Al4C3, Al2S3,

AlP, etc.

DepoTech 2012 O.Univ.Prof.Dipl.-Ing.Dr.techn. Karl E. Lorber, 20.12.2012, Folie 4

DROSS FORMATION PROCESS
STEPS:
Surface Oxidation
Oxidized Skin (Al2O3) Cracking
Sinking & Floating of Al2O3
Conglomeration of Al2O3
Interspace filling by metallic Al
Inside Oxidation of metallic Al
Skimming
Metallic Al Separation

DEPENDING ON:
INPUT MATERIAL (e.g. Type of
SCRAP etc.)
TECHNOLOGY and
OPERATION applied

DepoTech 2012 O.Univ.Prof.Dipl.-Ing.Dr.techn. Karl E. Lorber, 20.12.2012, Folie 5

 1.2 Metal Recovery from Dross

WASTE-Problem: FINE RESIDUES from Al-Recovery

DepoTech 2012 O.Univ.Prof.Dipl.-Ing.Dr.techn. Karl E. Lorber, 20.12.2012, Folie 6

 CHARACTERIZATION of DROSS
OECD-Definition:
SKIMMINGS: > 45% METALLIC ALUMINIUM
DROSS: < 45% METALLIC ALUMINIUM

- WHITE DROSS: from PRIMARY SMELTER

without SALT COVER
- BLACK DROSS: from SECONDARY SMELTER
(e.g. ROTARY FURNACE) with SALT COVER

ENVIRONMENTAL PROBLEM:
HIGH REACTIVITY (i.e. stron exo thermic reaction) with WATER or HUMIDITY in Air

2Al + 3H2O Al2O3 + 3H2 (1)

2AlN + 3 H 2O Al2O3 + 2NH3 (2)
Al4C3 + 6H2O 2Al2O3 + 3CH4 (3)
Al2S3 + 3H2O Al2O3 + 3H2S (4)
Al4C3 + 6N2 + 9C 4Al(CN)3 (5)
4Al(CN)3 + 6H2O + 2Al2O3 + 12 HCN (6)
2 AlP + 3 H2O Al2O3 + 2 H3P (7)

PHENOMENA of SURFACE PASSIVATION by Al2O2 Skin formation

DepoTech 2012 O.Univ.Prof.Dipl.-Ing.Dr.techn. Karl E. Lorber, 20.12.2012, Folie 7

 1.3 DROSS is HAZARDOUS WASTE

WASTE PROPERTIES
H3-A: Highly flammable
H 4: Irritant
H 5: Harmfull
H 13: Toxic Leachate (i.e. Fluoride content)

EC-List of HAZARDOUS WASTES

100308* Salt slags from secondary smelting.
100309* Black drosses from secondary smelting.
100310* Waste from treatment of salt slags and black drosses.
100315* Skimmings that are flammable or emit, upon contact with water, flammable gases in
dangerous quantities
100304* Primary smelting slags and white dross

DepoTech 2012 O.Univ.Prof.Dipl.-Ing.Dr.techn. Karl E. Lorber, 20.12.2012, Folie 8

 2. LANDFILLING of FINE DROSS
RESIDUES
About 15-20 years ago:
FINE RESIDUES from Al-RECOVERY Process for Dross were
LANDFILLED.
ENVIRONMENTAL PROBLEMS:
High REACTIVITY of FINE DROSS RESIDUES with WATER or
HUMIDITY in Air.

OLD LANDFILLS:
- Insufficient Surface Capping:
Gas Migration (e.g. H2, CH4, NH3)
- Insufficient Bottom Sealing:
Groundwater Pollution (e.g. F-, Cl-, NH4+(NO3-),
CN-, etc.)
by vertical MOLECULAR DIFFUSION

DepoTech 2012 O.Univ.Prof.Dipl.-Ing.Dr.techn. Karl E. Lorber, 20.12.2012, Folie 9

2.1 Gas Formation Potential & Gas
Migration
Laboratory Test:
over 24 days

Average Gas Formation

Potential:
8.4 NmL/kgDM per day
Field Measurements of Soil
Gas: Explosive Mixture
H2: > 4.2 Vol%
CH4: > 7.2 Vol%
NH3: > 2.4 Vol%

DepoTech 2012 O.Univ.Prof.Dipl.-Ing.Dr.techn. Karl E. Lorber, 20.12.2012, Folie 10

 2.2 Site-Investigation Results
(Case Study)

LANDFILLED DROSS: SITE INVESTIGATION

MIGRATION of TOXIC GASES

SITE INVESTIGATION by
EXCAVATION &
DRILLING
DepoTech 2012 O.Univ.Prof.Dipl.-Ing.Dr.techn. Karl E. Lorber, 20.12.2012, Folie 11
 Site-Investigation Results
(Case Study)

LANDFILLED DROSS: SITE INVESTIGATION by EXCAVATION

COMPACTED WET FOLLOWING DRY LAYER with

SURFACE LAYER SANDWICH-STRUCTURE
0.5 1.5 m: ON TOP 1.5 5.5 m
14.5 15.5 m: AT BOTTOM (Dust like MATERIAL: 1.5m 14.5m)

DepoTech 2012 O.Univ.Prof.Dipl.-Ing.Dr.techn. Karl E. Lorber, 20.12.2012, Folie 12

MULTIPLE LAYER DEPTH PROFILE
(Case Study)

DepoTech 2012 O.Univ.Prof.Dipl.-Ing.Dr.techn. Karl E. Lorber, 20.12.2012, Folie 13

 2.3 Groundwater Pollution
(Case Study)

GROUND WATER POLLUTION caused by MOLECULAR DIFFUSION TRANSPORT

PROCESS.
Correlation between GROUND WATER TABLE HEIGHT [m] and
CONCENTRATION of POLLUTANT (e.g. Chloride) in GROUNDWATER-PROBE [mg/L].

MODEL PREDICTION

(source: RAUPENSTRAUCH & SCHNBERG 2010)

DepoTech 2012 O.Univ.Prof.Dipl.-Ing.Dr.techn. Karl E. Lorber, 20.12.2012, Folie 14

 Groundwater Pollution
(Case Study)
OBSERVED FIELD MEASUREMENT RESULTS

(source: RAUPENSTRAUCH & SCHNBERG 2010)

Observed TEMPERATUR INCREASE with local HOT-SPOTS (EXOTHERMIC

REACTION) during high GROUNDWATER TABLES.
No Correlation with local PRECIPITATION.
Nitrification Phenomena: NH4+ NO3-

DepoTech 2012 O.Univ.Prof.Dipl.-Ing.Dr.techn. Karl E. Lorber, 20.12.2012, Folie 15

 3. PYROMETALLURGICAL
TREATMENT
STATE-OF-THE-ART: Melting of FINE DROSS RESIDUES together with
Al-SCRAP in a salt cover Rotary Furnace (RF) or Tilting Rotary
Furnace (TRF).

Tilting Rotary Furnace in secondary Aluminium Industry

Product: Metallic Aluminium
Residue: Salt Slag or Salt Cake (i.e. Hazardous Waste EC
100310*)
DepoTech 2012 O.Univ.Prof.Dipl.-Ing.Dr.techn. Karl E. Lorber, 20.12.2012, Folie 16
 3.1 Treatment & Recovery Process
for Aluminium Dross and Salt Cake
SALT CAKE LEACHING & CRYSTALLIZATION PROCESS
followed by CALCINATION of OXIDIC RESIDUES

DepoTech 2012 O.Univ.Prof.Dipl.-Ing.Dr.techn. Karl E. Lorber, 20.12.2012, Folie 17

3.2 Calcination & Refining of OXIDIC
RESIDUES
Oxidic Residue (i.e. Hazardous Waste EC 100310*) can be
REFINED by CALCINATION (e.g. 24h Treatment at 1200 C)
VALUE ADDED PRODUCTS

MATERIALS COMPOSITION

unwanted compounds

DepoTech 2012 O.Univ.Prof.Dipl.-Ing.Dr.techn. Karl E. Lorber, 20.12.2012, Folie 18

 4. Conclusions
Due to the Properties of Wastes Criteria H3-A, H4, H5 and
H13, ALUMINIUM DROSS as well as FINE DROSS RESIDUES
are HAZARDOUS WASTES.
Al-DROSS shows high reactivity with water and moisture,
leading to high GAS FORMATION POTENTIAL and strong
LEACHABILITY.
Landfilling of Dross nowadays is forbidden, because of H2, CH4,
NH3 Migration with soil gas and groundwater pollution by F-,
Cl-, NH4+ (respectively NO3-) and CN-.
Groundwater Pollution cannot be prevented by surface capping, as
the pollution transport process is not percolation (advection)but
molecular diffusion.
STATE-OF-THE ART is the PYROMETALLURGICAL Treatment of
Dross under salt cover in a Rotary Furnace.
The remaining SALT CAKE is treated in the LEACHING &
CRYSTALLIZATION-Process for recovery of Al-Metal & Salt
Flux.
By CALCINATION-REFINING, remaining OXIDIC RESIDUES
can be converted into value added products.
DepoTech 2012 O.Univ.Prof.Dipl.-Ing.Dr.techn. Karl E. Lorber, 20.12.2012, Folie 19