Norddeutsche Affinerie Group

From Anode slime to silver-doré

silver doré

Production control by XRF

D Michael Steffen
Dr.

Norddeutsche Affinerie AG, Hamburg, Germany

Aurubis AG, Hamburg, Germany

1 Production
1.

2. XRF analysis

3. Basics for XRF

The LBMA Assaying & Refining

Seminar, 24-25 March 2009 1
 1 Production
1.

2. XRF analysis

3. Basics for XRF

Aurubis
One of the largest
g copper
pp smelter and refiner p
produce ca. 1 Mio. t
Kupfercathodes from copper concentrates, copper scrap and
copper containing residues

Silver (ca. 1000 t) and Gold (ca. 30 t) from PM containing

slimes, sweep and fines, computer scrap and PM alloys.
Anode slime (product from electrolytic refining of copper
cathodes), is one of the most important source for precious
metals production.
p

At Aurubis anode slimes are treated in a modern Boliden top

blown rotary converter (TBRC) process in two routes and fully
controlled by XRF

The LBMA Assaying & Refining

Seminar, 24-25 March 2009 2
 Production line 1 (Detail)

Copper line Roasting, smelting,

converting to metal
phase PbO, SeO2, slag

Raw material

Anode slime, Cu-rich ( ~20 % PM) Ag-Doré (~ 92 % PM)

PM-dross (~ 2 % PM) TBRC 1

PbO
R
Raw material
t i l

Ag-Doré (~ 98 % PM) Rich bullion ( ~ 70 % PM)

To analyse by XRF silver anode TBRC 2

PM = Ag, Au, Pt, Pd, Rh, Ir, Ru Cupellation process
Impurities = Pb, As, Sb, Se, Sn,
Te, Bi, Ni, Cu, Cl

Production line 2 (Detail)

ZnPbAg-crust
Lead line
ZnPbAgAlloy (~25 % PM)

Raw material

Anode slime, Cu-poor (~ 7 % PM) Bullion (~ 4 % PM)

Cu/Pb-matte ( ~ 0,3 % PM) Electric Lead refining
furnace
Pb-concentrate (~ 0,01 % PM)
Rich bullion (~ 70 % PM)

PbO

To analyse by XRF
PM = Ag, Au, Pt, Pd, Rh, Ir, Ru Ag-Doré (~ 98 % PM)
Silver anode TBRC 2
Impurities = Pb, As, Sb, Se, Sn,
Te, Bi, Ni, Cu, Cl Cupellation process

The LBMA Assaying & Refining

Seminar, 24-25 March 2009 3
 Production lines

Copper line

Anode slime Ag-Doré

Silver anode
TBRC 1 TBRS 2

Lead line

Anode slime Silver tankhouse

Electric Lead refining

furnace Silver ingots
Playground for OES

1 Production
1.

2. XRF analysis

3. Basics for XRF

The LBMA Assaying & Refining

Seminar, 24-25 March 2009 4
 Sample preparation

Delivering by preparation milling sieving

pneumatic post

Ready for analysis pressing decomposition Weighing,

mixing with flux

XRF-Analysis

QS check by monitor sample XRF analysis

Direct pressed Metall sample

decomposed, milled, pressed with

binder

The LBMA Assaying & Refining

Seminar, 24-25 March 2009 5
 1 Production
1.

2. XRF analysis

3. Basics for XRF

Basics for XRF analysis

XRF mashines are stupid

They look only intensities

The LBMA Assaying & Refining

Seminar, 24-25 March 2009 6
 Basics for XRF analysis

reference essential !!!

Reference samples /
Calibration samples

calculation of functionally
available on the marked ? calibration
dependence

if not sufficient

create by yourself
analysing all elements >0,1 %,
or
influence of the intensities by
Collecting from the production attenuation

Example: Determination of Ag in Ag-Doré

Calibration ranges

Ag: 0,01 - 100 %

Au: 0,01 - 20,0 % Bi : 0,01 - 5,0 %

Pt : 0,002 - 1,0 % Cu: 0,01 - 10,0 %
Pd: 0,002 - 2,0 % Pb: 0,01 - 30,0 %
Rh: 0,002 - 0,5 % Sb: 0,001 - 0.5 %
Ir : 0,001 - 0,4 % Se: 0,001 - 5,0 %
Ru: 0,002 - 0,5 % Te : 0,001 - 6,0 %

Conclusion
Determination of Ag in Ag-Doré will be interact by 12 elements.
Calibration range will be made by 64 calibration samples.
Calculation of α-correction only for Ag will be made by 38 calibration samples.

The LBMA Assaying & Refining

Seminar, 24-25 March 2009 7
 Example: Determination of Ag in Ag-Doré
Calibration range without α−correction

Example: Determination of Ag in Ag-Doré

Calibration range after α-correction

The LBMA Assaying & Refining

Seminar, 24-25 March 2009 8
 Basic for correct analysis

Only possible with motivated, well skilled employees

The LBMA Assaying & Refining

Seminar, 24-25 March 2009 9