Slags, copper refining

Additional physico-chemical information

Administrative data

Endpoint:

other: representative mineralogy

Type of information:

experimental study

Adequacy of study:

key study

Reliability:

2 (reliable with restrictions)

Rationale for reliability incl. deficiencies:

other: No GLP study but other quality assurance

Cross-reference

Cross-reference 1

Reason / purpose for cross-reference:

reference to same study

Cross-reference 2

Reason / purpose for cross-reference:

reference to other study

Data source

Reference

Reference Type:

study report

Title:

Unnamed

Year:

2010

Materials and methods

Principles of method if other than guideline:

Chemistry /elemental analysis was determined using ICP (inductively Coupled Plasma spectroscopy). Metal speciation/metal mineralogy was assessed from Sequential extraction/metal analysis and mineralogical analysis (XRD and microscopes equipped with EDS (Energy Dispersive Spectrometry) and WDS (Wavelength Dispersive Spectrometry) analysers. The interpretation of the overall results was performed by expert (with profound knowledge of metal particularities).

GLP compliance:

no

Remarks:

but equivalent Quality Assurance

Test material

Test material information

Constituent 1

Reference substance name:

Slags, copper refining

EC Number:

266-970-4

EC Name:

Slags, copper refining

Cas Number:

67711-94-8

Molecular formula:

The substance is a UVCB for which it is not possible to provide a molecular formula and a molecular weight.

IUPAC Name:

slag, copper refining

Details on test material:

Sample collection made according to ECI/REACH Copper Consortium Standards Protocols (see IUCLID section 1.4 and 4.1 attachment)
Sample Description Sample Code Lab code
B8 copper-rich slag from Secondary smelter MC_B8_531_xxx_0904 09TT03335
B8 Cu-rich slag, from slag concentrator, primary smelter (representative, homogenized) slag concentrate 09TT03987
B8 Cu-rich slag from FSF, primary smelter (representative, homogenized) slag from FSF, primary smelter 09TT05248
B8 Cu-rich slag from anode furnace, primary smelter (representative, homogenized) slag from anode furnace 09TT05247

Results and discussion

Results:

The tested materials were characterized (physico-chemical and mineralogical properties) in view of the upcoming REACH registrations of copper intermediates and copper slags by the Copper Consortium.

Any other information on results incl. tables

The studied four (4) slag samples from copper refining contain 1- 38% copper, 16.1- 40.3% iron, 0.01- 3.1% nickel, 0.4- 11.2% lead, 0.01- 8.8% tin, 0.8- 3.5% zinc, 12.5- 32% SiO2 and 0.05- 5.6% sulphur. As they vary in chemical composition, also the mineral composition varies between different samples.

Sample 09TT03335 consist mainly of amorphous glass (24.8%), metallic copper (12.7%), stannopalladinite –type copper –tin compound and lead –bearing amorphous glass (11.6%). Sample 09TT03987 consist mainly of fayalite (30.6%), magnetite (22.4%), chalcocite (17.7%) and amorphous glass (15.7%). Sample 09TT05247 consist mainly of delafossite (27.6%), magnetite (22.4%), cuprite (20.8%) and amorphous glass (20%) and the last sample 09TT05248 consist mainly of fayalite (61.1%) and amorphous glass (28.8%).

The chemical analysis of studied sampled are given in Table 7 and Table 8 and their mineralogical composition in Table 9 and Table 10 with distribution of copper.

 

Table7: Chemical composition of studied sample, part 1

Lab code			09TT03335	09TT03987	09TT05247	09TT05248
Sample code			B8	B8	B8	B8
Cu	P1	%	< 0.004	<0.005	0.02	<0.005
	P2	%	4.15	1.78	18.10	0.31
	P3	%	7.32	16.00	11.40	0.40
	P4	%	7.32	1.50	6.04	0.16
	Sum		18.79	19.28	35.56	0.87
	TOT	%	21.80	19.80	38.00	0.99
As	P1	%	< 0.004	<0.005	<0.005	<0.005
	P2	%	< 0.010	0.04	<0.011	0.03
	P3	%	< 0.02	0.03	<0.005	0.01
	P4	%	< 0.002	0.11	0.01	0.01
	Sum		0.00	0.17	0.01	0.05
	TOT	%	0.06	0.23	0.07	0.06
Fe	P1	%	< 0.004	<0.005	<0.005	<0.005
	P2	%	9.27	14.20	6.62	18.80
	P3	%	0.07	1.11	0.05	0.12
	P4	%	2.66	7.29	2.70	12.30
	Sum		12.00	22.60	9.37	31.22
	TOT	%	16.10	36.70	21.40	40.30
Ni	P1	%	< 0.004	<0.005	<0.005	<0.005
	P2	%	0.14	<0.014	0.20	0.02
	P3	%	0.04	0.01	0.01	<0.005
	P4	%	1.23	0.01	0.13	0.02
	Sum		1.41	0.01	0.34	0.04
	TOT	%	3.06	0.01	2.06	0.06
Pb	P1	%	0.12	<0.005	<0.005	<0.005
	P2	%	0.22	0.09	0.12	0.07
	P3	%	0.10	0.05	0.01	0.01
	P4	%	8.85	0.35	0.53	0.17
	Sum		9.29	0.48	0.67	0.25
	TOT	%	11.30	0.55	3.76	0.40

P1= H₂O, P2= H₂SO₄, P3= KCN+Br-MeOH, P4= HNO₃–soluble, TOT= total -, BM= bromine-methanol dissolutions, KEM= ion exchange chromatography, LECO = S/C analyzer, satmagan = Fe₃O₄analyzer, n.a. = not analyzed

 

Table 8: Chemical composition of studied sample, part 2

Lab code			09TT03335	09TT03987	09TT05247	09TT05248
Sample code			B8	B8	B8	B8
Co	TOT	%	0.32	0.03	0.09	0.02
Sb	TOT	%	0.43	0.06	0.06	0.03
Sn	TOT	%	8.82	0.01	0.36	0.12
Zn	TOT	%	3.45	0.75	2.08	1.99
Mo	TOT	%	0.01	n.a.	n.a.	n.a.
Ag	TOT	%	0.01	0.00	<0.010	<0.010
Se	TOT	%	< 0.003	<0.006	n.a.	n.a.
Sr	TOT	%	0.01	n.a.	n.a.	n.a.
Te	TOT	%	< 0.002	<0.006	n.a.	n.a.
Cd	TOT	%	n.a.	0.01	n.a.	n.a.
SiO2	KEM	%	20.50	17.70	12.50	32.00
Al2O3	TOT	%	2.51	2.23	1.01	2.96
Cr2O3	TOT	%	0.42	0.05	0.07	0.05
K2O	TOT	%	0.06	0.06	0.20	0.74
MgO	TOT	%	0.39	0.50	0.60	0.74
MnO	TOT	%	0.17	0.02	0.03	0.05
Na2O	TOT	%	0.35	0.25	6.97	0.39
CaO	TOT	%	3.07	1.57	0.51	2.06
TiO2	TOT	%	0.04	n.a.	n.a.	n.a.
Ba	TOT	%	0.02	0.04	n.a.	n.a.
B	TOT	%	0.07	n.a.	n.a.	n.a.
S	Leco	%	0.08	5.60	0.05	0.58
SO42-	KEM	%	n.a.	0.06	<0.025	<0.025
C	Leco	%	0.07	0.08	0.07	0.08
Satmagan		%	5.43	22.40	22.40	7.16
Surface area		m2/g	0.4	1.97	0.13	0.06
Density		g/cm3	5.04	5.57	4.8	3.8

P1= H₂O , P2= H₂SO₄, P3= KCN+Br-MeOH, P4= HNO₃–soluble, TOT= total -, BM= bromine-methanol dissolutions, KEM= ion exchange chromatography, LECO = S/C analyzer, satmagan = Fe₃O₄analyzer, n.a. = not analyzed

Applicant's summary and conclusion

Conclusions:

good quality study that assessed full chemistry and mineralogy of several representative Copper rich-slags. A RWC mineralogy can be derived for each specific slag (distribution pattern for each key element, i.e. % from Total into the various mineralogical forms/species present into the UVCB). They can be used for classification of the UVCB substance (mixture toxicity rules)

Executive summary:

The chemistry and mineralogy of Slag, copper refining B8 intermediate was assessed by Liippo et al, 2010 . In this assessment, samples of slags, corresponding to different types of materials were characterized. Samples were selected as representative for the production processes, depending on origin of the raw material (primary or secondary smelter). Sampling and sample preparation was performed according to the “ECI sampling protocol REACH B8” (see IUCLID Section 1.4 Analytical information):

Type I: slag concentrate, from concentrator (primary smelter)

Type II: slag from FSF flash furnace, primary smelter

Type III: slag from anode furnace, primary smelter

Type IV: slag from recycler, secondary smelter

The studied four (4) slag samples from copper refining contain 1- 38% copper, 16.1- 40.3% iron, 0.01- 3.1% nickel, 0.4- 11.2% lead, 0.01- 8.8% tin, 0.8- 3.5% zinc, 12.5- 32% SiO2 and 0.05- 5.6% sulphur. As they vary in chemical composition, also the mineral composition varies between different samples.

Sample 09TT03335 (type IV secondary smelter) consist mainly of amorphous glass (24.8%), metallic copper (12.7%), stannopalladinite –type copper –tin compound and lead –bearing amorphous glass (11.6%). Sample 09TT03987 (type I concentrator) consist mainly of fayalite (30.6%), magnetite (22.4%), chalcocite (17.7%) and amorphous glass (15.7%). Sample 09TT05247 (type III anode furnace) consist mainly of delafossite (27.6%), magnetite (22.4%), cuprite (20.8%) and amorphous glass (20%) and the last sample 09TT05248 (type II flash furnace/primary smelting) consist mainly of fayalite (61.1%) and amorphous glass (28.8%).

The chemistry and mineralogical data demonstrated that all tested slags correspond to the identity described above, although the mineralogical composition of the UVCB may vary slightly (see composition IUCLID Section 1.2). Slags from copper refining are made mainly of various glass, fayalite and/or magnetite, with largely varying amounts of elements such as Cu, Ni, Pb, etc. Depending on the process, these elements are mainly in the forms of sulphides + alloy/metal inclusions (e.g. slags from primary smelters), or mainly in the forms of oxides + alloy/metal inclusions (e.g. slags from converter and refining slags).

For each type of slag, characteristic distribution patterns for each constituting element were observed:

Type I: Representative slag was from concentrator (Sample code 09TT03987)

Copper is in the form of metal/inclusion (WC powder, 2.58% from total CU) + sulphides (88.43% from total Cu)+ oxides (8.99% from total Cu)

Lead in the form of Pb compounds (20% from total Pb)+ metal (WC powder, 80% from total Pb)

Nickel is in the form of metal/inclusion (WC powder, 100% from total Ni)

Zinc is in the form of sulphides (100% from total Zn)

Arsenic is in the form of alloy/inclusions (100% from total As)

Antimony is in the form of alloy/inclusion (100% from total Sb)

other metal elements: same distribution pattern than copper (WC)

Type II: Representative slag was from FSF primary smelter (sample code 09TT05248)

Copper is in the form of metal/inclusion (WC powder, 61.47% from total CU) + sulphides (38.52% from total Cu)

Lead in the form of Pb compounds (100% from total Pb)

Nickel is in the form of metal (WC powder, 50% from total Ni) + sulphides (50% from total Ni)

Zinc is in the form of metal (WC powder, 77.4% from total Zn) + sulphides (22.6% from total Zn)

Arsenic is in the form of alloy/inclusions (100% from total As)

Antimony is in the form of alloy/inclusion (100% from total Sb)

other metal elements: same distribution pattern than copper (WC)

Type III: Representative slag was from Anode furnace (Sample code 09TT05247)

Copper is in the form of metal/inclusion (WC powder, 61.5% from total CU) + oxides (38.5% from total Cu)

Lead in the form of Pb compounds (78.94% from total Pb) + metal (21.06% from total Pb)

Nickel is in the form of metal (WC powder, 61.50% from total Ni) + oxides (38.50% from total Ni)

Zinc is in the form of metal/inclusion in silicates (WC powder, 100% from total Zn)

Arsenic is in the form of alloy/inclusions (100% from total As) other metal elements: same distribution pattern than copper (WC)

Type IV: Representative slag was from Secondary smelter(Sample code 09TT03335)

Copper is in the form of metal/inclusion (WC powder, 74.21% from total CU) + oxides (25.79% from total Cu)

Lead in the form of Pb compounds (57% from total Pb) + metal (43% from total Pb)

Nickel is in the form of metal (WC powder, 67.12% from total Ni) + oxides (32.88% from total Ni)

Zinc is in the form of oxides (100% from total Zn)

Arsenic is in the form of alloy/inclusions (100% from total As)

Antimony is in the form of oxides (100% from total Sb) other metal elements: same distribution pattern than copper (WC)

For classification purposes, the two following Reasonable Worst Case (RWC) scenarios were retained:

RWC Sulphide scenario (applicable to major (primary) smelting and slags from concentrator):

Copper is in the form of metal/inclusion (WC powder, 2.58% from total CU) + sulphides (88.43% from total Cu)+ oxides (8.99% from total Cu)

Lead in the form of Pb compounds (WC, 100% from total Pb)

Nickel is in the form of sulphides (WC, 100% from total Ni)

Zinc is in the form of sulphides (WC, 100% from total Zn) Arsenic is in the form of alloy/inclusions (100% from total As)

Antimony is in the form of alloy/inclusion (100% from total Sb)

other metal elements: same distribution pattern than copper (WC)

RWC Oxide scenario (applicable to (primary and secondary) converting and refining slags):

Copper is in the form of metal/inclusion (WC powder, 61.5% from total CU) + oxides (38.5% from total Cu)

Lead in the form of Pb compounds (WC, 100% from total Pb)

Nickel is in the form of oxides (WC, 100% from total Ni)

Zinc is in the form of metal/inclusion in silicates (WC powder, 100% from total Zn)

Arsenic is in the form of alloy/inclusions (100% from total As)

other metal elements: same distribution pattern than copper (WC)

The above distributions patterns are conservative, in particular in respect to Pb (assuming Pb is either soluble compound form or partially soluble powder form) and to Nickel (assuming Ni is always in soluble compound forms). Considering the chemical compositions across industry, two grades for each of the above scenarios were derived in order to cover the worst cases for key drivers of classifications.