Vous êtes sur la page 1sur 15

RMZ - Materials and Geoenvironment, Vol. 50, No. 3, pp.

627-640, 2003 627

Copper and Tin in Steel Scrap Recycling


Institute of Iron and Steel Technology, TU Bergakademie Freiberg, D-09596 Freiberg

Received: December 1, 2003 Accepted: December 10, 2003

Abstract: Copper is the key element related to surface defects of steel caused by a loss of
ductility in the temperature range of 1050-1200 C. Tin increases the negative effect of
copper. The main source of copper and tin in the steelmaking is obsolete scrap. The
possibilities and limits of contaminated steel scrap recycling and methods of scrap puri-
fication are discussed.

Key words: steelmaking, scrap recycling, scrap purification, copper, tin, tramp elements

1 COPPER AND TIN IN THE STEEL Alloying and tramp elements in steel, espe-
cially tin, modify the negative effect of cop-
per [2]. This interaction between alloying and
1.1 Effect of copper and tin on steel ser- tramp elements is considered a synergism
vice properties effect. Some elements amplify while others
neutralise the negative effect of copper. This
Copper and tin are harmful tramp elements effect can be illustrated by empirical expres-
in steels. They can directly influence the me- sions for the so-called copper equivalent
chanical properties of steel products. Cop- (Figure 1). From this equivalent it is con-
per contributes generally to an increase in cluded, that elements such as antimony, tin
corrosion resistance and mechanical strength and arsenic when present in steel increase
associated with a ductility loss of steels. the harmful effect of copper while the pres-
Copper is the key element related to hot ence of nickel reduced it. 0.4 % of copper in
shortness caused by a loss of ductility in the steel exerts the same negative influence on
temperature range from 1100 to 1300 C. the steel product properties as the sum of (0.3
Surface defects can appear along the whole % Cu + 0.02 % Sn). Due to this synergism
hot processing line, during casting or hot effect, the tramp elements copper and tin
rolling (Figure 1). must be considered together. The tolerable
contents of copper and tin are fixed by stan-
It can be seen that hot cracks begin to form dards for different steel qualities. Whereas
at copper contents above 0.2 % [1] where the the maximum content of copper in bar steel
crack depth is a function of copper content is 0.4 %, that of cold-rolled sheet is only 0.04
in the steel. The crack depth increases with % (Figure 1). In the course of casting and
increased copper content. hot rolling not only copper and tin content
in steel must be fixed, but also the sum of all

Scientific paper
628 SAVOV, L. ET AL.

Figure 1. Copper problems in steelmaking

tramp element contents has to be considered. Obsolete scrap consists of iron or steel prod-
For example, the sum of copper, chromium, ucts discarded after the end of their service
molybdenum and nickel contents is con- life. Post-consumer steel products include old
trolled. passenger cars, steel cans, electric appliances
and other items. Obsolete scrap is often
1.2 Main sources of copper and tin mixed or coated with other materials, such
as copper, tin, glass and polymers. For this
Copper and tin are introduced to steel using reason the content of tramp elements in ob-
steel scrap in the steelmaking process (Fig- solete scrap is usually high and this scrap is
ure 2). Generally, steel scrap is divided into a main source of copper and tin in steelmak-
the three categories: ing processes. Obsolete scrap is usually pro-
home scrap from steelmaking and roll- cessed by shredding. Thereby the scrap is
ing mills, crushed and the steel parts are separated from
process scrap from steel processing the other nonferrous parts. In spite of crush-
lines, ing, a mix of steel and copper parts exists.
obsolete scrap from consumer goods. This is the main cause for the fact that non-
magnetic copper remains in the magnetic,
iron-rich fraction.

RMZ-M&G 2003, 50
Copper and Tin in Steel Scrap Recycling 629

Scrap from higher copper containing steels ing of 1t steel plate depending on the thick-
such as concrete reinforcing steels or stain- ness of steel plate and tin layer. This means
less steels, is a second main source of cop- that the steel melt can contain 0.2 to 0.8%
per in steelmaking. Copper appears in this tin after the smelting of the tinplate scrap. In
scrap in the dissolved state. Germany, the largest amount of tinplate scrap
Tin is supplied by tinplate from beverage and is obtained by separation from household
food cans and other packages. Tinplate is a refuse. The average tin content in the refuse
cold-rolled steel plate coated with a thin layer of separation scrap is 0.3 % [3].
of tin. 2 to 8 kg pure tin is used for the coat-

Figure 2. Main sources of the steel impurities copper and tin

RMZ-M&G 2003, 50
630 SAVOV, L. ET AL.

1.3 Appearance of copper and tin in charge materials,

steel scrap and steelmaking dust

The main impurity contents in steel charge materials of Voest-Alpine Linz AG are shown in
(Figure 3) [4].

Figure 3. Main impurity contents in charge materials Voest-Alpine Linz AG

(oxygen steel plant) [4].

Copper impurities coming with the hot metal can be neglected. But the copper impurities
from shredder and obsolete scrap are remarkably high.

Figure 4. Copper impurities of steel scrap in Japan 1996 [5].

RMZ-M&G 2003, 50
Copper and Tin in Steel Scrap Recycling 631

A Japanese study deals with steel scrap pol- established that in contrast to tin and lead no
lution by tramp elements [5]. The samples essential copper upgrading occurs in the
from the scrap were taken nationwide in Ja- steelmaking dust.
pan. Copper, tin and chromium contents in
the scrap samples were controlled. The fre- Copper and tin are not found in steelmaking
quencies of the measured copper contents are slag. The melting temperatures of pure cop-
given in Figure 4. The average copper con- per and tin are much lower in comparison
tent in the steel scrap is 0.297 %. with steel (1083 C for copper and 232 C
for tin), Figure 5. At typical steelmaking tem-
Dust emissions in steelmaking processes peratures, around or above 1600 C, the solu-
exhibit higher levels of tin and other heavy bilities of copper and tin in the steel melt are
metals contained in the zinc coating [6]. The practically unlimited.
tin content of EAF dusts is not sufficient to
ensure economically viable recovery. On the In comparison with iron, copper and tin are
other hand, increased levels of tin in the BOF characterized by a lower oxygen affinity.
dust make their usual recycling via the sin- Accordingly, they are not removed by oxi-
ter plant/blast furnace route problematic be- dation and transferred to the slag.
cause of the harmful effects of zinc in the It is therefore understood, that copper and
blast furnace. In steelmaking practice, it was tin stood appear only in the steel.

Figure 5. Behaviour of copper and tin in steelmaking processes.

RMZ-M&G 2003, 50
632 SAVOV, L. ET AL.

2 ENRICHMENT OF COPPER AND TIN per contents in the obsolete scrap. There ex-
IN STEELMAKING PROCESSES ists a tendency to employ more electric mo-
tors and copper holding electronic elements
2.1 Development of scrap quality in the cars. Due to the miniaturization of
these parts, they are difficult to crush and to
The development and forecast of scrap qual- sort by shredding, with the result of increas-
ity standards is given in Figure 6 for the pe- ing copper contents in the scrap, which are
riod 1985-2015 [6]. During this period the accumulated. In the steel and lead to a regu-
amount of home scrap is falling, but no lar copper upgrading in the steel circle. Tin
changes of the processing scrap occur. On content in the steel circle increases at the
the other hand, the obsolete scrap, which is same time. This is caused by increasing re-
the main source of the tramp elements in- cycling rates of tin-plate packages. The de-
creases. The development in the automobile velopment of material flow is schematically
industry is the cause for the increasing cop- shown in Figure 7. The copper and tin con-
tents are given as dark-grey areas.

Figure 6. Development of scrap quality standards [6].

RMZ-M&G 2003, 50
Copper and Tin in Steel Scrap Recycling 633

Figure 7. Development of scrap material flow.

2.2 NEED FOR COPPER AND TIN Thus copper and tin removal from scrap by
REMOVAL pre-treatment is desirable. With the follow-
ing benefits to be aimed at:
The developments in steel making and non- use of contaminated, low-cost steel
ferrous metal making are illustrated in scraps to produce higher steel grades,
Figure 8. avoidance of dumping of higher cop-
per and tin containing scraps as waste
The steel industry has always aimed at a materials,
higher steel yield through rationalisation of support of a sustainable strategy to in-
equipment and technology. The customer tegrate contaminated steel scrap into a
demands for improved steel service proper- secondary material circuit of the met-
ties require lower impurity levels. On the als copper and tin.
other hand, the incoming scraps feature in-
creased impurity levels, so that the steel-
makers face the difficult task to produce
steels with lower tramp element contents
from higher tramp element holding scraps.

RMZ-M&G 2003, 50
634 SAVOV, L. ET AL.

Figure 8. Developments in steel making and nonferrous (NF) metal making economy.

3 PROPOSED METHODS FOR SCRAP to the first route. The second route encom-
AND MELT PURIFICATION passes the chemical and metallurgical re-
moval methods. The main advantage of met-
3.1 Suggested methods allurgical separation consists in the fact that
the tramp elements can be removed indepen-
Copper and tin dissolved in steel melts are dent of the their appearing form in the scrap,
not oxidised in the presence of iron due to e.g.. as segregations coatings or in the dis-
their lower affinity for oxygen. This means solved state.
that these elements cannot be removed from For the treatment of molten steel several pro-
a steel scrap melt in a common pyrometal- cedures were suggested and tested on an ex-
lurgical process, as is the case with alu- perimental scale:
minium, i.e., which is easily oxidised and treatment by reaction with sulphur-con-
dissolved in the slag. In order to remove taining slag,
tramp elements from scrap, there exist es- vacuum distillation and
sentially two different pre-treatment routes other treatment methods.
(Figure 9). Mechanical separation belongs

RMZ-M&G 2003, 50
Copper and Tin in Steel Scrap Recycling 635

Figure 9. Steel scrap pre-treatment to remove copper.

3.2 Steel scrap pre-treatment In Japan, the flow-off of copper droplets from
the steel surface as a function of the oxygen
Laboratory-scale tests of scrap pre-treatment partial pressure has been investigated [9].
to remove copper are explained in Figure 10. Copper easily flows down the magnetite and
In the separation method by smelting of cop- iron-silica surfaces, but the adherence be-
per parts from a mix with solid steel (1), tween copper droplets and wustite is remark-
the difference in the melting temperatures of ably high.
the impurity elements and the steel is used.
The pre-melted copper is separated by liq- The disadvantages of the separation by
uid flow and is collected while the steel parts smelting of copper parts are due to a low
remain in the solid state. This method was separation rate, which is caused by copper
investigated and realised for automobile losses (for example flow of copper into cavi-
scrap and scrap from electromotors in the ties) and steel losses caused by oxidation and
USA [7, 8] with the result that the copper re- are particularly due to the remarkable fuel
moval rate was insufficient. Through oxi- costs. On the other hand, energy can be saved
dization, some copper was enclosed in the when the separation by smelting is combined
iron oxide. Under reduced conditions, the with scrap preheating.
alloying of the liquid copper with the steel
was increased.

RMZ-M&G 2003, 50
636 SAVOV, L. ET AL.

Figure 10. Proposed methods to remove copper and tin from steel.

The extraction method of copper by nonfer- temperature range from 800 to 1000 C [8].
rous metal baths (2) is based on the fact For the treatment of 1 t of scrap, at least 4 kg
that the copper solubility in a metal bath of of slag were necessary to decrease the cop-
lead [10] or aluminium [11, 12] is higher than that per content from 0.3 to 0.1 % under a nitro-
of steel. But for the reduction of the copper gen or argon gas atmosphere.
content in 1t of scrap from 0.3 % to 0.1 %,
1000 kg lead would be necessary [10]. In spite A gas mix of chlorine, hydrogen and air (4)
of a considerable degree of copper removal, was used for the removal of copper in refer-
the high lead consumption makes this ence [13]. In this procedure, the surface of the
method unacceptable. The solubility of cop- steel parts in the scrap was oxidized by air
per in an aluminium bath is 65 % at 730 C. with respect to the iron loss by chlorination.
At a temperature of 750 C, 80 % of the cop- 74 % of the copper was removed from 3.5
per can be removed in only 20 min [11, 12]. But kg of scrap at a time of 90 min. A gas mix
in this study [11, 12], it is not clear which amount consisting of chlorine and air was also used
of aluminium-copper-alloy is enclosed in the for copper removal [14]. The advantage of this
scrap in a real process. treatment is due to the fact that simulta-
neously with the copper other tramp elements
To remove copper from steel, an extraction such as lead and tin can be removed while
method using sulphur-containing slag disadvantages such as:
melts (3) can be used [8] where the slag con- - the presence of toxic treatment gases
sists of sodium sulphide and iron sulphide. and
Copper is concentrated in this slag during - oxidation of iron,
the treatment. The sodium sulphide content, have to be taken into account.
e.g., was increased from 19 to 25 % in the

RMZ-M&G 2003, 50
Copper and Tin in Steel Scrap Recycling 637

3.3 Slag extraction Together with the slag composition, tempera-

ture and composition of the steel bath, espe-
Figure 11 illustrates the conditions of cop- cially its carbon content, are important pa-
per removal from steel melts using sulphur- rameters in this removal process. Sodium
containing slags. The principle is based on sulphide, sodium sulphate or sodium carbon-
the fact that copper sulphide is more stable ate were added to the slag for fluidisation.
than iron sulphide at temperatures above Because of the rather low copper distribu-
600 C [8, 10, 15-18]. tion coefficient, the consumption of S-con-
taining slag is high. For example, a treatment
In various publications, the copper removal of 1 t of steel requires 100 kg of slag. An-
capacity of slags based on iron sulphide and other disadvantage of this method is related
sodium sulphide was investigated [10, 15-18]. to increasing sulphur contents in the steel.

Figure 11. Copper removal from steel melts using S-containing slags.

RMZ-M&G 2003, 50
638 SAVOV, L. ET AL.

3.4 Other scrap purification methods An unusual method for copper removal from
steel melts has been tested in the Ukraine [20,
Figure 12 shows other methods for copper 21]
. The steel was filtrated using filters from
removal from steel. Al2O3-ZrO2 ceramics. The rate of removal
was about 30 %. The effect was explained
The dilution by addition of copper-free ma- by the absorption of copper on the ceramic
terial to the steel bath represents an appar- surfaces. The injection of ceramic particles
ent purification method but is not accept- into a Cu-containing steel bath caused an
able as a real long-term metallurgical so- increase of the removal rate.
lution to the problem.
The negative effect of copper on crack for-
The harmful effect of copper can be balanced mation in construction steels can also be re-
out by addition of alloying elements such as duced through controlled process manage-
Ni and Al [19]. The addition of nickel in a pro- ment. A decreased secondary cooling rate in
portion of 2:1 or 1:1 neutralizes the harmful continuous casting of copper-containing
properties of the copper. In a recent study steels lead to a decrease of crack depth [22]
from Leeds University, England, the increas- (Figure 12).
ing of aluminium content in the steel with
respect to neutralisation of copper has been
investigated [19].

Figure 12. Further methods of copper removal from steel [19-22].

RMZ-M&G 2003, 50
Copper and Tin in Steel Scrap Recycling 639

3.5 Vacuum distillation does not influence the distillation rate. In this
range of pressure the distillation rate is de-
Copper can be removed from steel baths by termined by diffusion in the steel melt rather
vacuum distillation. This separation method than by gas diffusion or free surface vapor-
is based on the distinct differences in vapour ization.
pressure between copper and steel. The cop-
per vaporizes both in the elementary state The ratio of free-surface to volume of the
and in the form of volatile copper com- steel melt also has a considerable influence
pounds [24, 25]. on the distillation rate. The steel bath sur-
face during vacuum distillation must be free
The vacuum distillation of copper and tin- from slag and reaction products in order to
containing steel melts has been investigated avoid blockage of the distillation.
in a vacuum induction furnace [23] (Figure
13). It was found that the removal of a con- The distillation rate further increases with
siderable amount of copper and tin from steel increasing steel bath temperature (Figure 13),
melts under reduced pressure is possible and intensified stirring. Inductive stirring of
(Figure 13). The reduced pressure was the the steel bath, e.g., in the vacuum induction
main factor in the vacuum distillation pro- furnace, generates a strong flow field, which
cess, which must be below 1 mbar. The de- is unfavourable for vacuum distillation from
crease of the gas pressure in the range from the free surface. Turbulence of the steel flow
1 to 0.1 mbar leads to a clear increase of the near the free surface becomes as a main in-
distillation rate of copper, while a further fluencing factor on the distillation rate when
decrease of the gas pressure below 0.1 mbar diffusion in the steel bath is negligible.

Figure 13. Copper removal from steel melts by vacuum distillation [23].

RMZ-M&G 2003, 50
640 SAVOV, L. ET AL.

4 SUMMARY AND OUTLOOK In future studies it will be necessary to in-

vestigate the influence of the turbulent flow
In the present paper the methods of removal of the steel bath on the distillation rate of
of tramp elements such as copper and tin copper and tin, e.g., during electromagnetic
from steel scrap are presented. Theoretical stirring of the melt. It is assumed that the
concepts and methods of steel scrap purifi- distillation rate increases with a specified
cation have been discussed along with de- magnetic field imposed on the steel bath.
tails regarding practical performance.

Effect of Tramp Elements in Flat and Long Prod- [11]
IWASE, M., TOKINORI, K., OHSHITA, H. (1993): Iron
ucts. Final Report, Contract No. 7210-ZZ/ and Steelmaker 20, No. 7, pp. 61-66.
555+ZZ/564, EGKS, Brussels, 1995. [12]
IWASE, H., OHSHITA, H. (1994): Steel Research 65,
HERMAN, J. C., LEROY, V. (1996): Iron and Steelmaker No. 9, pp, 362-367.
23, No. 12, pp. 35-43. [13]
H ATSCHER , N. (1998): Informations-Zentrum Iron and Steelmaker 23, No. 8, pp. 43-45.
Weissblech e. V., Kasernenstr. 36, 40213 [14]
MATSUMARU, K. (1993): Removal of copper from iron-
Duesseldorf, persnliche Mitteilung. based scraps by Cl2-O2 gas mixtures. Current
PRELINGER, H. (1997): Verhalten der Begleit- und Advances in Materials and Processes 6, p. 1087.
Spurenelemente bei der LD-Stahlerzeugung und [15]
BURSTROEM, E., YE, G. (1991): Scand. J. Metallurgy
deren Auswirkungen auf die Stahleigenschaften. 20, No. 2, pp. 126-134.
In VDEh Kontaktstudium Metallurgie, Teil IV: [16]
PRELINGER, H., HIEBLER, H. (1984): Berg- und
Recycling, Freiberg, 26-28 Mai 1997. Httenmnnische Monatshefte 129, No. 9, pp.
TOI, A., SATO, J., KANERO, T. (1997): Tetsu-to-Hagane 333-338.
83, No. 12, pp. 850-855. [17]
COHEN, A., BLANDER, M. (1998): Metallurgical
NORO, K., TAKEUCHI, M., MIZUKAMI, Y. (1997): ISIJ Transactions B 29B, No. 4, pp. 493-495.
International 37, No. 3, pp. 198-206. [18]
L EE , J. (1997): Kupferproblematik beim
LEAK, V. G., FINE, M. M., DOLEZAL, H. (1973): Sepa- Schrottschmelzen. Aachen: Shaker Verlag, ISBN
rating Copper from Scrap by Preferential Melt- 3-8265-2320-2.
ing. US Dept. of the Interior, Bureau of Mines [19]
COCHRANE, B. (2000): Materials World, July, pp. 17-19.
Report of Investigation 7809. [20]
JIMBO, I., SULSKY, M. S., FRUEHAN, R. J. (1988): Iron VELICHKO, A. G. (1991): Copper in Steel and
and Steelmaker 15, No. 8, pp. 20-23. Problems in Removing it. In Steel in the USSR
SANO, N., KATAYAMA, H., SASABE, M., MATSUOKA, S. 21, No. 7, pp. 299-302.
(1997): Research Activities in Japan on Removal [21]
of Residual Elements from Ferrous Scrap. In: (1997): Journal of the University of Science and
Iron and Steel Today, Yesterday and Tomor- Technology Beijing 19, No. 6, pp. 538-541.
row. A Conference to Celebrate the 250th Anni- [22]
versary of Jernkontoret (Stockholm 11-14 June International 26, Supplement, pp. S18-S21.
1997). Stockholm: Norstedts Tryckeri, 1997. [23]
SAVOV, L., JANKE, D. (2000): ISIJ International 40,
Conference Proceedings, Vol. 1, pp. 15-26. No.2 , pp.95-104.
ISBN 91-973072-1-1. [24]
J ANKE , D. (1987): Entwicklungen der Tetsu-to-Hagane 82, No. 2, pp. 31-36.
Stahlraffination zur Absenkung der Gehalte an [25]
ONO, K., ICHISE, E., SUZUKI, R., HIDANI, T. (1995):
unerwnschten Begleitelementen. In: Freiberger Steel Research 66, No. 9, pp. 372-376.
Forschungshefte B259, VEB Deutscher Verlag [26]
fr Grundstoffindustrie, Leipzig, S. 73-105. (2000): Materiali in Technologie 34,No. 6, pp.
RMZ-M&G 2003, 50
Copper and Tin in Steel Scrap Recycling 641

Baker in kositer v recikliranem starem elezu

Povzetek: Oligoelementi v jeklu praviloma povzroajo napake pri vroi predelavi. Glavni
koliini bakra in kositra prideta v jeklo pri taljenju razlinih vrst starega eleza. Bakra je
zelo malo v grodlju, veliko pa ga je v starem elezu dobljenem pri razgradnji avtomobilov,
saj ti vsebujejo veliko elektromotorkov in elektronskih delov. V jeklarskem vloku se
pojavlja edalje ve ploevink, kar pomeni poveanje koliine kositra.
V lanku so obravnavane razne metode odstranjevanja bakra iz starega eleza ali iz
taline. Opisani so mehanizmi postopkov ter priakovana stopnja odstranitve bakra. Lahko
ga odstranimo s segrevanjem vloka na temperaturo njegovega talia, s topnostjo bakra
v razlinih barvnih kovinah, s pomojo uporabe sulfidnih linder in s plinskimi
meanicami, ki vsebujejo klor ter z vakuumsko destilacijo.
Z uinkovitim odstranjevanjem bakra in kositra iz vloka bo mono uporabljati razne
odpadne surovine z vijim deleem teh dveh elementov.

RMZ-M&G 2003, 50