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Metallurgist, Vol. 54, Nos. 1112, March, 2011 (Russian Original Nos. 1112, Nov.Dec.

2010)

SYSTEMATIC USE OF WASTES FROM STEEL


PRODUCTION

A. N. Dildin, V. I. Chumanov,
and I. V. Chumanov

UDC 669.054.82

A feasibility study is made of the systematic recycling of bank slags from the Zlatoust Metallurgical Plant.
Thermodynamic and kinetic analyses are made of the metalslag system in the liquid-phase reduction of
bank steelmaking slags under laboratory conditions. The results that are obtained show that it is possible
to systematically recycle steelmaking slags of complex composition.
Key words: steelmaking slags, recycling, thermodynamic analysis, reduction of components.

The recycling and use of slag formed in steelmaking operations including bank slag is an important problem for
Russian metallurgy. This problem is especially acute at conversion facilities such as the Zlatoust Metallurgical Plant (ZMZ),
due to the complex composition of the compounds that are formed and the lack of relatively simple and efficient technologies for recycling them. According to one estimate, of the 5 million tons of material in the slag banks formed as a result of
production operations at the plant, 61% is slag from steel production, 19% is metallic material, 12% is refractory scrap, and
the rest is debris.
Resolving the problem of making efficient use of slag formed in steel production is currently the matter that is of the
greatest interest. The main approaches being taken to recycling this slag are well-known use of the slag in the construction
industry (including in the production of binders for low-grade cement), recovery of metals from the slags oxide component,
use of the slag in road building, etc. [13]. One scheme was proposed earlier [4] for utilizing bank slag of complex composition such as that formed by the ZMZ. Presented below are generalized results of studies that have been performed.
Physicochemical analysis of slag taken from different levels of slag banks shows that the contents of the simple oxides
in the slag change within the following ranges, mass %: SiO2 17.726.6, CaO 21.947.4, MgO 6.218.5, Al2O3 4.19.8,
MnO 2.15.3, Cr2O3 1.711.3, TiO2 0.31.5, V2O5 0.10.3, FeO 3.743.9, NiO 0.10.4 The phase composition of the slag
is relatively complex, and x-ray analysis reveals the presence of such compounds as instalite MgSiO3, ilmenite FeTiO3, augite
Ca(Fe, Mg)Si2O6, plagioclase (albite, calcine) (Na, Ca)(Si, Al)4O8, magnetite FeFe2O4, fayalite (Fe, Mg)2SiO4, and
hematite Fe2O3.
Determination of the average composition of ZMZ slags based on seven samples and its comparison with the composition of the metallurgical slags recommended for use in the production of hydraulic binders [5] showed that the ZMZ slags
have good binding properties (all the slags are basic). The activity modulus Ma of these slags, which characterizes their
hydraulic activity, changes within the range 0.170.49. This shows that the silica in the compounds which comprise the slags
is very active, and this was confirmed by the estimate of the silicate (silica) modulus Ms. The silicate modulus characterizes
the ratio of silicon oxide to the total content of oxides of aluminum and iron. On the whole, based on qualitative criteria the
bank slags can be regarded as basic, hydraulically active slags and can be used as raw materials in cement production.
We subsequently examined the feasibility of processing the bank slags in order to extract several alloying elements,
especially Mn, Cr, V, and Ti. These elements are present in the slags in the form of magnetic and nonmagnetic compounds,
South Ural State University (branch), Zlatoust, Russia; e-mail: zlat-susu@yandex.ru. Translated from Metallurg,
No. 11, pp. 4244, November, 2010. Original article submitted February 17, 2010.
0026-0894/11/1112-0737 2011 Springer Science+Business Media, Inc.

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TABLE 1. Chemical Composition of the Smelted Metal, mass %


C

Mn

Si

Ni

Cr

Ti

Cu

Al

Fe

5.34

1.5

0.07

0.75

3.30

0.15

0.02

0.16

0.04

0.2

0.08

87.9

4.92

7.6

3.50

1.26

8.85

0.41

0.45

0.57

0.02

0.3

0.16

70.1

6.34

4.5

2.2

0.6

21.0

0.5

0.55

0.25

0.02

0.1

0.8

62.8

Fig. 1. Dependence of the yield of usable metal on holding


time in the furnace.

which complicates their extraction by traditional methods. We thus performed theoretical and experimental studies of the
solid- and liquid-phase reduction of these metals in order to obtain a metallic semifinished product.
As is known, the completeness with which the alloying components in a metalslag system are reduced depends
on the temperature at which the process is carried out, the activities of the components of the slag melt, and the amount of
reducing agent that is used. Principles from the theory of regular ionic solutions were used to evaluate the activity of several
components of slag melts: it was determined for the oxide systems which were analyzed that at 13001600C the activity of
manganese oxide MnO changes within the range 0.0150.074 and the activity of ferrous oxide FeO changes within the range
0.220.66. Calculations performed for the system FeCO showed that the actual concentrations of FeO in slags of the aboveindicated composition exceed the equilibrium values. Thus, it is best to use carbon as the reducing agent and to attempt to
recycle the slag by a reaction of the type
(MeO) + Cs = [Me] + {CO}.
(1)
We constructed diagrams of the solubility surfaces of the components of the metal (MCSSD) in order to perform a
thermodynamic analysis of multi-component oxide systems that model the composition of the above-described steelmaking
slags. The analysis was performed to determine the conditions under which these systems are stable and are in equilibrium
with one another and the metallic melt. It was found that a metallic melt can be obtained from the given slags above 1300C
by using carbon, silicon, and aluminum as reducing agents. However, it is best if carbon is used to reduce the slags at the
ZMZ, since the silicon and aluminum already present in the above-indicated complex compounds would impede the reduction of the target metals. Here, silicon and aluminum would slow the reduction reactions even though they have a greater
affinity for oxygen than does carbon.
Trial heats involving the liquid-phase reduction of an enriched slag were conducted in a Tamman furnace. The demagnetized and nonmagnetic parts of the slag were reduced. The slag was mixed with crushed coke in a 10:1 ratio, poured into a
graphite crucible, and placed in the working space of the furnace. The time taken to form the liquid phase was 2040 min, the
exact time depending on the mass of the weighed sample and amount of heat supplied; the melt was held at a temperature
within the range 13501500C. Reducing time was increased by 10 min from one heat to the next. A total of 10 heats were
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completed. The results obtained from chemical analysis of the metal of the three most characteristic heats are shown in
Table 1; the dependence of the yield of usable metal on the length of the reducing period is shown in Fig. 1.
The quantity of metallic phase that was formed averaged 35% of the mass of the initial slag. The relatively high carbon content of the resulting metal can be attributed to the fact that some of the carbon in the graphite crucible was transferred
to the metallic melt. The data obtained from the trial heats were used to calculate coefficients describing the distribution of
several of the elements between the metal and the slag. For example, LCr = 5.83, LMn = 1.17, LNi = 12.37, LFe = 14.31.
The kinetic laws governing the behavior of the components in the metalslag system were studied on the trial heats.
The kinetics of the reduction process were described analytically by using an equation of chemical kinetics in the form
m

c j

dci ( ) / d = kni exp ( Eni / RT )

nj

(2)

j =1

where kn = [c]1n[]1 = const; ci is the concentration of the ith component, %; nj is the order of the reaction with respect to
the jth component; En is the activation energy of the process, J/mole; R is the gas constant, J/(moleK); T is the temperature
m
of the metal, K; is the time of the process, min; j = 1, 2, ..., m is the number of components in the melt; and n = j=1
nj is
the order of the reaction.
The temperature at which the metallic phase is formed depends in a complex manner on several factors, and as a
first approximation it can either be stabilized or can assumed to be linearly dependent on the time of the reduction process.
In connection with this, we simplified Eq. (2) and used the following relation to calculate the rate of change in the concentrations of the components
k n
(3)
dci ( ) / d = ni c i ,
M
where M is the mass of the melt, kg.
The results obtained from analyzing the experimental data were used to obtain the rate constants for the reactions in
which oxides are reduced from slag melts: kFeO = 0.067 kg/min, kCr 2O3 = 0.011 kg/min.
Conclusions. Results obtained from a thermodynamic analysis of the stability of oxide systems modeling the composition of banked steelmaking slags within a wide range of temperatures were used to develop and lab-test a technology for
recycling such slag. Use of the technology makes it possible to recycle the slag so as convert up to 35% of it into a high-carbon low-alloy charge material in billet form for use in production operations.
Studies were made of kinetic aspects of the reduction of the components of the metalslag system under transient
conditions.

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