Metallurgist, Vol. 49, Nos.

78, 2005

RECYLCING OF THE DROSS FORMED IN HOT GALVANIZING

A. V. Shitov, A. N. Klimushkin, O. A. Stolyarskii, E. N. Agapeev, and P. V. Lobachev*

UDC 669.53

A comparison is made of the characteristics of dross formed on lines that make rolled products with anticorrosion coatings. Two methods of recycling dross to rid it of harmful impurities are examined. In distillation sublimation, an increase in temperature to 1280C helps maximize the amount of zinc that is transferred from the dross to the storage container. In this case, 7085% of the zinc is recovered from the dross. The resulting melt contains 99.5% zinc, 0.03% iron, and 0.04% aluminum. Up to 70% of the metallic zinc in dross is recovered when the dross is dissolved in an aluminum melt containing 1025% aluminum. The use of ammonium chloride increases the amount of iron removed from the secondary zinc and shortens the recycling operation.

In connection with the high cost of zinc, expenditures on this element constitute the main cost item in the hot galvanizing of steel rolled products. Developing an effective technology for recycling the dross, recovering zinc from it, and returning that zinc to the production cycle would significantly reduce the cost of obtaining galvanized rolled products. The company Mittal Stil Temirtau applies an anti-corrosion coating to products on two production lines a continuous hot-galvanizing and aluminizing unit (ANGA 1700) and a continuous hot-galvanizing line (CHGL). It was discovered during the operation of the lines that although both lines employ the same type of furnace-bath and the same methods to charge the zinc ingots and remove the dross, the chemical compositions of the galvanizing wastes on the lines are different especially in regard to their content of iron (see Table 1). The amount of dross formed on the CHGL is 1.5 times greater than on the ANGA 1700. An analysis of the operation of the lines showed that this difference is connected mainly with an increase in the amount of air used by the pneumatic shears of the CHGL. This air oxidizes the metal on the surface of the bath and leads to overcooling of microvolumes of the melt and consequent formation of conglomerates of zinc. The amount of dross formed also affects the speed of the strip as it moves through the bath. For example, it is 2.71 m/sec on the ANGA 1700 and 3 m/sec on the CHGL. The complex composition of dross makes it difficult to recycle. Dross includes roughly equal amounts of metallic and oxidized zinc in combination with intermetallic inclusions of iron and aluminum [1]. It is known from practical experience [2] that the complex composition prevents the dross from separating into metallic and oxidized zinc during melting. Thus, the metallic zinc can be separated from the oxidized zinc and the impurities of iron only by distillation sublimation. The latter operation is used by factories that make zinc. A laboratory unit has also been developed to realize this method. Inert gas is fed into the unit to prevent repeat oxidation of the zinc that is obtained. In tests that were performed, we used dross containing 94.498.7% Zn, 0.422.85% Fe, and 0.683.12% Al. The heats were made using a temperature regime
*

Yu. A. Kabanov, V. V. Polshikov, V. D. Petrov, and R. A. Mukaev also participated in this study.

Mittal Stil Temirtau AO. Translated from Metallurg, No. 7, pp. 6061, July, 2005.

296

0026-0894/05/0708-0296 2005 Springer Science+Business Media, Inc.

TABLE 1. Chemical Composition of Dross

Ahead of the strip Behind the inclined guide

99.15 98.04

0.492 1.105

0.199 0.784

99.43 98.01

0.363 1.235

0.046 0.577

Yield of secondary dross, % 22 17 12 5 0 1 2 3 4 5 Amount of NH4Cl, g/kg melt y = 0.4191x2 4.5255x + 21.668

Fig. 1. Yield of secondary dross in heats made with the use of flux.

which ensured the largest possible yield of metallic zinc. The results that were obtained showed that raising the temperature to 1280C helped maximize the amount of zinc recovered from the dross. The yield of useable zinc was 7085% in this case. The resulting melt contained 99.5% Zn, 0.03% Fe, and 0.04% Al. The distillation sublimation technology is relatively complex, so that its commercial use may not be feasible despite the large amount of zinc separated from the impurities; its realization will entail high material costs to build a suitable production facility. When dross is removed from the surface of the bath, about 75% of the dross is composed of portions of the pure part of the melt. It turns out that this part of the melt can be separated from the dross fairly simply by dissolving it in an aluminumzinc melt. Studies of this technique have been conducted under laboratory and factory conditions. It is known that when a melt is refined with just aluminum, the process of removing iron is fairly lengthy and only 2535% of the iron is separated from the impurities. Studies have shown that dissolving dross in an aluminumzinc melt containing 1025% Al makes it possible to recover up to 70% metallic zinc from the dross. Here, most of the zinc is transferred to the melt during the first two hours. The optimum melt/dross ratio is 2:1.5. It was established that the process of removing iron from the melt is affected only by the aluminum present in the initial melt, not the total amount of aluminum coming from the refining products. It is known [3, 4] that high temperatures increase the solubility of iron in zinc melts and thus decrease the amount of iron that is recovered. We thus conducted a study with temperatures in the range 580600C. In this case, 70% of the iron is removed from the melt, and the iron content of the final melt is only 0.05%. A decrease in temperature appreciably lengthened the time of dissolution of the dross while failing to produce a large amount of zinc. To be able to extract more secondary zinc from iron, shorten the melting operation, and decrease the amount of aluminum that is used, we conducted subsequent studies with the use of ammonium chloride. This made it possible to reduce the surface tension of the melt. When dross is melted without fluxing additions, impurity oxides and salts will envelop the zinc droplets and form a film around them that will inhibit their coalescence into larger inclusions. Fluxes destroy these films, thus freeing the metallic zinc. We dissolved dross in a zinc melt and corrected the melt with additions of aluminum in the range 15%. The temperature of the heats was kept at a constant level (580600C). The content of ammonium chloride was varied within the range 0.54.5 g/kg melt (see Fig. 1). 297

It follows from the results obtained from studying heats with the use of ammonium chloride that the optimum flux content ensures that the iron content of the final melt will be less than 0.01%; the amount of iron that enters the secondary dross is quite high about 90%. Chemical analysis of intermediate samples of the alloy taken during the heats showed that the contents of aluminum and ammonium chloride were optimal and the content of iron in the melt gradually decreased. In cases in which the content of even one of the refining materials did not correspond to this level, the iron content of the melt increased and later stabilized. The above-described method of recycling dross was used under factory conditions to correct the chemical composition of a furnace-bath as it was being changed over from the aluminizing-galvanizing regime to the galvanizing regime. This regime change involves bringing the aluminumzinc melt to the chemical composition 0.250.30% Al, 0.050.20% Pb, no more than 0.02% Fe, and the remainder Zn. This composition is obtained by melting zincaluminum ingots in the bath. Calculations showed that 370 tons of these ingots are needed to bring the aluminum content to the required level. Thus, in order to conserve ingots while still being able to correct the chemical composition of the melt, we used some dross that had a zinc content of 9899%. The technology developed here to correct the chemical composition of melts by using dross provides a relatively simple method for its partial recycling.

REFERENCES 1. 2. 3. 4. I. I. Teindl, New Methods of Applying Metallic Coatings [in Russian], Metallurgizdat, Moscow (1963). R. M. Cherkasskii, A. V. Maksimova, et al., Recovering zinc from galvanizing wastes, Stal, No. 2, 89 (1993). A. V. Vitkin and I. I. Teindl, Metallugical Coatings for Steel Sheet and Strip [in Russian], Metallurgiya, Moscow (1971). Tekhnologiya BIEK: Inform. Bull.

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