23. - 25. 5.

2012, Brno, Czech Republic, EU

IMPACT RAW MATERIAL FOR PRODUCTION ZINC OXIDE IN RETORT FURNACES

Natalia LUPTAKOVA1 , Jarmila KEBISKOVA1, Evgeniy ANISIMOV2, Michal BENAK3,
Frantiska PESLOVA1
1

University of Alexander Dubcek in Trencin, Faculty of Industrial Technologies in Puchov,, I. Krasku 1809/34,
020 01 Puchov, Slovakia, natalia.luptakova@fpt.tnuni.sk, jarmila.kebiskova@fpt.tnuni.sk,
frantiska.peslova@fpt.tnuni.sk
2

Czech Technical University in Prague, Department of Materials Engineering, Faculty of Mechanical

Engineering, Karlovo nam. 13, 121 32 Prague 2, Czech republic, evgeniy.anisimov@fs.cvut.cz
3

SlovZink, a .s., Tovarenska 545, 018 64 Koseca, benak@nfs.sk

Abstract
The given paper is closely connected with the whole process of the manufacturing of zinc white (Zinc oxide ZnO) and specification of various problems which occur during the metallographic process. The purity of the
given zinc has crucial influence on the final quality of zinc white and occurrence of unused slag which is
stuck on the casement walls because ZnO is normally prepared in melting furnaces, the part of which is
casement wall.
We can assume that the zinc as a raw material has a different composition because of various European
suppliers and it means that the commercially pure zinc contains various phases in its structure. Considering
the suppliers, commercially pure zinc can be different with the reference to used zinc ore and the type of
production technology. On the basis of the occurrence of the residual content of other elements, it is possible
to make prediction about the material behavior in the metallographic process.
The melting process is carried out in specific types of furnace aggregates, which can be characterized by
different selection of ceramics for casement walls. Interaction of the molten zinc together with the casement
walls will have significant influence on extract of ZnO from commercially pure zinc.
The input raw materials of zinc were investigated in the given work and this investigation was done from the
aspect of structural and chemical composition of the material.
Keywords: zinc, zinc oxide, commercially pure zinc, casement walls of furnace aggregates, metallography,
phases
1.

INTRODUCTION

World-wide use of zinc oxide is in excess of 1.2 million tonnes annually [1]. Demand for zinc generally
follows industrial production or, more generally, global economic growth [2]. To name just a few everyday
items zinc or zinc compounds are used in paint pigments, plastics and rubbers, cosmetics, pharmaceuticals,
batteries, textiles. [3].
The work is focused on production of ZnO, where the primary material is crucial factor for high-quality of
output product and this primary is the input material for production. It follows work [4]. In this case, the
character of determination of occurred phases of cast is not such important but on the other hand, the
chemical composition as well as content of elements seems to be the most important.

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Zinc is a metal but it never occurs as a pure metal in the Earths crust [3]. Nowadays, American standards
are used for nomenclature of the commercial pure zinc (ASTM B6:07) and it is SHG (Special High Grade).
According to its chemical composition and additive elements, there are determined other nomenclatures,
such as: HG (High Grade) with the minimum content of Zn 99.95% and Prime Western (PW) with the
minimum content of Zn 98.50 % [5].
Impure zinc is called spelter and it stands for hard zinc [6]. Today, this nomenclature has been still used
for secondary or waste zinc. Nowadays, zinc is the most used metal in the galvanising process [3].
During the galvanising process, there is the occurrence of a few solid products, waste. The most important
type of the waste is the hard zinc (ZnH) which is on the bottom dross of the sediment and this sediment
reflects from 5 to 7 % of zinc usage in this process. The waste can be characterized by high content of zinc
[7]. During the galvanising processes, the waste is normally obtained and this waste has more than 80% of
zinc, it depends whether it is the hard zinc or it can even be in the form of ash [8]. The input raw material for
production of ZnO can be various types of zinc material.
2.

PROBLEMS WITH PRODUCTION OF ZnO

All the methods for production of ZnO depend on raw material base of zinc. Zinc can form various
compounds (ZnS, ZnSO4, ZnCO3) but zinc oxide is usually the most common used type [3]. The various
technological methods are used for its production, e.g.: direct method (American method) or indirect method
(French method). Slovak production of zinc oxide is based on the indirect method of production (French
method) in rotary furnace and this method was developed by firm Le Clair in 1840. The production process is
concerned with evaporation of zinc and its following oxidation with the oxide in air and it is according to
chemical reaction hereinafter [10]:
Zn (l) Zn (g)
(1)
Zn (g) + O2 (g) ZnO (s)
(2)
Rotary furnaces were developed with the view of minimal fuel usage. The exothermic combustion of zinc
vapour can be used to melt and vaporize the zinc. Rotary furnaces use a coke generator which provides a
high temperature carbon monoxide feed. The combustion of zinc vapour within the furnace provides radiant
heat to the furnace interior. The furnace must be fed solid zinc on a continuous basis. The disadvantage of
this furnace is that the yield of product is lower than alternate routes. It is the best suited to recovery of
bottom dross from hot dip galvanizing [9]. Zinc is used only in metal form in relation to French process and it
is the most significant factor for quality of zinc oxide. This is the reason why Zn has to have a content which
is more than 80%.
3.

EXPERIMENTAL PART

The attention was paid to the selected sample of zinc alloy for investigation of the microctructural phases
which occur in the zinc alloys. This given selected sample is different from other input materials as well as it
is inhomogeneous from the chemical aspect.
It is commonly fulfilled that the hard zinc created by intermetallic compounds, such as aluminium- saturated
(FeZn7) phase or phase which is determined by x-rays diffraction analysis [7]. It is easy to release zinc from
its compounds because it is not noble metal [10].
Intermetallic compounds in the hard zinc occur when there is the higher concentration of aluminium and iron
in the molten zinc and it is beyond the melting point at their given temperature. Although there is the perfect
management of zinc bath, the creation of the intermetallic phases can not be influenced due to addition of
aluminium during the melting process of iron in relation to galvanising process [7].

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Evaluation of the sample was done on the basis of chemical way (analysis by help of atomic absorption
spectrofotometric device VARIAN) and it is shown in the tab.1. The samples were removed as well as
processed from the ingot which contained hard zinc obtained from the galvanising industry (It was the
waste).
Table 1 Chemical composition (wt. %) of sample Project 1
Name of Sample

Pb

Cu

Cd

Ni

Fe

Zn

Al

Project 1

0.0006

0.00041

0.00033

0.0015

1.2

96.14

1.74

The specific areas of microstructures are shown in the figures from 1 to 7. Chemical composition was
processed by help of spectra (obtained with BDS method on JOEL Thermal FE SEM JSM-7600F) and
theyare introduced in the tables from 2 to 5. According to evaluation of occurrence of various elements which
can create various intermediate phases, it can be concluded partially.
Project 1 A

Fig. 1 Area analysis SEM microstructure

of Sample Project 1Aa

C,

O,

Al,

Si,

Cr,

Mn,

Fe,

Ni

Fig. 2 Linear and Area analysis of chemical

elements for sample Project 1Aa

Observation of the sample microstructure released that there were such areas which did not contain Zn. One
of such areas is shown in the figure 1. It is mosaic structure of grains where there are the carbides (content
of carbon is 15.35%) in the chain arrangement (spectrum 6) on the boundaries of the grains. The given area
in the figure 2 was also used for linear and area analysis and it showed that there are the elements which
are introduced in the table 2. The ratio of pale and dark areas is 5.4/2. The point analysis enabled to observe
chemical composition of elements relating to spectra from 2 to 5 and they were not different therefore they
are not presented in the table 2. On the other hand, high content of Cr, Fe and Ni seemed to be unusual.
Table 2 EDAX spectrum analysis of sample Project 1 Aa in Fig. 1 (in percentages)
Spectrum

Al

Si

Cr

Mn

Fe

Ni

Spectrum 2

8.32

3.18

0.63

2.12

2.10

0.97

44.85

17.83

Spectrum 6

15.35

3.38

0.60

1.72

21.55

1.03

40.48

15.90

Sum Spectrum

8.92

3.33

0.63

2.15

22.11

0.92

44.48

17.46

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Fig. 3 Sample Project 1Ab

C,

Al,

Si,

Cr,

Mn,

Fe,

Ni,

S,

Fig. 4 Area analysis of chemical elements

for sample Project 1Ab
The more detailed image of the grain boundaries (Fig. 3) represented the morphological arrangement of
individual carbides. Next, these carbides were investigated in the more detailed way. The research of the
structure showed that there is the occurrence of chrome oxides (Fig. 4). The chain arrangement is also on
the basis of the Cr, Fe, Ni spectrum 5. Analysis of sample Project 1Ab showed that the particular phases
are mutually different from the chemical aspect.
Table 3 Chemical composition of the elements for sample Project 1Ab
Spectrum

Al

Si

Cr

Mn

Fe

Ni

Spectrum 2

10.25

0.63

2.24

22.46

0.88

45.75

17.78

Spectrum 3

8.63

0.61

2.16

22.41

0.95

47.08

18.16

Spectrum 4

19.51

0.59

0.67

55.83

0.83

18.20

4.37

Spectrum 5

14.13

0.63

1.16

49.51

0.92

25.96

7.68

Sum Spectrum

10.27

0.64

2.15

24.92

0.94

44.11

16.98

The area analysis can be used for the much more precise determination of the occurrence of the elements,
which are in the individual modifications and they are normally created on the boundaries of grains (Fig. 4).
Project 1B

Fig. 5 Sample Project 1Ba

Fig. 6 Sample Project 1Bb

The detailed observation of the particular areas relating to microstructure (Fig. 5) released that chain
arrangement obtains sulphur (S = 0.48%). This area has high weight percentage of Fe, Ni, Cr. The chemical
composition of spectra from 2 to 5 seems to be the same in the contrast to spectrum 6 (tab. 4).

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Table 4 Chemical composition of the elements for sample Project 1Ba

Spectrum

Al

Si

Cr

Mn

Fe

Ni

Spectrum 2

8.18

0.56

2.46

0.11

22.83

1.03

46.07

18.77

Spectrum 6

14.01

0.47

0.26

0.48

65.42

1.02

14.89

3.45

Sum Spectrum

8.22

0.56

2.30

0.09

22.88

0.96

46.57

18.42

The detailed image of areas relating to microstructure can be seen in the figure 6. The chemical composition of
elements seems to be the same. Spectrum 5 contains high amount of C (13.93 wt. %) as well as Cr (60 wt %).
Project 1C
In the comparison with the investigated sample, it is
possible to conclude that the chemical composition is
different (see Fig. 7 and Tab. 5) and the given sample has
modification which is typical for input materials. The given
area can be characterized that it has non-uniform size of
grains where the phase is excluded on the boundaries
of grains. Zinc as well as other observed metals are
presented mostly in the oxide form or even in the form of
complex oxides. Matrix is mostly formed by zinc oxides.

Fig. 7 Sample Project 1C

Table 5 Chemical composition of the elements for sample Project 1C
Spectrum

Al

Zn

Spectrum 2

4.67

0.62

0.20

3.13

91.38

Spectrum 3

4.22

1.02

0.46

3.03

91.27

Spectrum 4

4.91

3.56

2.08

2.54

86.91

Sum Spectrum

4.83

2.13

0.98

2.88

89.18

The given area contains oxides, carbides, phosphorus and a little bit of aluminium. These compounds and
elements do not have negative influence on the production process of ZnO.
CONCLUSION
Conclusions can by summarised in the following point:

The production of zinc oxide utilizes the pure zinc (SHG) and secondary zinc (ZnH) as a input raw
material. According to study of the technological process, it is possible to conclude that there is the
continual proportion between the quality of raw material and input material (ZnO)

The best choice for other processing of the metallic zinc is closely connected with the usage of
chemical pure zinc. Because of the prize and technological difficulty, it is necessary to evaluate
processing of the waste zing in relation to galvanising process because the French method for
production of the zinc oxide in rotary furnaces is very effective.

23. - 25. 5. 2012, Brno, Czech Republic, EU

During the production of the ZnO, the primary raw material is seriously influenced by the other
additives. This fact is closely connected with the decrease of lifetime of furnace aggregates as well
as there is the increase of the fuel. The occurrence of the additive or impurities as well as other
unsuitable phases will have the significant influence on the whole technological process therefore
the attention must be paid to the input raw materials.

In the case of the occurrence of the structural phases, which do not contain zinc (but they can
contain the high chemical amount of Cr, Fe and Ni or other elements), it was proved from the
practical aspect that these phases have the negative influence on the whole process. There will be
the occurrence of the unwanted and negative chemical reactions and it will have also the negative
effect in relation to the ceramics of furnace case.

In relation to the selected sample which does not contain zinc (but high chemical amount of Cr, Fe
and Ni or other elements), there is the occurrence of the grains with the different morphology in the
comparison to grains containing zinc. This morphology reflects the occurrence of stress states I the
primary structure and these stress states have following influence on the decomposition of solid
phase. The phase transition of solid phase to gaseous phase will be carried out in the different
places of furnace at different thermal gradients and it has also negative influence on production
process of ZnO.

There is the recommendation to perform much more detailed analysis of the input material as wel as
research interactions of the molten secondary zinc with the other elements and with aggregates of
furnace case.

REFERENCES
[1]

International Zinc Association: Zinc Oxide Applications, Begium, 2011.

[2]

TOLCIN A.M. Zinc, U.S. Geological Survey. Mineral Commodity Summaries. USA. January 2011.

[3]

MCNAMARA, G. Fact-ite. Planet Earth. Earth Sciences for Society. Geological Society of Australia.

[4]

LUPTKOV, N. and kol. Microstructure Analysis of Zinc and Zinc Alloys. Machine Modeling and Simulations.
2011. ISBN 978-80-8075-494-5.

[5]

BS EN 1179:2003: Zinc and zinc alloys - Primary zinc. 2003.

[6]

JARE, V. Metalografie neeleznch kov. esk matice technick. Praha. 1950. 318-319 s.

[7]

TRPEVSK, J. and kol. Spracovanie odpadov zo zinkovn. Katedra neeleznch kovov a spracovania odpadov.
Hutncka fakulta. TU Koice.

[8]

SEDLKOV, Z., HAVLK, T. Vskyt neeleznch kovov v hutnctve eleze a ocele ich mon spracovanie,
TUKE. Katedra neeleznch kovov a spracovania odpadov. Acta Metallurgica Slovaca, 12, 2006, 2 p. 209-218.

[9]

International Zinc Association: Zinc Oxide Production Technology, Begium, 2011.

[10]

KOUDELKA, L., HORK, J., JARIABKA, P. Morfology of polycrystalline ZnO and its physical properties. Jourmal
of Materials Science. 1994. pp. 1497-1500.