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Introduction
Zinc has been widely used over the past century for numerous products such as precision die
castings and zinc sheet products, brass components and platings, and industrial chemicals
utilizing zinc oxide and other zinc derivatives. Moreover, due to its electrochemical features, the
predominant application for zinc is as a galvanic protective coating for steel and, as outlined in
Figure 1, nearly 50% of the annual zinc tonnage is consumed by galvanizing processes [Ref. 1].
Miscellaneous,
4%
Chemicals, 7%
Sheet, 7%
Galvanizing, 47%
Die Casting,
17%
Brass, 18%
8.0
7.5
7.0
Demand
6.5
Supply
6.0
5.5
Jan-07
Jan-06
Jan-05
Jan-04
Jan-03
Jan-02
Jan-01
Jan-00
Jan-99
5.0
FIGURE 2: Zinc Supply and Demand Trends with Projections for 2007 [Ref. 3]
Consequently, the negative impact that has developed as a result of the depleted zinc production
has been a sharp rise in primary zinc prices. Over a twelve month period from May 2005 to May
2006 (Figure 3), zinc prices rose at an unprecedented pace from US$0.565/lb. to US$1.625/lb.
In addition, these LME cash prices did not reflect surcharges, delivery fees and other extras
imposed by the zinc producers.
$4,000
$3,500
$3,000
$2,500
Zinc
HDG
$2,000
$1,500
$1,000
September-06
July-06
May-06
March-06
January-06
September-05
July-05
May-05
March-05
January-05
$0
November-05
$500
FIGURE 3: LME Cash Price for Zinc and Hot-Dipped Galvanized Steel (HDG) [Ref. 7 & 8]
Meanwhile, as the costs of zinc were rising rapidly, galvanized steel producers tried to maintain
analogous price increases for the finished hot-dip galvanized sheet steel (Figure 3), however, the
cost differential still impacted the bottom line for many producers. Zinc is now reported to
account for 25% to 30% of the cost of HDG steel, as compared to around 5% before the price of
zinc headed skywards [Ref. 5]. Hence, steel companies must now start to consider alternative
technologies for minimizing their zinc consumption such as tighter coating weight control and
recycling of metallic zinc waste materials.
Zinc Recycling
Zinc, like most other metals, is easily recycled and approximately 30% of the overall zinc
consumption is currently from secondary sources [Ref. 2]. Many zinc-based products can
reintroduce scrap components back into the production process with little variation. Brass scrap
and zinc die castings can be directly remelted and recast as new parts much in the same manner
as aluminum and iron castings. However, zinc-coated steel scrap and galvanizing process wastes
are not as readily returned to the manufacturing process flow. In 1996, it was reported [Ref. 2]
that the utilization of secondary zinc ingot by galvanizing facilities equated to less than 40% of
the tonnage of the zinc scrap, drosses, residues and wastes produced by the coating process.
Galvanized steel that has been either scrapped or recycled is typically just remelted through a
specialized system (quite prevalent in Electric Arc Furnaces) and the mill dust and volatized
galvanized coating ash are collected and stored. The zinc content of this mill dust has been
measured to be greater than 20wt% Zn [Ref. 9]. Although a significant amount of research has
been devoted toward converting this zinc-rich ash into a functional product, the results have been
mixed and a consistent, economically viable process has not been widely utilized. On the other
hand, it has been proven that metallic zinc may be recovered from unpainted galvanized steel
using a dedicated electrochemical process [Ref. 10] and the practicality of these procedures is
now being realized. Thus, only a minimal quantity of metallic zinc is currently recycled from
galvanized steel substrates.
Conversely, the largest source of zinc waste for galvanizing plants is zinc drosses and residues
from the molten galvanizing bath. Dross forms as a result of either oxidation of the zinc at the
bath surface or by intermetallic reactions with the iron in the bath that has been introduced by the
steel substrates being coated. In the two typical categories of galvanizing, general (or batch)
galvanizing and continuous galvanizing (CGL), the zinc baths possess variable amounts of
aluminum (0-0.05wt%Al: General & 0.12-0.3wt%Al: Continuous) resulting in different dross
compounds being formed. Looking at the zinc-rich corner of the Zn-Fe-Al phase diagram
[Figure 4], the Fe solubility and subsequent dross compounds can be observed for each of the
galvanizing regimes.
0.08
0.07
L+
0.06
L+
Iron (wt%)
0.05
L+
465C
0.04
0.03
L
0.02
0.01
0
0
0.02
0.04
0.06
0.08
0.1
0.12
0.14
0.16
0.18
0.2
0.22
0.24
Aluminum (wt%)
FIGURE 4: Zinc-Rich Corner of Zn-Fe-Al Ternary Phase Diagram at 465C [Ref. 11]
By analysis [Refs. 12, 13, 14] the floating top drosses (also known as ash or skimmings)
for general galvanizing consist primarily of ZnO with varying amounts of Zn5(OH)8Cl2 while the
dross on the bottom of the kettle is FeZn13 () [Ref. 15]. Analogously, the top dross in
continuous galvanizing is Fe2Al5 () and the bottom dross is FeZn10 () [Refs. 11, 15]. However,
during typical cleaning procedures to remove the accumulation of these drosses, a tremendous
amount of clean metallic zinc is also extracted from the galvanizing pots. General galvanizing
dross can contain between 40% to 80% metallic zinc [Refs. 12, 13, 14] while CGL dross may
contain up to 95% usable zinc [Ref. 14]. In 2003, DuBois [Ref. 16] noted that CGL drosses
contain minimal amounts of oxide particles (<1%) and the percentage of zinc entrained in the
removed dross volume is proportional to the operator skimming practices. Hence, when these
drosses are discarded and sold to recycling or metal trading companies, a phenomenal amount of
good zinc is also being lost with the waste material. A typical batch galvanizing plant may
generate up to 18 tonnes of ash (i.e. top dross) each month. If this dross contains 70% metallic
zinc, then it equates to over US$40,000 per month in lost zinc. A nominal buyback rate may be
recouped from a zinc recycling company, but, in general, a significant financial loss is being
incurred by the discarded zinc.
As one example of the zinc chemistry effects in the MZR, Table 1 provides an outline of the ICP
(Inductively Coupled Plasma) analysis of a representative processing run. Approximately
550kgs. (1210 lbs.) of top dross (skimmings) from a general galvanizing pot were heated for 3
hours with over 400kgs. (880 lbs.) metallic zinc extracted, resulting in a metal recovery in excess
of 70%. Furthermore, the zinc purity of the recovered metal was >99.6wt% Zn and was
analogous to the chemistry of the production galvanizing bath. Previous research [Ref. 21] has
indicated that controlled usage of secondary recycled zinc ingot in galvanizing operations can
provide a functional enhancement to primary zinc supply. Moreover, the zinc-depleted ash
(residual ash) from the MZR processing was still viable for sale at a reasonable rate due to the
induced purity of the retained ZnO and residual elemental Zn content.
TABLE 1: Identification of Zinc Chemistry for Input and
Output Products from a MZR System [Ref. 20]
Zn:
Fe:
Al:
Si:
Ca:
Pb:
Mg:
Dross
Analysis
Recovered
Metallic
Zinc
Residual
Ash
87.37
0.61
1.33
0.21
0.01
0.002
0.003
99.66
0.316
0.001
<0.001
0.001
0.008
<0.001
74.86
0.637
1.99
0.929
1.08
0.024
0.059
Inadvertent disposal of large volumes of metallic zinc in conjunction with dross waste from a
galvanizing bath is a significant problem that many coating companies may not be aware they
have. However, by utilizing a safe, effective thermal processing system, such as the Metaullics
MZR System, galvanizing operations can reclaim their own clean zinc, minimizing waste and
substantially impacting their bottom line.
Conclusions
Rising primary zinc prices have reached historic levels and are greatly impacting the raw
material costs of zinc consuming industries such as galvanizing, die casting and brass
manufacturing.
The quantity of metallic zinc contained within the waste materials of these zinc processing
facilities is extremely high, especially for producers of galvanized steel products.
The metallic zinc content of the waste drosses which are discarded from a molten zinc pot in a
galvanizing operation may exceed 90%.
Unlike die casting and brass manufacturing, currently only a minimal volume of recycled zinc
is directly returned to an industrial galvanizing pot.
Implementation of defined in-house procedures by galvanizing operations could help extract
higher fractions of valuable zinc from their process wastes.
Utilization of a Metaullics MZR Zinc Recovery System may enhance retention of zinc
inventories by providing an on-site secondary processing technique for recovery of usable
metallic zinc.
References:
1. Smale, D., Zinc in galvanizing: a world view, with special reference to China,
Intergalva2006 Conference, Naples, Italy, June 2006
2. Zinc Recycling: The General Picture, 1996, International Zinc Association
3. Deller, G., Zinc price forecasting explaining the limitations, Intergalva2006
Conference, Naples, Italy, June 2006
4. Schauman, M., Outlook for zinc market: will supply meet growing demand?, 11th
International Galvanizing and Coil Coating Conference, Metal Bulletin, September 2006
5. Platts Metals Daily LME Close Edition, September 21, 2006, McGraw-Hill Co.
6. Market Analysis, Metal Bulletin Monthly, September 2006, issue 429, pp. 15
7. MBR Coated Steels Monthly, August 2006, issue 91, Metal Bulletin
8. London Metals Exchange, www.lme.com
9. Lopez, F. A., Medina, F., Medina, J., Palacios, M. A., Process for recovery of nonferrous metals from steel mill dusts involving pelletising and carbothermic reduction,
1991, Ironmaking and Steelmaking, vol. 18, no. 4, pp. 292 295
10. Everitt, M., Profitable recycling of galvanized scrap, 11th International Galvanizing
and Coil Coating Conference, Metal Bulletin, September 2006
11. Shastry, C. R., Galka, J. J., Analysis of zinc melt for aluminum, iron and dross
intermetallics, Galvanizers Association Annual Meeting, 1998, Indianapolis, Indiana
12. Barakat, M. A., Recovery of zinc from zinc ash and flue dust by pyrometallurgical
processing, Recycling of Metals and Engineered Materials, 2000, TMS, pp. 211 223
13. Barakat, M. A., The pyrometallurgical processing of galvanizing zinc ash and flue
dust, Journal of Metals, August 2003, TMS, pp. 26 29
14. Unpublished research, Metaullics Systems (div. of Pyrotek Inc.), Solon, Ohio 2004-2006
15. Marder, A. R., The metallurgy of zinc-coated steel, Progress in Materials Science,
2000, vol. 45
16. DuBois, M., Top drosses: the undocumented gold mine, Galvanizers Association
Annual Meeting, 2003, Monterrey, Mexico
17. Davies, J., Galvanized Iron: Its Manufacture and Uses, 1914, Spon and Chamberlain, pp.
99 - 101
18. Daesen, J. R., Galvanizing Handbook, 1946, Reinhold Publishing, pp. 133 136
19. Fryatt, J., Vanska, J., In-house recovery of metallic zinc and other metals from
continuous process drosses and residues, 11th International Galvanizing and Coil
Coating Conference, Metal Bulletin, September 2006
20. Deem, N., In-house recovery of metallic zinc from galvanizing bath skimmings, AGA
TechForum Conference, American Galvanizers Association, October 5-7, 2005
21. Shastry, C. R., Galka, J. J., A comparative evaluation of jumbo ingots produced from
primary zinc and from zinc recovered from dross, Galvanizers Association Annual
Meeting, 2000, Toronto, Ontario