US3685985A - Method for the removal of impurities from metallic zinc - Google Patents
Method for the removal of impurities from metallic zinc Download PDFInfo
- Publication number
- US3685985A US3685985A US96235A US3685985DA US3685985A US 3685985 A US3685985 A US 3685985A US 96235 A US96235 A US 96235A US 3685985D A US3685985D A US 3685985DA US 3685985 A US3685985 A US 3685985A
- Authority
- US
- United States
- Prior art keywords
- zinc
- silicon
- impurities
- removal
- metallic zinc
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000011701 zinc Substances 0.000 title abstract description 50
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title abstract description 49
- 229910052725 zinc Inorganic materials 0.000 title abstract description 48
- 239000012535 impurity Substances 0.000 title abstract description 13
- 238000000034 method Methods 0.000 title description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 27
- 229910052710 silicon Inorganic materials 0.000 abstract description 27
- 239000010703 silicon Substances 0.000 abstract description 25
- 229910017052 cobalt Inorganic materials 0.000 abstract description 4
- 239000010941 cobalt Substances 0.000 abstract description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 4
- 238000000926 separation method Methods 0.000 abstract description 2
- -1 IROM Substances 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 20
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 11
- 229910052742 iron Inorganic materials 0.000 description 11
- 239000011572 manganese Substances 0.000 description 9
- 229910052759 nickel Inorganic materials 0.000 description 8
- 229910001297 Zn alloy Inorganic materials 0.000 description 7
- 229910052748 manganese Inorganic materials 0.000 description 7
- 239000007788 liquid Substances 0.000 description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- 229910000765 intermetallic Inorganic materials 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000007664 blowing Methods 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000001939 inductive effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 150000003377 silicon compounds Chemical class 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 229910020521 Co—Zn Inorganic materials 0.000 description 1
- 229910005347 FeSi Inorganic materials 0.000 description 1
- 229910018605 Ni—Zn Inorganic materials 0.000 description 1
- 229910000676 Si alloy Inorganic materials 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 238000005246 galvanizing Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- KFZAUHNPPZCSCR-UHFFFAOYSA-N iron zinc Chemical class [Fe].[Zn] KFZAUHNPPZCSCR-UHFFFAOYSA-N 0.000 description 1
- 229910001338 liquidmetal Inorganic materials 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000010587 phase diagram Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 229910021332 silicide Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/32—Refining zinc
Definitions
- High-purity zinc may be obtained by distilling Fe-, Co-, Nior Mn-containing zinc or zinc alloys. While the yield is good in view of the thermal decomposition of said intermetallic zinc compounds, power consumption is high and elaborate equipment is needed.
- intermetallic compounds of zinc with Fe, Co, Ni and/ or Mn can be converted with silicon to stable silicon compounds (silicides), the very low solubility of silicon in zinc and high-zinc alloys being a factor that greatly favors refining.
- the zinc purified of Fe, Co, Ni and Mn contains no demonstrable amounts of silicon.
- the silicon compounds forming with said impurities are crystalline up to the boiling point of zinc, have low specific gravity and are diflicultly wettable by zinc. Thus they can be readily separated.
- Method for removing metallic impurities selected from the group of iron, cobalt, nickel, manganese or mixtures thereof from molten zinc which comprises admixing molten zinc with silicon thereby binding said impurities and thereafter separating the thus bound impurities.
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Silicon Compounds (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
IMPURITIES SUCH AS IROM, COBALT, NICKEL AND/OR MANGANESS ARE REMOVED FROM MOLTEN ZINC BY BINDING THE IMPURITIES WITH SILICON FOLLOWED BY SEPARATION.
Description
United States Patent Ofiice 3,585,985 Patented Aug. 22, 1972 U.S. CI. 7586 8 Claims ABSTRACT OF THE DISCLOSURE Impurities such as iron, cobalt, nickel and/or manganese are removed from molten zinc by binding the impurities with silicon followed by separation.
BACKGROUND Among the elements which are readily picked up by zinc and zinc alloys in the production and utilization of the metal (as in the hot-dip galvanizing of iron parts, for example) are iron, cobalt, nickel and manganese. From the Fe-Zn, Co-Zn, Ni-Zn and Mn-Zn phase diagrams, which resemble one another closely, it is apparent that zinc forms intermetallic, and primarily peritectically melting, compounds with these metals. They materially impair the processing and utilization properties of zinc. Since the solubility in zinc of these elements is very low and the intermetallic compounds are very rich in zinc (for example, one part of the elements Fe, Co, Ni or Mn will bind some 10 to parts of zinc) these compounds manifest themselves even in the structure of zinc and zinc alloys that are very poor in these elements.
In order to avoid the segregation of primary, coarsely crystalline intermetallic compounds in the solidification of zinc and zinc alloys, it is usually specifiedin DIN 1706, Zinc, for examplethat the elements Fe, Co, Ni and Mn shall be limited to a few hundreds or thousandths of one weight percent.
It is a known and common practice to purify zinc and zinc alloys of said impurities, and particularly of Fe, by liquation and distillation. In liquation, zinc and zinc alloys can be purified down to the eutectic concentrations (for example, about 0.018% Fe in the -Fe-Zn system) by letting the primary crystals settle out at temperatures just above the melting point of zinc, for example. However, zinc losses in the separated layer enriched in impurities, the so-called hard zinc, are relatively high.
High-purity zinc may be obtained by distilling Fe-, Co-, Nior Mn-containing zinc or zinc alloys. While the yield is good in view of the thermal decomposition of said intermetallic zinc compounds, power consumption is high and elaborate equipment is needed.
SUMMARY It has now been found that intermetallic compounds of zinc with Fe, Co, Ni and/ or Mn can be converted with silicon to stable silicon compounds (silicides), the very low solubility of silicon in zinc and high-zinc alloys being a factor that greatly favors refining. The zinc purified of Fe, Co, Ni and Mn contains no demonstrable amounts of silicon.
DESCRIPTION The silicon compounds forming with said impurities are crystalline up to the boiling point of zinc, have low specific gravity and are diflicultly wettable by zinc. Thus they can be readily separated.
Since silicon is only very slightly soluble in zinc over the temperature range between the melting point and the boiling point of zinc, the zinc impurities Fe, Co, Ni and Mn can actually be bound only at the interface between zinc melt and silicon crystal. For this reason, provision must be made for adequate contact between the silicon and the melt, for example, by mechanical or inductive stirring, by blowing in the silicon with an inert gas, by dipping, whirling, shaking or pouring the silicon in, or by similar known methods. Moreover, oxidizing atmospheres should be avoided.
Since the binding of the zinc impurities occurs on the solid silicon and consequently is diffusion-dependent to a high degree, it will be advisable to use as high a reaction temperature as possible. The decomposition temperatures of the intermetallic iron-zinc compounds (6 and 7 phases) may be exceeded without drawbacks. The zinc-containing a Fe crystalline solid solutions forming along with other phases will be bound by silicon in all cases in accordance with the known equilibrium relations in the Fe-Zn-Si system. In the drosses containing Fe and Si which are produced in the purification of zinc with silicon, these a-Fe crystalline solid solutions can often be demonstrated by testing for magnetizability.
Of advantage is also preheating or supplementary heating (for example, by radiation or induction) of the silicon added to the zinc melt. In thermal zinc production, it will suffice to deposit granular silicon or high-silicon alloys on the interface between liquid metal and zinc vapor.
EXAMPLE Through a charging valve, about to 250 g. of silicon metal containing 98.5% Si is introduced approximately every two hours into the spray condenser space of an electrothermic zinc reduction furnace. The amount of silicon is roughly equal to 200 g. Si per ton of metallic zinc produced. Through this addition, the average iron content of the zinc obtained without silicion treatment is reduced from 0.015 to 0.0025 Fe. The reaction products of this refining operation (FeSi for example) are found together with excess silicon metal in the zinc dust and in the dross.
What is claimed is:
1. Method for removing metallic impurities selected from the group of iron, cobalt, nickel, manganese or mixtures thereof from molten zinc which comprises admixing molten zinc with silicon thereby binding said impurities and thereafter separating the thus bound impurities.
2. Method of claim 1 wherein the silicon is deposited in granular form on the liquid zinc/zinc vapor interface.
3. Method of claim 1 wherein the silicon is dipped into the impure liquid zinc and good contact between the zinc melt and the silicon is promoted by mechanical or inductive stirring.
4. Process of claim 3 wherein the silicon is preheated prior to being dipped into the liquid zinc.
5. Method of claim 1 wherein the silicon is contacted with the liquid zinc by blowing, stirring, whirling or shaking the Si into the zinc melt.
6. Method of claim 1 wherein preheated silicon is poured over liquid zinc which is overheated in the presence of a reducing atmosphere.
7. Method of claim 1 wherein preheated silicon is deposited in granular form on an agitated zinc melt in the presence of a nonoxidizing atmosphere.
an alloy with a high silicon content.
4 References Cited UNITED STATES PATENTS 905,280 12/1908 Betts 7586 X 2,029,898 2/1936 Schmidt et al. 75-63 X OTHER REFERENCES J. W. Mellor: A Comprehensive Treatise on Inorganic and Theoretical Chemistry, vol. VI, Longmans, Green & Co., N.Y. 1925, p. 168.
OSCAR R. VERTIZ, Primary Examiner G. ALVARO, Assistant Examiner US. Cl. X.R.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19691962608 DE1962608B2 (en) | 1969-12-13 | 1969-12-13 | METAL REMOVAL PROCESS FROM METALLIC ZINC |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3685985A true US3685985A (en) | 1972-08-22 |
Family
ID=5753799
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US96235A Expired - Lifetime US3685985A (en) | 1969-12-13 | 1970-12-08 | Method for the removal of impurities from metallic zinc |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US3685985A (en) |
| BE (1) | BE759638A (en) |
| DE (1) | DE1962608B2 (en) |
| ES (1) | ES386415A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4657585A (en) * | 1984-11-29 | 1987-04-14 | Ishikawajima-Harima Jukogyo Kabushi Kaisha | Method for separating cobalt, nickel and the like from alloys |
| WO2005083134A1 (en) * | 2004-02-26 | 2005-09-09 | Umicore | Recycling of hot-dip zinc galvanizing bath |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3734204A1 (en) * | 1987-10-09 | 1989-04-20 | Solms Juergen | Process for reducing the iron content of zinc melts |
-
0
- BE BE759638D patent/BE759638A/en unknown
-
1969
- 1969-12-13 DE DE19691962608 patent/DE1962608B2/en active Pending
-
1970
- 1970-12-08 US US96235A patent/US3685985A/en not_active Expired - Lifetime
- 1970-12-12 ES ES386415A patent/ES386415A1/en not_active Expired
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4657585A (en) * | 1984-11-29 | 1987-04-14 | Ishikawajima-Harima Jukogyo Kabushi Kaisha | Method for separating cobalt, nickel and the like from alloys |
| WO2005083134A1 (en) * | 2004-02-26 | 2005-09-09 | Umicore | Recycling of hot-dip zinc galvanizing bath |
Also Published As
| Publication number | Publication date |
|---|---|
| DE1962608B2 (en) | 1971-05-19 |
| ES386415A1 (en) | 1973-11-16 |
| DE1962608A1 (en) | 1971-05-19 |
| BE759638A (en) | 1971-04-30 |
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