US3910784A - Process for the preparation of a raw material suitable for iron production - Google Patents

Process for the preparation of a raw material suitable for iron production Download PDF

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US3910784A
US3910784A US43751874A US3910784A US 3910784 A US3910784 A US 3910784A US 43751874 A US43751874 A US 43751874A US 3910784 A US3910784 A US 3910784A
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precipitate
iron
zinc
slurry
ferrite
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Jussi Rastas
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Outokumpu Oyj
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Outokumpu Oyj
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    • 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
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • 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
    • C22B1/00—Preliminary treatment of ores or scrap
    • C22B1/005—Preliminary treatment of scrap
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Definitions

  • ABSTRACT A process for manufacturing a raw material suitable for'iron production, from a precipitate derived from the electrolytic zinc process and mainly containing alkaline sulfates of iron, such as glockerite Fe SO (OHM), ferrihydroxosulfate FeSO OH, or jarosite A[- Fe (SO (OI-I)6], in which A is an alkali metal, NH or H 0, and hydroxides, such as goethite FeOOl-l and ferrite (mainly zinc ferrite ZnFe O and for recovering the valuable metals, such as zinc, copper, cadmium, etc., present in the precipitate, is disclosed in which a precipitate slurried in water or a mild sulfuric acid solution is treated hydrothermally at an elevated temperature so that the operation remains within the stability range of haematite Fe O in the system Fe O SO H O, whereafter the
  • the present invention relates to a process for producing, from a precipitate from an electrolytic zinc process, a raw material suitable for iron production.
  • a sulfidic concentrate which is the raw material used in a conventional electrolytic zinc process, normally contains, in addition to zinc sulfide, which is its principal component, Fe 3-12 percent, Pb and SiO each about 1 percent, and Cu, Cd, Mn, Mg, Ca, Ba, Al a few tenths of a percent.
  • the concentrate also contains small amounts of silver (-100 ppm) and gold 1 p
  • the oxidation sulfides, some ferrite formation also takes place in the oxidating roasting of a sulfidic concentrate:
  • the leach residue contains 3-12 percent of the total zinc fed into the process.
  • the percentages of copper and cadmium in the leach residue are considerably higher than that of zinc.
  • the ferric iron has been precipitated as alkaline sulfate and/or oxohydroxide.
  • a roasted zinc product has usually been used for neutralizing the sulfuric acid released in the precipitation reactions.
  • the ferrite part of the roasted product does not dissolve during the precipitation stage but remains in the iron precipitate.
  • salts of sodium or ammonium have also been fed into the iron precipitation process, in which case the iron precipicorresponding to some 2-6 percent of the total zinc feed of the process, remains after the process.
  • the main disadvantage of these processes consists of the high iron precipitate rates (the zinc production being 3-12 percent, about 20,00080,000 t/yr of iron precipitate) in most cases this precipitate must be considered as waste.
  • the acid wash of ferrite-containing jarosite precipitate has been developed for a partial recovery of the zinc present in the iron precipitate. A considerable part of the ferrites of the precipitate can be brought into a solution by an acid wash.
  • the leach residue of a conventional process and the ferrite-containing iron precipitates mentioned above have also been treated with a combination of chlorinating and sulfating roasting (A. Roeder, H. Junghans, H. Kudelka, Process for Complete Utilization of Zinc Leach Residues, Journal of Metals 21 (1969) 31-37).
  • the product of this treatment is an iron oxide ore with such a low non-iron content that it can be used as such Moriyama, Y. Yamamoto, Akita Electrolytic Zinc.
  • U.S. Pat. No. l 834 960 discusses a case in a roasted zinc product, the ferrites of which had been left in the iron precipitate in accordance with the cases described above, was used for the neutralization. Thereafter, the iron precipitate was roasted in a Wedge furnace within the temperature range 500-600C.
  • the sufficiently complete sulfating of the zinc ferrites remains an unsolved problem.
  • the zinc content of the iron oxide precipitate i.e., the zinc in ferrite form, remained in both cases at 2-3 percent, in which case the iron oxide precipitates were not directly applicable to iron production.
  • a well washed iron oxide precipitate can be fed into iron production.
  • To bring the zinccontent of the washed iron oxide precipitate to 0.1-0.2 percent prerequires a rather complete sulfating of the zinc ferrite on the one hand, and a precise control of the circumstances on the other hand, so that the recompounding of zinc ferrite can be prevented as completely as possible.
  • a precise control of the S0 and O rates in the gas phase and the appropriate temperature corresponding to them can be best obtained in a fluidizedbed reactor.
  • a precipitate derived from the electrolytic zinc process is slurried in water or a mild sulfuric acid solution, then the slurry is treated hydrothermally at an elevated temperature under conditions wherein haematite is stabile in the system Fe O SO I-I O and finally the raw material is separated from the metal value containing solution.
  • the present invention is specifically based on the principle that the conversion, into an oxidic, zinc-poor form, of the alkaline sulfates and zinc ferrites produced in electrolytic zinc processes is carried out hydrothermally, in which case, when suitable roasted zinc products are used for the precipitation of the iron, the precipitate which has undergone the hydrothermal conversion is directly usable as raw material in iron production in which case the waste problem caused by large iron precipitate amounts in connection with an 4 electrolytic Zinc process is solved, and the iron previ ously bound to waste can be channeled to useful purposes.
  • This hydrothermal conversion can be carried out in an autoclave, preferably within the temperature range l50-280C.
  • the thickened or filtered and water-slurried solid material emerging from the iron precipitation of the zinc process or from the acid wash of this precipitate is fed into an autoclave, which is preferably of the tubular type.
  • the temperature in the autoclave is controlled within l50-280C.
  • the delay period of the solid material at the maximum temperature can be reduced to some tens of minutes, in which case the space requirement of the autoclave treatment is relatively small especially when considering that the solid material content of the slurry in the autoclave can be quite high, e.g., 300-800 g/l.
  • the process can be achieved with moderate equipment costs, which is especially important in this case because the valuable content of the solid material to be treated is low, and the point is mainly to solve the waste problem caused by an iron precipitate with a great volume but a low valuable content.
  • These treatment and equipment costs are considerably less than if the precipitate were treated purely thermally from a sulfate form to an oxidic form.
  • the treatment in the process according to the present invention is considerably simpler and more economic than when combining as is done in some processes the leaching of ferrites and the precipitation of iron in an autoclave in one treatment stage (A. S. Yarolavtsev, V. I.
  • the solid is separated from the solution after the hydrothermal treatment and washed well in water.
  • the solution is returned to the leaching circuit of the electrolytic zinc process and the washed precipitate can be fed as raw material into iron production.
  • FIG. 1 shows some phase diagrams of the system Fe O SO H O at the temperature interval 75l25C and FIG. 2 at the temperature interval l40200C.
  • FIGS. 1 and 2 show the stability graphs of the system Fe O -SO H O drawn on the basis of the following articles: E. Posnjak, H. E. Merwin, J. Amer. Chem. Soc. 44 (1922) 1965, L. Walter-Levy, E. Quemeneur, C. R. Acad. Sc., Paris, 258 (1964) 3028, L. Walter- Levy, E. Quemeneur, Bull Soc. Chim., France 6 (1966) 1947.
  • Fe O xSO -yl-I O(s) (3 x)H SO (aq) or in the corresponding ionic form 2Fe (aq) xSO (aq) (3 x y)H Of- Fe O xSO -yH O(s) 2(3 x)H (aq) (3
  • the following solid material phases Fe O 'xSO 'yH O appear within this interesting concentration and temperature range:
  • the conditions prevailing in the solution at the initial stage of the iron precipitation are such that the solid phase in balance with it is H O jarosite. Even in this case, there is around the ZnO particles a diffusion layer; the stable balance phase in the conditions of this layer is glockerite or goethite.
  • the pH of the solution is higher the goethite and glock erite precipitates formed on the surfaces of the ZnO particles will not dissolve under the average solution conditions and the final precipitate will contain these compounds.
  • the pH of the solution is lower there is a greater possibility that the formed goethite and glockerite in the form of H jarosite.
  • Roasted zinc product is generally used at the precipitation stage of ferric iron for neutralizing the sulfuric acid released in the precipitation reactions.
  • the ferrite part of the roasted product is then not dissolved to a noteworthy extent but remains almost completely in the iron precipitate and causes a considerable zinc ferrite content in it.
  • the iron has been precipitated in a pure jarosite form, it is possible as shown in Norwegian Pat. No. 123 214 and as said earlier to selectively leach the zinc ferrite from the iron precipitate by an acid wash. If an appropriate amount of sulfuric acid or electrolysis return acid is added to the thickened jarosite precipitate slurry and the leaching conditions are kept corresponding to those of the ferrite leaching stage (temperature 90lOOC, H 50 content 30-50 g/l, solid content of the slurry 300-500 g/l, and delay period 4-10 h), the zinc ferrite dissolves while the most of the jarosite remains undissolved. If the precipitate contains glockerite and goethite, these also dissolve under the above conditions. In terms of a selective leaching of zinc ferrites, it is thus important that the precipitated iron is in jarosite form.
  • the iron has been precipitated in an atmosphere devoid of or poor in Na or NH.
  • the obtained precipi tate contains glockerites, jarosites, and zinc ferrites.
  • An acid wash is not according to the above suitable for this precipitate. To lower the zinc content of this precipitate, however, it is possible to carry out a modified acid wash of the precipitate, utilizing the stability data of the system Fe O SO H O.
  • the highly ferrite-containing solution obtained as a result of this treatment is returned after the separation of the solid material to the iron precipitation stage.
  • the high iron content at the precipitation stage favors H O jarosite formation (FIG. 1), which again reduces the dissolution of iron at the acid wash stage.
  • the system is driven to a stationary state where there is a certain circulating Fe load between the precipitation and the washing stage.
  • the iron precipitate emerging from the system is not in the form of H 0 jarosite.
  • zinc-poor material is obtained by hydrothermal methods, i.e., by reforming the iron precipitate by an autoclave treatment, in which case the temperature suitable for, for example, a glockerite-containing precipitate is l60-200C; within this temperature range the conversion already takes place rapidly enough.
  • a sulfuric acid addition is usually not necessary in this process.
  • the product of the treatment is so-called purple ore or, when operating at lower temperatures, often also jarosite-containing cut zinc-poor purple ore.
  • a corresponding autoclave conversion can also be used for pure jarosite precipitates instead of an acid wash or as a stage thereafter to convert a sulfateeontaining iron precipitate into an oxide-containing iron precipitate.
  • the operation must now take place at relatively high temperature, 220250C.
  • EXAMPLE 1 In the trials, precipitates containing varying rates of zinc ferrites and varying alkaline sulfates of iron were slurried in a dilute sulfuric acid solution and closed in glass ampoules. The ampoules were immersed in oil thermostats, and put in a slow revolving motion, in which case the contents of the ampoules were subjected to a mild mixing. After a delay period of three days, the ampoules were opened and the solution and solid phases were analyzed. The aim of the trials was to obtain an approximate idea of the temperature range within which the operation should take place with each precipitate composition to achieve moderate reaction periods.
  • Example 3 Procedure as in Example 2, but without sulfuric acid addition. Temperature T 220C, and reaction period 6 h.
  • Period Fe Fe Zn H SO, Fe Zn S Na Nl-l h g/l Example Procedure as in Example 4, but g of sulfuric acid has been added to the initial solution.
  • Period Fe Fe Zn H SO Fe Zn S Na NH h g/l A 4.5 4.3 24.6 31.4 57.0 1.1 2.2 0.03 0.0l V2 4.1 4.0 24.0 30.7 58.5 0.34 1.8 0.03 0.0l l 5.4 5.4 25.8 30.4 58.5 0.30 1.8 0.03 0.01 2 5.4 5.2 27.1 31.9 58.6 0.26 1.7 0.03 0.0l
  • the precipitate contains zinc ferrite and at least one of the following basic sulfates of iron: glockerite. ferrihydroxosulfate. and jarosite A/Fe SO (Ol-l) in which A is selected from the group consisting of an alkali metal ion, NH. and H O 4.
  • the precipitate contains at least one of the following hydroxides of iron, namely goethite and a ferrite.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
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  • Geology (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Materials Engineering (AREA)
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  • Compounds Of Iron (AREA)
US43751874 1973-02-01 1974-01-28 Process for the preparation of a raw material suitable for iron production Expired - Lifetime US3910784A (en)

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FI29473A FI50141C (fi) 1973-02-01 1973-02-01 Menetelmä raudan valmistukseen soveltuvan raaka-aineen valmistamiseksi sinkin elektrolyyttisestä valmistuksesta peräisin olevasta sakasta.

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JP (1) JPS507711A (enrdf_load_stackoverflow)
CA (1) CA1012362A (enrdf_load_stackoverflow)
DE (1) DE2401768C3 (enrdf_load_stackoverflow)
FI (1) FI50141C (enrdf_load_stackoverflow)
GB (1) GB1456263A (enrdf_load_stackoverflow)

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4150095A (en) * 1978-01-12 1979-04-17 Sherritt Gordon Mines Limited Recovering magnetite and ammonium sulphate from ammonium jarosite
US4219354A (en) * 1977-11-28 1980-08-26 Outokumpu Oy Hydrometallurgical process for the treatment of oxides and ferrites which contain iron and other metals
US4355005A (en) * 1980-09-30 1982-10-19 Outokumpu Oy Process for the treatment of a raw material which contains oxide and ferrite of zinc, copper and cadmium
US4362702A (en) * 1980-09-30 1982-12-07 Outokumpu Oy Hydrometallurgical process for the treatment of a raw material which contains oxide and ferrite of zinc, copper and cadmium
US4464344A (en) * 1979-05-25 1984-08-07 Saikkonen Pekka J Process for recovering non-ferrous metal values from ores, concentrates, oxidic roasting products or slags
US5078786A (en) * 1986-11-26 1992-01-07 Resource Technology Associates Process for recovering metal values from jarosite solids
US5489373A (en) * 1995-02-02 1996-02-06 Olin Corporation Aqueous zinc solution resistant to precipitation
US20040096380A1 (en) * 2002-08-16 2004-05-20 Steenwinkel Edgar Evert Preparation of iron compounds by hydrothermal conversion
CN105800694A (zh) * 2016-02-01 2016-07-27 四川大学 一种黄铁矾水热转化制备云母氧化铁的方法
CN109250760A (zh) * 2018-07-25 2019-01-22 桂林理工大学 利用铁矾渣硫酸浸出液制备高性能片状多孔结构铁酸锌负极材料的方法及应用
CN115094240A (zh) * 2022-07-25 2022-09-23 中南大学 一种含铁废渣中铁铅分离和铁元素富集的方法
WO2023286061A1 (en) * 2021-07-14 2023-01-19 Helios Project Ltd. A process for transition metal oxide reduction

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5745759A (en) * 1980-09-03 1982-03-15 Hitachi Ltd Communication control method for a plurality of slave stations
JPS59135596A (ja) * 1983-01-10 1984-08-03 株式会社山武 空調制御装置
JPS59135595A (ja) * 1983-01-10 1984-08-03 株式会社山武 空調制御装置
JPS61192143A (ja) * 1985-02-20 1986-08-26 Victor Co Of Japan Ltd デ−タ通信システム

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3434947A (en) * 1965-04-30 1969-03-25 Norske Zinkkompani As Process for the separation of iron from metal sulphate solutions and a hydrometallurgic process for the production of zinc
US3493365A (en) * 1965-03-31 1970-02-03 Electrolyt Zinc Australasia Treatment of zinc plant residue
US3676107A (en) * 1971-01-04 1972-07-11 Us Interior Refining iron-bearing wastes

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3493365A (en) * 1965-03-31 1970-02-03 Electrolyt Zinc Australasia Treatment of zinc plant residue
US3434947A (en) * 1965-04-30 1969-03-25 Norske Zinkkompani As Process for the separation of iron from metal sulphate solutions and a hydrometallurgic process for the production of zinc
US3676107A (en) * 1971-01-04 1972-07-11 Us Interior Refining iron-bearing wastes

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4219354A (en) * 1977-11-28 1980-08-26 Outokumpu Oy Hydrometallurgical process for the treatment of oxides and ferrites which contain iron and other metals
US4150095A (en) * 1978-01-12 1979-04-17 Sherritt Gordon Mines Limited Recovering magnetite and ammonium sulphate from ammonium jarosite
US4464344A (en) * 1979-05-25 1984-08-07 Saikkonen Pekka J Process for recovering non-ferrous metal values from ores, concentrates, oxidic roasting products or slags
US4355005A (en) * 1980-09-30 1982-10-19 Outokumpu Oy Process for the treatment of a raw material which contains oxide and ferrite of zinc, copper and cadmium
US4362702A (en) * 1980-09-30 1982-12-07 Outokumpu Oy Hydrometallurgical process for the treatment of a raw material which contains oxide and ferrite of zinc, copper and cadmium
US5078786A (en) * 1986-11-26 1992-01-07 Resource Technology Associates Process for recovering metal values from jarosite solids
US5489373A (en) * 1995-02-02 1996-02-06 Olin Corporation Aqueous zinc solution resistant to precipitation
US20040096380A1 (en) * 2002-08-16 2004-05-20 Steenwinkel Edgar Evert Preparation of iron compounds by hydrothermal conversion
US7217400B2 (en) * 2002-08-16 2007-05-15 Albemarle Netherlands B.V. Preparation of iron compounds by hydrothermal conversion
CN105800694A (zh) * 2016-02-01 2016-07-27 四川大学 一种黄铁矾水热转化制备云母氧化铁的方法
CN109250760A (zh) * 2018-07-25 2019-01-22 桂林理工大学 利用铁矾渣硫酸浸出液制备高性能片状多孔结构铁酸锌负极材料的方法及应用
CN109250760B (zh) * 2018-07-25 2020-10-09 桂林理工大学 利用铁矾渣硫酸浸出液制备高性能片状多孔结构铁酸锌负极材料的方法及应用
WO2023286061A1 (en) * 2021-07-14 2023-01-19 Helios Project Ltd. A process for transition metal oxide reduction
US12104224B2 (en) 2021-07-14 2024-10-01 Helios Project Ltd. Process for transition metal oxide reduction
CN115094240A (zh) * 2022-07-25 2022-09-23 中南大学 一种含铁废渣中铁铅分离和铁元素富集的方法

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DE2401768C3 (de) 1978-07-13
GB1456263A (en) 1976-11-24
FI50141C (fi) 1975-12-10
CA1012362A (en) 1977-06-21
FI50141B (enrdf_load_stackoverflow) 1975-09-01
JPS507711A (enrdf_load_stackoverflow) 1975-01-27
DE2401768B2 (de) 1977-12-01
DE2401768A1 (de) 1974-08-15

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