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Long-Term Leaching Effects on CaO-Modified Iron Silicate Slag
Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Minerals and Metallurgical Engineering.ORCID iD: 0000-0003-1907-5291
Boliden Mineral AB, Boliden Rönnskär, 932 81 Skelleftehamn, Sweden.
Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Minerals and Metallurgical Engineering.ORCID iD: 0000-0003-1511-8020
Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Minerals and Metallurgical Engineering.ORCID iD: 0000-0001-9297-8521
2022 (English)In: Minerals, E-ISSN 2075-163X, Vol. 12, no 11, article id 1442Article in journal (Refereed) Published
Abstract [en]

Granulated iron silicate slag, a by-product of pyrometallurgical copper extraction, has excellent properties for construction applications. Slag modification with CaO enhances the application properties regarding pozzolanic reactivity, potentially extending slag use in the future. The slags’ short-term leaching behavior has already been investigated with promising results, while the long-term leaching effects are less studied. Therefore, this study aims to determine the long-term leaching effects on CaO-modified iron silicate slags. The CaO-modifications were conducted during full-scale slag treatment operation. The slags were characterized and leached, and the remaining slags were investigated regarding the formation of secondary phases. The long-term leaching of main and trace elements was determined over 30 days using a dynamic leaching method corresponding to an extended time period. The leaching tests showed increased leaching of the main slag elements (Si, Ca). Zn and Cu showed peak leaching after four days of leaching, and the leaching of As and Sb decreased with the increasing CaO content in the samples. After dynamic leaching, secondary phases formed on the Cu-containing inclusions on the sample surfaces. Independent of the CaO content, the leaching of Cu was increased when subjected to external acidic and oxidating conditions using static pH titration at pH 5 in dilute nitric acid.

Place, publisher, year, edition, pages
MDPI, 2022. Vol. 12, no 11, article id 1442
Keywords [en]
leaching behavior, granulated fayalite slag, iron silicate, slag properties, dissolution
National Category
Metallurgy and Metallic Materials
Research subject
Process Metallurgy; Centre - Centre for Advanced Mining & Metallurgy (CAMM)
Identifiers
URN: urn:nbn:se:ltu:diva-93604DOI: 10.3390/min12111442ISI: 000912415000001Scopus ID: 2-s2.0-85149595483OAI: oai:DiVA.org:ltu-93604DiVA, id: diva2:1704950
Note

Validerad;2022;Nivå 2;2022-11-15 (hanlid);

Funder: Boliden;

This article has previously appeared as a manuscript in a thesis

Available from: 2022-10-20 Created: 2022-10-20 Last updated: 2024-01-17Bibliographically approved
In thesis
1. Leaching of water-granulated iron silicate slags and their compounds: A study of synthetic and industrial slag systems
Open this publication in new window or tab >>Leaching of water-granulated iron silicate slags and their compounds: A study of synthetic and industrial slag systems
2022 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Copper smelter slag is a residue product of the pyrometallurgical extraction of copper. Due to its physical properties, the iron silicate type of copper smelter slag has many possible application areas, e.g., different aggregates and abrasives. During the copper-making process, some copper becomes distributed in the slag; therefore, copper recovery from the slag is commonly done through slag treatment processes. Despite treatment, copper-containing inclusions can remain in the final slag. In order to secure the environmental properties of slags containing inclusions, the leaching mechanisms needs to be understood, which is the focus of the thesis presented.

Synthetic and industrial iron silicate slags have been studied with respect to the impact of the slag constituent’s oxide (glass), sulfide (matte) and metalloids (speiss) on leaching as well as the impact of chemical composition (ZnO and CaO content). The synthetic slags are melted in laboratory furnaces. The industrial slags have undergone a Zn-fuming and settling process (including CaO additions for some slags) to recycle and reduce the zinc content and further separate copper-containing inclusions such as sulfide (matte) and metalloid (speiss) species. The materials investigated in the thesis are solidified using water granulation.

All materials are characterized by their chemical compositions and mineralogy. Further, industrial slag constituents are investigated regarding their leaching contribution. Syntheticiron silicate (oxide) is investigated regarding the influence of ZnO content and granulation temperature on Zn leaching. CaO-modified industrial iron silicate slags are investigated regarding the leaching of specific elements (e.g., Cu, Zn, Ni, As, Sb). The leaching tests examine the effect of pH, oxidation and time using water leaching, acid and oxidating leaching and dynamic leaching methods.

Characterizing the slag constituents shows that the glass mainly contains amorphous iron silicate. The matte contains mainly copper sulfides, and speiss contains copper metalloids. The leaching results show that the glass contributes to Cu and Zn leaching at pH 8.4, and the speiss contributes to Ni and Sb leaching at pH 7.8. Further, the leaching contribution of matte and speiss increased with decreasing pH. The main leaching elements from the matte and speiss include Cu, Ni, As and Sb.

Characterization of the ZnO-modified iron silicate shows that Zn is mainly distributed in glass and partly in fayalite. Further, the Zn leaching increases with granulation temperature, ZnO content in the glass and decreasing pH.

Characterization of CaO-modified slags shows that up to 20 wt.% CaO dissolves into the glass phase. An increased CaO content resulted in increased Ca leaching, yielding higher pH. Leaching of Zn, Cu, Ni and Sb was on the other hand shown to decrease. Further, long-term leaching studies confirm increasing pH and Ca leaching. In contrast, the leaching of Cu, Zn and Ni showed a peak after a certain time, which was lowered with increasing CaO content in the slags. The leaching of As and Sb increased with increasing leaching time, but the increase diminished with increasing CaO content in the slags. A lower pH and an oxidating environment increased the leaching of Zn, Cu and Ni.

The summarized results from this thesis indicate that the glass contributes to Zn leaching while copper-containing inclusions matte and speiss contribute to the leaching of Cu, Ni, As and Sb. The leaching of elements from the copper-containing inclusions matte and speiss can be limited by ensuring a pH buffer preventing acidification, for example, by CaO modification. CaO modifications decrease the slag leaching resistance, which contributes to increasing pH in the leachate by Ca-dissolution and hence decreased leaching of copper-containing inclusions in the slag. Also, the Zn leaching from the slag decreased with increasing pH in the leachate.

Place, publisher, year, edition, pages
Luleå: Luleå University of Technology, 2022. p. 68
Series
Doctoral thesis / Luleå University of Technology 1 jan 1997 → …, ISSN 1402-1544
National Category
Metallurgy and Metallic Materials
Research subject
Process Metallurgy
Identifiers
urn:nbn:se:ltu:diva-93275 (URN)978-91-8048-194-6 (ISBN)978-91-8048-195-3 (ISBN)
Public defence
2022-12-15, F531, Luleå tekniska universitet, Luleå, 10:00 (English)
Opponent
Supervisors
Available from: 2022-10-20 Created: 2022-10-20 Last updated: 2022-11-24Bibliographically approved

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Kero Andertun, JakobSamuelsson, CaisaEngström, Fredrik

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