Thermodynamic properties of WEEE-based minor elements in copper smelting processes

Katri Avarmaa

Thermodynamic properties of WEEE-based minor elements in copper smelting processes

Julkaisun otsikon käännös: SER-lähtöisten hivenaineiden termodynaamiset ominaisuudet kuparin sulatusprosesseissa

Katri Avarmaa

Tutkimustuotos: Doctoral Thesis › Collection of Articles

Abstrakti

Nykyisin primääri- ja sekundäärikuparisulattoja hyödynnetään kierrätyslaitoksina erilaisille jätteille, kuten Sähkö- ja Elektroniikkaromu (SER) -pohjaiselle kuparille ja teolliselle värimetallijätteelle. Tämän seurauksena erilaisia arvokkaita ja harvinaisia metalleja, joista useat ovat epätyypillisiä primäärisissä raaka-aineissa, päätyy kasvavissa määrin kuparituotannon prosessikiertoihin. Näiden SER-hivenainemetallien termodynaamisia aineominaisuuksia ei tyypillisesti tunneta kovin tarkasti tai ollenkaan kuparin sulatusprosessien olosuhteissa. Tässä väitöskirjassa tutkittiin kokeellisesti arvometallien (Ag, Au, Pd and Pt) ja huipputeknisten metallien (Ga, Ge, In and Sn) tasapainojakaumia primäärisen ja sekundäärisen kuparisulatuksen sekä konvertoinnin olosuhteissa. Kokeet toteutettiin pitkälle kehitetyllä tasapainotus – sammutustekniikalla, jota seurasi suorat faasikoostumusanalyysit elektronimikrosondilla (EPMA) ja laserablaatioon induktiivisesti kytketyllä plasma-massaspektrometrillä (LA-ICP-MS). Tämä oli ensimmäinen hivenainetutkimus kuparikivi/metalli-kuona systeemeissä, jossa hyödynnettiin kyseisiä kokeellisia ja analyyttisiä tekniikoita. Erityisesti viimeksi mainitun analyysitekniikan käyttö oli merkittävä edistysaskel, joka mahdollisti hivenainemittauksia jopa alle 1 ppbw pitoisuuksilla metallurgisista kuonista. Merkittävin tarkasteltu termodynaaminen suure oli jakaumakerroin, L = m% metallia kivessä tai kuparissa / m% metallia kuonassa, joka kuvaa kunkin hivenainemetallin käyttäytymistä sulatuksen olosuhteissa. Tutkimus toteutettiin monitieteellisenä ja sen tulokset on suunnattu usealle eri tieteen ja teollisuuden alalle. Tuloksissa on esitetty, kuinka prosessiolosuhteet (erityisesti pO2), kyllästysfaasi ja kuonakoostumus vaikuttavat hivenainemetallien käyttäytymiseen. Lisäksi työssä on tarkasteltu kuonien kemiaa ja kuparimenetyksiä kuoniin. Arvometallien tulokset osoittivat kuinka Au, Pd ja Pt on mahdollista saada talteen kuparikiveen (L (m/s) > 10^2) ja metalliin (L (Cu/s) > 10^4) kaikissa prosessiolosuhteissa, ja jopa huomattavasti tehokkaammin kuin metallurgisessa kirjallisuudessa on aiemmin esitetty. Huipputeknisten metallien Ga ja Ge tulokset tutkituissa kupari-kuona systeemeissä ovat ainutlaatuisia ja ensimmäiset julkaisut kirjallisuudessa. Jakaumatulokset metalleille Ag, Sn ja In olivat samoilla suuruusluokilla kirjallisuudessa esitettyjen kanssa. Työssä määritetyt termodynaamiset aineominaisuudet auttavat teollisuutta kehittämään prosesseja, parantamaan resurssitehokkuutta ja metallien talteen saanteja. Prosessien ja metallien käyttäytymisen luotettavan simuloinnin ja mallinnuksen aikaansaamiseksi määritetyt tulokset tulisi saattaa osaksi laskennallisten ohjelmien termodynaamisia tietopankkeja.

Julkaisun otsikon käännös	SER-lähtöisten hivenaineiden termodynaamiset ominaisuudet kuparin sulatusprosesseissa
Alkuperäiskieli	Englanti
Pätevyys	Tohtorintutkinto
Myöntävä instituutio	Aalto-yliopisto
Valvoja/neuvonantaja	Jokilaakso, Ari, Vastuuprofessori Taskinen, Pekka, Ohjaaja
Kustantaja	Aalto University
Painoksen ISBN	978-952-60-8605-7
Sähköinen ISBN	978-952-60-8606-4
Tila	Julkaistu - 2019
OKM-julkaisutyyppi	G5 Artikkeliväitöskirja

Tutkimusalat

arvometallit
huipputekniset metallit
sekundääri kupari
jakaumakerroin
kierrätys

Pääsy asiakirjaan

http://urn.fi/URN:ISBN:978-952-60-8606-4

Raaka-aineiden tutkimusinfrastruktuuri
Karppinen, M. (Manager)
Kemian tekniikan korkeakoulu
Laitteistot/tilat: Facility

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@phdthesis{e8320267dc444b47b851383d6ad89720,

title = "Thermodynamic properties of WEEE-based minor elements in copper smelting processes",

abstract = "Today, primary and secondary copper smelters are used as recycling facilities for different wastes, such as Waste Electric and Electronic Equipment (WEEE) -based copper scrap and industrial nonferrous waste. Consequently, multiple precious and rare metals, many of them not typical in primary concentrates, are entering the copper-making circuits with increasing concentrations. Thermodynamic properties of these WEEE-based minor elements are not known well enough or at all in copper smelting processes. In this study, the distribution equilibria of precious (Ag, Au, Pd and Pt) and high-tech (Ga, Ge, In and Sn) metals were investigated experimentally under primary and secondary copper smelting, as well as converting conditions. The experiments were executed employing a well-developed equilibration – quenching technique followed by direct phase analyses with electron microprobe (EPMA) and laser ablation inductively coupled plasma mass spectrometer (LA-ICP-MS). This study applied these experimental and analytical techniques to study minor element behaviour in copper/matte-slag systems for the first time. Especially, the use of the latter analytical technique was a great leap forward and enabled minor element concentration analyses even below 1 ppbw in metallurgical slags. The main thermodynamic parameter examined was the distribution coefficient, L = wt% of metal in matte or copper / wt% of metal in slag, which describes the behaviour of a minor element in smelting conditions. This research was implemented with a multi-disciplinary approach providing results for different fields of sciences and industries. The results present influences of different smelting conditions (especially pO2), primary saturation phase and slag composition on minor element equilibria. Moreover, the slag chemistry and copper losses in slags were examined. Precious metals – Au, Pd, Pt – were distributed and recovered efficiently in copper matte (L (m/s) > 10^2) and metal (L (Cu/s) > 10^4) in all conditions, much greater than previously considered in metallurgical literature. The results for high-tech metals Ga and Ge in the investigated copper-slag systems are novel and present the first data published in the literature. The distribution results for Ag, Sn and In were close to the distribution data found in literature. The thermodynamic data acquired is useful for industry in multiple purposes, such as process development, improving resource efficiencies and recoveries of the minor elements. To attain reliable simulation and modelling data of processes and metals behaviour, the presented properties need to be added into the thermodynamic databases of calculation programs.",

keywords = "precious metals, high-tech metals, black copper, distribution coefficient, recycling, arvometallit, huipputekniset metallit, sekund{\"a}{\"a}ri kupari, jakaumakerroin, kierr{\"a}tys, precious metals, high-tech metals, black copper, distribution coefficient, recycling",

author = "Katri Avarmaa",

year = "2019",

language = "English",

isbn = "978-952-60-8605-7",

series = "Aalto University publication series DOCTORAL DISSERTATIONS",

publisher = "Aalto University",

number = "115",

address = "Finland",

school = "Aalto University",

}

TY - BOOK

T1 - Thermodynamic properties of WEEE-based minor elements in copper smelting processes

AU - Avarmaa, Katri

PY - 2019

Y1 - 2019

N2 - Today, primary and secondary copper smelters are used as recycling facilities for different wastes, such as Waste Electric and Electronic Equipment (WEEE) -based copper scrap and industrial nonferrous waste. Consequently, multiple precious and rare metals, many of them not typical in primary concentrates, are entering the copper-making circuits with increasing concentrations. Thermodynamic properties of these WEEE-based minor elements are not known well enough or at all in copper smelting processes. In this study, the distribution equilibria of precious (Ag, Au, Pd and Pt) and high-tech (Ga, Ge, In and Sn) metals were investigated experimentally under primary and secondary copper smelting, as well as converting conditions. The experiments were executed employing a well-developed equilibration – quenching technique followed by direct phase analyses with electron microprobe (EPMA) and laser ablation inductively coupled plasma mass spectrometer (LA-ICP-MS). This study applied these experimental and analytical techniques to study minor element behaviour in copper/matte-slag systems for the first time. Especially, the use of the latter analytical technique was a great leap forward and enabled minor element concentration analyses even below 1 ppbw in metallurgical slags. The main thermodynamic parameter examined was the distribution coefficient, L = wt% of metal in matte or copper / wt% of metal in slag, which describes the behaviour of a minor element in smelting conditions. This research was implemented with a multi-disciplinary approach providing results for different fields of sciences and industries. The results present influences of different smelting conditions (especially pO2), primary saturation phase and slag composition on minor element equilibria. Moreover, the slag chemistry and copper losses in slags were examined. Precious metals – Au, Pd, Pt – were distributed and recovered efficiently in copper matte (L (m/s) > 10^2) and metal (L (Cu/s) > 10^4) in all conditions, much greater than previously considered in metallurgical literature. The results for high-tech metals Ga and Ge in the investigated copper-slag systems are novel and present the first data published in the literature. The distribution results for Ag, Sn and In were close to the distribution data found in literature. The thermodynamic data acquired is useful for industry in multiple purposes, such as process development, improving resource efficiencies and recoveries of the minor elements. To attain reliable simulation and modelling data of processes and metals behaviour, the presented properties need to be added into the thermodynamic databases of calculation programs.

AB - Today, primary and secondary copper smelters are used as recycling facilities for different wastes, such as Waste Electric and Electronic Equipment (WEEE) -based copper scrap and industrial nonferrous waste. Consequently, multiple precious and rare metals, many of them not typical in primary concentrates, are entering the copper-making circuits with increasing concentrations. Thermodynamic properties of these WEEE-based minor elements are not known well enough or at all in copper smelting processes. In this study, the distribution equilibria of precious (Ag, Au, Pd and Pt) and high-tech (Ga, Ge, In and Sn) metals were investigated experimentally under primary and secondary copper smelting, as well as converting conditions. The experiments were executed employing a well-developed equilibration – quenching technique followed by direct phase analyses with electron microprobe (EPMA) and laser ablation inductively coupled plasma mass spectrometer (LA-ICP-MS). This study applied these experimental and analytical techniques to study minor element behaviour in copper/matte-slag systems for the first time. Especially, the use of the latter analytical technique was a great leap forward and enabled minor element concentration analyses even below 1 ppbw in metallurgical slags. The main thermodynamic parameter examined was the distribution coefficient, L = wt% of metal in matte or copper / wt% of metal in slag, which describes the behaviour of a minor element in smelting conditions. This research was implemented with a multi-disciplinary approach providing results for different fields of sciences and industries. The results present influences of different smelting conditions (especially pO2), primary saturation phase and slag composition on minor element equilibria. Moreover, the slag chemistry and copper losses in slags were examined. Precious metals – Au, Pd, Pt – were distributed and recovered efficiently in copper matte (L (m/s) > 10^2) and metal (L (Cu/s) > 10^4) in all conditions, much greater than previously considered in metallurgical literature. The results for high-tech metals Ga and Ge in the investigated copper-slag systems are novel and present the first data published in the literature. The distribution results for Ag, Sn and In were close to the distribution data found in literature. The thermodynamic data acquired is useful for industry in multiple purposes, such as process development, improving resource efficiencies and recoveries of the minor elements. To attain reliable simulation and modelling data of processes and metals behaviour, the presented properties need to be added into the thermodynamic databases of calculation programs.

KW - precious metals

KW - high-tech metals

KW - black copper

KW - distribution coefficient

KW - recycling

KW - arvometallit

KW - huipputekniset metallit

KW - sekundääri kupari

KW - jakaumakerroin

KW - kierrätys

KW - precious metals

KW - high-tech metals

KW - black copper

KW - distribution coefficient

KW - recycling

M3 - Doctoral Thesis

SN - 978-952-60-8605-7

T3 - Aalto University publication series DOCTORAL DISSERTATIONS

PB - Aalto University

ER -

Thermodynamic properties of WEEE-based minor elements in copper smelting processes

Abstrakti

Tutkimusalat

Pääsy asiakirjaan

Sormenjälki

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