Behaviour of trace elements in copper smelting processes - LA-ICP-MS as a tool for sample characterisation

Lassi Klemettinen

Behaviour of trace elements in copper smelting processes - LA-ICP-MS as a tool for sample characterisation

Julkaisun otsikon käännös: Hivenaineiden käyttäytyminen kuparinsulatusprosesseissa - LA-ICP-MS työkaluna näytteiden analysoimisessa

Lassi Klemettinen

Tutkimustuotos: Doctoral Thesis › Collection of Articles

Abstrakti

Nopeasti kasvavaa tarvetta metalleille, joita käytetään akuissa, elektroniikassa sekä uusiutuvan energian tuotannossa, ei voida kattaa pelkästään louhimista ja primäärituotantoa lisäämällä. Jotta metallien riittävyys voidaan paremmin turvata ja päästä lähemmäs kiertotaloutta, elinkaarensa päässä olevien tuotteiden kierrätystä ja metallien talteenottoa niistä tulee lisätä merkittävästi. Yksi varteenotettava vaihtoehto useiden metallien kierrätykselle on käyttää olemassa olevia primääri- ja sekundäärikuparisulattoja. Monet näistä on optimoitu primääririkasteiden käsittelemiseen, minkä vuoksi tarvitaan enemmän tutkimusta ymmärtääksemme sekundääristen raaka-aineiden lisäämisen vaikutukset prosesseihin. Tämän väitöstutkimuksen tavoitteena oli selvittää usean, sekundääriraaka-aineissa läsnä olevan hivenainemetallin (Ir, Mo, Pb, Re, Sn, Sb, Te, Ga, In, La, Nd, Li, Co, Mn) käyttäytymistä laboratoriomittakaavan kokeissa. Näiden metallien jakautumista tutkittiin termodynaamisessa tasapainossa tai ajan funktiona 1300 °C:ssa, ja teollisten kuparinsulatusprosessien olosuhteita simuloitiin käyttämällä useaa eri kaasuatmosfääriä. Faasikohtaiset alkuaineiden pitoisuudet analysoitiin käyttäen kolmea suoraa faasi-analyysitekniikkaa: pyyhkäisyelektronimikroskooppi–energiadispersiivinen röntgenspektroskopia (SEM-EDS), elektronisäde–mikroanalyysi (EPMA) sekä laserablaatio–induktiivisesti kytketty plasma–massaspektrometria (LA-ICP-MS). Näistä viimeisimmällä voidaan analysoida erittäin pieniä hivenainepitoisuuksia tarkasti eri faaseista. Jakaumakerroin (L = m.% alkuainetta metalliseoksessa tai kivessä / m.% alkuainetta kuonassa) on kätevä tapa esittää ja vertailla eri hivenaineiden käyttäytymistä. Osa työn jakaumakerrointuloksista edustaa ensimmäisiä kirjallisuudesta löytyviä arvoja, ja osa parantaa huomattavasti aiemmin raportoitujen tulosten tarkkuutta. Galliumin, indiumin ja lantaanin jakaumakertoimille kuparikivien ja rautasilikaattikuonien välillä ei löytynyt vertailuarvoja aiemmin julkaistusta kirjallisuudesta, kuten ei myöskään litiumin ja lantaanin jakaumakertoimille kupariseoksen ja korkea-alumiinioksidisen rautasilikaattikuonan välillä. Mangaanin osalta uudet tulokset osoittavat selvästi aiemmin raportoiduista tuloksista pienempiä jakaumakertoimia eli mangaani jakautuu erittäin vahvasti kuonaan. Tulosten parempi tarkkuus ja luotettavuus johtuvat suorien faasianalyysitekniikoiden käytöstä sekä LA-ICP-MS tekniikan alhaisista määritysrajoista. Tässä väitöskirjassa raportoituja tuloksia voidaan soveltaa teollisuudessa, kun suunnitellaan, optimoidaan, mallinnetaan ja arvioidaan prosesseja esimerkiksi elektroniikkaromun ja käytettyjen akkujen kierrätykseen teollisessa mittakaavassa.

Julkaisun otsikon käännös	Hivenaineiden käyttäytyminen kuparinsulatusprosesseissa - LA-ICP-MS työkaluna näytteiden analysoimisessa
Alkuperäiskieli	Englanti
Pätevyys	Tohtorintutkinto
Myöntävä instituutio	Aalto-yliopisto
Valvoja/neuvonantaja	Jokilaakso, Ari, Vastuuprofessori Taskinen, Pekka, Ohjaaja Jokilaakso, Ari, Ohjaaja
Kustantaja	Aalto University
Painoksen ISBN	978-952-64-0583-4
Sähköinen ISBN	978-952-64-0584-1
Tila	Julkaistu - 2021
OKM-julkaisutyyppi	G5 Artikkeliväitöskirja

Tutkimusalat

kuparinsulatus
jakautuminen
kierrätys
kiertotalous

YK:n kestävän kehityksen tavoitteet

Tämä tuotos edistää seuraavia kestävän kehityksen tavoitteita:

Pääsy asiakirjaan

http://urn.fi/URN:ISBN:978-952-64-0584-1

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

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@phdthesis{2ed3a709b127457dbdf1e88f06f68fd7,

title = "Behaviour of trace elements in copper smelting processes - LA-ICP-MS as a tool for sample characterisation",

abstract = "The rapidly increasing demand for metals used for instance in batteries, electronics and renewable energy production cannot be satisfied merely by increasing mining and primary production capacities. In order to better secure the metal supply and achieve a circular economy, metal recycling and recovery from End-of-Life (EoL) products must be significantly increased. One viable option for recycling several metals is to utilise existing primary or secondary copper smelters. Many of these smelters have been optimised for handling primary ores, which means that more research is needed in order to understand and quantify the effects of introducing secondary raw materials into the process circuits. In this thesis, the behaviour of several trace elements present in secondary raw materials (Ir, Mo, Pb, Re, Sn, Sb, Te, Ga, In, La, Nd, Li, Co, Mn) was investigated in laboratory-scale primary and secondary copper smelting experiments. The experiments were conducted in equilibrium conditions or as a function of time at 1300 °C. Different gas atmospheres were utilised for simulating the process conditions in different stages of industrial smelting operations. The phase-by-phase elemental concentrations were analysed using scanning electron microscopy–energy dispersive spectroscopy (SEM-EDS), electron probe micro-analysis (EPMA), as well as the state-of-the-art laser ablation–inductively coupled plasma–mass spectrometry (LA-ICP-MS) technique. A convenient way of presenting and comparing the behaviour of different trace elements is via distribution coefficients (L = wt.% metal in alloy or matte / wt.% metal in slag). Some of the obtained distribution coefficient data represents the first reported values in the literature, whereas some provide significantly more accurate results compared to earlier results. For the distributions of gallium, indium and lanthanum between copper sulphide mattes and iron silicate slags, no previous data was found in the literature. This also applies to the experimentally verified distribution coefficients of lithium and lanthanum between copper-rich alloy and high-alumina iron silicate slags. Regarding manganese, the new data indicates significantly lower distribution coefficients compared to previous data, i.e. manganese deports extremely heavily to slag. The improved accuracy and reliability in distribution data is due to the use of direct phase-by-phase analysis techniques without the need of manual phase separation, as well as the extremely low detection limits obtained with the LA-ICP-MS. The results of this thesis can be applied to industrial processes in designing, optimising, modelling and evaluating processes for industrial-scale recycling of electronic scrap and EoL batteries, for example.",

keywords = "copper smelting, distribution, recycling, circular economy, kuparinsulatus, jakautuminen, kierr{\"a}tys, kiertotalous, copper smelting, distribution, recycling, circular economy",

author = "Lassi Klemettinen",

year = "2021",

language = "English",

isbn = "978-952-64-0583-4",

series = "Aalto University publication series DOCTORAL DISSERTATIONS",

publisher = "Aalto University",

number = "155",

address = "Finland",

school = "Aalto University",

}

TY - BOOK

T1 - Behaviour of trace elements in copper smelting processes - LA-ICP-MS as a tool for sample characterisation

AU - Klemettinen, Lassi

PY - 2021

Y1 - 2021

N2 - The rapidly increasing demand for metals used for instance in batteries, electronics and renewable energy production cannot be satisfied merely by increasing mining and primary production capacities. In order to better secure the metal supply and achieve a circular economy, metal recycling and recovery from End-of-Life (EoL) products must be significantly increased. One viable option for recycling several metals is to utilise existing primary or secondary copper smelters. Many of these smelters have been optimised for handling primary ores, which means that more research is needed in order to understand and quantify the effects of introducing secondary raw materials into the process circuits. In this thesis, the behaviour of several trace elements present in secondary raw materials (Ir, Mo, Pb, Re, Sn, Sb, Te, Ga, In, La, Nd, Li, Co, Mn) was investigated in laboratory-scale primary and secondary copper smelting experiments. The experiments were conducted in equilibrium conditions or as a function of time at 1300 °C. Different gas atmospheres were utilised for simulating the process conditions in different stages of industrial smelting operations. The phase-by-phase elemental concentrations were analysed using scanning electron microscopy–energy dispersive spectroscopy (SEM-EDS), electron probe micro-analysis (EPMA), as well as the state-of-the-art laser ablation–inductively coupled plasma–mass spectrometry (LA-ICP-MS) technique. A convenient way of presenting and comparing the behaviour of different trace elements is via distribution coefficients (L = wt.% metal in alloy or matte / wt.% metal in slag). Some of the obtained distribution coefficient data represents the first reported values in the literature, whereas some provide significantly more accurate results compared to earlier results. For the distributions of gallium, indium and lanthanum between copper sulphide mattes and iron silicate slags, no previous data was found in the literature. This also applies to the experimentally verified distribution coefficients of lithium and lanthanum between copper-rich alloy and high-alumina iron silicate slags. Regarding manganese, the new data indicates significantly lower distribution coefficients compared to previous data, i.e. manganese deports extremely heavily to slag. The improved accuracy and reliability in distribution data is due to the use of direct phase-by-phase analysis techniques without the need of manual phase separation, as well as the extremely low detection limits obtained with the LA-ICP-MS. The results of this thesis can be applied to industrial processes in designing, optimising, modelling and evaluating processes for industrial-scale recycling of electronic scrap and EoL batteries, for example.

AB - The rapidly increasing demand for metals used for instance in batteries, electronics and renewable energy production cannot be satisfied merely by increasing mining and primary production capacities. In order to better secure the metal supply and achieve a circular economy, metal recycling and recovery from End-of-Life (EoL) products must be significantly increased. One viable option for recycling several metals is to utilise existing primary or secondary copper smelters. Many of these smelters have been optimised for handling primary ores, which means that more research is needed in order to understand and quantify the effects of introducing secondary raw materials into the process circuits. In this thesis, the behaviour of several trace elements present in secondary raw materials (Ir, Mo, Pb, Re, Sn, Sb, Te, Ga, In, La, Nd, Li, Co, Mn) was investigated in laboratory-scale primary and secondary copper smelting experiments. The experiments were conducted in equilibrium conditions or as a function of time at 1300 °C. Different gas atmospheres were utilised for simulating the process conditions in different stages of industrial smelting operations. The phase-by-phase elemental concentrations were analysed using scanning electron microscopy–energy dispersive spectroscopy (SEM-EDS), electron probe micro-analysis (EPMA), as well as the state-of-the-art laser ablation–inductively coupled plasma–mass spectrometry (LA-ICP-MS) technique. A convenient way of presenting and comparing the behaviour of different trace elements is via distribution coefficients (L = wt.% metal in alloy or matte / wt.% metal in slag). Some of the obtained distribution coefficient data represents the first reported values in the literature, whereas some provide significantly more accurate results compared to earlier results. For the distributions of gallium, indium and lanthanum between copper sulphide mattes and iron silicate slags, no previous data was found in the literature. This also applies to the experimentally verified distribution coefficients of lithium and lanthanum between copper-rich alloy and high-alumina iron silicate slags. Regarding manganese, the new data indicates significantly lower distribution coefficients compared to previous data, i.e. manganese deports extremely heavily to slag. The improved accuracy and reliability in distribution data is due to the use of direct phase-by-phase analysis techniques without the need of manual phase separation, as well as the extremely low detection limits obtained with the LA-ICP-MS. The results of this thesis can be applied to industrial processes in designing, optimising, modelling and evaluating processes for industrial-scale recycling of electronic scrap and EoL batteries, for example.

KW - copper smelting

KW - distribution

KW - recycling

KW - circular economy

KW - kuparinsulatus

KW - jakautuminen

KW - kierrätys

KW - kiertotalous

KW - copper smelting

KW - distribution

KW - recycling

KW - circular economy

M3 - Doctoral Thesis

SN - 978-952-64-0583-4

T3 - Aalto University publication series DOCTORAL DISSERTATIONS

PB - Aalto University

ER -

Behaviour of trace elements in copper smelting processes - LA-ICP-MS as a tool for sample characterisation

Abstrakti

Tutkimusalat

YK:n kestävän kehityksen tavoitteet

Pääsy asiakirjaan

Sormenjälki

Laitteet

Raaka-aineiden tutkimusinfrastruktuuri

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