Innovative Valorization of Secondary Raw Materials

Petteri Halli

Innovative Valorization of Secondary Raw Materials

Julkaisun otsikon käännös: Innovatiivinen sekundääristen raaka-aineiden hyödyntäminen

Tutkimustuotos: Doctoral Thesis › Collection of Articles

Abstrakti

Tässä väitöskirjassa tutkittiin valokaariuunipölyn, Doré kuonan ja sulfaattipohjaisten prosessiliuosten sisältämien metallien hyödyntämistä ja kierrättämistä. Ensimmäisessä työn osassa perehdyttiin valokaariuunin pölyn hyödyntämiseen liuottamalla siinä esiintyviä tyypillisiä metalleja (Fe, Pd ja Zn) 27 eri liuottimeen. Tutkituista liuottomista prosessikehitykseen valittiin sitruunahappo. Testeissä käytetty pasutettu valokaariuunipöly sisälsi 33,2 p-% sinkkiä, 17,9 p-% rautaa ja 1,6 p-% lyijyä. Selektiivisen liuotuksen (0,8 M ja 2h) jälkeen saatiin kiinteä liuosjäännös, joka olisi kemiallisesti sopiva syöte valokaariuuniprosessiin, mutta jonka fysikaalisia ominaisuuksia pitäisi kuitenkin muokata esimerkiksi pelletoinnilla. Liuospuhdistuksen jälkeen tutkitussa prosessissa tuotettiin kiinteä lyijypitoinen raaka-aine ja sinkkipitoinen liuos, jotka ovat yhdistettävissä raaka-aineeksi nykyisiin primäärimetalliprosesseihin. Lisäksi työssä esitettiin uudenlainen valokaariuunipölyn käsittelyn juoksukaavio. Toisessa osassa tutkittiin telluurin talteenottoa TROF (Tilting, Rotating Oxy Fuel) Doré-prosessissa tuotetusta kuonasta. Tämä toteutettiin tavanomaisten hydrometallurgisten yksikköprosessien avulla, joihin oli yhdistetty uusi sähkökemialliseen pulssitukseen perustuva menetelmä, EDRR (electrodeposition – redox replacement). Doré kuona liuotettiin ensin 30 til-% kuningasveteen, jonka jälkeen tuotettu monimetalliliuos ([Te] = 421 ppm) johdettiin ensin tavanomaiseen talteenottoelektrolyysiin, ja tämän jälkeen vielä sekundääriseen telluurin talteenottoon EDRR-menetelmällä. Vertailun vuoksi telluurin talteenottoa tutkittiin myös pelkällä talteenottoelektrolyysillä, ja sen havaittiin olevan tehokkain menetelmä liuoksissa, joissa telluuria on yli 300 ppm. Tämän kynnyspitoisuuden alapuolella EDRR-menetelmä oli tehokkaampi yksikköprosessi telluurin talteenottoon. Työn kolmannessa osassa todettiin, että EDRR:n soveltuvuus hopean (1 ppb – 250 ppm) talteenottoon sulfaattipohjaisista sinkkiliuoksista (60 g/L Zn) on erinomainen, ja menetelmää käyttämällä päästiin korkeisiin hopean rikastumiskertoimiin (9,86, määrä liuoksessa vs. elektrodin pinnalla). Tämän lisäksi EDRR:n todettiin olevan huomattavasti perinteistä hopeantalteenottoelektrolyysiä tehokkaampi. Myös platinan talteenottoa tutkittiin EDRR:n avulla teollisesta nikkelisulfaattiliuoksesta (> 140 g/L Ni), jossa platinan konsentraatio oli ~1 ppb. Alhaisesta pitoisuudesta huolimatta platinan rikastumiskerron oli korkea (1011) samoin kuin puhtauskin (n. 90 p-%). Platinan lisäksi onnistuttiin rikastamaan muita liuoksessa olevia arvometalleja (Pd ja Ag). Työssä käytettiin uuden EDRR-menetelmän lisäksi myös aivan uudenlaista elektrodimateriaalia, pyrolysoitua 3D-hiiltä.

Julkaisun otsikon käännös	Innovatiivinen sekundääristen raaka-aineiden hyödyntäminen
Alkuperäiskieli	Englanti
Pätevyys	Tohtorintutkinto
Myöntävä instituutio	Aalto-yliopisto
Valvoja/neuvonantaja	Lundström, Mari, Vastuuprofessori Aromaa, Jari, Ohjaaja Yliniemi, Kirsi, Ohjaaja Wilson, Ben, Ohjaaja
Kustantaja	Aalto University
Painoksen ISBN	978-952-64-0056-3
Sähköinen ISBN	978-952-64-0057-0
Tila	Julkaistu - 2020
OKM-julkaisutyyppi	G5 Artikkeliväitöskirja

Tutkimusalat

teolliset jäte-/prosessiliuokset
hydrometallurgia
arvometalli
kiertotalous
kestävä kehitys

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@phdthesis{3822381c496d4ed2a3c6adaca731101b,

title = "Innovative Valorization of Secondary Raw Materials",

abstract = "In order to answer the ever-growing demand for more sustainable metal resources, a number of new and distinct approaches for the treatment of different secondary raw materials were investigated in detail. These included recovery of metals from electric arc furnace dust (EAFD), recovery of tellurium from Dor{\'e} slag, and recovery of noble metals from base metal sulfate solutions. In the first method, the effect of 27 different lixiviants on the dissolution of electric arc furnace dust (about 12 Mt produced globally every year) was explored. From these results, citric acid was selected as the most suitable medium to produce three base metal fractions—Fe-, Pb- and Zn-rich streams—from the EAFD containing 33.2 wt-% Zn, 17.9 wt-% Fe and 1.6 wt-% Pb. The complete process developed consisted of several metallurgical unit processes including an initial alkaline roasting stage with NaOH at 450 °C, followed by selective leaching with 0.8 M citric acid for 120 min. The residue formed after leaching was shown to be a chemically suitable raw material for reuse in the EAF, whereas the related pregnant leach solution (PLS) could be further purified to produce a Pb-rich residue, and a Zn-rich electrolyte appropriate for use in state-of-the-art metallurgical plants. A new, innovative process flowchart for industrial application was proposed as a result of these findings. The recovery of tellurium from Dor{\'e} slag produced in a TROF (Tilting, Rotating Oxy Fuel) furnace was also demonstrated via a combined conventional hydrometallurgical and innovative electrochemical route. The Dor{\'e} slag was first leached (30% aqua regia) to produce a multimetal solution that contained 421 ppm of Te. From the experiments undertaken it was determined that electrowinning (EW) is the preferable Te recovery method at concentrations above 300 ppm, whereas below this threshold value, an innovative method based on electrodeposition redox replacement (EDRR) was demonstrated to be more effective. EDRR was also investigated for Ag recovery from synthetic zinc sulfate solutions (Zn 60 g/L) where the content of Ag varied between 1 ppb to 250 ppm. The investigations show that an exceptionally high enrichment ratio of Ag (9.86) from solution to the electrode could be achieved. Furthermore, although H2 evolution was also shown to affect overall energy efficiency, EDRR was shown to outperform conventional EW. In addition, Pt—present as a trace amount (~1 ppb) in complex multimetal Ni-rich (>140 g/L) industrial process solution—was also successfully recovered by the EDRR method on a novel electrode comprised of pyrolysed carbon, PyC. In this case, the results indicated that high purity (90 wt-% Pt) and extraordinary enrichment ratio (1011) were detected on the electrode surface compared to the industrial process solution. Moreover, it was also found that other precious metals like Pd and Ag could be simultaneously enriched on the PyC electrode surface.",

keywords = "industrial waste/process streams, hydrometallurgical processing, precious metals, circular economy of metals, sustainability, teolliset j{\"a}te-/prosessiliuokset, hydrometallurgia, arvometalli, kiertotalous, kest{\"a}v{\"a} kehitys, industrial waste/process streams, hydrometallurgical processing, precious metals, circular economy of metals, sustainability",

author = "Petteri Halli",

year = "2020",

language = "English",

isbn = "978-952-64-0056-3",

series = "Aalto University publication series DOCTORAL DISSERTATIONS",

publisher = "Aalto University",

number = "146",

address = "Finland",

school = "Aalto University",

}

TY - BOOK

T1 - Innovative Valorization of Secondary Raw Materials

AU - Halli, Petteri

PY - 2020

Y1 - 2020

N2 - In order to answer the ever-growing demand for more sustainable metal resources, a number of new and distinct approaches for the treatment of different secondary raw materials were investigated in detail. These included recovery of metals from electric arc furnace dust (EAFD), recovery of tellurium from Doré slag, and recovery of noble metals from base metal sulfate solutions. In the first method, the effect of 27 different lixiviants on the dissolution of electric arc furnace dust (about 12 Mt produced globally every year) was explored. From these results, citric acid was selected as the most suitable medium to produce three base metal fractions—Fe-, Pb- and Zn-rich streams—from the EAFD containing 33.2 wt-% Zn, 17.9 wt-% Fe and 1.6 wt-% Pb. The complete process developed consisted of several metallurgical unit processes including an initial alkaline roasting stage with NaOH at 450 °C, followed by selective leaching with 0.8 M citric acid for 120 min. The residue formed after leaching was shown to be a chemically suitable raw material for reuse in the EAF, whereas the related pregnant leach solution (PLS) could be further purified to produce a Pb-rich residue, and a Zn-rich electrolyte appropriate for use in state-of-the-art metallurgical plants. A new, innovative process flowchart for industrial application was proposed as a result of these findings. The recovery of tellurium from Doré slag produced in a TROF (Tilting, Rotating Oxy Fuel) furnace was also demonstrated via a combined conventional hydrometallurgical and innovative electrochemical route. The Doré slag was first leached (30% aqua regia) to produce a multimetal solution that contained 421 ppm of Te. From the experiments undertaken it was determined that electrowinning (EW) is the preferable Te recovery method at concentrations above 300 ppm, whereas below this threshold value, an innovative method based on electrodeposition redox replacement (EDRR) was demonstrated to be more effective. EDRR was also investigated for Ag recovery from synthetic zinc sulfate solutions (Zn 60 g/L) where the content of Ag varied between 1 ppb to 250 ppm. The investigations show that an exceptionally high enrichment ratio of Ag (9.86) from solution to the electrode could be achieved. Furthermore, although H2 evolution was also shown to affect overall energy efficiency, EDRR was shown to outperform conventional EW. In addition, Pt—present as a trace amount (~1 ppb) in complex multimetal Ni-rich (>140 g/L) industrial process solution—was also successfully recovered by the EDRR method on a novel electrode comprised of pyrolysed carbon, PyC. In this case, the results indicated that high purity (90 wt-% Pt) and extraordinary enrichment ratio (1011) were detected on the electrode surface compared to the industrial process solution. Moreover, it was also found that other precious metals like Pd and Ag could be simultaneously enriched on the PyC electrode surface.

AB - In order to answer the ever-growing demand for more sustainable metal resources, a number of new and distinct approaches for the treatment of different secondary raw materials were investigated in detail. These included recovery of metals from electric arc furnace dust (EAFD), recovery of tellurium from Doré slag, and recovery of noble metals from base metal sulfate solutions. In the first method, the effect of 27 different lixiviants on the dissolution of electric arc furnace dust (about 12 Mt produced globally every year) was explored. From these results, citric acid was selected as the most suitable medium to produce three base metal fractions—Fe-, Pb- and Zn-rich streams—from the EAFD containing 33.2 wt-% Zn, 17.9 wt-% Fe and 1.6 wt-% Pb. The complete process developed consisted of several metallurgical unit processes including an initial alkaline roasting stage with NaOH at 450 °C, followed by selective leaching with 0.8 M citric acid for 120 min. The residue formed after leaching was shown to be a chemically suitable raw material for reuse in the EAF, whereas the related pregnant leach solution (PLS) could be further purified to produce a Pb-rich residue, and a Zn-rich electrolyte appropriate for use in state-of-the-art metallurgical plants. A new, innovative process flowchart for industrial application was proposed as a result of these findings. The recovery of tellurium from Doré slag produced in a TROF (Tilting, Rotating Oxy Fuel) furnace was also demonstrated via a combined conventional hydrometallurgical and innovative electrochemical route. The Doré slag was first leached (30% aqua regia) to produce a multimetal solution that contained 421 ppm of Te. From the experiments undertaken it was determined that electrowinning (EW) is the preferable Te recovery method at concentrations above 300 ppm, whereas below this threshold value, an innovative method based on electrodeposition redox replacement (EDRR) was demonstrated to be more effective. EDRR was also investigated for Ag recovery from synthetic zinc sulfate solutions (Zn 60 g/L) where the content of Ag varied between 1 ppb to 250 ppm. The investigations show that an exceptionally high enrichment ratio of Ag (9.86) from solution to the electrode could be achieved. Furthermore, although H2 evolution was also shown to affect overall energy efficiency, EDRR was shown to outperform conventional EW. In addition, Pt—present as a trace amount (~1 ppb) in complex multimetal Ni-rich (>140 g/L) industrial process solution—was also successfully recovered by the EDRR method on a novel electrode comprised of pyrolysed carbon, PyC. In this case, the results indicated that high purity (90 wt-% Pt) and extraordinary enrichment ratio (1011) were detected on the electrode surface compared to the industrial process solution. Moreover, it was also found that other precious metals like Pd and Ag could be simultaneously enriched on the PyC electrode surface.

KW - industrial waste/process streams

KW - hydrometallurgical processing

KW - precious metals

KW - circular economy of metals

KW - sustainability

KW - teolliset jäte-/prosessiliuokset

KW - hydrometallurgia

KW - arvometalli

KW - kiertotalous

KW - kestävä kehitys

KW - industrial waste/process streams

KW - hydrometallurgical processing

KW - precious metals

KW - circular economy of metals

KW - sustainability

M3 - Doctoral Thesis

SN - 978-952-64-0056-3

T3 - Aalto University publication series DOCTORAL DISSERTATIONS

PB - Aalto University

ER -

Innovative Valorization of Secondary Raw Materials

Abstrakti

Tutkimusalat

YK:n kestävän kehityksen tavoitteet

Pääsy asiakirjaan

Sormenjälki

Laitteet

Design Factory

OtaNano

OtaNano Nanofab

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