Ministry of Education, Science and Technological Development, Republic of Serbia, Grant no. 200288 (Innovation Center of the Faculty of Chemistry)

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Ministry of Education, Science and Technological Development, Republic of Serbia, Grant no. 200288 (Innovation Center of the Faculty of Chemistry) (en)
Ministarstvo prosvete, nauke i tehnološkog razvoja Republike Srbije, Ugovor br. 200288 (Inovacioni centar Hemijskog fakulteta u Beogradu doo) (sr_RS)
Министарство просвете, науке и технолошког развоја Републике Србије, Уговор бр. 200288 (Иновациони центар Хемијског факултета у Београду доо) (sr)
Authors

Publications

Jarosite sludge - utilization and valuable metals recovery applying roasting-leaching process

Đokić, Jovana; Gajić, Nataša; Anđić, Dimitrije; Kamberović, Željko

(Beograd : Srpsko hemijsko društvo, 2023)

TY  - CONF
AU  - Đokić, Jovana
AU  - Gajić, Nataša
AU  - Anđić, Dimitrije
AU  - Kamberović, Željko
PY  - 2023
UR  - https://ritnms.itnms.ac.rs/handle/123456789/1234
AB  - During the conventional roast–leach–electrolysis (RLE) zinc production process,
precipitation of the jarosite-type compounds is widely used to remove iron and other metal
impurities from the solution. Above mentioned compounds, with the general formula
MFe3(SO4)2(OH)6, (M+=NH4, Na, K, Ag, etc.), in addition to iron, contain a high
concentration of Pb, Cd, Cr, As, Zn, In, Ga, Ge as metal oxides and/or sulfates [1].
Consequently, jarosite is considered hazardous yet valuable waste [2]. In addition, every
year around 6-7 million tonnes of jarosite waste is generated globally [3]. Due to large waste
volumes and its chemical characteristics, jarosite requires a lot of storage space and
monitoring. Unfortunately, this type of waste is often landfilled causing serious
environmental problems and irreversible metal and value losses. Hence, an urgent solution
for both managing and utilization/recycling is required, to face needs regarding ecological
demands and circular economy goals.
In this paper, jarosite sludge, as a specific type of hazardous industrial waste, is used
to investigate transformation to the targeted compounds through the comprehensive
thermodynamic analysis and experimental roasting process tests. The roasting was
conducted to transform iron into insoluble hematite (Fe2O3), valuable metals (Zn, Cu, and
In) into water-soluble sulfates, and to keep Pb in the form of water-insoluble anglesite
(PbSO4). The solid residue obtained after roasting was used in leaching tests to further
evaluate the efficiency of the targeted phase transformations.
Theoretical considerations of chemical reactions and phase thermodynamics were
performed using the HSC Chemistry v.9.2.3 software [4] to define potential chemical
reactions, examine the feasibility of the target transformations, and set the limiting reaction
parameters. Further, in the first part of the experimental work, the influence of the roasting
process and reaction parameters on the transformation of jarosite sludge phases into target
compounds was investigated. This included variations in the reaction time, temperature, and
furnace atmosphere influence. The leaching conditions were kept constant (temperature of
25 °C, during 60 min, and solid to liquid ratio of 1/5) to determine the efficiency of phase
transformations in the samples obtained by roasting. Changes in the chemical and
mineralogical composition and microstructure were analyzed using different analytical
methods, including XRD and SEM analysis.
According to the obtained results of the roasting process, it was determined that the
phase transformation of jarosite sludge compounds into targeted insoluble hematite and
water-soluble sulfates occurs at 730 °C, the time required is 60 min in the air (oxidizing) atmosphere of 1-2 [dm3/h]/kg of the input material, which is in accordance with the results
of the theoretical indications. Also, it is experimentally confirmed that the introduction of
sulfate into the roasting atmosphere leads to the incomplete transformation of jarosite and
the formation of the unwanted Fe2(SO4)3. Leaching results of the sample obtained by the
abovementioned optimal roasting conditions show that only 4.5 % of Fe is leached while
the rest remains as solid targeted hematite. Also, more than 75 % of In and more
than 90 % of other targeted metals (Cu and Zn) are leached, indicating the high efficiency
of the roasting process. Phase transformation was confirmed by SEM analysis, showing that
hexagonal crystals of jarosite, dominating in the starting material, were completely replaced
with the globular microstructure of Fe2O3, in the roasted samples. SEM analysis of the
leaching residue also confirmed the absence of the water-soluble sulfates and the presence
of the anglesite as water-insoluble sulfate. The phase composition of the samples is
confirmed by XRD analysis.
This research shows that the proposed process enables the recycling of jarosite through
metal transformation and further utilization. The obtained products can be used in industry,
while the metal ions can be selectively separated from the sulfate solution and returned to the
production streams. This approach contributes to the utilization of jarosite, as hazardous
waste, in order to obtain valuable metals, and generally reduces the negative environmental
impact by decreasing the amount of disposed waste and reducing the need for primary
exploitation.
PB  - Beograd : Srpsko hemijsko društvo
C3  - 9. simpozijum Hemija i zaštita životne sredine EnviroChem2023
T1  - Jarosite sludge - utilization and valuable metals recovery applying roasting-leaching process
EP  - 180
SP  - 179
ER  - 
@conference{
author = "Đokić, Jovana and Gajić, Nataša and Anđić, Dimitrije and Kamberović, Željko",
year = "2023",
abstract = "During the conventional roast–leach–electrolysis (RLE) zinc production process,
precipitation of the jarosite-type compounds is widely used to remove iron and other metal
impurities from the solution. Above mentioned compounds, with the general formula
MFe3(SO4)2(OH)6, (M+=NH4, Na, K, Ag, etc.), in addition to iron, contain a high
concentration of Pb, Cd, Cr, As, Zn, In, Ga, Ge as metal oxides and/or sulfates [1].
Consequently, jarosite is considered hazardous yet valuable waste [2]. In addition, every
year around 6-7 million tonnes of jarosite waste is generated globally [3]. Due to large waste
volumes and its chemical characteristics, jarosite requires a lot of storage space and
monitoring. Unfortunately, this type of waste is often landfilled causing serious
environmental problems and irreversible metal and value losses. Hence, an urgent solution
for both managing and utilization/recycling is required, to face needs regarding ecological
demands and circular economy goals.
In this paper, jarosite sludge, as a specific type of hazardous industrial waste, is used
to investigate transformation to the targeted compounds through the comprehensive
thermodynamic analysis and experimental roasting process tests. The roasting was
conducted to transform iron into insoluble hematite (Fe2O3), valuable metals (Zn, Cu, and
In) into water-soluble sulfates, and to keep Pb in the form of water-insoluble anglesite
(PbSO4). The solid residue obtained after roasting was used in leaching tests to further
evaluate the efficiency of the targeted phase transformations.
Theoretical considerations of chemical reactions and phase thermodynamics were
performed using the HSC Chemistry v.9.2.3 software [4] to define potential chemical
reactions, examine the feasibility of the target transformations, and set the limiting reaction
parameters. Further, in the first part of the experimental work, the influence of the roasting
process and reaction parameters on the transformation of jarosite sludge phases into target
compounds was investigated. This included variations in the reaction time, temperature, and
furnace atmosphere influence. The leaching conditions were kept constant (temperature of
25 °C, during 60 min, and solid to liquid ratio of 1/5) to determine the efficiency of phase
transformations in the samples obtained by roasting. Changes in the chemical and
mineralogical composition and microstructure were analyzed using different analytical
methods, including XRD and SEM analysis.
According to the obtained results of the roasting process, it was determined that the
phase transformation of jarosite sludge compounds into targeted insoluble hematite and
water-soluble sulfates occurs at 730 °C, the time required is 60 min in the air (oxidizing) atmosphere of 1-2 [dm3/h]/kg of the input material, which is in accordance with the results
of the theoretical indications. Also, it is experimentally confirmed that the introduction of
sulfate into the roasting atmosphere leads to the incomplete transformation of jarosite and
the formation of the unwanted Fe2(SO4)3. Leaching results of the sample obtained by the
abovementioned optimal roasting conditions show that only 4.5 % of Fe is leached while
the rest remains as solid targeted hematite. Also, more than 75 % of In and more
than 90 % of other targeted metals (Cu and Zn) are leached, indicating the high efficiency
of the roasting process. Phase transformation was confirmed by SEM analysis, showing that
hexagonal crystals of jarosite, dominating in the starting material, were completely replaced
with the globular microstructure of Fe2O3, in the roasted samples. SEM analysis of the
leaching residue also confirmed the absence of the water-soluble sulfates and the presence
of the anglesite as water-insoluble sulfate. The phase composition of the samples is
confirmed by XRD analysis.
This research shows that the proposed process enables the recycling of jarosite through
metal transformation and further utilization. The obtained products can be used in industry,
while the metal ions can be selectively separated from the sulfate solution and returned to the
production streams. This approach contributes to the utilization of jarosite, as hazardous
waste, in order to obtain valuable metals, and generally reduces the negative environmental
impact by decreasing the amount of disposed waste and reducing the need for primary
exploitation.",
publisher = "Beograd : Srpsko hemijsko društvo",
journal = "9. simpozijum Hemija i zaštita životne sredine EnviroChem2023",
title = "Jarosite sludge - utilization and valuable metals recovery applying roasting-leaching process",
pages = "180-179"
}
Đokić, J., Gajić, N., Anđić, D.,& Kamberović, Ž.. (2023). Jarosite sludge - utilization and valuable metals recovery applying roasting-leaching process. in 9. simpozijum Hemija i zaštita životne sredine EnviroChem2023
Beograd : Srpsko hemijsko društvo., 179-180.
Đokić J, Gajić N, Anđić D, Kamberović Ž. Jarosite sludge - utilization and valuable metals recovery applying roasting-leaching process. in 9. simpozijum Hemija i zaštita životne sredine EnviroChem2023. 2023;:179-180..
Đokić, Jovana, Gajić, Nataša, Anđić, Dimitrije, Kamberović, Željko, "Jarosite sludge - utilization and valuable metals recovery applying roasting-leaching process" in 9. simpozijum Hemija i zaštita životne sredine EnviroChem2023 (2023):179-180.

Significance of infrared spectroscopic branching factor for investigation of structural characteristics of alkanes, geochemical properties and viscosity of oils

Stevanović, Jelena Z.; Rakitin, Anton; Kojić, Ivan; Vuković, Nikola; Stojanović, Ksenija

(Srpsko hemijsko društvo, Beograd, 2022)

TY  - JOUR
AU  - Stevanović, Jelena Z.
AU  - Rakitin, Anton
AU  - Kojić, Ivan
AU  - Vuković, Nikola
AU  - Stojanović, Ksenija
PY  - 2022
UR  - https://ritnms.itnms.ac.rs/handle/123456789/637
AB  - A detailed investigation of significance of the infrared (IR) spectroscopic branching factor (CH2/CH3; the ratio of methylene and methyl group peak heights at 2917-2921 and 2951-2954 cm(-1), respectively in the IR spectra) for characterization of alkane structure, geochemical properties and viscosity of 76 oil samples was performed. These oils, originating from 13 Serbian oil fields in SE Pannonian Basin, differ according to source and depositional environment of organic matter (OM), as well as by thermal maturity and biodegradation stage. Methylene and methyl asymmetric stretching peak absorbances were used for the branching factor calculation. CH2 peak positions exhibited 3-4 cm(-1) red shift with increasing the CH2/CH3 ratio, due to a greater contribution of trans vs. gauche rotamers in aliphatic chains. Comparing IR spectra of the oils and model n-alkanes, it was established that the average (CH2)(n) methylene chain length per CH3 group varied from n = 3.5 to 6.5. The CH2/CH3 ratio showed significant concordance with geochemical parameters, enabling clear distinction of the oils according to source and depositional environment of OM. At the same time, dependence of the CH2/CH3 ratio on oil maturity in the range from immature to mature was not observed, allowing for an accurate determination of oil genetic types irrespective of maturity. The CH2/CH3 ratio showed good accordance with oil biodegradation scale and oil viscosity.
PB  - Srpsko hemijsko društvo, Beograd
T2  - Journal of the Serbian Chemical Society
T1  - Significance of infrared spectroscopic branching factor for investigation of structural characteristics of alkanes, geochemical properties and viscosity of oils
EP  - 55
IS  - 1
SP  - 41
VL  - 87
DO  - 10.2298/JSC210830091S
UR  - conv_937
ER  - 
@article{
author = "Stevanović, Jelena Z. and Rakitin, Anton and Kojić, Ivan and Vuković, Nikola and Stojanović, Ksenija",
year = "2022",
abstract = "A detailed investigation of significance of the infrared (IR) spectroscopic branching factor (CH2/CH3; the ratio of methylene and methyl group peak heights at 2917-2921 and 2951-2954 cm(-1), respectively in the IR spectra) for characterization of alkane structure, geochemical properties and viscosity of 76 oil samples was performed. These oils, originating from 13 Serbian oil fields in SE Pannonian Basin, differ according to source and depositional environment of organic matter (OM), as well as by thermal maturity and biodegradation stage. Methylene and methyl asymmetric stretching peak absorbances were used for the branching factor calculation. CH2 peak positions exhibited 3-4 cm(-1) red shift with increasing the CH2/CH3 ratio, due to a greater contribution of trans vs. gauche rotamers in aliphatic chains. Comparing IR spectra of the oils and model n-alkanes, it was established that the average (CH2)(n) methylene chain length per CH3 group varied from n = 3.5 to 6.5. The CH2/CH3 ratio showed significant concordance with geochemical parameters, enabling clear distinction of the oils according to source and depositional environment of OM. At the same time, dependence of the CH2/CH3 ratio on oil maturity in the range from immature to mature was not observed, allowing for an accurate determination of oil genetic types irrespective of maturity. The CH2/CH3 ratio showed good accordance with oil biodegradation scale and oil viscosity.",
publisher = "Srpsko hemijsko društvo, Beograd",
journal = "Journal of the Serbian Chemical Society",
title = "Significance of infrared spectroscopic branching factor for investigation of structural characteristics of alkanes, geochemical properties and viscosity of oils",
pages = "55-41",
number = "1",
volume = "87",
doi = "10.2298/JSC210830091S",
url = "conv_937"
}
Stevanović, J. Z., Rakitin, A., Kojić, I., Vuković, N.,& Stojanović, K.. (2022). Significance of infrared spectroscopic branching factor for investigation of structural characteristics of alkanes, geochemical properties and viscosity of oils. in Journal of the Serbian Chemical Society
Srpsko hemijsko društvo, Beograd., 87(1), 41-55.
https://doi.org/10.2298/JSC210830091S
conv_937
Stevanović JZ, Rakitin A, Kojić I, Vuković N, Stojanović K. Significance of infrared spectroscopic branching factor for investigation of structural characteristics of alkanes, geochemical properties and viscosity of oils. in Journal of the Serbian Chemical Society. 2022;87(1):41-55.
doi:10.2298/JSC210830091S
conv_937 .
Stevanović, Jelena Z., Rakitin, Anton, Kojić, Ivan, Vuković, Nikola, Stojanović, Ksenija, "Significance of infrared spectroscopic branching factor for investigation of structural characteristics of alkanes, geochemical properties and viscosity of oils" in Journal of the Serbian Chemical Society, 87, no. 1 (2022):41-55,
https://doi.org/10.2298/JSC210830091S .,
conv_937 .

Coordination preferences of NNO and NNS Schiff base ligands with Co(III) complexes: Synthesis, characterization and DFT calculation

Darmanović, Darinka; Radanović, Dušanka; Jevtović, Mima; Turel, Iztok; Pevec, Andrej; Milcić, Miloš; Gruden, Maja; Zlatar, Matija; Đorđević, Nataša; Anđelković, Katarina; Čobeljić, Božidar

(Elsevier, Amsterdam, 2022)

TY  - JOUR
AU  - Darmanović, Darinka
AU  - Radanović, Dušanka
AU  - Jevtović, Mima
AU  - Turel, Iztok
AU  - Pevec, Andrej
AU  - Milcić, Miloš
AU  - Gruden, Maja
AU  - Zlatar, Matija
AU  - Đorđević, Nataša
AU  - Anđelković, Katarina
AU  - Čobeljić, Božidar
PY  - 2022
UR  - https://ritnms.itnms.ac.rs/handle/123456789/638
AB  - Two Co(III) complexes with condensation product of thiosemicarbazide and 2-acetylthiazole ( HL 1 ligand, ( E )-2-(1-(thiazol-2-yl)ethylidene)hydrazine-1-carbothioamide) and the condensation product of 2-acetylpyridine and Girard's P reagent ( HL 2 Cl ligand, ( E )-1-(2-oxo-2-(2-(1-(pyridin-2yl)ethylidene)hydrazinyl)ethyl)pyridin-1-ium chloride) have been synthesized and characterized based on the results of single-crystal X-ray diffraction, NMR and IR spectroscopy and elemental analysis. Cobalt(III) complex with HL 1 ligand, [Co( L 1 ) 2 ]BF 4 center dot H 2 O ( 1 ), is bis octahedral complex in which two deprotonated ligand molecules coordinate in a mer arrangement through two NNS sets of donor atoms. In cobalt(III) complex with HL 2 Cl, [Co( L 2 )(N 3 ) 3 ] ( 2 ), the ligand is coordinated in deprotonated, formally neutral, form to Co(III) ion in tridentate fashion through NNO set of donor atoms, and the other three coordination sites of a monokis octahedron are occupied by meridionally coordinated azide anions. DFT calculations were performed to elucidate coordination preferences of these ligands toward Co(III) ion.
PB  - Elsevier, Amsterdam
T2  - Journal of Molecular Structure
T1  - Coordination preferences of NNO and NNS Schiff base ligands with Co(III) complexes: Synthesis, characterization and DFT calculation
VL  - 1266
DO  - 10.1016/j.molstruc.2022.133509
UR  - conv_943
ER  - 
@article{
author = "Darmanović, Darinka and Radanović, Dušanka and Jevtović, Mima and Turel, Iztok and Pevec, Andrej and Milcić, Miloš and Gruden, Maja and Zlatar, Matija and Đorđević, Nataša and Anđelković, Katarina and Čobeljić, Božidar",
year = "2022",
abstract = "Two Co(III) complexes with condensation product of thiosemicarbazide and 2-acetylthiazole ( HL 1 ligand, ( E )-2-(1-(thiazol-2-yl)ethylidene)hydrazine-1-carbothioamide) and the condensation product of 2-acetylpyridine and Girard's P reagent ( HL 2 Cl ligand, ( E )-1-(2-oxo-2-(2-(1-(pyridin-2yl)ethylidene)hydrazinyl)ethyl)pyridin-1-ium chloride) have been synthesized and characterized based on the results of single-crystal X-ray diffraction, NMR and IR spectroscopy and elemental analysis. Cobalt(III) complex with HL 1 ligand, [Co( L 1 ) 2 ]BF 4 center dot H 2 O ( 1 ), is bis octahedral complex in which two deprotonated ligand molecules coordinate in a mer arrangement through two NNS sets of donor atoms. In cobalt(III) complex with HL 2 Cl, [Co( L 2 )(N 3 ) 3 ] ( 2 ), the ligand is coordinated in deprotonated, formally neutral, form to Co(III) ion in tridentate fashion through NNO set of donor atoms, and the other three coordination sites of a monokis octahedron are occupied by meridionally coordinated azide anions. DFT calculations were performed to elucidate coordination preferences of these ligands toward Co(III) ion.",
publisher = "Elsevier, Amsterdam",
journal = "Journal of Molecular Structure",
title = "Coordination preferences of NNO and NNS Schiff base ligands with Co(III) complexes: Synthesis, characterization and DFT calculation",
volume = "1266",
doi = "10.1016/j.molstruc.2022.133509",
url = "conv_943"
}
Darmanović, D., Radanović, D., Jevtović, M., Turel, I., Pevec, A., Milcić, M., Gruden, M., Zlatar, M., Đorđević, N., Anđelković, K.,& Čobeljić, B.. (2022). Coordination preferences of NNO and NNS Schiff base ligands with Co(III) complexes: Synthesis, characterization and DFT calculation. in Journal of Molecular Structure
Elsevier, Amsterdam., 1266.
https://doi.org/10.1016/j.molstruc.2022.133509
conv_943
Darmanović D, Radanović D, Jevtović M, Turel I, Pevec A, Milcić M, Gruden M, Zlatar M, Đorđević N, Anđelković K, Čobeljić B. Coordination preferences of NNO and NNS Schiff base ligands with Co(III) complexes: Synthesis, characterization and DFT calculation. in Journal of Molecular Structure. 2022;1266.
doi:10.1016/j.molstruc.2022.133509
conv_943 .
Darmanović, Darinka, Radanović, Dušanka, Jevtović, Mima, Turel, Iztok, Pevec, Andrej, Milcić, Miloš, Gruden, Maja, Zlatar, Matija, Đorđević, Nataša, Anđelković, Katarina, Čobeljić, Božidar, "Coordination preferences of NNO and NNS Schiff base ligands with Co(III) complexes: Synthesis, characterization and DFT calculation" in Journal of Molecular Structure, 1266 (2022),
https://doi.org/10.1016/j.molstruc.2022.133509 .,
conv_943 .
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