Change search
CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • ieee
  • modern-language-association-8th-edition
  • vancouver
  • Other style
More styles
Language
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Other locale
More languages
Output format
  • html
  • text
  • asciidoc
  • rtf
Metal-Chelate Complexes in Alkaline Solution: On Recovery Techniques and Cellulose-based Hybrid Material Synthesis
Mid Sweden University, Faculty of Science, Technology and Media, Department of Chemical Engineering. (Surface and Colloid Engineering)ORCID iD: 0000-0001-6270-2970
2018 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

For decades, aminopolycarboxylate chelating agents have been extensively used in various industrial applications. The ability of chelating agents to form stable metal-chelate complexes is the main reason for using them to manage metal ions within water-based industrial processes. Considerable quantities of industrial effluent containing chelating agents and heavy metals are produced and often discharged into the environment. The toxicity of heavy metals and the non-biodegradability of the chelating agents, as well as their accumulation in the environment, has become cause for concern. The main purpose of this thesis was to evaluate and develop processes for recovery of chelated metal complexes from aqueous solution. In this regard, the membrane electrolysis technique was evaluated for recovery of copper and aminopolycarboxylic chelating ligands such as ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA), diethylenetriaminepentaacetic acid (DTPA), and a surface-active derivative of DTPA, 2-dodecyldiethylenetriaminepentaacetic acid (C12-DTPA) from aqueous solution. By using this method, it was possible to simultaneously recover the chelating ligand for further reuse and collect the metals by electrodeposition, making the process more cost-effective and hindering the discharge of copper ions and chelating ligands as pollutants into the environment. In addition, the ion flotation technique with the chelating surfactant C12-DTPA could be employed to separate metal ions, especially from their dilute solutions, and concentrate them in a foam phase. This is because C12-DTPA has a purpose-built functionality; besides forming strong coordination complexes with metal ions, it is also surface-active and will readily adsorb at air-water interfaces. In this study, C12-DTPA was effectively used in combination with foaming agents for the removal of toxic metal ions such as Cd2+, Zn2+, and Sr2+ from aqueous solution using ion flotation. From an economical perspective, this method could be combined with the membrane electrolysis technique to recover metal and regenerate chelating surfactant so that it can be reused.

The present work also shows the synthesis of metal and metal oxide(s) nanoparticles (NPs) in alkaline aqueous solution containing chelated metal ions, in order to fabricate metal NPs–cellulose hybrid materials. Cellulose is the most abundant renewable material, with good mechanical performance and chemical resistivity in a wide range of solvents, which makes it a promising material to support metal NPs. In this respect, we developed a rapid and inexpensive one-pot synthesis of spherical copper NPs in a cellulose matrix. The hybrid material displayed antibacterial properties for both the gram-negative and gram-positive bacteria. The synthesis was further developed by studying the influence of various chelating ligands and surfactants on the NPs’ morphology and chemical composition. According to the results, DDAO, a zwitterionic surfactant, was found to mediate the formation of pure octahedral Cu2O NPs. In addition, a hybrid material film composed of regenerated cellulose and synthesized Cu2O nano-octahedrons was fabricated by spin-coating.

Place, publisher, year, edition, pages
Sundsvall: Mid Sweden University , 2018. , p. 68
Series
Mid Sweden University doctoral thesis, ISSN 1652-893X ; 282
National Category
Other Chemical Engineering
Identifiers
URN: urn:nbn:se:miun:diva-33975ISBN: 978-91-88527-54-7 (print)OAI: oai:DiVA.org:miun-33975DiVA, id: diva2:1228557
Public defence
2018-06-05, M102, Sundsvall, 13:00 (English)
Opponent
Supervisors
Available from: 2018-06-28 Created: 2018-06-28 Last updated: 2018-06-28Bibliographically approved
List of papers
1. Influences of the operational variables on electrochemical treatment of chelated Cu(II) in alkaline solutions using a membrane cell
Open this publication in new window or tab >>Influences of the operational variables on electrochemical treatment of chelated Cu(II) in alkaline solutions using a membrane cell
2017 (English)In: Journal of chemical technology and biotechnology (1986), ISSN 0268-2575, E-ISSN 1097-4660, Vol. 92, no 6, p. 1436-1445Article in journal, Editorial material (Refereed) Published
Abstract [en]

BACKGROUND

The electrochemical recovery of copper and chelating agent from their complex solution using a membrane flow cell was investigated. The parameters electrolysis time, solution pH, current density, and temperature were investigated.

RESULTS

Electrochemical investigation indicated that chelating ligands can be recovered by the electrodeposition of copper ions on the cathode. For copper and EDTA recovery, the results indicated that recovery efficiency was affected by time, current density, and temperature. The recovery process was not influenced by pH in the range studied (pH 8–12), which can be explained by the low variation in the conditional stability constant, i.e. Δlog10 K' ≤ 0.7, over the pH range. However, when NTA, EDTA, and DTPA were compared, the results indicated that the recovery efficiency decreased as the conditional stability constant of the chelating agent–Cu(II) complex increased. The maximum current efficiency of copper and EDTA recovery after 5 h of treatment was approximately 85%, whereas the recovery was 80% of the initial concentration (0.05 mol L−1) at a current density of 1 A dm−2, temperature of 333 K, and pH of 10.

CONCLUSION

Relatively high recovery efficiency makes the process fairly sustainable and hinders the discharge of copper ions and chelating ligands as pollutants into the environment. 

Keywords
electrochemistry, heavy metals, recovery, waste-water, hydrometallurgy
National Category
Chemical Sciences
Identifiers
urn:nbn:se:miun:diva-29558 (URN)10.1002/jctb.5141 (DOI)000403025100035 ()2-s2.0-85006827367 (Scopus ID)
Available from: 2016-12-14 Created: 2016-12-14 Last updated: 2018-06-28Bibliographically approved
2. Electrochemical recovery of copper complexed by DTPA and C12-DTPA from aqueous solution using a membrane cell
Open this publication in new window or tab >>Electrochemical recovery of copper complexed by DTPA and C12-DTPA from aqueous solution using a membrane cell
2018 (English)In: Journal of chemical technology and biotechnology (1986), ISSN 0268-2575, E-ISSN 1097-4660, Vol. 93, no 5, p. 1421-1431Article in journal (Refereed) Published
Abstract [en]

BACKGROUND

The electrochemical recovery of copper from DTPA and C12-DTPA (a surface-active derivative of DTPA) complex solutions was investigated in a membrane flow cell. Electrolysis time, solution flow rate, applied current density, and solution pH were evaluated.

RESULTS

The chelating surfactant C12-DTPA can promote the kinetics of copper electrodeposition more than DTPA depending on the experimental conditions. At a current density of 30 A m–2, a solution flow rate of 0.6 L min–1, and pH 10 after 180 min treatment, the copper recovery and current efficiency were 50% and 43.3%, respectively, in the Cu(II)-DTPA system and about 65% and 53.6%, respectively, in the Cu(II)-C12-DTPA system. The differences in the amount of recovery could be explained in terms of differences in the diffusion of copper complexes with DTPA and C12-DTPA to the cathode, as well as their solution behavior and pH-dependent conditional stability constants (log10 K’CuDTPA3-).

CONCLUSION

Electrochemical methods could be effectively combined with foam flotation for the chelating surfactant C12-DTPA, to recover copper and C12-DTPA. This makes the overall treatment more sustainable, and can be helpful in complying with the increasingly stringent environmental regulations

National Category
Chemical Sciences
Identifiers
urn:nbn:se:miun:diva-32251 (URN)10.1002/jctb.5510 (DOI)000429714500022 ()
Note

Available from: 2017-12-05 Created: 2017-12-05 Last updated: 2018-06-28Bibliographically approved
3. Removal of Cd2+, Zn2+, and Sr2+ by Ion Flotation, Using a Surface-Active Derivative of DTPA (C12-DTPA)
Open this publication in new window or tab >>Removal of Cd2+, Zn2+, and Sr2+ by Ion Flotation, Using a Surface-Active Derivative of DTPA (C12-DTPA)
Show others...
2017 (English)In: Industrial & Engineering Chemistry Research, ISSN 0888-5885, E-ISSN 1520-5045, Vol. 56, no 38, p. 10605-10614Article in journal (Refereed) Published
Abstract [en]

Ion flotation was studied for the removal of cadmium, zinc, and strontium ions from aqueous solutions at pH 5–9 in a customized flotation cell, using an aminopolycarboxylic chelating surfactant, 2-dodecyldiethylenetriamine pentaacetic acid (C12-DTPA) in combination with two foaming agents: dodecyltrimethylammonium chloride (DoTAC) and dimethyldodecylamine-N-oxide (DDAO). The results from experiments showed that both Zn2+ and Cd2+ could be removed via ion flotation to 100% at pH 5, and Sr2+ could be removed via ion flotation to 60%–70% at pH 7–9. The removal of metal ions from the flotation cell was seen to vary with pH, but this was not exclusively related to the magnitudes of the formed metal ion-chelating surfactant conditional stability constants. The removal was also dependent on the foam properties of the samples that were found to vary over the investigated pH interval. The outcome of the investigation points to the chelating surfactant C12-DTPA having excellent chelating properties for all of the studied ions above pH 7. In combination with correctly chosen foaming agents, the optimized surfactant system could be expected to provide very efficient remediation of waters polluted with metal ions via ion flotation.

National Category
Engineering and Technology
Identifiers
urn:nbn:se:miun:diva-31643 (URN)10.1021/acs.iecr.7b03100 (DOI)000412043400007 ()2-s2.0-85030457973 (Scopus ID)
Available from: 2017-09-20 Created: 2017-09-20 Last updated: 2018-06-28Bibliographically approved
4. One-pot synthesis of cellulose-templated copper nanoparticles with antibacterial properties
Open this publication in new window or tab >>One-pot synthesis of cellulose-templated copper nanoparticles with antibacterial properties
Show others...
2017 (English)In: Materials letters (General ed.), ISSN 0167-577X, E-ISSN 1873-4979, Vol. 187, p. 170-172Article in journal (Refereed) Published
Abstract [en]

We report a facile in situ synthesis of spherical copper nanoparticles (NPs) templated by a gelled cellulose II matrix under alkaline aqueous reaction conditions. In under 20 min, the hybrid material could be obtained in a one-pot reaction. Field-emission scanning electron microscopy (FE-SEM) revealed that the polycrystalline NPs of 200–500 nm were well distributed in the regenerated cellulose matrix. The average Cu crystallite size was of the order of 20 nm, as estimated from both X-ray diffraction (XRD) and FE-SEM. XRD data also indicated that the composite contained up to approximately 20% Cu2O. In suspensions containing the hybrid material, growth of Escerichia coli and Staphylococcus aureus strains was inhibited by 80% and 95%, respectively, after 72 h. The synthesis procedure offers a general approach to designing various low-cost hybrid materials of almost any shape, and the concept could be extended to utilization areas such as catalysis, functional textiles, and food packaging as well as to electronic applications.

Keywords
One-pot synthesis, Copper nanoparticles, Cellulose, Hybrid material, Antibacterial properties
National Category
Nano Technology Chemical Engineering Composite Science and Engineering
Identifiers
urn:nbn:se:miun:diva-29336 (URN)10.1016/j.matlet.2016.10.026 (DOI)000390628200045 ()2-s2.0-84994876232 (Scopus ID)FSCN (Local ID)FSCN (Archive number)FSCN (OAI)
Projects
NovoCell - Novel use of native cellulose in dispersions and functional biocomposites
Funder
Swedish Research Council Formas, 942-2015-251
Available from: 2016-11-24 Created: 2016-11-24 Last updated: 2018-06-28Bibliographically approved
5. Controlled Synthesis of Cu and Cu2O NPs and Incorporation of Octahedral Cu2O NPs in Cellulose II Films
Open this publication in new window or tab >>Controlled Synthesis of Cu and Cu2O NPs and Incorporation of Octahedral Cu2O NPs in Cellulose II Films
2018 (English)In: Nanomaterials, ISSN 2079-4991, Vol. 8, no 4, article id 238Article in journal (Refereed) Published
Abstract [en]

In this study, Cu and Cu2O nanoparticles (NPs) were synthesized through chemical reduction of soluble copper-chelating ligand complexes using formaldehyde as a reducing agent. The influence of various chelating ligands, such as ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), and a surface-active derivative of DTPA (C12-DTPA), as well as surfactants (i.e., hexadecyltrimethylammonium bromide (CTAB), dodecyltrimethylammonium chloride (DoTAC), sodium dodecyl sulfate (SDS), and dimethyldodecylamine-N-oxide (DDAO)), on morphology and the composition of produced NPs was investigated. In the absence of surfactants, spherical copper particles with polycrystalline structure could be obtained. X-ray diffraction (XRD) analysis revealed that, in the presence of EDTA, the synthesized NPs are mainly composed of Cu with a crystallite size on the order of 35 nm, while with DTPA and C12-DTPA, Cu2O is also present in the NPs as a minority phase. The addition of ionic surfactants to the copper–EDTA complex solution before reduction resulted in smaller spherical particles, mainly composed of Cu. However, when DDAO was added, pure Cu2O nano-octahedrons were formed, as verified by high-resolution scanning electron microscopy (HR-SEM) and XRD. Furthermore, a hybrid material could be successfully prepared by mixing the octahedral Cu2O NPs with cellulose dissolved in a LiOH/urea solvent system, followed by spin-coating on silica wafers. It is expected that this simple and scalable route to prepare hybrid materials could be applied to a variety of possible applications.

Keywords
copper nanoparticles; cuprous oxide nano-octahedrons; hybrid material; regenerated cellulose; chemical reduction; chelating agent; surfactant
National Category
Nano Technology Chemical Engineering Materials Engineering
Identifiers
urn:nbn:se:miun:diva-33497 (URN)10.3390/nano8040238 (DOI)000434889100059 ()2-s2.0-85045875998 (Scopus ID)
Available from: 2018-04-16 Created: 2018-04-16 Last updated: 2018-07-04Bibliographically approved

Open Access in DiVA

fulltext(4743 kB)35 downloads
File information
File name FULLTEXT01.pdfFile size 4743 kBChecksum SHA-512
a3fa9c9b50ab21f216b27c6bb0239ea74d7b8a7f2220e397957729a4e46019f345fd223c7b7f247641337c0d224a3c960e4adcb8d3bfd6b9cf31482aa2ca4c1d
Type fulltextMimetype application/pdf

Search in DiVA

By author/editor
Eivazihollagh, Alireza
By organisation
Department of Chemical Engineering
Other Chemical Engineering

Search outside of DiVA

GoogleGoogle Scholar
Total: 35 downloads
The number of downloads is the sum of all downloads of full texts. It may include eg previous versions that are now no longer available

isbn
urn-nbn

Altmetric score

isbn
urn-nbn
Total: 109 hits
CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • ieee
  • modern-language-association-8th-edition
  • vancouver
  • Other style
More styles
Language
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Other locale
More languages
Output format
  • html
  • text
  • asciidoc
  • rtf