Synthesis of Novel Ether Thionocarbamates and Study on Their Flotation Performance for Chalcopyrite
Abstract
:1. Introduction
2. Materials and Methods
2.1. Preparation of Ether Thionocarbamates
2.1.1. Synthesis of Ethoxycarbonyl Isothiocyanate
2.1.2. Synthesis of Ether Thionocarbamates
2.2. Determination of the Frothing Properties
2.3. Micro Flotation Experiments
2.4. Batch Flotation Tests
2.5. Adsorption Capacity Measurement
2.6. UV Spectra
2.7. FTIR Spectra
2.8. Computation
3. Results and Discussion
3.1. Characterization of the Products
Product Characterization:
3.2. Frothing Performance of Ether Thionocarbamates
3.3. Micro Flotation
3.4. Batch Flotation Tests
3.5. Adsorption Tests
3.6. UV Spectra of Collectors and Metal Ions
3.7. FTIR Spectra of Chalcopyrite
3.8. Quantum Chemistry Calculation
3.8.1. Molecular Geometry
3.8.2. Molecular Electrostatic Potential
3.8.3. Frontier Molecular Orbitals
3.8.4. Binding Model
4. Conclusions
Acknowledgments
Author Contributions
Conflicts of Interest
References
- Acres, R.G.; Harmer, S.L.; Beattie, D.A. Synchrotron XPS, NEXAFS, and ToF-SIMS studies of solution exposed chalcopyrite and heterogeneous chalcopyrite with pyrite. Miner. Eng. 2010, 23, 928–936. [Google Scholar] [CrossRef]
- Kalegowda, Y.; Chan, Y.L.; Wei, D.H.; Harmer, S.L. X-PEEM, XPS and ToF-SIMS characterization of xanthate induced chalcopyrite flotation: Effect of pulp potential. Surf. Sci. 2015, 635, 70–77. [Google Scholar] [CrossRef]
- Liu, G.Y.; Zhong, H.; Dai, T.G. Investigation of the selectivity of ethoxylcarbonyl thionocarbarbanmetes during the flotation copper sulfides. Miner. Metall. Proc. 2008, 25, 19–24. [Google Scholar]
- Qin, W.Q.; Wei, Q.; Jiao, F.; Yang, C.R.; Liu, R.Z.; Wang, P.P.; Ke, L.F. Utilization of polysaccharides as depressants for the flotation separation of copper/lead concentrate. Int. J. Min. Sci. Technol. 2013, 23, 179–186. [Google Scholar] [CrossRef]
- Nagaraj, D.R. Development of new flotation chemicals. Trans. Indian Inst. Metall. 1997, 50, 355–363. [Google Scholar]
- Bogdanov, O.S.; Vainshenker, I.A.; Podnek, A.K. Trends in the search for effective collectors. Tsvetn. Met. 1976, 9, 72–80. [Google Scholar]
- Milosavljević, M.M.; Marinković, A.D.; Veljković, V.B.; Milenković, D.D. Syntheses of N-alkyl, N,N-dialkyl, and N-(4-substituted phenyl) O-ethyl thioncarbamates: A kinetic study. Monatshefte Chem. 2012, 143, 43–49. [Google Scholar] [CrossRef]
- Wang, S.S.; Magliocco, L.G. Process of Alkoxy and Aryloxy Isothiocyanate Preparation. U.S. Patent 5,194,673, 16 March 1993. [Google Scholar]
- Buckley, A.N.; Hope, G.A.; Lee, K.C.; Petrovic, E.A.; Woods, R. Adsorption of O-isopropyl-N-ethyl thionocarbamate on Cu sulfide ore minerals. Miner. Eng. 2014, 69, 120–132. [Google Scholar] [CrossRef]
- Glembotskii, A.V. Theoretical principles of forecasting and modifying collector properties. Tsvetn. Met. 1978, 51, 86–89. [Google Scholar]
- Ackerman, P.K.; Harris, G.H.; Klimpel, R.R.; Aplan, F.F. Effect of alkyl substituents on performance of thionocarbamates as copper sulphides and pyrite collectors. In Reagents in the Minerals Industry; Jones, M.P., Oblatt, R., Eds.; Publishing House of the Institution of Mining and Metallurgy: London, UK, 1984; pp. 251–264. [Google Scholar]
- Sheridana, M.S.; Nagaraj, D.R.; Fornasiero, D.; Ralston, J. The use of a factorial experimental design to study collector properties of N-allyl-O-alkyl thionocarbamate collector in the flotation of a copper ore. Miner. Eng. 2002, 15, 333–340. [Google Scholar] [CrossRef]
- Porento, M.; Hirva, P. Theoretical studies on the interaction of anionic collectors with Cu+, Cu2+, Zn2+ and Pb2+ ions. Theor. Chem. Acc. 2002, 107, 200–205. [Google Scholar] [CrossRef]
- Yekeler, M.; Yekeler, H. Reactivities of some thiol collectors and their interactions with Ag (+1) ion by molecular modeling. Appl. Surf. Sci. 2004, 236, 435–443. [Google Scholar] [CrossRef]
- Yekeler, M.; Yekeler, H. A density functional study on the efficiencies of 2-mercaptobenzoxazole and its derivatives as chelating agents in flotation processes. Physicochem. Eng. Asp. 2006, 286, 121–125. [Google Scholar] [CrossRef]
- Liu, G.Y.; Zhong, H.; Dai, T.G. The separation of Cu/Fe sulfide minerals at slightly alkaline conditions by using ethoxycarbonyl thionocarbamates as collectors: Theory and practice. Miner. Eng. 2006, 19, 1380–1384. [Google Scholar] [CrossRef]
- Liu, G.Y.; Zhong, H.; Dai, T.G.; Xia, L.Y. Investigation of the effect of N-substituents on performance of thionocarbamates as selective collectors for copper sulfides by ab initio calculations. Miner. Eng. 2008, 21, 1050–1054. [Google Scholar] [CrossRef]
- Bulatovic, S.M. Handbook of Flotation Reagents: Chemistry, Theory and Practice, 1st ed.; Elsevier: Amsterdam, The Netherlands, 2007. [Google Scholar]
- Gupta, A.K.; Banerjee, P.K.; Mishra, A.; Satish, P.; Pradip. Effect of alcohol and polyglycol ether frothers on foam stability, bubble size and coal flotation. Int. J. Miner. Process. 2007, 82, 126–137. [Google Scholar] [CrossRef]
- Yuan, L.; Zhong, H. Synthesis and reaction with metal ions of a new thionocarbamate. Res. Chem. Intermed. 2012, 38, 903–909. [Google Scholar] [CrossRef]
- Gu, Y.L.; Feng, Q.M.; Ou, L.M.; Lü, P.C. A new method of testing frother performance. Trans. Nonferr. Met. Soc. China 2013, 23, 2776–2780. [Google Scholar] [CrossRef]
- Lomolino, G.; Vincenzi, S.; Gazzola, D.; Crapisi, A.; Curioni, A. Foaming properties of potato (Solanum tuberosum) proteins: A study by the gas sparging method. Physicochem. Eng. Asp. 2015, 475, 75–83. [Google Scholar] [CrossRef]
- Becke, A.D. Density-functional thermochemistry. III. The role of exact exchange. J. Chem. Phys. 1993, 98, 5648. [Google Scholar] [CrossRef]
- Frisch, M.J.; Trucks, G.W.; Schlegel, H.B.; Scuseria, G.E.; Robb, M.A.; Cheeseman, J.R.; Scalmani, G.; Barone, V.; Mennucci, B.; Petersson, G.A.; et al. Gaussian 09, Revision A. 02; Gaussian, Inc.: Wallingford, CT, USA, 2009. [Google Scholar]
- Gece, G.; Bilgiç, S. A theoretical study of some hydroxamic acids as corrosion inhibitors for carbon steel. Corros. Sci. 2010, 52, 3304–3308. [Google Scholar] [CrossRef]
- Liu, G.Y.; Zeng, H.B.; Lu, Q.Y.; Zhong, H.; Choi, P.; Xu, Z.H. Adsorption of mercaptobenzoheterocyclic compounds on sulfide mineral surfaces: A density functional theory study of structure–reactivity relations. Physicochem. Eng. Asp. 2012, 409, 1–9. [Google Scholar] [CrossRef]
- Scrocco, E.; Tomasi, J. Electronic molecular structure, reactivity and intermolecular forces: An euristic interpretation by means of electrostatic molecular potentials. Adv. Quantum Chem. 1978, 11, 115–193. [Google Scholar]
- Luque, F.J.; López, J.M.; Orozco, M. Perspective on “Electrostatic interactions of a solute with a continuum. A direct utilization of ab initio molecular potentials for the prevision of solvent effects”. Theor. Chem. Acc. 2000, 103, 343–345. [Google Scholar] [CrossRef]
- Fukui, K. Role of Frontier Orbitals in Chemical Reactions. Science 1982, 218, 747–754. [Google Scholar] [CrossRef] [PubMed]
- Padmaja, L.; Ravikumar, C.; Sajan, D.; Joe, I.H.; Jayakumar, V.S.; Pettict, G.R.; Nielson, O.F. Density functional study on the structural conformations and intramolecular charge transfer from the vibrational spectra of the anticancer drug combretastatin-A2. J. Raman Spectrosc. 2009, 40, 419–428. [Google Scholar] [CrossRef]
- Arjunan, V.; Devi, L.; Subbalakshmi, R.; Rani, T.; Mohan, S. Synthesis, vibrational, NMR, quantum chemical and structure-activity relation studies of 2-hydroxy-4-methoxyacetophenone. Mol. Biomol. Spectrosc. 2014, 130, 164–177. [Google Scholar] [CrossRef] [PubMed]
- El-Gammal, O.A.; Rakha, T.H.; Metwally, H.M.; Abu El-Reash, G.M. Synthesis, characterization, DFT and biological studies of isatinpicolinohydrazone and its Zn(II), Cd(II) and Hg(II) complexes. Mol. Biomol. Spectrosc. 2014, 127, 144–156. [Google Scholar] [CrossRef] [PubMed]
- Bag, B.; Das, B.; Mishra, B.K. Geometrical optimization of xanthate collectors with copper ions and their response to flotation. Miner. Eng. 2011, 24, 760–765. [Google Scholar] [CrossRef]
- Zhao, G.; Zhong, H.; Qiu, X.Y.; Wang, S.; Gao, Y.D.; Dai, Z.L.; Huang, J.P.; Liu, G.Y. The DFT study of cyclohexyl hydroxamic acid as a collector in scheelite flotation. Miner. Eng. 2013, 49, 54–60. [Google Scholar] [CrossRef]
- Deng, J.S.; Lei, Y.H.; Wen, S.M.; Chen, Z.X. Modeling interactions between ethyl xanthate and Cu/Fe ions using DFT/B3LYP approach. Int. J. Miner. Proces. 2015, 140, 43–49. [Google Scholar] [CrossRef]
- Wiberg, K.B. Application of the pople-santry-segal CNDO Method to the cyclopropylcarbinyl and cyclobutyl cation and to bicyclobutane. Tetrahedron 1968, 24, 1083–1096. [Google Scholar] [CrossRef]
- Szczepanik, D.W.; Mrozek, J. Ground-state projected covalency index of the chemical bond. Comput. Theor. Chem. 2013, 1023, 83–87. [Google Scholar] [CrossRef]
- Sizova, O.V.; Sokolov, A.Y.; Skripnikov, L.V.; Baranovski, V.I. Quantum chemical study of the bond orders in the ruthenium, diruthenium and dirhodium nitrosyl complexes. Polyhedron 2007, 26, 4680–4690. [Google Scholar] [CrossRef]
Elements | Cu (%) | Mo (%) | S (%) | Fe (%) | Au (g/t) | Ag (g/t) |
---|---|---|---|---|---|---|
Compositions | 0.385 | 0.008 | 1.212 | 4.071 | 0.286 | 0.950 |
Species | Sulfides | Oxides | Total Cu |
---|---|---|---|
Mass Fraction (%) | 0.334 | 0.051 | 0.385 |
Distribution Ratio (%) | 86.75 | 13.25 | 100.00 |
Collector and Dosage (g/t) | Products | Yields (%) | Cu Grades (%) | Cu Recoveries (%) |
---|---|---|---|---|
IPETC(24) + MIBC(12) | rough concentrate | 5.54 | 5.73 | 82.88 |
tail | 94.46 | 0.069 | 17.12 | |
crude | 100.00 | 0.383 | 100.00 | |
RSD | - | 2.13 | 0.35 | |
IBECTC(24) + MIBC(12) | rough concentrate | 5.76 | 5.58 | 83.26 |
tail | 94.24 | 0.069 | 16.74 | |
crude | 100.00 | 0.386 | 100.00 | |
RSD | - | 2.45 | 0.38 | |
BIPECTC(24) + MIBC(8) | rough concentrate | 6.23 | 5.12 | 84.39 |
tail | 93.77 | 0.063 | 15.61 | |
crude | 100.00 | 0.378 | 100.00 | |
RSD | - | 1.87 | 0.15 | |
BMIPECTC(24) + MIBC(8) | rough concentrate | 6.57 | 5.06 | 85.02 |
tail | 93.43 | 0.063 | 14.98 | |
crude | 100.00 | 0.391 | 100.00 | |
RSD | - | 2.01 | 0.24 |
Species | HOMO | LUMO | ΔEHOMO–LUMO |
---|---|---|---|
IPETC | −0.23145 | −0.02526 | 0.20619 |
IBECTC | −0.23961 | −0.05855 | 0.18106 |
BIPECTC | −0.23890 | −0.05866 | 0.18024 |
BMIPECTC | −0.23845 | −0.05838 | 0.18007 |
Species | C1–S3 | C1–O2 | C1–N4 | S1–Cu | - | - | - | - |
---|---|---|---|---|---|---|---|---|
IPETC | 1.4345 | 1.0777 | 1.3048 | - | - | - | - | - |
IPETC–Cu | 1.0784 | 1.2252 | 1.4671 | 0.5393 | - | - | - | - |
Species | C1–S7 | C1–O3 | C1–N6 | C2–N6 | C2–O4 | C2–O5 | S7–Cu | O4–Cu |
IBECTC | 1.6164 | 1.0844 | 1.1274 | 1.0486 | 1.6778 | 1.0432 | - | - |
IBECTC–Cu | 1.3515 | 1.2410 | 1.1745 | 1.0999 | 1.3949 | 1.2162 | 0.4657 | 0.2286 |
BIPECTC | 1.6112 | 1.0772 | 1.1358 | 1.0471 | 1.6776 | 1.0447 | - | - |
BIPECTC–Cu | 1.3538 | 1.2280 | 1.1807 | 1.1019 | 1.4001 | 1.2087 | 0.4773 | 0.2347 |
BMIPECTC | 1.6123 | 1.0771 | 1.1352 | 1.0473 | 1.6774 | 1.0446 | - | - |
BMIPECTC–Cu | 1.3532 | 1.2292 | 1.1810 | 1.1016 | 1.3999 | 1.2089 | 0.4778 | 0.2344 |
Energies | IPETC | IBECTC | BIPECTC | BMIPECTC |
---|---|---|---|---|
Collectors/(a.u.) | −764.6715 | −992.5607 | −1185.7237 | −1378.8811 |
Complexes/(a.u.) | −2404.6498 | −2632.5428 | −2825.7229 | −3018.8804 |
Binding/(kJ/mol) | −477.0428 | −486.8878 | −532.0930 | −532.3246 |
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Zhao, G.; Peng, J.; Zhong, H.; Wang, S.; Liu, G. Synthesis of Novel Ether Thionocarbamates and Study on Their Flotation Performance for Chalcopyrite. Minerals 2016, 6, 97. https://doi.org/10.3390/min6030097
Zhao G, Peng J, Zhong H, Wang S, Liu G. Synthesis of Novel Ether Thionocarbamates and Study on Their Flotation Performance for Chalcopyrite. Minerals. 2016; 6(3):97. https://doi.org/10.3390/min6030097
Chicago/Turabian StyleZhao, Gang, Jing Peng, Hong Zhong, Shuai Wang, and Guangyi Liu. 2016. "Synthesis of Novel Ether Thionocarbamates and Study on Their Flotation Performance for Chalcopyrite" Minerals 6, no. 3: 97. https://doi.org/10.3390/min6030097