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Conclusion defined as following: reaction temperature was studied,
Thus, the import-substituting sulphanole has been initial substance and reaction time and the influence of
synthesized based on local raw materials and intermedi- the sulfonating agent to yield. ates. The optimal conditions for the synthesis have been
References:
1. Shexter Yu. N., Kreyn S.E., Poverxnostno-aktivnie veshestva iz neftyanogo sirya. M:., 1971, 112-116 p.
2. Shexter Yu.N., Kreyn S.E., Teterina L. N., Maslorastvorimie poverxnostno-aktivnie veshestva. M., 1978, 224-226 p.
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DOI: http://dx.doi.org/10.20534/AJT-16-9.10-79-82
Daminova Shahlo Sharipovna, Tashkent Chemical Technological Institute, Department of "Technology of silicate materials and rare precious metals",
Scientific Researcher E-mail: [email protected] Kadirova Zukhra Chingizovna, Tashkent Chemical Technological Institute, Center of Excellence,
Dr. Engineering, PhD in Chemistry, E-mail: [email protected] Sharipov Kasan Turabovich, Tashkent Chemical Technological Institute, Department of "Technology of silicate materials and rare precious metals",
Professor
E-mail: [email protected]
Investigation of copper, nickel (II) and iron (III) ions sorption on sir by using FTIR and DRS methods
Abstract: The solvent impregnated resins (SIRs) based on Porolas resin impregnated with diisipropyl-dithiophosphoric acid were studied by Fourier transform infrared (FTIR) and electronic diffuse reflectance spectroscopic (DRS) methods. Physical sorption of diisopropyldithiophosphoric acid on macroporous Porolas resin in impregnation and sorption of metal ions on SIR were confirmed. The prepared SIR can be very useful for extraction of metals from hydrometallurgical solutions.
Keywords: Solvent impregnated resin, dialkyldithiophosphoric acid, infrared spectroscopy, electronic spectroscopy.
1. Introduction
Organophosphorus compounds are well known agents for impregnation of polymeric sorbents used for sorption ofmetal ions [1, 174-175]. Literature describes liquid phase sorption of Pb, Cd, Cu and Hg (II) ions by dialkyldithiophosphorous acids without detailed investigation of solid phase and effects of solid phase in solvent impregnated resins (SIR) [2, 1641]. The solvent impregnated resins (SIR) can be modeled as a "liq-
uid complexing agent dispersed homogeneously in a solid polymeric medium" [3, 353]. The impregnated should behave as in the liquid state but exhibit strong affinity to the matrix. It is known different acidic organophosphorus ex-tractants: di (2-ethylhexyl)phosphoric acid (DEHPA) [4, 126] used for extraction of Zn, Cu and Cd (II) [5, 131], V (IV) [6, 109], La and Ce (III) [7, 511]; di (2-ethylhexyl) dithiophosphoric acid (DEHTPA) [8, 201] applied for extraction of Pd (II) [9, 545], Cu [10, 149].
The aim of work is study Porolas resin impregnated by diisopropyldithiophosphoric acid (i-PrO)2PS2H by Fourier transform infrared (FTIR) and electronic diffuse reflectance spectroscopic (DRS) methods. The FTIR method permits to describe a solid phase after impregnation while the diffuse reflectance spectroscopy (DRS) method permits to trace changing concentration of metal ions in the solid phase. Therefore, both methods are suitable for possible application to study sorption of Cu, Ni (II) and Fe (III) on the (i-PrO)2PS2H solvent impregnated resin.
2. Experimental
Porolas is a commercial resin (Ukraine) with a mac-roporous structure and styrene-divinylobenzene skeleton. Diisopropyldithiophosphoric acid was purchased from Sigma Aldrich GmbH. Before impregnation Po-rolas was rinsed with methanol and then with water to remove impurities. 10 g of potassium diisopropyldithio-phosphate dissolved in 250 cm 3 of methanol was added to 10 g of Porolas, all ingredients were shaken for 3 h at 293 K. After impregnation, SIR was rinsed by deion-ized water. The concentration of diisopropyldithiophosphoric acid in Porolas was determined by using gravimetric method. The content of (i-PrO2PS)2H in Porolas was ~ 50%. The prepared SIR was used in further metal sorption studies in batch reactor. The metal ions contents were analyzed by using atomic absorption spectroscopy after sorption from 0.05-0.02-0.04 mol/l solutions.
The FTIR absorption spectra recorded by means IRAffinity-1 spectrometer (Shimadzu, Japan) over the 4000-400 cm1 range at the resolution of 4 cm-1
Table 1. - Spectral data of Porolas
in KBr pellet. The DRS spectra were measured by using the UV-2600 spectrometer (Shimadzu, Japan) equipped with a diffuse reflectance attachment.
3. Results and discussion
The Porolas resins (analogues of XAD-2, XAD-4 Amberlite resins) are macroporous (macroreticular) hydrophobic syrene-divinylbenzene copolymer resins, having a rigid three-dimensional structure suitable to incorporate large amounts of extractants due to the high specific surface area (~900 m 2/g, average pore diameter of 4~9 nm, and a pore volume of 1.1 cm 3/g), high mechanical strength, and rather low solvent swelling during the impregnation process.
The FTIR spectra of Porolas were recorded before and after impregnation to estimate the efficiency of the applied procedure. The broad band with the maximum located at 3430 cm 1 (Fig. 1) can be attributed to the stretching vibrations of adsorbed water. The bands of carbon-hydrogen strong stretching vibrations from alkyl groups of (i-PrO)2PS2 H were observed in the range 2900-2800 cm-1. This part of spectrum is very similar to that for free diisopropyldithiophosphate, and gives an undeniable proof that the surface of resins is modified after the impregnation. The absence of SH vibration bands at 2550-2600 cm-1 confirmed impregnant anion state. The region of spectra between 1200 and 400 cm-1 is the most significant and informative because signals at 677 and 559 cm-1 are related to PSS ions. The signal at 559 is shifted to 548 cm-1 after sorption and it can be interpreted that metal ions are coordinated (Table 1).
impregnated with (i-PrO)2PS2 H
Sample FTIR spectra DRS spectra
n A n A
(i- PrO)2PS2 K 679 587, 560 226
(i- Pro)2PS2 K — Porolas 677 2 559 28 226
(i-PrO)2PS2 — Porolas+ Cu 2+ 710 31 548 39 255 (226)*, 421 (416)*
(i-PrO)2PS2 — Porolas+ Fe 3+ - - - - 259, 426
(i-PrO)2PS2 — Porolas+ Ni 2+ - - - - 262, 325, 528, 702
* - spectra in ethanol solution
The DRS spectra of Porolas impregnated with diisopropyldithiophosphoric acid after sorption of metal ions at different concentration in the range 1200400 nm are shown in Fig.2. The DRS was used in order to improve the results obtained by using the FTIR method. The DRS method permits to trace changing of metal ions in time during experiment.
In Figure 2 the signal at 255 nm is related to dithio-phosphoric acid ions in the solid phase of SIR from de-localized P=S double bond. The shift signal of dialkyl-dithiophosphate in solution from 226 nm to 255 nm in solid states confirmed physical interaction between resin and impregnated ligand. The reflectance spectra of the solid Ni complexes exhibit two broad bands in the visible
region (Table 1). The reflectance spectra of the solid Fe, transition. The band profile look similar for both Fe, Cu Cu complexes exhibit one broad band in the visible region complexes, but band maxima are observed to be sensitive (Figure 2, Table 1) based sulphur to metal charge-transfer to Cu ions.
vf cm"
Figure 1. The FTIR spectra of Porolas (a) and (i-PrO)2PS)2 K (b) SIR (c)
Figure 2. The DRS spectra of Porolas impregnated with (i-PrO)2PS)2 H after sorption of metal ions measured after 24 h (a — Cu sorption (1-0.05, 2-0.1, 3-0.25. 4-0.4 mol/l); b — Fe sorption (1-0.05, 2-0.25. 3-0.4 mol/l); c — Ni sorption (1-0.05, 2-0.25. 3-0.4 mol/l))
4. Conclusion
Both FTIR and DRS methods are very useful in the investigations of SIRs based on Porolas resin and diisopropyldithiophosphoric acid. The FTIR spectra provide information about physical sorption of diisopro-
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