Absorption, desorption and spectroscopic investigation of sulfur dioxide in the binary system ethylene glycol + dimethyl sulfoxide

doi:10.1016/j.fluid.2015.06.047

Fluid Phase Equilibria

Volume 405, 15 November 2015, Pages 7-16

https://doi.org/10.1016/j.fluid.2015.06.047 Get rights and content

Abstract

Isothermal gas–liquid equilibrium (GLE) data were measured at 298.15 K and 122.66 kPa for dilute SO₂ in the binary system ethylene glycol (EG) + dimethyl sulfoxide (DMSO), in which SO₂ partial pressures were calculated in range of (0–130) Pa. The solubility of dilute SO₂ in the binary system gradually increased with the increasing DMSO concentration in the whole composition. Based on the GLE data, Henry’s law constants (HLC) of dilute SO₂ in the binary system EG (1) + DMSO (2) were obtained. The regeneration experiments showed that the 97.6% SO₂ could be separated from the dissolving SO₂ solution at 80 °C and bubbling N₂ within 30 min; meanwhile, SO₂ desorption ran smoothly and solubility of SO₂ no significant dropped after five-successive absorption–desorption cycles. Furthermore, to obtain important reaction mechanism, the intermolecular interaction among SO₂, EG, and DMSO were investigated by UV–vis, FTIR, and ¹H NMR spectroscopic techniques. Spectral results showed that the interaction among EG, DMSO, and SO₂ were resulted from both the O → S charge-transfer interaction and intermolecular hydrogen bonding.

Introduction

SO₂, which mainly emitted from fossil fuel burning power plants, sulfide-based metal smelters, petroleum, and other SO₂-emitting industries, caused harmful impacts on the environment and human health [1], [2], [3]. Consequently, the control of the concentration level of SO₂ had been a worldwide issue to be urgently solved in the atmosphere [4], [5], [6]. The conventional technologies for flue gas desulfurization (FGD) had been applied in industry, including lime–limestone scrubbing and amine remove procedure [7], [8], [9], [10], which could pose serious inherent disadvantages, such as formation of low-cost byproducts, high capital and operating costs, large volumes of solid gypsum waste, solvent volatilization, and secondary pollution [7], [8]. Accordingly, to develop efficient desulfurizer and techniques that could reversibly and economically remove SO₂ was highly desirable.

The promising alternative EG and its derivatives had become the subject of the increasing interests in FGD processes, because of their favorable absorption and regeneration properties for SO₂ [11], [12], [13], [14], [15], [16]. In the recent work, we discovered that the SO₂ solubility in DMSO was stronger than in EG, which agreed well with literature [17], and DMSO also showed a remarkable regeneration properties for SO₂. Regrettably, pure DMSO with relatively high freezing point was about 18 °C, which was limited to wash SO₂ at low operational temperature. To overcome disadvantages, EG was added into DMSO to drop the freezing point of DMSO and stabilize SO₂ absorption performance in the binary system EG (1) + DMSO (2). As a whole, the treatment of SO₂ by the binary system EG (1) + DMSO (2) included the following four steps: (1) density, viscosity, and excess properties for the binary system EG + DMSO, (2) absorption and desorption properties of SO₂ in the binary system EG + DMSO, (3) intermolecular interaction in the system EG (1) + DMSO (2) + SO₂ (3), and (4) simulation of industrial experiment. The first part was reported in the previous work [18], and the parts of (2) and (3) were researched in this work. The present works were mainly focused on providing the important GLE data and HLC values for SO₂ + N₂ mixtures in various EG (1) + DMSO (2) systems at 298.15 K and 122.66 kPa; meanwhile, regeneration capability of mixture and intermolecular interaction among EG, DMSO and SO₂ by UV, FTIR, and ¹H NMR detecting techniques were systemic studied. These results could be used to provide important absorption mechanism for the design and operation of the absorption and desorption processes in FGD processes with potential industrial application of the binary system EG (1) + DMSO (2).

Section snippets

Materials

The analytical grade EG (Tianjin, China, Residue on ignition ≤ 0.01) and DMSO (Tianjin, China, Residue on ignition ≤ 0.02) were purchased from Tianjin Reagent Company. It was used after drying with molecular sieves (type 4 Å) and degassing by ultrasound just before the experiment. The density values of EG and DMSO at 298.15 K were found to be 1.1098 g cm⁻³ and 1.0693 g cm⁻³, respectively, in good agreement with literatures [19], [20]. Sodium thiosulfate (≥99.9; Na₂S₂O₃) and iodine (≥99.5; I₂) were

GLE data

A series of isothermal GLE data of dilute SO₂ in the binary system EG (1) + DMSO (2) were measured at 298.15 K and 122.66 kPa, and the GLE data were listed in Table 2.

As shown in Table 2, $y_{{SO}_{2}}$ (ppmv) denoted the volume fraction of SO₂ in the gas phase, which could be calculated form Eq. (2) as follows: $y_{{SO}_{2}} \approx \frac{V_{{SO}_{2}}}{V_{{SO}_{2}} + V_{N_{2}} + V_{N_{2}} + V_{ED} + V_{DMSO}} = \frac{V_{{SO}_{2}}}{V_{total}}$ where $V_{{SO}_{2}}$ and V_total denote the partial volume of SO₂ in the gas phase and total gas volume, respectively. The $C_{{SO}_{2}}$ ₍mol m⁻³₎ denotes the concentration of SO₂

Conclusions

In summary, the results of fundamental investigations on isothermal GLE data of various EG (1) + DMSO (2) mixtures with SO₂ were presented at 298.15 K and 122.66 kPa. The GLE data showed that the solubility of SO₂ in the system EG (1) + DMSO (2) increased with the decreasing EG concentration in the whole mass fraction range. When SO₂ in the gas phase was designed at $y_{{SO}_{2}}$ = 500 ppmv, the solubility of SO₂ in the mixtures presented an extreme minimum at the mass fraction of w₁ = 1.00 of 3.26 mol m⁻³, and the

Acknowledgements

This work was supported by the National Natural Science Foundation of China (21166017), the Research Fund for the Doctoral Program of Higher Education of China (20111514120002), Natural Science Foundation of Inner Mongolia Autonomous Region (2014MS0208), the Inner Mongolia Science and Technology Key Projects, the Program for Grassland Excellent Talents of Inner Mongolia Autonomous Region, Program for New Century Excellent Talents in University (NCET-12-1017), and the Inner Mongolia Talented

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Absorption, desorption and spectroscopic investigation of sulfur dioxide in the binary system ethylene glycol + dimethyl sulfoxide

Abstract

Introduction

Section snippets

Materials

GLE data

Conclusions

Acknowledgements

Chem. Eng. Sci.

J. Mol. Liq.

J. Mol. Struct.

Vib. Spectrosc.

J. Electroanal. Chem.

Fluid Phase Equilibr.

J. Chem. Thermodyn.

Fluid Phase Equilibr.

Fluid Phase Equilibr.

An evaluation of desulfurization technologies for sulfur removal from liquid fuels

RSC Adv.

Chemical and physical absorption of SO2 by N-functionalized lmidazoles: experimental results and molecular-level insight

Ind. Eng. Chem. Res.

SO2 scrubbing technologies: a review

Environ. Prog.

Desulfurzation of flue gas: SO2 absorption by an ionic liquid

Angew. Chem. Int. Ed.

Highly efficient and reversible SO2 capture by tunable azole-based ionic liquids through multiple-site chemical absorption

J. Am. Chem. Soc.

Comparative study of the solubilities of SO2 in five low volatile organic solvents (sulfolane, ethylene glycol, propylene carbonate, N-methylimidazole, and N-methylpyrrolidone)

J. Chem. Eng. Data

A nonequilibrium stage model to simulate the chemical absorption of SO2

Ind. Eng. Chem. Res.

Selective sulfur dioxide removal using organic solvents

Ind. Eng. Chem. Res.

Efficient SO2 capture by amine functionalized PEG

Phys. Chem. Chem. Phys.

An equation of state based on PC-SAFT for physical solvents composed for polyethylene glycol dimethylethers

Ind. Eng. Chem. Res.

Chemical and physical absorption of SO₂ by N-functionalized lmidazoles: experimental results and molecular-level insight

SO₂ scrubbing technologies: a review

Desulfurzation of flue gas: SO₂ absorption by an ionic liquid

Highly efficient and reversible SO₂ capture by tunable azole-based ionic liquids through multiple-site chemical absorption

Comparative study of the solubilities of SO₂ in five low volatile organic solvents (sulfolane, ethylene glycol, propylene carbonate, N-methylimidazole, and N-methylpyrrolidone)

A nonequilibrium stage model to simulate the chemical absorption of SO₂

Efficient SO₂ capture by amine functionalized PEG