Experimental and DFT insights into nitrogen and sulfur co-doped carbon nanotubes for effective desulfurization of liquid phases: Equilibrium & kinetic study

doi:10.1007/s11783-021-1397-3

Front. Environ. Sci. Eng.

2021, Vol. 15

Issue (5) : 109 https://doi.org/10.1007/s11783-021-1397-3

RESEARCH ARTICLE

Experimental and DFT insights into nitrogen and sulfur co-doped carbon nanotubes for effective desulfurization of liquid phases: Equilibrium & kinetic study

Seyyed Salar Meshkat¹(

), Ebrahim Ghasemy², Alimorad Rashidi³(

), Omid Tavakoli⁴, Mehdi Esrafili⁵

¹. Faculty of Chemical Engineering, Urmia University of Technology, Urmia 57166-419, Iran
². Nanotechnology Departments, School of New Technologies, Iran University of Science and Technology, Tehran 16846-13114, Iran
³. Nanotechnology Research Center, Research Institute of Petroleum Industry (RIPI), Tehran 14856-13111, Iran
⁴. School of Chemical Engineering, College of Engineering, University of Tehran, Tehran 14155-6619, Iran
⁵. Department of Chemistry, Faculty of Basis Sciences, University of Maragheh, Maragheh 55136-553, Iran

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Abstract

• Synthesis of NS-CNTS is used in a high desulfurization performance.

• Synthesizing NS-CNT is considered as a novel adsorbent from low-cost precursors.

• A high sulfur removal capacity for NS-CNT is attained compared with recent works.

Herein, nitrogen and sulfur co-doped carbon nanotubes (NS-CNT) adsorbents were synthesized via the chemical vapor deposition technique at 1000°C by employing the camphor, urea and sulfur trioxide pyridine. In this study, desulfurization of two types of mercaptans (dibenzothiophene (DBT) and tertiary butyl mercaptan (TBM) as nonlinear and linear forms of mercaptan) was studied. In this regard, a maximum capacity of NS-CNT was obtained as 106.9 and 79.4 mg/g and also the removal efficiencies of 98.6% and 88.3% were achieved after 4 h at 298K and 0.9 g of NS-CNT for DBT and TBM, respectively. Characterization of the NS-CNTs was carried out through exploiting scanning electron microscopy (SEM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and elemental analysis (CHN). The isotherm equilibrium data could be ascribed to the Freundlich nonlinear regression form and the kinetic data was fitted by nonlinear form of the pseudo second order model. The negative values of ΔS⁰, ΔH⁰ and ΔG⁰ specify that the adsorption of both types of mercaptans was a natural exothermic process with a reduced entropy. Maintenance of more than 96% of the adsorption capacity even after nine cycles suggest the NS-CNT as a superior adsorbent for mercaptans removal in the industry. Density functional theory (DFT) calculations were also performed to peruse the effects of S/N co-doping and carbon monovacancy defects in CNTs toward the adsorption of DBT and TBM.

Keywords Dibenzothiophene (DBT) Tertiary methyl mercaptan Adsorption Carbon nano tube (CNT) Desulfurization Doping

Corresponding Author(s): Seyyed Salar Meshkat,Alimorad Rashidi

Issue Date: 03 February 2021

Cite this article:

Seyyed Salar Meshkat,Ebrahim Ghasemy,Alimorad Rashidi, et al. Experimental and DFT insights into nitrogen and sulfur co-doped carbon nanotubes for effective desulfurization of liquid phases: Equilibrium & kinetic study[J]. Front. Environ. Sci. Eng., 2021, 15(5): 109.

URL:

https://academic.hep.com.cn/fese/EN/10.1007/s11783-021-1397-3
https://academic.hep.com.cn/fese/EN/Y2021/V15/I5/109

Fig.1 The schematic illustration of the experimental setup.

Fig.2 FTIR spectra of the synthesized NS-CNT and CNT.

Fig.3 FE-SEM images of synthesized (a) CNT and (b) NS-CNT.

Fig.4 XRD pattern of synthesized the NS-CNT, N-CNT, and pristine CNT.

Tab.1 Elemental analysis of the synthesized adsorbent

Fig.5 TGA weight loss curve of the synthesized NS-CNT.

Fig.6 The FE-SEM image of the adsorbent after adsorption process.

Fig.7 TGA curve of the adsorbent before and after adsorption process.

Fig.8 Removal efficiency of TBM & DBT vs. mass loaded.

Fig.9 Removal efficiency of DBT adsorption on the different synthesized adsorbents.

Tab.2 Kinetic model parameters for the adsorption of DBT onto NS-CNT

Fig.10 (a) Linear form of pseudo first order model; (b) Linear pseudo second order model; (c) Experimental and nonlinear forms of kinetic models.

Tab.3 Results of the DBT adsorption equilibrium analysis

Fig.11 (a) Langmuir linear form; (b) Freundlich linear form; (c) nonlinear fittings of Langmuir and Freundlich model for DBT adsorption

Tab.4 Thermodynamic parameters for DBT and TBM adsorption

Fig.12 Regeneration of NS-CNT for DBT and TBM adsorption.

Tab.5 Elemental analysis of the NS-CNT (weight %)

Tab.6 The comparison of the DBT removal by different adsorbents

Tab.7 The optimized binding distances (R, Å), adsorption energies (E_ads, kJ/mol) and charge-transferred values due to the adsorption of DBT or TBM molecules over different models of CNTs

Fig.13 Optimized models of NS-CNTs used in the DFT calculations.

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