Mechanism insight into the formation of H2S from thiophene pyrolysis: A theoretical study

ShiGuan, Yang; Fan, Xin-rui; Liu, Ji; Zhao, Wei; Hu, Bin; Lü, Qiang

doi:10.1007/s11783-021-1404-8

Cited by 13 publications

(13 citation statements)

References 31 publications

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“…DFT is a useful tool to simulate and gain information about molecular structure-property relationships; and the CO 2capturing mechanism, helping researchers to develop and synthesize new task-specific solvents for CO 2 capture (Altamash et al, 2016). Therefore, the geometry optimizations were performed using DFT with Becke threeparameter (Exchange), Lee, Yang, and Parr correlation (B3LYP) and basis set of 6-31 + G (d, p) which is widely used in computational studies (Yang et al, 2021;Khan et al, 2020). B3LYP was selected for all calculations due to its remarkable performance over a wide range of systems.…”

Section: Density Functional Theory (Dft)mentioning

confidence: 99%

Potassium carbonate-based ternary transition temperature mixture (deep eutectic analogues) for CO2 absorption: Characterizations and DFT analysis

Ghaedi

Kalhor

Zhao

et al. 2021

Front. Environ. Sci. Eng.

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Is it possible to improve CO2 solubility in potassium carbonate (K2CO3)-based transition temperature mixtures (TTMs)? To assess this possibility, a ternary transition-temperature mixture (TTTM) was prepared by using a hindered amine, 2-amino-2-methyl-1,3-propanediol (AMPD). Fourier transform infrared spectroscopy (FT-IR) was employed to detect the functional groups including hydroxyl, amine, carbonate ion, and aliphatic functional groups in the prepared solvents. From thermogravimetric analysis (TGA), it was found that the addition of AMPD to the binary mixture can increase the thermal stability of TTTM. The viscosity findings showed that TTTM has a higher viscosity than TTM while their difference was decreased by increasing temperature. In addition, Eyring’s absolute rate theory was used to compute the activation parameters (∆G*, ∆H*, and ∆S*). The CO2 solubility in liquids was measured at a temperature of 303.15 K and pressures up to 1.8 MPa. The results disclosed that the CO2 solubility of TTTM was improved by the addition of AMPD. At the pressure of about 1.8 MPa, the CO2 mole fractions of TTM and TTTM were 0.1697 and 0.2022, respectively. To confirm the experimental data, density functional theory (DFT) was employed. From the DFT analysis, it was found that the TTTM + CO2 system has higher interaction energy (|∆E|) than the TTM + CO2 system indicating the higher CO2 affinity of the former system. This study might help scientists to better understand and to improve CO2 solubility in these types of solvents by choosing a suitable amine as HBD and finding the best combination of HBA and HBD.

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Section: Density Functional Theory (Dft)mentioning

confidence: 99%

Potassium carbonate-based ternary transition temperature mixture (deep eutectic analogues) for CO2 absorption: Characterizations and DFT analysis

Ghaedi

Kalhor

Zhao

et al. 2021

Front. Environ. Sci. Eng.

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“…The hydrogen atom transfers from C(4) to S, destroying the symmetry of thiophene, but the ring structure has not been destroyed, which is different from the published result. 8 The MBOs of the intermediate were calculated for further verification; the MBO of C(1)−S decreases from 1.17 to 0.96, while that of C(4)−S decreases from 1.17 to 0.83, which indicates that the stability of C−S bonds is getting worse, but the C−S bonds have not been ruptured. Further hydrogentransfer reactions can lead to ring opening, as shown in Figure 8, and the changes of relative energy are shown in Figure 9.…”

Section: Resultsmentioning

confidence: 99%

“…Besides, the hydrogen-transfer reaction will occur between the carbon atom and sulfur atom, as shown in Figure . The hydrogen atom transfers from C(4) to S, destroying the symmetry of thiophene, but the ring structure has not been destroyed, which is different from the published result . The MBOs of the intermediate were calculated for further verification; the MBO of C(1)–S decreases from 1.17 to 0.96, while that of C(4)–S decreases from 1.17 to 0.83, which indicates that the stability of C–S bonds is getting worse, but the C–S bonds have not been ruptured.…”

Section: Resultsmentioning

confidence: 99%

“…The decomposition mechanism of thiophene is complex, and the conclusions of the published research are not consistent. For example, Yang et al reported that the conversion to chain mercaptan can be achieved by the hydrogen transfer of the C–S bond, while Li et al claimed that the destruction of the thiophene ring mainly depends on the hydrogen transfer of the C–C bond. Furthermore, thiophene is difficult to decompose in an inert atmosphere, but it will be promoted in the existence of H 2 , which is the main components in the pyrolysis gas .…”

Section: Introductionmentioning

confidence: 99%

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Mechanism Insight into the Conversion between H₂S and Thiophene during Coal Pyrolysis: A Theoretical Study

Xian,

Xu,

2023

ACS Omega

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Clean coal technology is the important thrust to the achievement of "carbon neutralization"; clearing the transformation mechanism of thiophene, the dominant organic sulfur species in coal, is conducive to promoting the development of sulfur removal technology. DFT calculations were performed, and 28 reaction paths were proposed in this research, clarifying the decomposition mechanism of thiophene and the fixation mechanism of H 2 S. Thiophene is pyrolyzed mainly through the hydrogentransfer reaction, which occurs at above 2000 K rather than 800 K. The hydrogen transfer between the C−C bond rather than the C−S bond causes the ring opening. Hydrogen promotes the decomposition of thiophene, which happens at 800 K, with a molar ratio of hydrogen to thiophene of 5. Therefore, thiophene is decomposed at 800 K mainly through the hydrogenation reaction that occurs at para carbons and the C−S bond, the H 2 S elimination reaction, and the generation of ethane. Furthermore, H 2 S can be converted into thiophene through the addition reaction with unsaturated hydrocarbon, or the dehydration reaction with hydroxyl or carboxyl groups. The combination between H 2 S and the aliphatic compound occurs at 800 K, which is mainly influenced by the species of the functional group rather than the composition and morphology of the carbon chain. Meanwhile, the conversion of aromatic compounds tends to the generation of aryl mercaptan rather than thiophene at around 800 K.

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“…In addition, the DFT method also can be used to explore the pyrolysis process. Yang et al [ 78 ] explored the decomposition of single thiophene molecular with or without an H atom and the formation of H 2 S during pyrolysis. Three possible pyrolysis pathways were proposed.…”

Section: Micro-scale Mechanism Of Physical-chemical Evolution Of Hspc...mentioning

confidence: 99%

The Effects of Physical-Chemical Evolution of High-Sulfur Petroleum Coke on Hg0 Removal from Coal-Fired Flue Gas and Exploration of Its Micro-Scale Mechanism

Jiang

Diao

2022

IJERPH

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As the solid waste by-product from the delayed coking process, high-sulfur petroleum coke (HSPC), which is hardly used for green utilization, becomes a promising raw material for Hg0 removal from coal-fired flue gas. The effects of the physical–chemical evolution of HSPC on Hg0 removal are discussed. The improved micropores created by pyrolysis and KOH activation could lead to over 50% of Hg0 removal efficiency with the loss of inherent sulfur. Additional S-containing and Br-containing additives are usually introduced to enhance active surface functional groups for Hg0 oxidation, where the main product are HgS, HgBr, and HgBr2. The chemical–mechanical activation method can make additives well loaded on the surface for Hg0 removal. The DFT method is used to sufficiently explain the micro-scale reaction mechanism of Hg0 oxidation on the surface of revised-HSPC. ReaxFF is usually employed for the simulation of the pyrolysis of HSPC. However, the developed mesoporous structure would be a better choice for Hg0 removal in that the coupled influence of pore structure and functional groups plays a comprehensive role in both adsorption and oxidation of Hg0. Thus, the optimal porous structure should be further explored. On the other hand, both internal and surface sulfur in HSPC should be enhanced to be exposed to saving sulfur additives or obtaining higher Hg0 removal capacity. For it, controllable pyrolysis with different pyrolysis parameters and the chemical–mechanical activation method is recommended to both improve pore structure and increase functional groups for Hg0 removal. For simulation methods, ReaxFF and DFT theory are expected to explain the micro-scale mechanisms of controllable pyrolysis, the chemical–mechanical activation of HSPC, and further Hg0 removal. This review work aims to provide both experimental and simulational guidance to promote the development of industrial application of Hg0 adsorbent based on HSPC.

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Mechanism insight into the formation of H2S from thiophene pyrolysis: A theoretical study

Cited by 13 publications

References 31 publications

Potassium carbonate-based ternary transition temperature mixture (deep eutectic analogues) for CO2 absorption: Characterizations and DFT analysis

Potassium carbonate-based ternary transition temperature mixture (deep eutectic analogues) for CO2 absorption: Characterizations and DFT analysis

Mechanism Insight into the Conversion between H₂S and Thiophene during Coal Pyrolysis: A Theoretical Study

The Effects of Physical-Chemical Evolution of High-Sulfur Petroleum Coke on Hg0 Removal from Coal-Fired Flue Gas and Exploration of Its Micro-Scale Mechanism

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Mechanism insight into the formation of H2S from thiophene pyrolysis: A theoretical study

Cited by 13 publications

References 31 publications

Potassium carbonate-based ternary transition temperature mixture (deep eutectic analogues) for CO2 absorption: Characterizations and DFT analysis

Potassium carbonate-based ternary transition temperature mixture (deep eutectic analogues) for CO2 absorption: Characterizations and DFT analysis

Mechanism Insight into the Conversion between H2S and Thiophene during Coal Pyrolysis: A Theoretical Study

The Effects of Physical-Chemical Evolution of High-Sulfur Petroleum Coke on Hg0 Removal from Coal-Fired Flue Gas and Exploration of Its Micro-Scale Mechanism

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Mechanism Insight into the Conversion between H₂S and Thiophene during Coal Pyrolysis: A Theoretical Study