The Hydrolysis of Carbonyl Sulfide at Low Temperature: A Review

Zhao, Shunzheng; Yi, Honghong; Tang, Xiaolong; Jiang, Shanxue; Gao, Feifei; Zhang, Bowen; Zuo, Yanran; Wang, Zhixiang

doi:10.1155/2013/739501

Cited by 45 publications

(30 citation statements)

References 57 publications

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“…Especially, it can be seen from the structure of TS1 that the chlorine ion also acts as Brønsted-base site and takes in one H atom from H 2 O to form active hydroxy, and the hydroxy attack COS and activate C = O bond ultimately to form MTA (IM2a). The result is well in accord with the proposed reaction mechanism catalysed by hydroxy (George 1974;Zhao et al 2013a). These results further con rm that the chloride ions in LDH can facilitate the activization and dissociation of H 2 O, which is also supported by the adsorption con gurations of reactants in Fig.…”

Section: The Possible Reaction Channelssupporting

confidence: 90%

The Catalytic Mechanism of Intercalated Chlorine Anions as Active Basic Sites in Mgal-layered Double Hydroxide for COS Hydrolysis

Liu

Zhao

Yao

et al. 2021

Preprint

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In order to make clear the role of intercalated anions in layered double hydroxides (LDHs) for catalytic hydrolysis of COS, the adsorption and reaction characteristics of COS over the simple Mg2Al-Cl-LDH model catalyst were studied by both theoretical and experimental methods. Density functional theory (DFT) calculations by CASTEP found that the chloride ions in LDH function as the key Brønsted-base sites to activate the adsorbed H2O with enlarged bond length and angle, facilitate the dissociative adsorption of intermediates including mono-thiocarbonic acid (MTA) and hydrogen thiocarbonic acid (HTA), and participate in the formation of transient states and subsequent hydrogen transfer process with decreased energy barriers during COS hydrolysis. COS hydrolysis will preferentially go through the dissociated intermediates of mono-thiocarbonates (MT) and hydrogen thiocarbonates (HT) with dramatically decreased energy barriers, and the rate-determining step of COS hydrolysis over Mg2Al-Cl-LDH will be the nucleophilic addition of C=O in COS by H2O (Ea = 1.10 eV). The experimental results further revealed that the apparent activation energy (0.89 eV) of COS hydrolysis over Mg2Al-Cl-LDH is close to theoretical value (1.10 eV), and the accumulated intermediates of MT, HT or carbonate were also observed by FT-IR around 1363 cm-1 on the used Mg2Al-Cl-LDH, which are well in accordance with the theoretical prediction. The demonstrated participation of intercalated chlorine anions in the evolution of intermediates and transient states as Brønsted-base sites during COS hydrolysis will give new insight into the basic sites in LDH materials.

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Section: The Possible Reaction Channelssupporting

confidence: 90%

The Catalytic Mechanism of Intercalated Chlorine Anions as Active Basic Sites in Mgal-layered Double Hydroxide for COS Hydrolysis

Liu

Zhao

Yao

et al. 2021

Preprint

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“…Nevertheless, COS formation should not be neglected in the presence of CO and CO 2 . Dedicated COS conversion is suggested and usually involves the hydrolysis route and catalysts that include metallic oxides with basic active sites …”

Section: Discussionmentioning

confidence: 99%

Desulfurization of Biomass Syngas Using ZnO-Based Adsorbents: Long-Term Hydrogen Sulfide Breakthrough Experiments

et al. 2020

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Dry-bed adsorptive desulfurization of biomass-based syngas with low to medium sulfur content using ZnO was investigated as an alternative to the conventional wet scrubbing processes. The technical feasibility of ZnO-based desulfurization was studied in laboratory-scale H2S breakthrough experiments. The experiments were set up to utilize realistic H2S concentrations from gasification and therefore long breakthrough times. Experiments were performed in a steam-rich model biosyngas in varying conditions. The long-term breakthrough experiments showed apparent ZnO utilization rates between 10 and 50% in the tested conditions, indicating intraparticle mass-transfer resistances partly due to space velocity and particle size constraints as well as the most likely product-layer resistances as evidenced by the large spent adsorbent surface area decrease. An empirical deactivation model to estimate full breakthrough curves was fitted to the laboratory-scale experimental data. Breakthrough experiment in tar-rich syngas was also performed with the conclusion that ZnO performance is not significantly affected by hydrocarbons despite carbon deposition on the particle surfaces.

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“…Within phases I and III, it is possible that the temperature incurred this pattern due to its dual effect on increasing COS formation with higher temperatures (in parallel, cysteine also decreased faster with greater temperature (Figure 1e)) but also increasing COS hydrolysis with higher temperatures. 39−42 In fact, both the hydrolysis and base-catalyzed hydrolysis rate constants for COS 39,40,42 and CS 2 43 are well established in literature. Thus, for COS, the hydrolysis and base-catalyzed hydrolysis rate constants over this temperature range were assessed based on the reaction rate constants and activation energies provided in Text S6.…”

Section: Environmental Science and Technologymentioning

confidence: 99%

Indirect Photochemical Formation of Carbonyl Sulfide and Carbon Disulfide in Natural Waters: Role of Organic Sulfur Precursors, Water Quality Constituents, and Temperature

Gharehveran

Shah

2018

Environ. Sci. Technol.

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Carbonyl sulfide (COS) and carbon disulfide (CS) are volatile sulfur compounds that are critical precursors to sulfate aerosols, which enable climate cooling. COS and CS stem from the indirect photolysis of organic sulfur precursors in natural waters, but currently the chemistry behind how this occurs remains unclear. This study evaluated how different organic sulfur precursors, water quality constituents, which can form important reactive intermediates (RIs), and temperature affected COS and CS formation. Nine natural waters ranging in salinity were spiked with cysteine, cystine, dimethylsulfide (DMS), or methionine and exposed to simulated sunlight over varying times and water quality conditions. Results indicated that COS and CS formation increased up to 11× and 4×, respectively, after 12 h of sunlight, while diurnal cycling exhibited varied effects. COS and CS formation was also strongly affected by the DOC concentration, organic sulfur precursor type, O concentration, and temperature, while salinity differences and CO addition did not play a significant role. Overall, important factors in forming COS and CS were identified, which may ultimately impact their atmospheric concentrations.

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The Hydrolysis of Carbonyl Sulfide at Low Temperature: A Review

Cited by 45 publications

References 57 publications

The Catalytic Mechanism of Intercalated Chlorine Anions as Active Basic Sites in Mgal-layered Double Hydroxide for COS Hydrolysis

The Catalytic Mechanism of Intercalated Chlorine Anions as Active Basic Sites in Mgal-layered Double Hydroxide for COS Hydrolysis

Desulfurization of Biomass Syngas Using ZnO-Based Adsorbents: Long-Term Hydrogen Sulfide Breakthrough Experiments

Indirect Photochemical Formation of Carbonyl Sulfide and Carbon Disulfide in Natural Waters: Role of Organic Sulfur Precursors, Water Quality Constituents, and Temperature

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