Hydrogen Sulfide to Sulfur (Claus Process)

Jüngst, Eckhard; Nehb, Wolfgang

doi:10.1002/9783527610044.hetcat0132

Cited by 6 publications

(4 citation statements)

References 9 publications

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“…Initially, the oxides are in the form of nanopowders with BET surface areas of ≥10 m 2 /g, except for WO 3 which has a surface area of 9.3 m 2 /g. As shown in Table , the surface areas are significantly reduced after SOCM at 950 °C, similar to previous observations on OCM with O 2 . ,, The surface areas of ZrO 2 , MgO, WO 3 , and La 2 O 3 are >1.5 m 2 /g, while the surface areas of the other oxides are smaller than 1 m 2 /g.…”

Section: Resultssupporting

confidence: 87%

“…Note that Δ G for CH 4 over-oxidation by S 2 is only −236 kJ/mol, versus −1294 kJ/mol for O 2 (Figure ), suggesting that higher ethylene selectivities/yields might be possible using less aggressive oxidants in the presence of an appropriate catalyst. The lower SOCM exothermicity versus OCM with O 2 might also offer advantages in reactor design, and the H 2 S co-product could be efficiently recycled to S 8 via the efficient Claus process …”

Section: Introductionmentioning

confidence: 99%

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Platinum Metal-Free Catalysts for Selective Soft Oxidative Methane → Ethylene Coupling. Scope and Mechanistic Observations

Peter

Marks

2015

J. Am. Chem. Soc.

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Using abundant soft oxidants, a high methane-to-ethylene conversion might be achievable due to the low thermodynamic driving force for over-oxidation. Here we report on the oxidative coupling of methane by gaseous S2 (SOCM). The catalytic properties of Pd/Fe3O4 are compared with those of Fe3O4, and it is found that high ethylene selectivities can be achieved without noble metals; conversion and selectivity on Fe3O4 are stable for at least 48 h at SOCM conditions. SOCM data for 10 oxides are compared, and ethylene selectivities as high as 33% are found; the C2H4/C2H6 ratios of 9-12 observed at the highest S2 conversions are significantly higher than the C2H4/C2H6 ratios usually found in the CH4 coupling with O2. Complementary in-detail analytical studies show that, on Mg, Zr, Sm, W, and La catalysts, which strongly coke during the reaction, lower ethylene selectivities are observed than on Fe, Ti, and Cr catalysts, which only coke to a minor extent. Further catalyst-dependent changes during SOCM in surface area, surface composition, and partial conversion to oxysulfides and sulfides are discussed. Evidence concerning the reaction mechanism is obtained taking into account the selectivity for the different reaction products versus the contact time. CH4 coupling proceeds non-oxidatively with the evolution of H2 on some catalysts, and evidence is presented that C2H4 and C2H2 formation occur via C2H6 and C2H4 dehydrogenation, respectively.

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Section: Resultssupporting

confidence: 87%

Section: Introductionmentioning

confidence: 99%

Platinum Metal-Free Catalysts for Selective Soft Oxidative Methane → Ethylene Coupling. Scope and Mechanistic Observations

Peter

Marks

2015

J. Am. Chem. Soc.

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“…Oil and gas extraction sites are one of the main sources of H 2 S emissions, and they are usually removed by means of the well-known Claus process. The reaction occurs via dissociative adsorption of H 2 S on a metal oxide [34], mainly on Al 2 O 3 but also on TiO 2 , used as catalyst.…”

Section: Introductionmentioning

confidence: 99%

Sulfur-Doped TiO2: Structure and Surface Properties

et al. 2017

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A comprehensive study on the sulfur doping of TiO 2 , by means of H 2 S treatment at 673 K, has been performed in order to highlight the role of sulfur in affecting the properties of the system, as compared to the native TiO 2 . The focus of this study is to find a relationship among the surface, structure, and morphology properties, by means of a detailed chemical and physical characterization of the samples. In particular, transmission electron microscopy images provide a simple tool to have a direct and immediate evidence of the effects of H 2 S action on the TiO 2 particles structure and surface defects. Furthermore, from spectroscopy analyses, the peculiar surface, optical properties, and methylene blue photodegradation test of S-doped TiO 2 samples, as compared to pure TiO 2 , have been investigated and explained by the effects caused by the exchange of S species with O species and by the surface defects induced by the strong H 2 S treatment.

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“…H 2 S and CS 2 are corrosive, but there are existing industrial processes that utilize them. The long-established industrial Claus process can be used to recycle H 2 S back to elemental sulfur (S 8 ), and Claus units are operated at most refineries . CS 2 is used in the production of cellophane, rayon, fertilizers, and carbon tetrachloride, and although the global market is not large, it is expected to grow at a compound annual growth rate of 2.4% by 2025 due to increases in cellophane demand .…”

Section: Introductionmentioning

confidence: 99%

Origin of Rate and Selectivity Trends and Exceptional Yield in Sulfur-Oxidative Propane Dehydrogenation Over Supported Vanadium Catalysts

Arinaga,

Biswas,

Zhang

et al. 2023

ACS Catal.

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Sulfur vapor (S2) is an effective alternative oxidant for propane dehydrogenation, (S)ODHP, with vanadium-based catalysts displaying promising performance and propylene selectivity significantly greater than with O2 as the oxidant (ODHP). However, a deeper mechanistic understanding of SODHP versus ODHP will be necessary for further catalytic performance. Here, we investigate these trends over vanadium catalysts supported by Al2O3, TiO2, ZrO2, and SiO2. First, support effects on V/M x O y -catalyzed SODHP are analyzed, revealing marked support effects on the catalyst reducibility and activity. The result is maximum propylene selectivity and yield of 96 and 41%, respectively, over a sulfided V/SiO2 catalyst, surpassing most metrics in the peer-reviewed ODHP literature. Second, propane overoxidation kinetic pathways for SODHP vs. ODHP are compared, revealing that, contrary to traditional oxide catalytic pathways, secondary oxidation of propylene is disfavored over sulfided surfaces. Density functional theory (DFT) analysis reveals that while the sulfided surfaces have propylene binding energies comparable to those of oxide surfaces, the former has less favorable thermodynamic barriers to deep propylene dehydrogenation pathways than the oxide surfaces. These results suggest more competitive propylene desorption vs. propylene overoxidation on sulfided surfaces leads to higher overall selectivity. Thus, SODHP is a promising catalytic alternative for propane oxidation that rivals the traditional O2-mediated approach.

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Hydrogen Sulfide to Sulfur (Claus Process)

Abstract: The sections in this article are Occurrence of Hydrogen Sulfide Hydrogen Sulfide Removal from Gases History of the Claus Process Chemistry of the Claus Process Typical Claus Plant Claus Catalysts Desirable Properties of Claus Catalysts Deactivation of Cla… Show more

Cited by 6 publications

References 9 publications

Platinum Metal-Free Catalysts for Selective Soft Oxidative Methane → Ethylene Coupling. Scope and Mechanistic Observations

Platinum Metal-Free Catalysts for Selective Soft Oxidative Methane → Ethylene Coupling. Scope and Mechanistic Observations

Sulfur-Doped TiO2: Structure and Surface Properties

Origin of Rate and Selectivity Trends and Exceptional Yield in Sulfur-Oxidative Propane Dehydrogenation Over Supported Vanadium Catalysts

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