Pyrite-Catalyzed Hydrogenolysis of Benzothiophene at Coal Liquefaction Conditions

Guin, J.A.; Lee, J. M.; Fan, Chen-Wen; Curtis, C.W.; Lloyd, J. L.; Tarrer, A.R.

doi:10.1021/i260075a019

Cited by 24 publications

(11 citation statements)

References 13 publications

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“…59−63 For comparison, while mineral pyrite from coal is active for hydrogenation of the heterocyclic ring in benzothiophene, it is much less effective for sulfur removal. 64 Both the trinuclear iron cluster (Fe 3 (CO) 12 ) 65 and a sulfided iron naphthenate-derived catalyst 59 promote desulfurization of benzothiophene to ethylbenzene but require much more forceful conditions than required for the Fe 2 S 2 (CO) 6 precatalyst. The present study results, along with past reports, 11,58 strongly suggest that the development of inexpensive iron catalysts for direct desulfurization is indeed feasible.…”

Section: Resultsmentioning

confidence: 99%

“…This suggests either a rapid conversion of 2,3-dihydrobenzothiophene to ethylbenzene at this temperature or alternatively a competitive direct desulfurization pathway. Both have been established for other catalysts. − For comparison, while mineral pyrite from coal is active for hydrogenation of the heterocyclic ring in benzothiophene, it is much less effective for sulfur removal . Both the trinuclear iron cluster (Fe 3 (CO) 12 ) and a sulfided iron naphthenate-derived catalyst promote desulfurization of benzothiophene to ethylbenzene but require much more forceful conditions than required for the Fe 2 S 2 (CO) 6 precatalyst.…”

Section: Resultsmentioning

confidence: 99%

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Sulfided Homogeneous Iron Precatalyst for Partial Hydrogenation and Hydrodesulfurization of Polycyclic Aromatic Model Asphaltenes

et al. 2020

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Here, we report the first study to use Fe 2 S 2 (CO) 6 as a well-defined petroleum-soluble precatalyst for partial hydrogenation of polycyclic aromatic and heteroaromatic compounds, including pyrene, phenanthrene, naphthalene, and benzothiophene. The in situ-generated heterogeneous catalyst was characterized using a combination of thermogravimetric analysis (TGA), combustion analysis (CHNS), Fourier transform infrared (FT-IR) spectroscopy, scanning transmission electron microscopy (STEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and scanning electron microscopy-energy dispersive Xray (SEM-EDX). Catalytic performance of Fe 2 S 2 (CO) 6 was evaluated in a batch microreactor coupled with an agitator, varying reaction temperature, pressure, and precatalyst loading. The active phase, consisting of iron sulfide nanoparticles, was prepared from purified Fe 2 S 2 (CO) 6 in toluene; no sulfur additive is required. The results demonstrate that a "presulfided" iron catalyst leads to partial hydrogenation of polycondensed aromatics under moderate conditions, with naphthalene showing only low conversion. Activated carbon, γ-alumina, and activated silica are all effective dispersants for the Fe precursor. The reactivity shows self-consistent substrate dependence, varying with the resonance energy stabilization of the starting compounds and partially saturated intermediates coupled with the surface adsorption enthalpy of the aromatic ring system. The active catalyst derived from this precursor exhibits higher catalytic activity than commercial iron sulfide precatalysts. Importantly, the catalyst is active for hydrodesulfurization (HDS) of benzothiophene, albeit modestly so.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Sulfided Homogeneous Iron Precatalyst for Partial Hydrogenation and Hydrodesulfurization of Polycyclic Aromatic Model Asphaltenes

et al. 2020

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“…Guin et al (1980) studied the effect of pyrite on the catalytic hydrogenolysis of benzothiophene at typical coal liquefaction conditions. They concluded that hydrogenolysis was promoted by pyrite but that pyrite was more effective as a hydrogenation catalyst than as a desulfurization catalyst.…”

Section: Previous Workmentioning

confidence: 99%

“…They postulated that this decomposition may proceed by radical formation mechanisms which could help to explain the catalytic effect of pyrite. Guin et al (1980) measured the nitrogen adsorption surface areas of several particle sizes of pyrite before and after reduction. Specific surface areas of unreacted pyrite were seen to vary approximately as the inverse of the particle diameter, which is consistent with a nonporous structure.…”

Section: Previous Workmentioning

confidence: 99%

Pyrite catalysis of coal liquefaction, hydrogenation, and intermolecular hydrogen transfer reactions

Brooks¹,

Guin²,

Curtis³

et al. 1983

Ind. Eng. Chem. Proc. Des. Dev.

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This work explores the effect of pyrite as a mineral catalyst on several types of reactions occurring in coal liquefaction. Both coal and model compound experiments are carried out. The effect of pyrite on the conversion of coal to preasphaltenos, asphaltenes, oils, and gases is determined. Model compound experiments are used to investigate the role of pyTite in catalyzing direct hydrogenation with molecular hydrogen as well as intermolecular hydrogen transfer reactions. Pyrite Is found to exert an influence on all of the above reactlon processes.

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“…The presence of pyrite affects coal utilisation processes due to sulphur dioxide (SO 2 ) emission in combustion processes or hydrogen sulphide (H 2 S) and COS formation in gasification processes, requiring additional emission control measures or clean-up [100]. On the other hand, pyrite is also known to catalyse coal reactions, including oxidation, gasification and liquefaction processes [4,[101][102][103]. However, it is not clear as yet how pyrite exerts its catalytic effect.…”

Section: Introductionmentioning

confidence: 99%

Sulphur transformation during pyrolysis of an Australian lignite

Zhang

Yani

2011

Proceedings of the Combustion Institute

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Sulphur Transformation during Pyrolysis of an Australian Lignite v moisture, very high ash, low fixed carbon and thus they have low calorific value, except for L1. The lignites contain considerable amount of total sulphur, except for L1. Mineralogy of the lignites showed that the lignites contain extremely high sodium and chlorine. FTIR and solid state 13 C NMR spectroscopy confirmed that oxygenated functional structures are significantly present in the lignites. Transformation of pyrite in the lignite during pyrolysis was studied using samples of a lignite with pyrite-free lignite (L1), a high pyrite lignite (L2), acid-washed lignites (AW L1 and AW L2), a pyrite mineral, and AW L1 blended with various amounts of the pyrite minerals. It was shown that in nitrogen the pyrite mineral (S/Fe = 2) decomposes to troilite (S/Fe =1) at ca 1200K and above this temperature, the troilite further decomposes to form elemental iron (S/Fe <1). However, when blended with the demineralised lignite, the pyrite mineral can be completely decomposed to troilite at 873 K as confirmed by FTIR, SEM-EDS and XRD analyses on the resulting chars. Using TGA-MS, it was revealed that hydrogen sulphide and a small quantity of sulphur dioxide were released during the pyrolysis of the pyrite-lignite blends. However, only sulphur dioxide was detected during the pyrolysis of the lignite with high pyrite content. By assuming that the pyrolysis follows the first-order reactions, kinetic parameters of the pyrolysis of the lignite samples and the pyrite-lignite blends were obtained. The activation energy values of the lignite samples decreased with increasing temperature. The transformation of sulphate during pyrolysis of the lignite was studied using pure sulphates (CaSO 4, FeSO 4 and Fe 2 (SO 4) 3), L1 and L4, and acid washed L1 doped with sulphates (CaSO 4 +L1 and FeSO 4 +L1), respectively. The TGA experiments showed that CaSO 4 decomposes between 1400-1700 K in nitrogen and a 50/50 N 2 /CO 2 mixture, while in air CaSO 4 decomposes between 1500-1700 K. Using a TGA-MS it was found that only a small fraction of CaSO 4 in CaSO 4 +L1 decomposed at 653 K, releasing SO 2 .

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Pyrite-Catalyzed Hydrogenolysis of Benzothiophene at Coal Liquefaction Conditions

Cited by 24 publications

References 13 publications

Sulfided Homogeneous Iron Precatalyst for Partial Hydrogenation and Hydrodesulfurization of Polycyclic Aromatic Model Asphaltenes

Sulfided Homogeneous Iron Precatalyst for Partial Hydrogenation and Hydrodesulfurization of Polycyclic Aromatic Model Asphaltenes

Pyrite catalysis of coal liquefaction, hydrogenation, and intermolecular hydrogen transfer reactions

Sulphur transformation during pyrolysis of an Australian lignite

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