{"title":"硫化铁钼碳化物和氮化物催化剂可提高特重质原油质量","authors":"","doi":"10.1016/j.cattod.2024.114964","DOIUrl":null,"url":null,"abstract":"<div><p>In the context of the energy transition scenario, effective sulfur management is crucial. Enhancing the quality of extra heavy crude oil (EHCO) through catalytic processes, specifically hydrotreatment, is essential for reducing pollutant emissions like SOx into the atmosphere. Traditional hydrotreatment, utilizing MoS<sub>2</sub>-based catalysts typically on Al<sub>2</sub>O<sub>3</sub> support, faces challenges with EHCO due to its elevated S and N content, which hampers catalyst efficiency. Metal carbides and nitrides exhibit promising electronic structures that confer resistance to deactivation in the presence of heteroatoms. This study compares the catalytic performances of Fe-promoted Mo sulfides, carbides, and nitrides (FeMoS(C,N)) in the thiophene hydrodesulfurization (HDS) reaction, serving as a model molecule for sulfur removal. Subsequently, we investigate the upgrading of a Venezuelan EHCO in terms of pollutant reduction, API gravity, and feedstock aromaticity. Catalysts were prepared from oxide precursors, varying the (Fe/(Fe+Mo)) atomic ratios (x = 0.00, 0.10, 0.33, 0.50, and 1.00), employing a temperature-programmed reaction protocol. Catalytic upgrading of EHCO was conducted in a stirred batch reactor, and the results were compared with a commercial CoMo-based catalyst. FeMoC(N) outperformed the commercial catalyst in sulfur removal. The elemental composition and nitrogen content of the feed remained constant; however, the sulfur content of asphaltenes decreased. Furthermore, the API gravity of crude oil increased when employing FeMoS and FeMoN catalysts, except with FeMoC, possibly linked to dealkylation reactions and the enrichment of lighter fractions with alkanes. FeMoN increased asphaltene aromaticity, while FeMoC decreased it. These results highlight the promise of FeMoC(N) as catalysts for HDS and upgrading heavy feedstocks.</p></div>","PeriodicalId":264,"journal":{"name":"Catalysis Today","volume":null,"pages":null},"PeriodicalIF":5.2000,"publicationDate":"2024-07-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S0920586124004589/pdfft?md5=8675757fbd06a7560bd2f332a245ff73&pid=1-s2.0-S0920586124004589-main.pdf","citationCount":"0","resultStr":"{\"title\":\"Sulfured FeMo carbides and nitrides catalysts upgrade extra heavy crude oil quality\",\"authors\":\"\",\"doi\":\"10.1016/j.cattod.2024.114964\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>In the context of the energy transition scenario, effective sulfur management is crucial. Enhancing the quality of extra heavy crude oil (EHCO) through catalytic processes, specifically hydrotreatment, is essential for reducing pollutant emissions like SOx into the atmosphere. Traditional hydrotreatment, utilizing MoS<sub>2</sub>-based catalysts typically on Al<sub>2</sub>O<sub>3</sub> support, faces challenges with EHCO due to its elevated S and N content, which hampers catalyst efficiency. Metal carbides and nitrides exhibit promising electronic structures that confer resistance to deactivation in the presence of heteroatoms. This study compares the catalytic performances of Fe-promoted Mo sulfides, carbides, and nitrides (FeMoS(C,N)) in the thiophene hydrodesulfurization (HDS) reaction, serving as a model molecule for sulfur removal. Subsequently, we investigate the upgrading of a Venezuelan EHCO in terms of pollutant reduction, API gravity, and feedstock aromaticity. Catalysts were prepared from oxide precursors, varying the (Fe/(Fe+Mo)) atomic ratios (x = 0.00, 0.10, 0.33, 0.50, and 1.00), employing a temperature-programmed reaction protocol. Catalytic upgrading of EHCO was conducted in a stirred batch reactor, and the results were compared with a commercial CoMo-based catalyst. FeMoC(N) outperformed the commercial catalyst in sulfur removal. The elemental composition and nitrogen content of the feed remained constant; however, the sulfur content of asphaltenes decreased. Furthermore, the API gravity of crude oil increased when employing FeMoS and FeMoN catalysts, except with FeMoC, possibly linked to dealkylation reactions and the enrichment of lighter fractions with alkanes. FeMoN increased asphaltene aromaticity, while FeMoC decreased it. 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引用次数: 0
摘要
在能源转型的背景下,有效的硫管理至关重要。通过催化工艺(特别是加氢处理)提高特重原油 (EHCO) 的质量,对于减少向大气排放 SOx 等污染物至关重要。传统的加氢处理通常使用以氧化铝(AlO)为载体的 MoS 催化剂,但由于 EHCO 中 S 和 N 的含量较高,会影响催化剂的效率,因此 EHCO 的加氢处理面临着挑战。金属碳化物和氮化物具有良好的电子结构,在杂原子存在的情况下可防止失活。本研究比较了铁促进的钼硫化物、碳化物和氮化物(FeMoS(C,N))在噻吩加氢脱硫(HDS)反应中的催化性能。随后,我们从污染物减少、API比重和原料芳香度等方面对委内瑞拉超高压碳酸氢盐的升级进行了研究。催化剂由氧化物前体制备而成,采用温度编程反应方案,改变(Fe/(Fe+Mo))原子比(x = 0.00、0.10、0.33、0.50 和 1.00)。在搅拌间歇反应器中进行了 EHCO 的催化升级,并将结果与商用 CoMo 基催化剂进行了比较。FeMoC(N) 的脱硫效果优于商用催化剂。进料中的元素组成和氮含量保持不变,但沥青质中的硫含量却降低了。此外,使用 FeMoS 和 FeMoN 催化剂(FeMoC 除外)时,原油的 API 重力增加,这可能与脱烷基化反应和烷烃富集轻质馏分有关。FeMoN 增加了沥青烯的芳香度,而 FeMoC 则降低了沥青烯的芳香度。这些结果凸显了 FeMoC(N) 作为加氢脱硫和重质原料升级催化剂的前景。
Sulfured FeMo carbides and nitrides catalysts upgrade extra heavy crude oil quality
In the context of the energy transition scenario, effective sulfur management is crucial. Enhancing the quality of extra heavy crude oil (EHCO) through catalytic processes, specifically hydrotreatment, is essential for reducing pollutant emissions like SOx into the atmosphere. Traditional hydrotreatment, utilizing MoS2-based catalysts typically on Al2O3 support, faces challenges with EHCO due to its elevated S and N content, which hampers catalyst efficiency. Metal carbides and nitrides exhibit promising electronic structures that confer resistance to deactivation in the presence of heteroatoms. This study compares the catalytic performances of Fe-promoted Mo sulfides, carbides, and nitrides (FeMoS(C,N)) in the thiophene hydrodesulfurization (HDS) reaction, serving as a model molecule for sulfur removal. Subsequently, we investigate the upgrading of a Venezuelan EHCO in terms of pollutant reduction, API gravity, and feedstock aromaticity. Catalysts were prepared from oxide precursors, varying the (Fe/(Fe+Mo)) atomic ratios (x = 0.00, 0.10, 0.33, 0.50, and 1.00), employing a temperature-programmed reaction protocol. Catalytic upgrading of EHCO was conducted in a stirred batch reactor, and the results were compared with a commercial CoMo-based catalyst. FeMoC(N) outperformed the commercial catalyst in sulfur removal. The elemental composition and nitrogen content of the feed remained constant; however, the sulfur content of asphaltenes decreased. Furthermore, the API gravity of crude oil increased when employing FeMoS and FeMoN catalysts, except with FeMoC, possibly linked to dealkylation reactions and the enrichment of lighter fractions with alkanes. FeMoN increased asphaltene aromaticity, while FeMoC decreased it. These results highlight the promise of FeMoC(N) as catalysts for HDS and upgrading heavy feedstocks.
期刊介绍:
Catalysis Today focuses on the rapid publication of original invited papers devoted to currently important topics in catalysis and related subjects. The journal only publishes special issues (Proposing a Catalysis Today Special Issue), each of which is supervised by Guest Editors who recruit individual papers and oversee the peer review process. Catalysis Today offers researchers in the field of catalysis in-depth overviews of topical issues.
Both fundamental and applied aspects of catalysis are covered. Subjects such as catalysis of immobilized organometallic and biocatalytic systems are welcome. Subjects related to catalysis such as experimental techniques, adsorption, process technology, synthesis, in situ characterization, computational, theoretical modeling, imaging and others are included if there is a clear relationship to catalysis.