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Solid acid catalysts produced by sulfonation of petroleum coke: Dominant role of aromatic hydrogen.
Chemosphere ( IF 8.1 ) Pub Date : 2020-01-22 , DOI: 10.1016/j.chemosphere.2020.125981
Ye Xiao 1 , Josephine M Hill 1
Affiliation  

Carbon based solid waste materials have been intensively investigated for the preparation of solid acid catalysts through sulfonation, but the acidity varies significantly depending on the material. In this study, the role of aromatic hydrogen in sulfonation with concentrated H2SO4 was investigated using petroleum coke (petcoke), graphite, and biochar as the carbon materials. Through ball milling and calcination, the amount of aromatic hydrogen on the petcoke could be increased or decreased, respectively. After sulfonation at 80 °C with concentrated H2SO4, the produced acidity (i.e., -SO3H groups) increased as the amount of aromatic hydrogen increased from essentially no acidity on graphite to 0.55 mmol/g on biochar and 1.25 mmol/g on petcoke (particle sizes of 45-90 μm) indicating the importance of aromatic hydrogen during sulfonation. Calcination (350 °C for 1 h) of the petcoke before sulfonation decreased the acidity to 0.59 mmol/g, while ball milling (with isopropanol and silica for 24 h) increased the acidity to 3.73 mmol/g. The sulfonated petcoke samples were used as catalysts for the esterification reaction between octanoic acid and methanol at 60 °C and the turnover frequencies were 48-85 h-1. The results give insights on the preparation of solid acid catalysts from carbon materials and highlight the application of petcoke without activation as a feedstock for esterification catalysts.

中文翻译:

石油焦磺化生产的固体酸催化剂:芳族氢的主要作用。

对于通过磺化制备固体酸催化剂,已经对碳基固体废料进行了深入研究,但是酸度根据材料的不同而有很大差异。在这项研究中,使用石油焦(石油焦),石墨和生物炭作为碳材料,研究了芳香族氢在浓H2SO4磺化中的作用。通过球磨和煅烧,可分别增加或减少石油焦上的芳族氢量。在80°C下用浓H2SO4磺化后,产生的酸度(即-SO3H基团)随着芳族氢量的增加而增加,从石墨上的基本上无酸增加到生物炭上的0.55 mmol / g和石油焦上的1.25 mmol / g(颗粒)尺寸为45-90μm),表明芳族氢在磺化过程中的重要性。磺化前煅烧(350℃,1小时)的石油焦可将酸度降至0.59 mmol / g,而球磨(用异丙醇和二氧化硅进行24小时)可将酸度提高至3.73 mmol / g。磺化的石油焦样品用作催化剂,在60°C下辛酸和甲醇之间进行酯化反应,周转频率为48-85 h-1。结果为从碳材料制备固体酸催化剂提供了见识,并突出了未经活化的石油焦作为酯化催化剂的原料的应用。磺化的石油焦样品用作催化剂,在60°C下辛酸和甲醇之间进行酯化反应,周转频率为48-85 h-1。结果为从碳材料制备固体酸催化剂提供了见识,并突出了未经活化的石油焦作为酯化催化剂的原料的应用。磺化的石油焦样品用作催化剂,在60°C下辛酸和甲醇之间进行酯化反应,周转频率为48-85 h-1。结果为从碳材料制备固体酸催化剂提供了见识,并突出了未经活化的石油焦作为酯化催化剂的原料的应用。
更新日期:2020-01-22
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