Nitric Acid Functionalization of Petroleum Coke to Access Inherent Sulfur

被引:16
作者
Huang, Qing [1 ]
Schafranski, Annelisa S. [1 ]
Hazlett, Melanie J. [1 ]
Xiao, Ye [1 ]
Hill, Josephine M. [1 ]
机构
[1] Univ Calgary, Dept Chem & Petr Engn, Calgary, AB T2N 1N4, Canada
关键词
petroleum coke; functionalization; solid acid catalyst; sulfur; esterification; SOLID ACID; ACTIVATED CARBON; HYDROGEN-PEROXIDE; LEVULINIC ACID; SURFACE GROUPS; DESULFURIZATION; ESTERIFICATION; OXIDATION; CATALYSTS; ADSORPTION;
D O I
10.3390/catal10020259
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Sulfonated carbon-based catalysts have been identified as promising solid acid catalysts, and petroleum coke (petcoke), a byproduct of the oil industry, is a potential feedstock for these catalysts. In this study, sulfur-containing (6.5 wt%) petcoke was used as a precursor for these catalysts through direct functionalization (i.e., without an activation step) with nitric acid to access the inherent sulfur. Catalysts were also prepared using sulfuric acid and a mixture of nitric and sulfuric acid (1:3 vol ratio). Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and titration were used to identify and quantify the acid sites. The activities of the prepared catalysts were determined for the esterification of octanoic acid with methanol. Petcoke had few -SO3H groups, and correspondingly no catalytic activity for the reaction. All acid treatments increased the number of -SO3H groups and promoted esterification. Treatment with nitric acid alone resulted in the oxidation of the inherent sulfur in petcoke to produce similar to 0.7 mmol/g of strong acid sites and a total acidity of 5.3 mmol/g. The acidity (strong acid and total) was lower with sulfuric acid treatment but this sample was more active for the esterification reaction (TOF of 31 h(-1) compared to 7 h(-1) with nitric acid treatment).
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页数:14
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