Preparation of Carbon-Based Solid Acid Catalyst from High-Sulfur Petroleum Coke with Nitric Acid and Ball Milling, and a Computational Evaluation of Inherent Sulfur Conversion Pathways
A series of petroleum coke (petcoke)-derived solid acid catalysts were prepared via nitric acid treatment with or without ball milling pretreatment. The inherent sulfur in petcoke was converted to sulfonic groups, which were active sites for the esterification of octanoic acid and methanol at 60 °C,...
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MDPI AG
2023-10-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/28/20/7051 |
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| author | Qing Huang Natalia M. Cabral Xing Tong Annelisa S. Schafranski Pierre Kennepohl Josephine M. Hill |
| author_facet | Qing Huang Natalia M. Cabral Xing Tong Annelisa S. Schafranski Pierre Kennepohl Josephine M. Hill |
| author_sort | Qing Huang |
| collection | DOAJ |
| description | A series of petroleum coke (petcoke)-derived solid acid catalysts were prepared via nitric acid treatment with or without ball milling pretreatment. The inherent sulfur in petcoke was converted to sulfonic groups, which were active sites for the esterification of octanoic acid and methanol at 60 °C, with ester yields of 14–43%. More specifically, samples without ball milling treated at 120 °C for 3 h had a total acidity of 4.67 mmol/g, which was 1.6 times that of the samples treated at 80 °C, despite their −SO<sub>3</sub>H acidities being similar (~0.08 mmol/g). The samples treated for 24 h had higher −SO<sub>3</sub>H (0.10 mmol/g) and total acidity (5.25 mmol/g) but not increased catalytic activity. Ball milling increased the defects and exposed aromatic hydrogen groups on petcoke, which facilitated further acid oxidation (0.12 mmol −SO<sub>3</sub>H/g for both materials and total acidity of 5.18 mmol/g and 5.01 mmol/g for BP-N-3/120 and BP-N-8/90, respectively) and an increased ester yield. DFT calculations were used to analyze the pathways of sulfonic acid group formation, and the reaction pathway with NO<sub>2</sub>• was the most thermodynamically and kinetically favourable. The activities of the prepared catalysts were related to the number of −SO<sub>3</sub>H acid sites, the total acidity, and the oxygen content, with the latter two factors having a negative impact. |
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| institution | Directory Open Access Journal |
| issn | 1420-3049 |
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| last_indexed | 2024-03-10T21:00:56Z |
| publishDate | 2023-10-01 |
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| series | Molecules |
| spelling | doaj.art-b200dd2adf86469ebff9ecf00477dbef2023-11-19T17:32:02ZengMDPI AGMolecules1420-30492023-10-012820705110.3390/molecules28207051Preparation of Carbon-Based Solid Acid Catalyst from High-Sulfur Petroleum Coke with Nitric Acid and Ball Milling, and a Computational Evaluation of Inherent Sulfur Conversion PathwaysQing Huang0Natalia M. Cabral1Xing Tong2Annelisa S. Schafranski3Pierre Kennepohl4Josephine M. Hill5Department of Chemical and Petroleum Engineering, Schulich School of Engineering, University of Calgary, 2500 University Drive NW, Calgary, AB T2N 1N4, CanadaDepartment of Chemical and Petroleum Engineering, Schulich School of Engineering, University of Calgary, 2500 University Drive NW, Calgary, AB T2N 1N4, CanadaDepartment of Chemistry, University of British Columbia, Vancouver, BC V6T 1Z1, CanadaDepartment of Chemical and Petroleum Engineering, Schulich School of Engineering, University of Calgary, 2500 University Drive NW, Calgary, AB T2N 1N4, CanadaDepartment of Chemistry, University of Calgary, 2500 University Drive NW, Calgary, AB T2N 1N4, CanadaDepartment of Chemical and Petroleum Engineering, Schulich School of Engineering, University of Calgary, 2500 University Drive NW, Calgary, AB T2N 1N4, CanadaA series of petroleum coke (petcoke)-derived solid acid catalysts were prepared via nitric acid treatment with or without ball milling pretreatment. The inherent sulfur in petcoke was converted to sulfonic groups, which were active sites for the esterification of octanoic acid and methanol at 60 °C, with ester yields of 14–43%. More specifically, samples without ball milling treated at 120 °C for 3 h had a total acidity of 4.67 mmol/g, which was 1.6 times that of the samples treated at 80 °C, despite their −SO<sub>3</sub>H acidities being similar (~0.08 mmol/g). The samples treated for 24 h had higher −SO<sub>3</sub>H (0.10 mmol/g) and total acidity (5.25 mmol/g) but not increased catalytic activity. Ball milling increased the defects and exposed aromatic hydrogen groups on petcoke, which facilitated further acid oxidation (0.12 mmol −SO<sub>3</sub>H/g for both materials and total acidity of 5.18 mmol/g and 5.01 mmol/g for BP-N-3/120 and BP-N-8/90, respectively) and an increased ester yield. DFT calculations were used to analyze the pathways of sulfonic acid group formation, and the reaction pathway with NO<sub>2</sub>• was the most thermodynamically and kinetically favourable. The activities of the prepared catalysts were related to the number of −SO<sub>3</sub>H acid sites, the total acidity, and the oxygen content, with the latter two factors having a negative impact.https://www.mdpi.com/1420-3049/28/20/7051petroleum cokesulfonic groupsolid acid catalystDFT calculationdibenzothiophenenitric acid |
| spellingShingle | Qing Huang Natalia M. Cabral Xing Tong Annelisa S. Schafranski Pierre Kennepohl Josephine M. Hill Preparation of Carbon-Based Solid Acid Catalyst from High-Sulfur Petroleum Coke with Nitric Acid and Ball Milling, and a Computational Evaluation of Inherent Sulfur Conversion Pathways Molecules petroleum coke sulfonic group solid acid catalyst DFT calculation dibenzothiophene nitric acid |
| title | Preparation of Carbon-Based Solid Acid Catalyst from High-Sulfur Petroleum Coke with Nitric Acid and Ball Milling, and a Computational Evaluation of Inherent Sulfur Conversion Pathways |
| title_full | Preparation of Carbon-Based Solid Acid Catalyst from High-Sulfur Petroleum Coke with Nitric Acid and Ball Milling, and a Computational Evaluation of Inherent Sulfur Conversion Pathways |
| title_fullStr | Preparation of Carbon-Based Solid Acid Catalyst from High-Sulfur Petroleum Coke with Nitric Acid and Ball Milling, and a Computational Evaluation of Inherent Sulfur Conversion Pathways |
| title_full_unstemmed | Preparation of Carbon-Based Solid Acid Catalyst from High-Sulfur Petroleum Coke with Nitric Acid and Ball Milling, and a Computational Evaluation of Inherent Sulfur Conversion Pathways |
| title_short | Preparation of Carbon-Based Solid Acid Catalyst from High-Sulfur Petroleum Coke with Nitric Acid and Ball Milling, and a Computational Evaluation of Inherent Sulfur Conversion Pathways |
| title_sort | preparation of carbon based solid acid catalyst from high sulfur petroleum coke with nitric acid and ball milling and a computational evaluation of inherent sulfur conversion pathways |
| topic | petroleum coke sulfonic group solid acid catalyst DFT calculation dibenzothiophene nitric acid |
| url | https://www.mdpi.com/1420-3049/28/20/7051 |
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