Catalytic synthesis of DHHB over home-made catalysts and its kinetic calculations
-
Xin Hui-Fen
Abstract
DHHB (n-hexyl 2-(4-N,N-diethylamino-2-hydroxybenzoyl) benzoate) is a recently developed UV absorber that demonstrates a high degree of safety, excellent efficiency, and favorable solubility properties. In this paper a catalyst was prepared to catalyze the esterification of DHHB with homemade sulfonic acid modified polystyrene microspheres coated with silica instead of conventional H2SO4. And the catalyst was characterized by scanning electron microscopy (SEM) and infrared spectroscopy (FT-IR). The effects of different conditions on the reaction rate and equilibrium conversion were also investigated using conventional H2SO4 as a benchmark. The results showed that the catalytic activity of the catalyst did not decrease significantly after 10 consecutive cycles, and the yield of DHHB could reach 90.21 % after 2 h of reaction at 150 °C. Meanwhile, The kinetic experimental data obtained were correlated using a proposed homogeneous phase model. The synthesis of DHHB is a heat-absorbing reaction with heat of reaction and activation energies of 4.6537 kJ/mol, 43.2157 kJ/mol and 37.5735 kJ/mol for the forward and reverse reactions, respectively. It was verified that the proposed homogeneous reaction kinetic model accurately described the kinetic processes of the DHHB esterification reaction.
Acknowledgments
The authors are thankful to Shandong Province Science and Technology-based Small and Medium-sized Enterprises nnovation Capacity Enhancement Project (2022TSGC2595).
-
Research ethics: Not applicable.
-
Informed consent: Not applicable.
-
Author contributions: All authors have accepted responsibility for the entire content of this manuscript and approved its submission.
-
Use of Large Language Models, AI and Machine Learning Tools: None declared.
-
Competing interests: The authors state no conflict of interest.
-
Research funding: None declared.
-
Data availability: Not applicable.
References
1. Díaz-Cruz, M. S.; Barceló, D. Chemical Analysis and Ecotoxicological Effects of Organic UV-absorbing Compounds in Aquatic Ecosystems. Trends Anal. Chem. 2009, 28 (6), 708–717; https://doi.org/10.1016/j.trac.2009.03.010.Search in Google Scholar
2. Nohynek, J. G.; Schaefer, H. Benefit and Risk of Organic Ultraviolet Filters. Regul. Toxicol. Pharmacol. 2001, 33 (3), 285–299; https://doi.org/10.1006/rtph.2001.1476.Search in Google Scholar PubMed
3. Richard, S.; Peter, L.; Willem, S.; Bart, V. D. B. Estrogenic Activity of UV Filters Determined by an in Vitro Reporter Gene Assay and an in vivo Transgenic Zebrafish Assay. Arch. Toxicol. 2002, 76, 257–261; https://doi.org/10.1007/s00204-002-0348-4.Search in Google Scholar PubMed
4. Giokas, D. L.; Salvador, A.; Chisvert, A. UV filters: From Sunscreens to Human Body and the Environment. Trends Analyt. Chem. 2007, 26 (5), 360–374; https://doi.org/10.1016/j.trac.2007.02.012.Search in Google Scholar
5. Puglia, C.; Damiani, E.; Offerta, A.; Rizza, L.; Tirendi, G. G.; Tarico, M. S.; Curreri, S.; Bonina, F.; Perrotta, R. E. Evaluation of Nanostructured Lipid Carriers (NLC) and Nanoemulsions as Carriers for UV-filters: Characterization, in Vitro Penetration and Photostability Studies. Eur. J. Pharm. Sci. 2014, 51, 211–217; https://doi.org/10.1016/j.ejps.2013.09.023.Search in Google Scholar PubMed
6. Tuchinda, C.; Lim, H. W.; Osterwalder, U.; Rougier, A. Novel Emerging Sunscreen Technologies. Clin. Dermatol. 2006, 24, 105–117; https://doi.org/10.1016/j.det.2005.09.003.Search in Google Scholar PubMed
7. Santos, A. J. M.; Miranda, M. S.; Esteves da Silva, J. C. G. The degradation Products of UV Filters in Aqueous and Chlorinated Aqueous Solutions. Water Res. 2012, 46, 3167–3176; https://doi.org/10.1016/j.watres.2012.03.057.Search in Google Scholar PubMed
8. Masteri-Farahani, M.; Hosseini, M.-S.; Forouzeshfar, N. Propyl-SO3H Functionalized Graphene Oxide as Multipurpose Solid Acid Catalyst for Biodiesel Synthesis and Acid-catalyzed Esterification and Acetalization Reactions. Renew Energ. 2020, 151, 1092–1101; https://doi.org/10.1016/j.renene.2019.11.108.Search in Google Scholar
9. Geng, Z.; Yang, Y.; Wang, Y.; Zhu, T.; Xu, W. Catalytic Regeneration of Amine-Based Absorbents for CO2 Capture: The Effect of Acidic Sites and Accessibility. Sep. Purif. 2023, 327, 124889; https://doi.org/10.1016/j.seppur.2023.124889.Search in Google Scholar
10. Guo, Y.; Delbari, S. A.; Sabahi Namini, A.; Le, Q. V.; Park, J. Y.; Kim, D.; Varma, R. S.; Jang, H. W.; T-Raissi, A.; Shokouhimehr, M.; Li, C. Recent Developments in Solid Acid Catalysts for Biodiesel Production. Mol. Catal. 2023, 547, 113362; https://doi.org/10.1016/j.mcat.2023.113362.Search in Google Scholar
11. Tan, X.; Sudarsanam, P.; Tan, J.; Wang, A.; Zhang, H.; Li, H.; Yang, S. Sulfonic Acid-functionalized Heterogeneous Catalytic Materials for Efficient Biodiesel Production: A Review. J. Environ. 2021, 9 (1), 104719; https://doi.org/10.1016/j.jece.2020.104719.Search in Google Scholar
12. Zhenzhen, W.; Rui, Z.; Dan, L.; Dabo, J.; Tingting, Y.; Pan, N.; Quanzhou, C.; Kejie, H.; Litao, R.; Longjun, X. Sulfamic Acid Functionalized PVC: A Remarkably Efficient Heterogeneous Reusable Catalyst for the Acid-Catalyzed Reactions. Res. Chem. Intermed. 2023, 49 (12), 5407–5429; https://doi.org/10.1007/S11164-023-05121-4.Search in Google Scholar
13. Wei, K.; Xing, L.; Li, Y.; Xu, T.; Li, Q.; Wang, L. Heteropolyacid Modified Cerium-Based MOFs Catalyst for Amine Solution Regeneration in CO2 Capture. Sep. Purif. 2022, 293, 121144; https://doi.org/10.1016/j.seppur.2022.121144.Search in Google Scholar
14. Hung, T. Q.; Van Phuc, B.; Loan, P. T. T.; Nhi, D. T. L.; Nguyen, H.; Vu, H. X.; Van, D.; Dang, T. T. Practical Synthesis of 1,4-Dihydropyridines on Heterogeneous SulfonicmodifiedSilica (SBA-15-SO3H) Catalyst Under Mild Condition. Curr. Org. Synth. 2023, 20 (8), 880–889; https://doi.org/10.2174/1570179420666230301143027.Search in Google Scholar PubMed
15. Huang, J.; Chen, J.; Huang, Z.; Liu, T.; Ding, Y.; Li, H.; He, C. Solventless Autothermic Production of Energy-intensive Furanic Biofuels Expedited by Photothermal Effect. Fuel 2024, 359, 130458; https://doi.org/10.1016/j.fuel.2023.130458.Search in Google Scholar
16. Huang, J.; Wang, J.; Huang, Z.; Liu, T.; Li, H. Photothermal Technique-enabled Ambient Production of Microalgae Biodiesel: Mechanism and Life Cycle Assessment. Bioresour. Technol. 2023, 369, 128390; https://doi.org/10.1016/j.biortech.2022.128390.Search in Google Scholar PubMed
17. Su, F.; Guo, Y. ChemInform Abstract: Advancements in Solid Acid Catalysts for Biodiesel Production. J. Cheminformatics. 2014, 45 (32), 2934; https://doi.org/10.1002/chin.201432273.Search in Google Scholar
18. Lilja, J.; Wärnå, J.; Salmi, T.; Pettersson, L. J.; Ahlkvist, J.; Grénman, H.; Rönnholm, M.; Murzin, D. Y. Esterification of Propanoic Acid with Ethanol, 1-Propanol and Butanol Over a Heterogeneous Fiber Catalyst. Chem. Eng. J. 2005, 115 (1), 1–12; https://doi.org/10.1016/j.cej.2005.08.012.Search in Google Scholar
19. Sun, Z.; Duan, X.; Tao, M.; Wang, X.; Zhou, D. Design of a Highly Efficient Indium-Exchanged Heteropolytungstic Acid for Glycerol Esterification with Acetic Acid. Catal. Surv. from Asia 2016, 20 (2), 82–90; https://doi.org/10.1007/s10563-016-9209-7.Search in Google Scholar
20. Nuntang, S.; Yokoi, T.; Tatsumi, T.; Ngamcharussrivichai, C. Enhanced Esterification of Carboxylic Acids with Ethanol Using Propylsulfonic Acid-functionalized Natural Rubber/hexagonal Mesoporous Silica Nanocomposites. Catal. Commun. 2016, 80, 5–9; https://doi.org/10.1016/j.catcom.2016.02.019.Search in Google Scholar
21. Kopyshev, M. V.; Khasin, A. V.; Minyukova, T. P.; Khassin, A. A.; Yurieva, T. M. Esterification of Pentaerythritol by Carboxylic Acids. React. Kinet. Mech. Catal. 2016, 117 (2), 417–427; https://doi.org/10.1007/s11144-015-0964-7.Search in Google Scholar
22. Bacilla, A. C. C.; Freitas, M. R. d.; Bail, A.; Santos, V. C. d.; Nagata, N.; Silva, Â.; Marçal, L.; Ciuffi, K. J.; Nakagaki, S. Heterogeneous/Homogeneous Esterification Reaction Catalyzed by a Solid Based on a Vanadium Salt. J Mol Catal. A Chem. 2016, 422, 221–233; https://doi.org/10.1016/j.molcata.2015.12.018.Search in Google Scholar
23. You, L.; Liu, H. A Pseudo-Homogeneous Model for Cathode Catalyst Layer of PEM Fuel Cells. IMECE 2000, 9, 51–59; https://doi.org/10.1115/imece2000-1366.Search in Google Scholar
24. Marghsi, M.; Benachour, D. Use of a Two-Dimensional Pseudo-Homogeneous Model for the Study of Temperature and Conversion Profiles during a Polymerization Reaction in a Tubular Chemical Reactor. Mater. Tehnol. 2012, 46, 539–546.Search in Google Scholar
25. Houten, J. V. A Century of Chemical Dynamics Traced through the Nobel Prizes. 1903: Svante Arrhenius. J. Chem. Educ. 2001, 78 (12), 1570; https://doi.org/10.1021/ed079p21.Search in Google Scholar
26. Lin, J. J.; Hwang, D. W.; Harich, S.; Lee, Y. T.; Yang, X. New Low Background Crossed Molecular Beam Apparatus: Low Background Detection of H2. Rev. Sci. Instrum. 1998, 69, 1642–1646; https://doi.org/10.1063/1.1148821.Search in Google Scholar
27. Giokas, D. L.; Salvador, A.; Chisvert, A. UV Filters: From Sunscreens to Human Body and the Environment. React. Funct. Polym. 2007, 67 (12), 1458–1464; https://doi.org/10.1016/j.trac.2007.02.012.Search in Google Scholar
28. Jiang, S.-T.; Liu, M.; Pan, L.-J. Kinetic Study for Hydrolysis of Methyl Lactate Catalyzed by Cation-exchange Resin. J. Taiwan Inst. Chem. Eng. 2010, 41 (2), 190–194; https://doi.org/10.1016/j.jtice.2009.06.006.Search in Google Scholar
29. Dassy, S.; Wiame, H.; Thyrion, F. C. Kinetics of the Liquid Phase Synthesis and Hydrolysis of Butyl Lactate Catalysed by Cation Exchange Resin. J. Chem. Tech. Biotechnol. 1994, 59, 149–156; https://doi.org/10.1002/jctb.280590206.Search in Google Scholar
30. Choi, J. I.; Hong, W. H.; Chang, H. N. Reaction Kinetics of Lactic Acid with Methanol Catalyzed by Acid Resins. Int. J. Chem. Kinet. 1996, 28, 37–41; https://doi.org/10.1002/(sici)1097-4601(1996)28:1<37::aid-kin5>3.3.co;2-l.10.1002/(SICI)1097-4601(1996)28:1<37::AID-KIN5>3.3.CO;2-LSearch in Google Scholar
31. You, L.; Liu, H. A Parametric Study of the Cathode Catalyst Layer of PEM Fuel Cells Using a Pseudo-Homogeneous Model. Int. J. Hydrogen Energy 2001, 26 (9), 991–999; https://doi.org/10.1016/S0360-3199(01)00035-0.Search in Google Scholar
32. Seo, Y.; Hong, W. H. Kinetics of Esterification of Lactic Acid with Methanol in the Presence of Cation Exchange Resin Using a Pseudo-Homogeneous Model. J. Chem. Eng. Japan. 2000, 33 (1), 128–133; https://doi.org/10.1252/jcej.33.128.Search in Google Scholar
© 2025 IUPAC & De Gruyter
Articles in the same Issue
- Frontmatter
- In this issue
- Review
- Blockchain technology: driving change in the scientific research workflow
- Research Articles
- Sequential sorption of crystal violet and emulsified oil onto poly(lauryl methacrylate-acrylamide) hybrid hydrogel
- Catalytic synthesis of DHHB over home-made catalysts and its kinetic calculations
- Synthesis and characterization of tricyclodecyl-containing methacrylate polymer for optoelectronics applications
- Spontaneous dehydration side reactions of core amino acids in GC-MS sample preparation: the role of drying conditions
- Optimizing corrosion resistance: how pH shapes the inhibition mechanism of ZnAl-NO3 - LDH on mild steel
Articles in the same Issue
- Frontmatter
- In this issue
- Review
- Blockchain technology: driving change in the scientific research workflow
- Research Articles
- Sequential sorption of crystal violet and emulsified oil onto poly(lauryl methacrylate-acrylamide) hybrid hydrogel
- Catalytic synthesis of DHHB over home-made catalysts and its kinetic calculations
- Synthesis and characterization of tricyclodecyl-containing methacrylate polymer for optoelectronics applications
- Spontaneous dehydration side reactions of core amino acids in GC-MS sample preparation: the role of drying conditions
- Optimizing corrosion resistance: how pH shapes the inhibition mechanism of ZnAl-NO3 - LDH on mild steel
