SYNTHESIS AND CHARACTERIZATION OF CHROMIUM-BASED CATALYSTS ON TITANIUM-MODIFIED-MCM-41 FOR OXIDATIVE DEHYDROGENATION OF ISOBUTANE

Abstract

This study aimed to prepare chromium-based catalysts on titanium-modified MCM-41 for oxidative dehydrogenation reactions. MCM-41 was synthesized hydrothermally. In order to increase the hydrothermal stability of support, titanium was added to the MCM-41. The titanium source (K2TiF6) was dissolved in two different solvents (hot water and sulfuric acid). The hydrothermal stability test was performed with the samples. The samples were characterized by XRD, N2 adsorption/desorption, FT-IR, and SEM/EDS analysis. When titanium was added to the MCM-41 structure, it was determined that the pore walls thickened, and the main peak characterizing the hexagonal structure was preserved. With the modification, the average pore diameter of MCM-41 decreased from 28Å to 22Å, and the surface area decreased from 1250 m2/g to 500 m2/g. The hydrothermal stability test indicated that the loading of titanium improved the stability of MCM-41. FT-IR results showed that titanium has formed strong bonds with oxygen atoms, creating Si-O-Ti, Ti-OH, and Ti-O bonds. These bonds enhanced to stabilize the MCM-41 structure, making it more resistant to structural changes. Smaller crystal size (178Å) and higher surface area (554 m2/g) were determined in the support prepared by dissolving the titanium source in hot water. Therefore, this support was used in catalyst synthesis. Chromium-based catalysts on titanium-modified MCM-41 were prepared by wet impregnation method at different chromium loading (3% and 10%, by mass). The presence of the anatase phase of TiO2 and inactive α-Cr2O3 in the high chromium-loaded sample was determined. Therefore, catalytic tests were carried out with a catalyst containing 3% chromium by mass, prepared using a Ti-modified support, as well as a catalyst prepared using an unmodified support. The highest isobutane conversion (94%) and isobutene selectivity (81%) values were obtained for catalyst supported on Ti-modified MCM-41. High activity predicted for catalyst supported on modified MCM-41 was explained by improving hydrophilic properties.

Keywords

• MCM-41
• Chromium-based catalysts
• Hydrothermal stability
• Oxidative Dehydrogenation of Isobutane

References

1. S. Çetinyokuş, M. Doğan and Z. Erol, "Investigation of the effectiveness of Cr@MCM-41 catalysts in isobutane dehydrogenation," The Faculty of Engineering and Architecture, vol. 36, no. 2, pp. 1075-1088, 2021, doi: 10.17341/gazimmfd.678990.
2. Y. Chen, J. Lyu, Y. Wang, T. Chen and Y. Tian, "Synthesis, characterization, adsorption, and isotopic separation studies of pyrocatechol-modified MCM-41 for efficient boron removal," Industrial & Engineering Chemistry Research, vol. 58, no. 8, pp. 3282-3292, Feb. 2019, doi: 10.1021/acs.iecr.8b04748.
3. T.H. Liou, S.M. Liu and G.W. Chen, "Utilization of e-wastes as a sustainable silica source in synthesis of ordered mesostructured titania nanocomposites with high adsorption and photoactivity," Journal of Environmental Chemical Engineering, vol. 10, no. 2, 2022, doi: 10.1016/j.jece.2022.107283.
4. W.Y. Sang and O.P. Ching, "Tailoring MCM-41 mesoporous silica particles through modified sol-gel process for gas separation," in AIP Conference Proceedings, 2017, vol. 1891, no. 1: AIP Publishing.
5. B. Szczesniak, J. Choma and M. Jaroniec, "Major advances in the development of ordered mesoporous materials," Chem Commun (Camb), vol. 56, no. 57, pp. 7836-7848, Jul. 2020, doi: 10.1039/d0cc02840a.
6. C.S. Ha, S.S. Park, C.S. Ha, and S.S. Park, "General synthesis and physico-chemical properties of mesoporous materials," Periodic Mesoporous Organosilicas: Preparation, Properties and Applications, pp. 15-85, 2019
7. S. C. Buratto, E. Latocheski, D.C.D. Oliveira and J. B. Domingos, "Influence of the capping agent PVP of the outer layer of Pd nanocubes surface on the catalytic hydrogenation of unsaturated C− C bonds," Journal of the Brazilian Chemical Society, vol. 31, pp. 1078-1085, 2020.
8. I. Safo and M. Oezaslan, "Electrochemical cleaning of polyvinylpyrrolidone-capped Pt nanocubes for the oxygen reduction reaction," Electrochimica Acta, vol. 241, pp. 544-552, 2017.

9. R.Y. Zhong, K.Q. Sun, Y.C. Hong and B.Q. Xu, "Impacts of organic stabilizers on catalysis of Au nanoparticles from colloidal preparation," Acs Catalysis, vol. 4, no. 11, pp. 3982-3993, 2014.
10. C. Prossl, M. Kubler, M.A. Nowroozi, S. Paul, O. Clemens and U. I. Kramm, "Investigation of the thermal removal steps of capping agents in the synthesis of bimetallic iridium-based catalysts for the ethanol oxidation reaction," Phys Chem Chem Phys, vol. 23, no. 1, pp. 563-573, Jan 6 2021, doi: 10.1039/d0cp04900j.
11. D.M. Bezerra, I.W. Zapelini, K.N. Franke, M.E. Ribeiro and D. Cardoso, "Investigation of the structural order and stability of mesoporous silicas under a humid atmosphere," Materials Characterization, vol. 154, pp. 103-115, 2019, doi: 10.1016/j.matchar.2019.05.032.
12. L. López Pérez, E. R. H. van Eck and I. Melián-Cabrera, "On the hydrothermal stability of MCM-41. Evidence of capillary tension-induced effects," Microporous and Mesoporous Materials, vol. 220, pp. 88-98, 2016, doi: 10.1016/j.micromeso.2015.08.024.
13. A. Ghasemi and H. Sanaeishoar, "An Efficient one-pot synthesis of 1H-Pyrazolo [1, 2-b] phthalazine-5, 10-dione derivatives using MCM-41," Journal of Chemical Reactivity and Synthesis, vol. 9, no. 3, pp. 58-64, 2019.
14. A. Ahmad, M. H. Razali, K. Kassim and K.A.M. Amin, "Synthesis of multiwalled carbon nanotubes supported on M/MCM-41 (M= Ni, Co and Fe) mesoporous catalyst by chemical vapour deposition method," Journal of Porous Materials, vol. 25, pp. 433-441, 2018.
15. R. De Clercq , M. Dusselier, C. Poleunis, D.P. Debecker, L. Giebeler, S. Oswald, E. Makshina and B.F. Sels, "Titania-silica catalysts for lactide production from renewable alkyl lactates: structure–activity relations," ACS Catalysis, vol. 8, no. 9, pp. 8130-8139, 2018, doi: 10.1021/acscatal.8b02216.
16. A. S. Al-Awadi, A.M. Toni, M. Alhoshan, A. Khan, J.P. Labis, A. Al-Fatesh, A. E. Abasaeed and S.M. Al-Zahrani, "Impact of precursor sequence of addition for one-pot synthesis of Cr-MCM-41 catalyst nanoparticles to enhance ethane oxidative dehydrogenation with carbon dioxide," (in English), Ceramics International, vol. 45, no. 1, pp. 1125-1134, Jan 2019, doi: 10.1016/j.ceramint.2018.10.002.
17. Q. Sun, N. Wang and J. Yu, "Advances in catalytic applications of zeolite-supported metal catalysts," Adv Mater, vol. 33, no. 51, p. e2104442, Dec 2021, doi: 10.1002/adma.202104442.
18. A. Wróblewska, M. Kujbida, G. Lewandowski, A. Kamińska, Z. C. Koren and B. Michalkiewicz, "Epoxidation of 1, 5, 9-Cyclododecatriene with hydrogen peroxide over Ti-MCM-41 Catalyst," Catalysts, vol. 11, no. 11, p. 1402, 2021.
19. H. Sekkiou, R. Hamacha, T. Ali-Dahmane, A. Morsli and A. Bengueddach, "The effect of the method of copper incorporation on the structure of Si-MCM-41 and Al-MCM-41," Journal de la Société Chimique de Tunisie, vol. 15, pp. 93-99, 2013.
20. P.H. Chao, W.C. C. Jean, H.-P. Lin and T.C. Tsai, "Intercalation of silanes by ion imprinting method for improving hydrothermal stability of mesoporous silica," Catalysis Today, vol. 212, pp. 175-179, 2013/09/01/ 2013, doi: 10.1016/j.cattod.2012.08.029.
21. M. Song, C. Zou, G. Niu and D. Zhao, "Improving the hydrothermal stability of mesoporous silica SBA-15 by pre-treatment with (NH4)2SiF6," Chinese Journal of Catalysis, vol. 33, no. 1, pp. 140-151, 2012/01/01/ 2012, doi: 10.1016/s1872-2067(10)60283-5.
22. C. Jiang, A. Su, X. Li, T. Zhou and D. He, "Study on the hydrothermal stability of MCM-41 via secondary restructure," Powder Technology, vol. 221, pp. 371-374, 2012, doi: 10.1016/j.powtec.2012.01.028.
23. Y. Luo, C. Miao, Y. Yue, W. Yang, W. Hua and Z. Gao, "Chromium oxide supported on silicalite-1 zeolite as a novel efficient catalyst for dehydrogenation of isobutane assisted by CO2," Catalysts, vol. 9, no. 12, 2019, doi: 10.3390/catal9121040.
24. Y. Luo, C. Wei, C. Miao, Y. Yue, W. Hua and Z. Gao, "Isobutane dehydrogenation assisted by CO2 over silicalite‐1‐supported ZnO Catalysts: Influence of Support Crystallite Size," Chinese Journal of Chemistry, vol. 38, no. 7, pp. 703-708, 2020, doi: 10.1002/cjoc.202000042.
25. A. S. Al-Awadi, A.M. El-Toni, S.M. Al-Zahrani, A.E. Abasaeed, M. Alhoshan, A. Khan, J.P. Labis and A. Al-Fatesh, "Role of TiO2 nanoparticle modification of Cr/MCM41 catalyst to enhance Cr-support interaction for oxidative dehydrogenation of ethane with carbon dioxide," Applied Catalysis A: General, vol. 584, 2019, doi: 10.1016/j.apcata.2019.117114.
26. T. Wan, F. Jin, X. Cheng, J. Gong, C. Wang, G. Wu and A. Liu, "Influence of hydrophilicity and titanium species on activity and stability of Cr/MWW zeolite catalysts for dehydrogenation of ethane with CO2," Applied Catalysis A: General, vol. 637, 2022, doi: 10.1016/j.apcata.2022.118542.
27. V. Elías, E. Sabre, K. Sapag, S. Casuscelli and G. Eimer, "Influence of the Cr loading in Cr/MCM-41 and TiO2/Cr/MCM-41 molecular sieves for the photodegradation of Acid Orange 7," Applied Catalysis A: General, vol. 413-414, pp. 280-291, 2012, doi: 10.1016/j.apcata.2011.11.019.
28. S. Kilicarslan, M. Dogan and T. Dogu, "Cr incorporated MCM-41 type catalysts for isobutane dehydrogenation and deactivation mechanism," Industrial & Engineering Chemistry Research, vol. 52, no. 10, pp. 3674-3682, 2013, doi: 10.1021/ie302543c.
29. R. S. Araújo, F. O. S. Costa, D. A. S. Maia, H. B. S. Ana and C. L. Cavalcante, "Synthesis and characterization of Al-and Ti-MCM-41 materials : Application To Oxidation Of Anthracene," 2007.
30. A. Wróblewska, P. Miądlicki, J. Tołpa, J. Sreńscek-Nazzal, Z. C. Koren and B. Michalkiewicz, "Influence of the titanium content in the Ti-MCM-41 catalyst on the course of the α-pinene isomerization process," Catalysts, vol. 9, no. 5, p. 396, 2019.
31. K. Sing, F. Schüth and T. Weitkamp, "Handbook of porous solids," Handb. Porous Solids, vol. 3, pp. 1543-1591, 2002.
32. F.J. Sotomayor, K.A. Cychosz and M. Thommes, "Characterization of micro/mesoporous materials by physisorption: concepts and case studies," Acc. Mater. Surf. Res, vol. 3, no. 2, pp. 34-50, 2018.
33. P. S. Niphadkar, S. K. Chitale, S. K. Sonar, S. S. Deshpande, P. N. Joshi and S. V. Awate, "Synthesis, characterization and photocatalytic behavior of TiO2–SiO2 mesoporous composites in hydrogen generation from water splitting," Journal of Materials Science, vol. 49, no. 18, pp. 6383-6391, 2014, doi: 10.1007/s10853-014-8365-2.
34. S. K. Roy, D. Dutta and A. K. Talukdar, "Highly effective methylated Ti MCM-41 catalyst for cyclohexene oxidation," (in English), Materials Research Bulletin, vol. 103, pp. 38-46, Jul 2018, doi: 10.1016/j.materresbull.2018.03.017.
35. A. Talati, M. Haghighi and F. Rahmani, "Impregnation vs. coprecipitation dispersion of Cr over TiO2 and ZrO2 used as active and stable nanocatalysts in oxidative dehydrogenation of ethane to ethylene by carbon dioxide," RSC Advances, vol. 6, no. 50, pp. 44195-44204, 2016, doi: 10.1039/c6ra05049b.
36. Y. Liu, Y. Liu, A. Peyrav, Z. Hashisho, S. Zheng, Z. Sun, X. Chen, Y. Tong, Y. Hao and J. Wang, "Experimental and simulation investigation of water vapor adsorption on mesoporous MCM-41 derived from natural Opoka," (in English), Separation and Purification Technology, vol. 309, p. 123056, Mar 15 2023, doi: 10.1016/j.seppur.2022.123056.
37. C. Gaidau, A. Petica, M. Ignat, L. M. Popescu, R.M. Piticescu, I.A. Tudor and R.R. Piticescu, "Preparation of silica doped titania nanoparticles with thermal stability and photocatalytic properties and their application for leather surface functionalization," (in English), Arabian Journal of Chemistry, vol. 10, no. 7, pp. 985-1000, Nov 2017, doi: 10.1016/j.arabjc.2016.09.002.
38. K. Bourikas, C. Kordulis and A. Lycourghiotis, "Titanium dioxide (anatase and rutile): surface chemistry, liquid-solid interface chemistry, and scientific synthesis of supported catalysts," Chem Rev, vol. 114, no. 19, pp. 9754-823, Oct 8 2014, doi: 10.1021/cr300230q.
39. A.D. Erdali, S. Cetinyokus and M. Dogan, "Investigation of isobutane dehydrogenation on CrOx/Al2O3 catalyst in a membrane reactor," Chemical Engineering and Processing - Process Intensification, vol. 175, p. 108904, 2022/05/01/ 2022, doi: 10.1016/j.cep.2022.108904.
40. T. Ehiro, A. Itagaki, H. Misu, M. Kurashina, K. Nakagawa, M. Katoh, Y. Katou, W. Ninomiya and S. Sugiyamaet, "Oxidative dehydrogenation of isobutane to isobutene on metal-doped MCM-41 catalysts," Journal of Chemical Engineering of Japan, vol. 49, no. 2, pp. 136-143, 2018.