skip to main content

MoO3/SiO2-ZrO2 Catalyst: Eeffect of Calcination Temperature on Physico-chemical Properties and Activities in Nitration of Toluene

Department of Applied Chemistry, J. L. Chaturvedi College of Engineering, 846-New Nandanvan, Nagpur-09, India

Received: 19 May 2012; Revised: 24 May 2012; Accepted: 26 May 2012; Published: 30 Dec 2012.
Editor(s): Istadi Istadi
Open Access Copyright (c) 2012 by Authors, Published by BCREC Group
Creative Commons License This work is licensed under a Creative Commons Attribution-ShareAlike 4.0 International License.
Fulltext View|Download

Citation Format:
Abstract
12 wt % molybdena was deposited over 1:1 silica zirconia mixed oxide support and the resultant catalyst was calcined between the 500 to 700 oC range of temperature. The samples were characterized by XRD, FT-IR, BET, SEM, NH3-TPD and pyridine adsorbed FT-IR techniques.  Nitration of toluene was studied as a model reaction over the prepared catalysts and parameters like effect of reaction temperature, effect of various solvents, catalyst reusability are studied. It was found that conversion of toluene varies with the presence of Brönsted acid sites over the catalyst surface and para-nitrotoulene selectivity is associated with pore size of the catalyst. Over the same catalysts, nitration was extended for some other aromatics. Avoid of sulfuric acid in the present process is an interesting concern in view of green chemistry. © 2012 by Authors, Published by BCREC Group. This is an open access article under the CC BY-SA License (https://creativecommons.org/licenses/by-sa/4.0)
Keywords: MoO3/SiO2-ZrO2; SO2-ZrO2; NH3-TPD; Nitration; ortho-nitro toluene

Article Metrics:

  1. Chun-Yu, C., Chia-wei, W. (1996). Thermal hazard assessment and macrokinetics analysis of toluene mononitration in batch reactor. J. Loss Prev. Process Ind. 9: 309-316. doi: 10.1016/0950-4230(96)00022-8
  2. Glusshko, V. P., eds. (1978). Thermodynamic Properties of Individual Substances, (Vol. 1), Nauka, Moscow
  3. McKee, M., Wilhelm, R.H. (1936) Catalytic vapour phase nitration of benzene. Ind. Eng. Chem. 28: 662-667
  4. Suzuki, S., Tahmori, K., Ono Y. (1986) Vapour phase nitration over poly-organo siloxanes bearing supho groups. Chem. Lett. 15: 747-750. doi: 10.1246/cl.1986.747
  5. Suzuki, S., Tahmori, K., Ono Y. (1987) Preparation of sulphonated polyorganosiloxanes and their acid catalysis. J. Mol. Catal. 43: 41-50. doi: 10.1016/0304-5102(87)87020-7
  6. Olah, G.A., Krishnamurthy, V.V., Narang, S.C. (1982) Aromatic substitution. 50. Mercury (II)-promoted azeotropic nitration of aromatics over Nafion-H solid superacidic catalyst. J. Org. Chem. 47: 596-598. doi: 10.1021/jo00342a052
  7. Cornelis, A., Gerstmans, A, Laszlo, P. (1988) Regio-selective liquid phase toluene nitration with modified clay as catalyst. Chem. Lett. 11: 1839 -1842. doi: 10.1246/cl.1988.1839
  8. German, A., Akouz, T., Figueras, F. (1996) Vapour-phase nitration of fluorobenzene with N2O4 over aluminosilicates. Effects of structure and acidity of the catalyst. Appl. Catal. A 136: 57-68. doi: 10.1016/0926-860X(95)00249-9
  9. German, A., Akouz, T., Figueras, F. Vapour phase aromatic nitration with dinitrogen tetroxide over solid acids: Kinetics and mechanism (1994) J. Catal. 147: 163-170. doi: 10.1006/jcat.1994.1126
  10. Akolekar, D.B, Lemay, G., Sayari, A., Kaliaguine, S. (1995) High pressure nitration of toluene using nitrogen dioxide on zeolite catalysts. Res. Chem. Interm. 21: 7-16. doi: 10.1163/156856795X00026
  11. Laszlo, P., Vandormael, J. (1988) Regioselective Nitration of Aromatic Hydrocarbons by Metallic Nitrates on the K10 Montmorillonite under Menke Conditions. Chem. Lett. 17: 1843-1846. doi: 10.1246/cl.1988.1843
  12. Riego, J.M., Sedin, Z., Zaldivar, J.M., Marziano, N.C. Toratato, C. (1996) Sulfuric acid on silica-gel: an inexpensive catalyst for aromatic nitration Tetrahedron Lett. 37: 513-516. doi: 10.1016/0040-4039(95)02174-4
  13. Suzuki, E., Tohmori, K., Ono, Y. (1987) Vapor-phase Nitration of Benzene over Silica-supported Benzenesulfonic Acid Catalyst. Chem. Lett. 11: 2273-2274. doi: 10.1246/cl.1987.2273
  14. Parac-Vogt, T.N., Deleersnyder, K., Binnemans, K. (2004) Lanthanide (III) complexes of aromatic sulfonic acids as catalysts for the nitration of toluene. J. Alloys Compd. 374: 46-49. doi: 10.1016/j.jallcom.2003.11.062
  15. Chaubal, N.S., Sawant, M.R. (2007) Vapor phase nitration of toluene over CuFe0.8Al1.2O4.. Catal. Commun. 8: 845-849. doi: 10.1016/j.catcom.2006.08.031
  16. Ullmann’s Encyclopedia of Industrial Chemistry. (1991) Vol. A (17) VCH, Weinheim, pp. 411
  17. Choudary, B.M., Sateesh, M., Lakshmi Kantam, M., Koteswara Rao, K., RamPrasad, K.V., Raghavan, K.V., Sharma, J.A. R.P. (2000) Selective nitration of aromatic compounds by solid acid catalysts. Chem. Commun. 1: 25-26. doi: 10.1039/A908011B
  18. Bertea, L. E., Kouwenhoven, H. W., Prins, R. (1993) Catalytic vapour-phase nitration of benzene over modified Y zeolites: influence of catalyst treatment. Stud. Surf. Sci. Catal. 78: 607-614. doi: 10.1016/S0167-2991(08)63373-X
  19. Bertea, L. E., Kouwenhoven, H. W., Prins, R. (1995) Vapour-phase nitration of benzene over modified mordenite catalysts. Appl. Catal. A. 129: 229-250. doi: 10.1016/0926-860X(95)00105-0
  20. Kogelbauer, A., Vassena, D., Prins, R., Armor, J. N. (2000) Solid acids as substitutes for sulfuric acid in the liquid phase nitration of toluene to nitrotoluene and dinitrotoluene. Catal. Today. 55: 151-160. doi: 10.1016/S0920-5861(99)00234-5
  21. Smith, K., Musson, A., De Boos, G.A. (1998) A Novel Method for the Nitration of Simple Aromatic Compounds. J. Org. Chem. 63: 8448-8454. doi: 10.1021/jo981557o
  22. Breysse, M., Portefaix, J.L., Vrinat, M. (1991) Support effects on hydrotreating catalysts. Catal. Today 10: 489-495. doi: 10.1016/0920-5861(91)80035-8
  23. Vrinat, M., Breysse, M., Geantet, C., Ramireze, J., Massoth, F.E. (1994) Effect of MoS2 morphology on the HDS activity of hydrotreating catalysts. Catal. Lett. 26 (1994) 25-35. doi: 10.1007/BF00824029
  24. Rana, M.S., Maity, S.K., Ancheyta, J., Murali Dhar, G., Prasada Rao, T.S.R. (2003) TiO2–SiO2 supported hydrotreating catalysts: physico-chemical characterization and activities. Appl. Catal. A 253: 165-176. doi: 10.1016/S0926-860X(03)00502-7
  25. Rana, M.S., Srinivas, B.N., Maity, S.K., Murali Dhar, G., Prasada Rao, T.S.R. (1999) Catalytic functionalities of TiO2 based SiO2, Al2O3, ZrO2 mixed oxide hydroprocessing catalysts. Stud. Surf. Sci. Catal. 127: 397-400. doi: 10.1016/S0167-2991(99)80439-X
  26. Gonella, F., Matter, G., Mazzoldi, P. (1999) Structural and Optical Properties of Silver-Doped Zirconia and Mixed Zirconia−Silica Matrices Obtained by Sol−Gel Processing. Chem. Mater. 11:814-821. doi: 10.1021/cm980749x
  27. Gomez, R., Tzompantzi, F., Lopez, T., Navaro, O. (1994) ZrO2−SiO2 mixed oxides as supports for platinum catalysts. React. Kinet. Catal. Lett. 53: 245-251. doi: 10.1007/BF02073027
  28. Damyanova, S., Petrov, L., Centeno, M.A., Grange, P. (2002) Characterization of molybdenum hydrodesulfurization catalysts supported on ZrO2-Al2O3 and ZrO2-SiO2 carriers. Appl. Catal. A. 224: 271-284. doi: 10.1016/S0926-860X(01)00849-3
  29. Kamiya, K., Sakka, S., Tatemichi, Y. (1980) Preparation of glass fibres of the ZrO2-SiO2 and Na2O-ZrO2-SiO2 systems from metal alkoxides and their resistance to alkaline solution. J. Mater. Sci. 15: 1765-1771. doi: 10.1007/BF00550596
  30. Reddy, B. M., Sreekanth, P. M., Yamada, Y., Xu, Q., Kobayashi, T. (2002) Surface characterization of sulfate, molybdate, and tungstate promoted TiO2-ZrO2 solid acid catalysts by XPS and other techniques. Appl. Catal. A 228: 269-278. doi: 10.1016/S0926-860X(01)00982-6
  31. Reddy, B. M., Chowdhury, B. (1998) Dispersion and Thermal Stability of MoO3 on TiO2-ZrO2 Mixed Oxide Support. J. Catal. 179: 413-419. doi: 10.1006/jcat.1998.2221
  32. Chen, K., Xie, S., Iglesia, E., Bell, A.T. Structure and Properties of Zirconia-Supported Molybdenum Oxide Catalysts for Oxidative Dehydrogenation of Propane. J. Catal. 189: 421-430. doi: 10.1006/jcat.1999.2720
  33. Nyquist, R.A., Putzig, C.L., Leugers M.A. eds. (1997) Handbook of Infrared and Raman spectra of Inorganic Compounds and Organic Salts. 295-350. Academic Press, New York
  34. Pecharroman, C., Ocana, M., Tartaj P., and Serna, C.J.(1994) Infrared optical properties of zircon. Mater. Res. Bull. 29: 417-426. doi: 10.1016/0025-5408(94)90074-4
  35. Dawson, P., Hargreave, M., Wilkison, G. (1971) The vibrational spectrum of zircon (zrsio4) J. Phys. C. 4: 240-256. doi: 10.1088/0022-3719/4/2/014
  36. Rayner Jr., G. B. (2002) Spectroscopic Investigation of Local Bonding in Zirconium Silicate High-k Dielectric Alloys for Advanced Microelectronic Applications. Ph.D. thesis, Department of physics, North Carolina State University, Raleigh
  37. Mohamed, M.M., Salama, T.M., Yamaguchi, T. (2002) Synthesis, characterization and catalytic properties of titania–silica catalysts. Coll. Surf. A 207: 25-32. doi: 10.1016/S0927-7757(02)00002-X
  38. Mao, D., Lu, G., Chen, Q. (2004) Influence of calcination temperature and preparation method of TiO2–ZrO2 on conversion of cyclohexanone oxime to ε-caprolactam over B2O3/TiO2–ZrO2 catalyst. Appl. Catal. A 263: 83-89. doi: 10.1016/j.apcata.2003.12.028
  39. Maria, J.P., Wicaksana, D., Kingon, A.I., Busch, B., Schulte, H., Garfunkel, E., and Gustafsson, T. (2001) High temperature stability in lanthanum and zirconia-based gate dielectrics. J. Appl. Phys. 90: 3476-3482. doi: 10.1063/1.1391418
  40. Wilk, G. D., Wallace R. W., and Anthony, J.M. (2001) High-κ gate dielectrics: Current status and materials properties considerations. J. Appl. Phys. 89: 5243-5275. doi: 10.1063/1.1361065
  41. Lonyl, F., and Valyon, J. (2001) On the interpretation of the NH3-TPD patterns of H-ZSM-5 and H-mordenite. Microporous Mesoporous Mater. 47: 293-301. doi: 10.1016/S1387-1811(01)00389-4
  42. Sawa, M., Niwa, M., Murakami, Y. (1990) Relationship between acid amount and framework aluminum content in mordenite. Zeolites 10: 532-538. doi: 10.1016/S0144-2449(05)80308-2
  43. Damyanova, S., Grange, P., Delmon, B. (1997) Surface Characterization of Zirconia-Coated Alumina and Silica Carriers. J. Catal. 168: 421-430. doi: 10.1006/jcat.1997.1671
  44. Massoth, F.E. (1978) Characterization of Molybdena Catalysts. Adv. Catal. 27: 265-309. doi: 10.1016/S0360-0564(08)60058-9
  45. Anderson, J.R., Boudart, M. eds. (1996). Hydrotreating Catalysis-Science and Technology, Vol. 11, Springer-Verlag: New York
  46. Murali Dhar, G., Srinivas, B.N., Rana, M.S., Kumar,M., Maity, S. K (2003) Mixed oxide supportedhydrodesulfurization catalysts-a review. Catal. Today 86: 45-60. doi: 10.1016/S0920-5861(03)00403-6
  47. Zhao, B., Wang, X., Ma, H., Tang, Y. (1996) Raman spectroscopy studies on the structure of MoO3/ZrO2 solid superacid. J. Mol. Catal. A 108: 167-174. doi: 10.1016/1381-1169(96)00008-8
  48. Rahman, A., Lemay, G., Adnot, A., Kaliaguine, S. (1988) Spectroscopic and catalytic study of P-modified ZSM-5. J. Catal. 112: 453-463. doi: 10.1016/0021-9517(88)90160-1
  49. Ward, D. A., Ko, E. I. (1994) One-Step Synthesis and Characterization of Zirconia-Sulfate Aerogels as Solid Superacids. J. Catal. 150 (1994) 18-33. doi: 10.1006/jcat.1994.1319
  50. Lopez, T., Tzompantzi, F., Navarrete, J., Gomez, R., Boldu, J.L., Munoz, E., and Novaro, O.(1999) Free Radical Formation in ZrO2–SiO2 Sol–Gel Derived Catalysts. J. Catal. 181: 285-293. doi: 10.1006/jcat.1998.2308
  51. Mmalysheva, L. V., Paukshtis, E. A., Ione, K. G. (1995) Nitration of Aromatics by Nitrogen Oxides on Zeolite Catalysts: Comparison of Reaction in the Gas Phase and Solutions. Catal. Rev. Sci. Eng. 37: 179-226. doi: 10.1080/01614949508007095
  52. Brei, V.V., Prudius, S.V., Melezhyk, O.V. (2003) Vapour-phase nitration of benzene over superacid WO3/ZrO2catalysts. Appl. Catal. A. 239: 11–16. doi: 10.1016/S0926-860X(02)00383-6
  53. Yoo, J.S., Sohail, A. R., Grimmer, S. S., Shyu, J. Z. (1994) One-step hydroxylation of benzene to phenol i.gas-phase nitric acid oxidation over Fe/Mo/SiO2. Appl. Catal. A 117: 1-16. doi: 10.1016/0926-860X(94)80154-1
  54. March, J. eds. (1999) Advanced Organic Chemistry, Fourth ed., 524. John Wiley: New York
  55. Waller, F.J., Barrett, A.G.M., Braddock, D.C., Ramprasad, D. (1997) Lanthanide (iii) triflates as recyclable catalysts for atom economic aromatic nitration. Chem. Comm. (1997) 613-614. doi: 10.1039/a700546f

Last update:

No citation recorded.

Last update:

No citation recorded.