اصلاح ویژگی‌های کانی‌های زئولیت EU-1 و موردنیت به روش آلومینیوم‌زدایی و بررسی و مقایسه عملکرد آن‌ها در فرآیند ایزومری شدن زایلن

نوع مقاله : مقاله پژوهشی

نویسندگان

دانشگاه شهید باهنر کرمان

چکیده

در این پژوهش، زئولیت­های EU-1 و موردنیت سنتز شده، توسط روش آلومینیوم­زدایی با اسید نیتریک، اصلاح شدند و تغییر ویژگی­های آن­ها از جمله مساحت سطح، قطر، حجم حفره­ها و نسبت سیلیسیوم/آلومینیوم بررسی شد. عملکرد کاتالیزوری این دو زئولیت در فرآیند ایزومری شدن زایلن در یک رآکتور بستر ثابت بررسی و با یکدیگر مقایسه شد. نتایج نشان داد که در اثر اصلاح کاتالیزورها با اسید، بعلت حذف بسیاری از اتم­­های آلومینیوم از شبکه زئولیت­ها، نسبت سیلیسیوم/آلومینیوم و مساحت سطح زئولیت­ها افزایش یافته است که در نتیجه، فعالیت و گزینش­پذیری آن­ها در فرآیند ایزومری­شدن زایلن افزایش می­یابد. چنان که انتظار می­رفت، در فرآیند ایزومری شدن زایلن، زئولیت های اصلاح شده دارای نسبت پارا زایلن/اورتو زایلن، پارا زایلن/زایلن و نیز درصد تبدیل متازایلن بسیار بیشتری بودند.    

کلیدواژه‌ها

عنوان مقاله [English]

Modification of the properties of EU-1 and mordenite zeolites by dealumination method and investigation and comparison of their performance in xylene isomerization process

نویسندگان [English]

  • Merji Khosrovam
  • Zahra Vosooghi Rahbari
چکیده [English]

The synthesized zeolites of EU-1 and mordenite were modified via dealumination process with Nitric acid and changes of their properties including surface area, diameter, pore volume and Si/Al ratio were investigated. The catalytic performance of these two zeolites was tested and compared together in xylene isomerization process at a fixed bed reactor. The results showed that due to modification of catalysts with acid, because of the removal of a large number of aluminum atoms from the zeolite network, the Si/Al ratio and surface area of zeolites were increased, which resulted in their activity and selectivity of xylene isomerization process. As expected, the modified zeolites had much higher para xylene/ortho xylene, para xylene/xylene and m-xylene conversion than before in xylene isomerization process.

کلیدواژه‌ها [English]

  • zeolite
  • EU-1
  • mordenite
  • dealumination process
  • xylene
  • isomerization

مراجع

  1. [1] Guillon E., Lacombe S., Sozinho T., Magnoux P., Gnep S., Moreau P., Guisnet M., "How to Improve the Selectivity of Zeolitic Catalysts in C8 Aromatic Cut Isomerization", Oil & Gas Science and Technology 64 (2009) 731-744. [DOI:10.2516/ogst/2009030]
  2. [1] Guillon E., Lacombe S., Sozinho T., Magnoux P., Gnep S., Moreau P., Guisnet M., "How to Improve the Selectivity of Zeolitic Catalysts in C8 Aromatic Cut Isomerization", Oil & Gas Science and Technology 64 (2009) 731-744. [DOI:10.2516/ogst/2009030]
  3. [2] Guisnet M., Gnep N.S., Morin S., "Influence of coke deposits on the selectivity of m-xylene transformation and on the isomerization mechanism", Applied Catalysis A: General 168 (1998) 63-68. [DOI:10.1016/S0926-860X(97)00336-0]
  4. [2] Guisnet M., Gnep N.S., Morin S., "Influence of coke deposits on the selectivity of m-xylene transformation and on the isomerization mechanism", Applied Catalysis A: General 168 (1998) 63-68. [DOI:10.1016/S0926-860X(97)00336-0]
  5. [3] Faghihian H., Maccizadeh M.A., "Characterization of Some Iranian Natural Zeolites", Iranian Journal of Crystallography and Mineralogy 10 (2002) 141-156.
  6. [3] Faghihian H., Maccizadeh M.A., "Characterization of Some Iranian Natural Zeolites", Iranian Journal of Crystallography and Mineralogy 10 (2002) 141-156.
  7. [4] Faghihian H., Kazemian H., and Nezamzadeh A., "Thermal Behaviour of Two Iranian Natural Zeolites", Iranian Journal of Crystallography and Mineralogy 6 (1998) 41-52.
  8. [4] Faghihian H., Kazemian H., and Nezamzadeh A., "Thermal Behaviour of Two Iranian Natural Zeolites", Iranian Journal of Crystallography and Mineralogy 6 (1998) 41-52.
  9. [5] Aghabozorg H.R., Salehi Rad F., Aghabozord H., Sharif M., "Synthesis and Characterization of Zeolite P using Technical-grade Materials", Iranian Journal of Crystallography and Mineralogy 9 (2001) 47-58.
  10. [5] Aghabozorg H.R., Salehi Rad F., Aghabozord H., Sharif M., "Synthesis and Characterization of Zeolite P using Technical-grade Materials", Iranian Journal of Crystallography and Mineralogy 9 (2001) 47-58.
  11. [6] Aghabozorg H.R., Ghassemi M.R., Salehirad F., Attarnejad M.A., ineralogy 8 (2000) 107-116.
  12. [6] Aghabozorg H.R., Ghassemi M.R., Salehirad F., Attarnejad M.A., ineralogy 8 (2000) 107-116.
  13. [7] Martens J.A., Perez-Pariente J., Sastre E., Corma A., Jacobs P.A., "Isomerization and disproportionation of m-xylene : Selectivities Induced by the Void Structure of the Zeolite Framework", Applied Catalysis 45 (1988) 85-101. [DOI:10.1016/S0166-9834(00)82395-7]
  14. [7] Martens J.A., Perez-Pariente J., Sastre E., Corma A., Jacobs P.A., "Isomerization and disproportionation of m-xylene : Selectivities Induced by the Void Structure of the Zeolite Framework", Applied Catalysis 45 (1988) 85-101. [DOI:10.1016/S0166-9834(00)82395-7]
  15. [8] Rao G.N., Kumar R., Ratnasamy P., "Shape selectivity of zeolite EU-1 in reactions of aromatic hydrocarbons", Applied Catalysis A: General 49 (1989) 307-318 . [DOI:10.1016/S0166-9834(00)83025-0]
  16. [8] Rao G.N., Kumar R., Ratnasamy P., "Shape selectivity of zeolite EU-1 in reactions of aromatic hydrocarbons", Applied Catalysis A: General 49 (1989) 307-318 . [DOI:10.1016/S0166-9834(00)83025-0]
  17. [9] Souverijns W., Rombouts L., Martens J.A., Jacobs P.A., "Molecular shape selectivity of EUO zeolites", Microporous Materials, 4 (1995) 123-130. [DOI:10.1016/0927-6513(94)00091-9]
  18. [9] Souverijns W., Rombouts L., Martens J.A., Jacobs P.A., "Molecular shape selectivity of EUO zeolites", Microporous Materials, 4 (1995) 123-130. [DOI:10.1016/0927-6513(94)00091-9]
  19. [10] Xiaoling L., Yan W., Xujin W., Yafei Z., Yanjun G., Qinghu X., Jun X., Feng D., Tao D., "Characterization and Catalytic Performance in n-Hexane Cracking of HEU-1 Zeolites Dealuminated Using Hydrochloric Acid and Hydrothermal Treatments", Chinese Journal of Catalysis 33 (2012) 1889-190 . [DOI:10.1016/S1872-2067(11)60454-3]
  20. [10] Xiaoling L., Yan W., Xujin W., Yafei Z., Yanjun G., Qinghu X., Jun X., Feng D., Tao D., "Characterization and Catalytic Performance in n-Hexane Cracking of HEU-1 Zeolites Dealuminated Using Hydrochloric Acid and Hydrothermal Treatments", Chinese Journal of Catalysis 33 (2012) 1889-190 . [DOI:10.1016/S1872-2067(11)60454-3]
  21. [11] Guillon E., Sanchez E., "Modified EU-1 zeolite and its use in the isomerization of aromatic C8 compounds", US Pat. NO 7,838,456 B2 (2010).
  22. [11] Guillon E., Sanchez E., "Modified EU-1 zeolite and its use in the isomerization of aromatic C8 compounds", US Pat. NO 7,838,456 B2 (2010).
  23. [12] Meier W., "The crystal structure of mordenite (ptilolite)", Z. Kristallogr Crystalline Materials 115 (1961) 439-450. [DOI:10.1524/zkri.1961.115.5-6.439]
  24. [12] Meier W., "The crystal structure of mordenite (ptilolite)", Z. Kristallogr Crystalline Materials 115 (1961) 439-450. [DOI:10.1524/zkri.1961.115.5-6.439]
  25. [13] Mignoni M.L., Petkowicz D.I., Machado N.R.F., Pergher S.B., "Synthesis of mordenite using kaolin as Si and Al source", Applied Clay Science 41 (2008) 99-104. [DOI:10.1016/j.clay.2007.09.010]
  26. [13] Mignoni M.L., Petkowicz D.I., Machado N.R.F., Pergher S.B., "Synthesis of mordenite using kaolin as Si and Al source", Applied Clay Science 41 (2008) 99-104. [DOI:10.1016/j.clay.2007.09.010]
  27. [14] Guisnet M., "Regeneration of coked zeolite catalysts. Deactivation and Regeneration of Zeolite Catalysts", Imperial College Press, Amazon, World Scientific Publishing Company: London, (2011). [DOI:10.1142/9781848166387_0012]
  28. [14] Guisnet M., "Regeneration of coked zeolite catalysts. Deactivation and Regeneration of Zeolite Catalysts", Imperial College Press, Amazon, World Scientific Publishing Company: London, (2011). [DOI:10.1142/9781848166387_0012]
  29. [15] Kooyman P., Van der Waal P., Van Bekkum H., "Acid dealumination of ZSM-5" Zeolites 18 (1997) 50-53. [DOI:10.1016/S0144-2449(96)00106-6]
  30. [15] Kooyman P., Van der Waal P., Van Bekkum H., "Acid dealumination of ZSM-5" Zeolites 18 (1997) 50-53. [DOI:10.1016/S0144-2449(96)00106-6]
  31. [16] Gnep N.S., Guillon E., Lacombe S., Simon L., Moreau P., Magnoux P., "Process for isomerizing aromatic C8 compounds in the presence of a catalyst comprising a modified EUO zeolite" Google Patents (2011).
  32. [16] Gnep N.S., Guillon E., Lacombe S., Simon L., Moreau P., Magnoux P., "Process for isomerizing aromatic C8 compounds in the presence of a catalyst comprising a modified EUO zeolite" Google Patents (2011).
  33. [17] Van Donk S., Broersma A., Gijzeman O., van Bokhoven J.A., Bitter J., De Jong K., "Combined diffusion, adsorption, and reaction studies of n-hexane hydroisomerization over Pt/H-mordenite in an oscillating microbalance", Journal of Catalysis 204 (2001) 272-280. [DOI:10.1006/jcat.2001.3393]
  34. [17] Van Donk S., Broersma A., Gijzeman O., van Bokhoven J.A., Bitter J., De Jong K., "Combined diffusion, adsorption, and reaction studies of n-hexane hydroisomerization over Pt/H-mordenite in an oscillating microbalance", Journal of Catalysis 204 (2001) 272-280. [DOI:10.1006/jcat.2001.3393]
  35. [18] Müller M., Harvey G., Prins R., "Comparison of the dealumination of zeolites beta, mordenite, ZSM-5 and ferrierite by thermal treatment, leaching with oxalic acid and treatment with SiCl4 by 1 H, 29 Si and 27 Al MAS NMR" Microporous and Mesoporous Materials 34 (2000) 135-147. [DOI:10.1016/S1387-1811(99)00167-5]
  36. [18] Müller M., Harvey G., Prins R., "Comparison of the dealumination of zeolites beta, mordenite, ZSM-5 and ferrierite by thermal treatment, leaching with oxalic acid and treatment with SiCl4 by 1 H, 29 Si and 27 Al MAS NMR" Microporous and Mesoporous Materials 34 (2000) 135-147. [DOI:10.1016/S1387-1811(99)00167-5]
  37. [19] Viswanadham N., Kumar M., "Effect of dealumination severity on the pore size distribution of mordenite", Microporous and Mesoporous Materials 92 (2006) 31-37. [DOI:10.1016/j.micromeso.2005.07.049]
  38. [19] Viswanadham N., Kumar M., "Effect of dealumination severity on the pore size distribution of mordenite", Microporous and Mesoporous Materials 92 (2006) 31-37. [DOI:10.1016/j.micromeso.2005.07.049]
  39. [20] Vosoughi Rahbari Z., Khosravan M., Nemati Kharat A., "Effect of Synthesis Parameters on the Crystallinity of EU-1 Zeolite for the m-Xylene Isomerization Reaction", Russian Journal of Applied Chemistry 90 (2017) 818−825, [DOI:10.1134/S107042721705024X]
  40. [20] Vosoughi Rahbari Z., Khosravan M., Nemati Kharat A., "Effect of Synthesis Parameters on the Crystallinity of EU-1 Zeolite for the m-Xylene Isomerization Reaction", Russian Journal of Applied Chemistry 90 (2017) 818−825, [DOI:10.1134/S107042721705024X]
  41. [21] Hossain M.M., Osman M., Al-Khattaf S., "Ethylation of Ethylbenzene with Ethanol over mordenite Based Catalysts: Effects of Acidity, Desilication and Kinetics Analysis", International Journal of Chemical Reactor Engineering 12 (2014) 487-496. [DOI:10.1515/ijcre-2014-0006]
  42. [21] Hossain M.M., Osman M., Al-Khattaf S., "Ethylation of Ethylbenzene with Ethanol over mordenite Based Catalysts: Effects of Acidity, Desilication and Kinetics Analysis", International Journal of Chemical Reactor Engineering 12 (2014) 487-496. [DOI:10.1515/ijcre-2014-0006]
  43. [22] Vosoughi Rahbari Z., Khosravan M., Nemati Kharat A., "Preparation and characterization of template-free mordenite type zeolite and comparison of m-xylene isomerization reaction over mordenite and SAPO-11", Iranian Journal of Catalysis 7 (2017) 217-223.
  44. [22] Vosoughi Rahbari Z., Khosravan M., Nemati Kharat A., "Preparation and characterization of template-free mordenite type zeolite and comparison of m-xylene isomerization reaction over mordenite and SAPO-11", Iranian Journal of Catalysis 7 (2017) 217-223.
  45. [23] Vosoughi Rahbari Z., Khosravan M., Nemati Kharat A., "Comparison of Catalytic Performance of Synthesized EU-1 Zeolite with Dealuminated EU-1 Zeolite for m-Xylene Isomerization Reaction", Russian Journal of Applied Chemistry 90 (2017) 1315−1319. [DOI:10.1134/S1070427217080201]
  46. [23] Vosoughi Rahbari Z., Khosravan M., Nemati Kharat A., "Comparison of Catalytic Performance of Synthesized EU-1 Zeolite with Dealuminated EU-1 Zeolite for m-Xylene Isomerization Reaction", Russian Journal of Applied Chemistry 90 (2017) 1315−1319. [DOI:10.1134/S1070427217080201]
  47. [24] Gui P., Li X., Zhang S., Xu Q., Dou T., "Quasi-solid state synthesis of EU-1 zeolite and its catalytic properties for the isomerization of C8 aromatics", Journal of Petroleum Science and Engineering 9 (2012) 544-550. [DOI:10.1007/s12182-012-0241-6]
  48. [24] Gui P., Li X., Zhang S., Xu Q., Dou T., "Quasi-solid state synthesis of EU-1 zeolite and its catalytic properties for the isomerization of C8 aromatics", Journal of Petroleum Science and Engineering 9 (2012) 544-550. [DOI:10.1007/s12182-012-0241-6]
  49. [25] Ahmed M.H., Muraza O., Al Amer A.M., "Effect of synthesis parameters and ion exchange on crystallinity and morphology of EU-1 zeolite", Journal of Alloys and Compounds 617(2014) 408-412. [DOI:10.1016/j.jallcom.2014.08.028]
  50. [25] Ahmed M.H., Muraza O., Al Amer A.M., "Effect of synthesis parameters and ion exchange on crystallinity and morphology of EU-1 zeolite", Journal of Alloys and Compounds 617(2014) 408-412. [DOI:10.1016/j.jallcom.2014.08.028]
  51. [26] Guillon E., Sanchez E., "Modified EU-1 zeolite and its use in the isomerization of aromatic C8 compounds" Google Patents (2010).
  52. [26] Guillon E., Sanchez E., "Modified EU-1 zeolite and its use in the isomerization of aromatic C8 compounds" Google Patents (2010).
  53. [27] Mohamed M.M., Salama T.M., Othman I., Ellah I.A., "Synthesis of high silica mordenite nanocrystals using o-phenylenediamine template", Microporous and Mesoporous Materials 84 (2005) 84-96. [DOI:10.1016/j.micromeso.2005.05.017]
  54. [27] Mohamed M.M., Salama T.M., Othman I., Ellah I.A., "Synthesis of high silica mordenite nanocrystals using o-phenylenediamine template", Microporous and Mesoporous Materials 84 (2005) 84-96. [DOI:10.1016/j.micromeso.2005.05.017]
  55. [28] Raatz F., Marcilly C., Freund E., "Comparison between small port and large port mordenites", Zeolites 5 (1985) 329-333. [DOI:10.1016/0144-2449(85)90168-X]
  56. [28] Raatz F., Marcilly C., Freund E., "Comparison between small port and large port mordenites", Zeolites 5 (1985) 329-333. [DOI:10.1016/0144-2449(85)90168-X]
  57. [29] Xu R., Gao Z., Chen J., Yan W., "From Zeolite to Porous MOF Materials-the 40th Anniversary of International Zeolite Conference, 2 Vol Set: Proceedings of the 15th International Zeolite Conference", Elsevier Beijing PR China (2007).
  58. [29] Xu R., Gao Z., Chen J., Yan W., "From Zeolite to Porous MOF Materials-the 40th Anniversary of International Zeolite Conference, 2 Vol Set: Proceedings of the 15th International Zeolite Conference", Elsevier Beijing PR China (2007).
  59. [30] Kalipcilar H., Culfaz A., "Template-free synthesis of ZSM-5 type zeolite layers on porous alumina disks", Turkish Journal of Chemistry 31 (2007) 233-42.
  60. [30] Kalipcilar H., Culfaz A., "Template-free synthesis of ZSM-5 type zeolite layers on porous alumina disks", Turkish Journal of Chemistry 31 (2007) 233-42.
  61. [31] Tukur N.M., Al-Khattaf S., "Comparison studies of xylene isomerization and disproportionation reactions between SSZ-33, TNU-9, mordenite and ZSM-5 zeolite catalysts", Chemical Engineering Journal 166 (2011) 348-357. [DOI:10.1016/j.cej.2010.11.004]
  62. [31] Tukur N.M., Al-Khattaf S., "Comparison studies of xylene isomerization and disproportionation reactions between SSZ-33, TNU-9, mordenite and ZSM-5 zeolite catalysts", Chemical Engineering Journal 166 (2011) 348-357. [DOI:10.1016/j.cej.2010.11.004]
  63. [32] Guillon E., Sanchez E., "Process for isomerizing an aromatic C8 cut in the presence of a catalyst based on a dealuminated EUO zeolite", Google Patents (2011).
  64. [32] Guillon E., Sanchez E., "Process for isomerizing an aromatic C8 cut in the presence of a catalyst based on a dealuminated EUO zeolite", Google Patents (2011).

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سابقه مقاله

  • تاریخ دریافت: 06 خرداد 1397
  • تاریخ بازنگری: 07 مهر 1397
  • تاریخ پذیرش: 05 آبان 1397

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