Citation: JIN Ya-mei, DONG Mei, WANG Guo-fu, WANG Hao, LI Jun-fen, FAN Wei-bin, WANG Jian-guo, QIN Zhang-feng. Synthesis of Silicalite-1 hollow sphere catalyst and its application for Beckmann rearrangement reaction[J]. Journal of Fuel Chemistry and Technology, ;2016, 44(08): 1001-1009. shu

Synthesis of Silicalite-1 hollow sphere catalyst and its application for Beckmann rearrangement reaction

  • Corresponding author: FAN Wei-bin, 
  • Received Date: 31 March 2016
    Available Online: 10 May 2016

    Fund Project:

  • Silicalite-1 zeolite hollow sphere structured material was hydrothermally synthesized via the aid of carbon microspheres as hard-template. The morphology, structure, textural and physicochemical properties of the material were characterized with XRD, SEM, FT-IR, N2 adsorption-desorption isotherm, 29Si MAS NMR, TG, and XPS techniques. It was suggested that the obtained Silicalite-1 hollow spheres were highly crystallized with developed multiple channel structure and abundant surface hydroxyl groups, which endowed the material with excellent catalytic properties in Beckmann rearrangement reaction of cyclohexanone-oxime. Compared with the Silicalite-1 catalyst prepared from conventional method, the Silicalite-1 hollow sphere catalyst showed much higher activity to the conversion of cyclohexanone-oxime (99%) and selectivity of caprolactam (94%), with excellent stability at the same time. The abundant nest silanols and terminal silanols in Silicalite-1 hollow sphere were main active sites for Beckmann rearrangement reaction, and could be easily recovered from the deactivated catalysts by calcination.
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    1. [1]

      [1] LI Y,SHI J.Hollow-structured mesoporous materials:Chemical synthesis,functionalization and applications[J].Adv Mater,2014,26(20):3176-3205.

    2. [2]

      [2] FUJI M,TAKAI C,RIVERA VIRTUDAZO R V.Development of new templating approach for hollow nanoparticles and their applications[J].Adv Powder Technol,2014,25(1):91-100.

    3. [3]

      [3] OKAMOTO M.Synthesis of core-shell structured porous materials and applications as catalysts and precursors for hollow porous materials[J].Bull Jpn Petro Inst,2013,56(4):198-205.

    4. [4]

      [4] 金炜阳,程党国,陈丰秋,詹晓力.分子筛膜包覆型催化剂的制备和应用[J].化学进展,2011,23(10):2021-2030.(JIN Wei-yang,CHENG Dang-guo,CHEN Feng-qiu,ZHAN Xiao-li.Synthesis and application of zeolite membrane encapsulated catalysts[J].Prog Chem,2011,23(10):2021-2030.)

    5. [5]

      [5] WANG X D,TANG Y,WANG Y J,GAO Z,YANG W L,FU S K.Fabrication of hollow zeolite spheres[J].Chem Commun,2000,21:2161-2162.

    6. [6]

      [6] LAI Z,BONILLA G,DIAZ I,NERY J G,SUJAOTI K,AMAT M A,KOKKOLI E,TERASAKI O,THOMPSON R W,TSAPATSIS M,VLACHOS D G.Microstructural optimization of a zeolite membrane for organic vapor separation[J].Science,2003,300(5618):456-460.

    7. [7]

      [7] YU G,SUN B,PEI Y,XIE S,YAN S,QIAO M,FAN K,ZHANG X,ZONG B.FexO<em>y@C spheres as an excellent catalyst for Fischer-Tropsch synthesis[J].J Am Chem Soc,2010,132(3):935-937.

    8. [8]

      [8] KHAN E A,HU E,LAI Z.Preparation of metal oxide/zeolite core-shell nanostructures[J].Microporous Mesoporous Mater,2009,118(1/3):210-217.

    9. [9]

      [9] WANG X D,ZHANG B Q,LIU X F,LIN J Y S.Synthesis of b-oriented TS-1 films on chitosan-modifiedα-Al2O3 substrates[J].Adv Mater,2006,18(24):3261-3265.

    10. [10]

      [10] WANG X,YAN J,HUANG W.Synthesis of b-oriented TS-1 zeolite membranes with high performance in the oxyfunctionalization of n-hexane[J].Thin Solid Films,2013,534:40-44.

    11. [11]

      [11] PENG H,XU L,WU H,WANG Z,LIU Y,LI X,HE M,WU P.Synthesis and formation mechanism of TS-1@mesosilica core-shell materials templated by triblock copolymer surfactant[J].Microporous Mesoporous Mater,2012,153:8-17.

    12. [12]

      [12] CHU N,WANG J,ZHANG Y,YANG J,LU J,YIN D.Nestlike hollow hierarchical MCM-22 microspheres:Synthesis and exceptional catalytic properties[J].Chem Mater,2010,22(9):2757-2763.

    13. [13]

      [13] GARCÍA-MARTÍNEZ J,CAZORLA-AMORÓ S D,LINARES-SOLANO A,LIN Y S.Synthesis and characterisation of MFI-type zeolites supported on carbon materials[J].Microporous Mesoporous Mater,2001,42(2/3):255-268.

    14. [14]

      [14] VALTCHEV V,MINTOVA S.Layer-by-layer preparation of zeolite coatings of nanosized crystals[J].Microporous Mesoporous Mater,2001,43(1):41-49.

    15. [15]

      [15] CARUSO F,CARUSO R A,MOHWALD H.Nanoengineering of inorganic and hybrid hollow spheres by colloidal templating[J].Science,1998,282(5391):1111-1114.

    16. [16]

      [16] VALTCHEV V.Silicalite-1 hollow spheres and bodies with a regular system of macrocavities[J].Chem Mater,2002,14(10):4371-4377.

    17. [17]

      [17] VALTCHEV V.Core-shell polystyrene/zeolite a microbeads[J].Chem Mater,2002,14(3):956-958.

    18. [18]

      [18] JI Y J,ZHANG B,XU L,WU H,PENG H,CHEN L,LIU Y,WU P.Core/shell-structured Al-MWW@B-MWW zeolites for shape-selective toluene disproportionation to para-xylene[J].J Catal,2011,283(2):168-177.

    19. [19]

      [19] LV Y,QIAN X,TU B,ZHAO D.Generalized synthesis of core-shell structured nano-zeolite@ordered mesoporous silica composites[J].Catal Today,2013,204:2-7.

    20. [20]

      [20] CHAMNANKID B,WITOON T,KONGKACHUICHAY P,CHAREONPANICH M.One-pot synthesis of core-shell silica-aluminosilicate composites:Effect of pH and chitosan addition[J].Colloids Surf A,2011,380(1/3):319-326.

    21. [21]

      [21] DONG A,WANG Y,TANG Y,REN N,ZHANG Y,GAO Z.Hollow zeolite capsules:A novel approach for fabrication and guest encapsulation[J].Chem Mater,2002,14(8):3217-3219.

    22. [22]

      [22] KIM J,PARK W,RYOO R.Surfactant-directed zeolite nanosheets:A high-performance catalyst for gas-phase beckmann rearrangement[J].ACS Catal,2011,1(4):337-341.

    23. [23]

      [23] TAKAHASHI T,NISHI M,TAGAWA Y,KAI T.Catalyst deactivation of high-silica HZSM-5 in the Beckmann rearrangement reaction of cyclohexanone oxime[J].Microporous Mater,1995,3(s 4/5):467-471.

    24. [24]

      [24] KUMAR R,CHOWDHURY B.Comprehensive study for vapor phase beckmann rearrangement reaction over zeolite systems[J].Ind Eng Chem Res,2014,53(43):16587-16599.

    25. [25]

      [25] 李倩,严罗一,夏定,申永存.贝克曼重排反应研究进展[J].有机化学,2011,31(12):2034-2042.(LI Qian,YAN Luo-yi,XIA Ding,SHEN Yong-cun.Research progress of Beckmann rearrangement[J].Chin J Org Chem,2011,31(12):2034-2042.)

    26. [26]

      [26] LI W C,LU A H,PALKOVITS R,SCHMIDT W,SPLIETHOFF B,SCHVTH F.Hierarchically structured monolithic silicalite-1 consisting of crystallized nanoparticles and its performance in the beckmann rearrangement of cyclohexanone oxime[J].J Am Chem Soc,2005,127(36):12595-12600.

    27. [27]

      [27] HEITMANN G P,DAHLHOFF G,HOLDERICH W F.Catalytically active sites for the beckmann rearrangement of cyclohexanone oxime to epsilon-caprolactam[J].J Catal,1999,186(1):12-19.

    28. [28]

      [28] YIN C,NI R,BAO X,CHEN Y.Synthesis of hierarchical porous silicalite-1 and its catalytic performance in Beckmann rearrangement[J].Microporous Mesoporous Mater,2015,202:133-137.

    29. [29]

      [29] SONG H,XING C,LI B,SHEN W.Spherical carbon with SO3H groups as an efficient solid acid catalyst for 2,4,5-triphenyl-imidazole synthesis[J].Chem Select,2016,1(2):301-308.

    30. [30]

      [30] BERENGUER-MURCIAÁ,GARCÍA-MARTÍNEZ J,CAZORLA-AMORÓ S D,LINARES-SOLANO Á,FUERTES A B.Silicalite-1 membranes supported on porous carbon discs[J].Microporous Mesoporous Mater,2003,59(2/3):147-159.

    31. [31]

      [31] LI Q,HEDLUND J,STERTE J,CREASER D,BONS A J.Synthesis and characterization of zoned MFI films by seeded growth[J].Microporous Mesoporous Mater,2002,56(3):291-302.

    32. [32]

      [32] KULKARNI S B S V P,KOTASTHANE A N BORADE R B,RATNASAMY P.Studies in the synthesis of ZSM-5 zeolites[J].Zeolites,1982,2(4):313-318.

    33. [33]

      [33] SUGIMOTO M K H,TAKATSU K,KAWATA N.Correlation between the crystal size and catalytic properties of ZSM-5 zeolite[J].Zeolites,1987,7(6):503-507.

    34. [34]

      [34] OUTIRITE M,LAGRENÉE M,LEBRINI M,TRAISNEL M,JAMA C,VEZIN H,BENTISS F.Ac impedance,X-ray photoelectron spectroscopy and density functional theory studies of 3,5-bis (n-pyridyl)-1,2,4-oxadiazoles as efficient corrosion inhibitors for carbon steel surface in hydrochloric acid solution[J].Electrochim Acta,2010,55(5):1670-1681.

    35. [35]

      [35] BOUMHARA K,TABYAOUI M,JAMA C,BENTISS F.Artemisia Mesatlantica essential oil as green inhibitor for carbon steel corrosion in 1M HCl solution:Electrochemical and XPS investigations[J].J Ind Eng Chem,2015,29:146-155.

    36. [36]

      [36] HUNGER M,KÄRGER J,PFEIFER H,CARO J,ZIBROWIUS B,BVLOW M,MOSTOWICZ R.Investigation of internal silanol groups as structural defects in ZSM-5-type zeolites[J].J Chem Soc Faraday Trans,1987,83(1):3459-3468.

    37. [37]

      [37] KUHN J,MOTEGH M,GROSS J,KAPTEIJN F.Detemplation of[B]MFI zeolite crystals by ozonication[J].Microporous Mesoporous Mater,2009,120(1/2):35-38.

    38. [38]

      [38] YAMAGISHI K,NAMBA S,YASHIMA T.Defect sites in highly siliceous HZSM-5 zeolites:A study performed by alumination and IR spectroscopy[J].J Phy Chem,1991,95(2):872-877.

    39. [39]

      [39] BARBERA K,BONINO F,BORDIGA S,JANSSENS T V W,BEATO P.Structure-deactivation relationship for ZSM-5 catalysts governed by framework defects[J].J Catal,2011,280(2):196-205.

    40. [40]

      [40] VASCHETTO E G,CASUSCELLI S G,EIMER G A.Improvements in the Beckmann rearrangement process by using highly selective mesoporous catalysts[J].Microporous Mesoporous Mater,2016,221:175-181.

    41. [41]

      [41] IZUMI Y,ICHIHASHI H,SHIMAZU Y,KITAMURA M,SATO H.Development and industrialization of the vapor-phase beckmann rearrangement process[J].Bull Chem Soc Jpn,2007,80(7):1280-1287.

    42. [42]

      [42] ICHIHASHI H,SATO H.The development of new heterogeneous catalytic processes for the production of ε-caprolactam[J].Appl Catal A:Gen,2001,221(1/2):359-366.

    43. [43]

      [43] SINGH P S,BANDYOPADHYAY R,HEGDE S G,RAO B S.Vapor phase Beckmann rearrangement of cyclohexanone oxime over SAPO-11 molecular sieve[J].Appl Catal A:Gen,1996,136:249-263.

    44. [44]

      [44] RÖSELER J,HEITMANN G,HÖLDERICH W F.Vapor-phase Beckmann using B-MFI zeolites[J].Appl Catal A:Gen,1996,144:319-333.

    45. [45]

      [45] KO A N,HUNG C C,CHEN C W,OUYANG K H.Mesoporous molecular sieve Al-MCM-41 as a novel catalyst for vapor-phase Beckmann rearrangement of cyclohexanone oxime[J].Catal Lett,2001,71(3/4):219-224.

    46. [46]

      [46] KELEMEN S R,M.AFEWORKI A,GORBATY M L,COHEN A D.Characterization of organically bound oxygen forms in lignites,peats,and pyrolyzed peats by X-ray photoelectron spectroscopy (XPS) and solid-state 13C NMR methods[J].Energy Fuels,2002,16(6):1450-1462.

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