바나듐 함유 MFI형 제올라이트의 제조 및 촉매적 특성

김건중; 고완석; 조병린

Journal of the Korean Industrial and Engineering Chemistry, Vol.5, No.2, 361-372, April, 1994

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바나듐 함유 MFI형 제올라이트의 제조 및 촉매적 특성

Preparation and Catalytic Properties of Vanadium-Containing MFI Type Zeolite

김건중, 고완석, 조병린

초록

수열합성법 및 탈알루미늄 처리 이후 NH₄VO₃ 담지법으로 바나듐이 함유된 MFI형 제올라이트를 제조하였다. X선 회절분석, 시차 열분석, 적외선 분광분석 및 전자스핀공명분석을 수행하여 바나듐의 격자구조 내로의 도입을 검토하였다. 탈알루미늄된 ZSM-5에 NH₄VO₃를 담지시키고 소성한 경우에도 수열합성법으로 제조한 시료와 같이 바나듐이 구조 내로 도입될 수 있었다. 제올라이트 구조 중의 바나듐은 고온처리에 의해 산화-환원과정을 거칠 수 있으며, 이들은 원자단위로 분산되어 고정됨을 나타내었다. 벤젠 수산화반응과 hexane 및 알코올의 산화반응을 바나듐 함유 MFI형 제올라이트의 특성 검토를 위한 시험반응으로 이용하였다.

Vanadium containing MFI type zeolites have been prepared hydrothermally or by the impregnation method with NH₄VO₃ solution after dealumination of HZSM-5. Incorporation of vanadium into the framework of zeolite has been demonstrated by XRD, DTA, FT-IR and ESR analyses. Upon NH₄VO₃ impregnation and calcination of dealuminated zeolite, vanadium substitution into the framework could be performed like a hydrothermally synthesized zeolite. Vanadium in zeolite is able to pass redox cycles at high temperatures, and it is shown that vanadium is probably fixed and atomically dispersed in the structure of zeolite. The catalytic benzene hydroxylation, hexanes and alcohols oxidation were used for evaluating the properties of vanadium incorporated MFI zeolite.

[References]

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Kraushaar B, VanHooff JHC, Catal. Lett., 2, 43 (1989)
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[1] Szostak R, "Molecular Sieves: Principles of Synthesis and Identification," Van Nostrand, New York (1989)

[2] Kim JH, Namba S, Yashima T, "Zeolites as Catalysts, Sorbents and Detergent Builders," ed. H.G. Karge and J. Weitkamp, 46, 71, Elsevier, Amsterdam (1989)

[3] Ko TS, Seo G, HWAHAK KONGHAK, 28(2), 163 (1990)

[4] Kim JS, Seo G, Kim JH, Park NC, HWAHAK KONGHAK, 27(3), 260 (1989)

[5] Hong SB, Woo SI, Uh YS, Korean J. Chem. Eng., 6(4), 357 (1989)

[6] Kim MH, Km HJ, Moon SK, HWAHAK KONGHAK, 31(3), 295 (1993)

[7] Kim CJ, Ahn WS, Appl. Catal., 71, 55 (1991)

[8] Taramasso M, Notari B, U.S. Patent, 4,410,501 (1983)

[9] Esposito A, Neri C, Buonomo F, Eur. Patent, 0102655 (1984)

[10] Neri C, Anfossi B, Esposito A, Buonomo F, Buonomo, Eur. Patent, 0100119 (1984)

[11] Thangaraj A, Kumar R, Ratnasamy P, Appl. Catal., 57, L1 (1990)

[12] Kraushaar B, VanHooff JHC, Catal. Lett., 2, 43 (1989)

[13] Clerici MG, Appl. Catal., 68, 249 (1991)

[14] Rigutto MS, VanBekkum H, Appl. Catal., 68, L1 (1991)

[15] HariPrasadRao PR, Ramaswamy AV, Ratnasamy P, J. Catal., 137, 225 (1992)

[16] Jhung SH, Uh YS, Chon HZ, Appl. Catal., 62, 61 (1990)

[17] Kraushaar B, VanHooff JHC, Catal. Lett., 1, 81 (1988)

[18] Gaffney TG, Pierantozzi R, Seger MR, "Zeolite Synthesis," ed. M.L. Occelli and H.E. Robson, ACS Sympsosium Series 398, 374, Am. Chem. Soc. (1989)

[19] Skeels GW, Flanigen EM, ACS Sympsosium Series 398, 420, Am. Chem. Soc., 398, 420 (1989)

[20] Miyamoto A, Medhanavyn D, Inui T, Appl. Catal., 28, 89 (1986)

[21] Kim GJ, Kwon LM, HWAHAK KONGHAK, 26(3), 261 (1988)

[22] Takahashi H, Shiotani M, Kobayashi H, Sohma J, J. Catal., 14, 134 (1969)

[23] Martini G, Ottaviani MF, Seravalli GL, J. Phys. Chem., 79, 1716 (1975)

[24] Fritsch E, Babonneau F, Sanchez C, Calas G, J. Non-Cryst. Solids, 92, 282 (1987)

[25] Perego G, Bellussi G, Corus C, Taramasso M, Buonomo F, Esposito A, "New Developments in Zeolite Science, and Technology, Kodansha and Elsevier, Tokyo (1986)

[26] Thangaraj A, Kumar R, Mirajkar SP, Ratnasamy P, J. Catal., 130, 1 (1991)

[27] Thangaraj A, Kumar R, Sivasanker S, Zeolites, 12, 135 (1992)

[28] Szostak R, Thomas TL, J. Catal., 100, 555 (1986)

[29] Wachs IE, Chan SS, Saleh RY, J. Catal., 91, 366 (1985)

[30] Olah GA, Paker DG, Yoneda N, Angew. Chem.-Int. Edit., 17, 909 (1978)