Synthesis of MFI-Type Zeolites Under Atmospheric Pressure

Hyung-Seuk Oh; Kyoung-Ku Kang; Man-Hoe Kim; Hyun-Ku Rhee

Korean Journal of Chemical Engineering, Vol.18, No.1, 113-119, January, 2001

DOI10.1007/BF02707207 Export Citation

Synthesis of MFI-Type Zeolites Under Atmospheric Pressure

Hyung-Seuk Oh, Kyoung-Ku Kang, Man-Hoe Kim¹, and Hyun-Ku Rhee^†

School of Chemical Engineering and Institute of Chemical Processes, Seoul National University, Seoul 151-742, Korea
¹Department of Chemistry, Air Force Academy of R.O.K., Chungbuk 363-849, Korea

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Silicalite and highly silicious ZSM-5 were synthesized using two reaction mixtures with different crystal growth environments, a dispersed low density mixture and a separated high density mixture, at 93±3 ℃ under the atmospheric pressure. Nucleation behavior and the transformation process of two mixtures were investigated utilizing various analytical techniques such as XRD, FT-IR, TGA, SEM, and pH measurement. During the induction period, the same intermediate phase was observed in both mixtures. The presence of this phase was found to be dependent on the degree of dilution of the reaction mixture. After the induction period, a sharp increase in both the degree of crystallization and the pH of the reaction mixture was detected. This indicates that the pH change in the reaction mixture is closely related to the crystallization process. From these observations, a crystallization mechanism is proposed on the basis of the appearance of stable silicate species and the role of OH- ions during the induction period. According to this mechanism, MFI-type zeolite grows by condensation reaction among the stable silicate species formed during the induction period.

Keywords:ZSM-5;Silicalite;Crystallization;Low Temperature;Atmospheric Pressure

[References]

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Burggraaf AJ, Vroon ZAEP, Keizer K, Verweij H, J. Membr. Sci., 144(1-2), 77 (1998)
Burkett SL, Davis ME, J. Phys. Chem., 98(17), 4647 (1994)
Casci JL, Lowe BM, Zeolites, 3, 186 (1983)
Chung K, Kim K, Seo G, Korean J. Chem. Eng., 9(3), 144 (1992)
Connor CTO, Van Steen E, Dry ME, Stud. Surf. Sci. Catal., 102, 323 (1996)
Corkery RW, Ninham BM, Zeolites, 18, 379 (1997)
Coudurier G, Naccache C, Verdrine JC, J. Chem. Soc. Chem. Comm., 1413 (1982)
Cundy CS, Lowe BM, Sinclair DM, J. Cryst. Growth, 100, 189 (1990)
Cundy CS, Hentry MS, Plaisted RJ, Zeolites, 15, 379 (1995)
Derouane EG, Detremmerie S, Gabelica Z, Blom N, Appl. Catal., 1, 201 (1981)
Fajula F, Plee D, Stud. Surf. Sci. Catal., 85, 587 (1994)
Feijen EJP, Martens JA, Jacobs PA, Stud. Surf. Sci. Catal., 84, 3 (1994)
Fukui K, Nishida S, Sens. Actuators B-Chem., 45, 101 (1997)
Iler RK, "The Chemistry of Silica: Solubility, Polymerization, Colloid and Surface Properties, and Biochemistry," John Wiley & Sons, New York (1972)
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Jansen JC, Stud. Surf. Sci. Catal., 58, 77 (1991)
Kim GJ, Ahn WS, Cho BR, Kwon LM, HWAHAK KONGHAK, 27(2), 198 (1989)
Kim WJ, Lee MC, Kim JW, Ha JM, J. Korean Ind. Eng. Chem., 8(2), 320 (1997)
Kim WJ, Lee MC, J. Korean Ind. Eng. Chem., 9(1), 38 (1998)
Kim WJ, Lee MC, David HT, Microporous Mesoporous Mater., 26, 133 (1998)
Kiyozumi Y, Shin S, Shul YG, Ihm SK, Koo KK, Korean J. Chem. Eng., 13(2), 144 (1996)
Oh HS, Kim MH, Rhee HK, Stud. Surf. Sci. Catal., 105, 2217 (1997)
Park JW, Hahm HS, Kim JW, Ha JM, Jeong TS, Park HY, HWAHAK KONGHAK, 36(3), 369 (1998)
Perez-Pariente J, Martens JA, Jacobs PA, Appl. Catal., 31, 35 (1987)
Scholle KFMGJ, Veeman WS, Frenken P, Van der Velden GPM, Appl. Catal., 17, 233 (1985)
Sie ST, Stud. Surf. Sci. Catal., 85, 587 (1994)
Szostak R, "Molecular Sieves: Principles of Synthesis and Identification," Van Nostrand Rhinhold, New York (1989)
Testa F, Szostak R, Chiappetta R, Aiello R, Fonseca A, Nagy JB, Zeolites, 18, 106 (1997)
van de Graaf JM, Kapteijn F, Moulijn JA, J. Membr. Sci., 144(1-2), 87 (1998)
van Hoff JHC, Roelofsen JW, Stud. Surf. Sci. Catal., 58, 241 (1991)
Yi KH, Ihm SK, Microporous Mesoporous Mater., 1, 115 (1993)
Woo MU, Kim MH, Rhee HK, Lee WY, HWAHAK KONGHAK, 25(4), 427 (1987)

[Referenced By]

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[1] Beelen TPM, Dokter WH, van Garderen HF, van Santan RA, Mario LO, Kessler H, "Synthsis of Porous Materials:Zeolites, Clays, and Nanostructures," Marcel Dekker, Inc., New York (1997)

[2] Burggraaf AJ, Vroon ZAEP, Keizer K, Verweij H, J. Membr. Sci., 144(1-2), 77 (1998)

[3] Burkett SL, Davis ME, J. Phys. Chem., 98(17), 4647 (1994)

[4] Casci JL, Lowe BM, Zeolites, 3, 186 (1983)

[5] Chung K, Kim K, Seo G, Korean J. Chem. Eng., 9(3), 144 (1992)

[6] Connor CTO, Van Steen E, Dry ME, Stud. Surf. Sci. Catal., 102, 323 (1996)

[7] Corkery RW, Ninham BM, Zeolites, 18, 379 (1997)

[8] Coudurier G, Naccache C, Verdrine JC, J. Chem. Soc. Chem. Comm., 1413 (1982)

[9] Cundy CS, Lowe BM, Sinclair DM, J. Cryst. Growth, 100, 189 (1990)

[10] Cundy CS, Hentry MS, Plaisted RJ, Zeolites, 15, 379 (1995)

[11] Derouane EG, Detremmerie S, Gabelica Z, Blom N, Appl. Catal., 1, 201 (1981)

[12] Fajula F, Plee D, Stud. Surf. Sci. Catal., 85, 587 (1994)

[13] Feijen EJP, Martens JA, Jacobs PA, Stud. Surf. Sci. Catal., 84, 3 (1994)

[14] Fukui K, Nishida S, Sens. Actuators B-Chem., 45, 101 (1997)

[15] Iler RK, "The Chemistry of Silica: Solubility, Polymerization, Colloid and Surface Properties, and Biochemistry," John Wiley & Sons, New York (1972)

[16] Jacobs PA, Derouane EG, Weitkamp J, J. Chem. Soc. Chem. Commun., 591 (1981)

[17] Jansen JC, Engelen CWR, van Bekkum H, "Crystal Growth Regulation and Morphology of Zeolite Single Crystals of the MFI Type," in M.L. Occelli and H.E. Robson (Eds.), "Zeolites Synthsis," ACS Symp. Ser., Am. Chem. Soc. Washington DC, 398, 257 (1989)

[18] Jansen JC, Stud. Surf. Sci. Catal., 58, 77 (1991)

[19] Kim GJ, Ahn WS, Cho BR, Kwon LM, HWAHAK KONGHAK, 27(2), 198 (1989)

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[21] Kim WJ, Lee MC, J. Korean Ind. Eng. Chem., 9(1), 38 (1998)

[22] Kim WJ, Lee MC, David HT, Microporous Mesoporous Mater., 26, 133 (1998)

[23] Kiyozumi Y, Shin S, Shul YG, Ihm SK, Koo KK, Korean J. Chem. Eng., 13(2), 144 (1996)

[24] Oh HS, Kim MH, Rhee HK, Stud. Surf. Sci. Catal., 105, 2217 (1997)

[25] Park JW, Hahm HS, Kim JW, Ha JM, Jeong TS, Park HY, HWAHAK KONGHAK, 36(3), 369 (1998)

[26] Perez-Pariente J, Martens JA, Jacobs PA, Appl. Catal., 31, 35 (1987)

[27] Scholle KFMGJ, Veeman WS, Frenken P, Van der Velden GPM, Appl. Catal., 17, 233 (1985)

[28] Sie ST, Stud. Surf. Sci. Catal., 85, 587 (1994)

[29] Szostak R, "Molecular Sieves: Principles of Synthesis and Identification," Van Nostrand Rhinhold, New York (1989)

[30] Testa F, Szostak R, Chiappetta R, Aiello R, Fonseca A, Nagy JB, Zeolites, 18, 106 (1997)

[31] van de Graaf JM, Kapteijn F, Moulijn JA, J. Membr. Sci., 144(1-2), 87 (1998)

[32] van Hoff JHC, Roelofsen JW, Stud. Surf. Sci. Catal., 58, 241 (1991)

[33] Yi KH, Ihm SK, Microporous Mesoporous Mater., 1, 115 (1993)

[34] Woo MU, Kim MH, Rhee HK, Lee WY, HWAHAK KONGHAK, 25(4), 427 (1987)