α-Ferric oxyhydroxide 입자의 핵성장 반응에 관한 연구

신동옥; 설수덕

Journal of the Korean Industrial and Engineering Chemistry, Vol.8, No.4, 602-609, August, 1997

Export Citation

α-Ferric oxyhydroxide 입자의 핵성장 반응에 관한 연구

Kinetics of Seed Growth of α-Ferric Oxyhydroxide

신동옥, 설수덕

초록

공기를 산화제로 하여 황산제일철 용액에 침전제로소 KOH, NaOH, Na₂CO₃ 및 K₂CO₃를 사용하여 산화침전반응을 행하여 생성되는 α-ferric oxyhydroxide입자의 생성 및 성장과정을 자유 pH 변화시험을 통해서 관찰하였다. α-ferric oxyhydroxide입자의 생성 및 성장과정은 모든 침전제에서 동일한 형태를 나타내었으며 KOH, NaOH에 의해 생성된 α-ferric oxyhydroxide 결정입자의 길이는 Na₂CO₃ 및 K₂CO₃에 의해 생성된 것보다 약 1.5배 정도 짧았다. KOH를 침전제로 황산제일철을 공기 산화한 결과 초기침전제의 몰비 (R_o=[Fe²⁺]_o/[OH^-]_o) 값이 작아질수록 결정 입자의 길이가 종축 방향으로 길게 성장하였으며 생성물은 1㎛ 이하의 균일한 침상형의 α-ferric oxyhydroxide였다. 또한 황산제일철에 KOH를 침전제로 공기를 산화제로 하여 고정 pH 실험법에 의하여, 공기 유속, 초기 침전제의 몰비 (R_o=[Fe²⁺]_o/[OH^-]_o) 및 반응 온도의 변화에 따른 α-ferric oxyhydroxide의 핵성장 반응속도에 관하여 알아보았다. 공기 유속, 반응 온도 및 R_o 값이 증가할수록 α-ferric oxyhydroxide 입자의 핵성장 반응속도는 점차적으로 증가하였으며, 핵성장의 활성화 에너지는 16.16 KJ/mol 이며, 공기 유속, R_o값 및 반응온도의 영향에 대한 핵성장 반응속도 관계식은 다음과 같다.
-d[Fe²⁺]/dt = 1.46×10⁴[Po₂]^0.66[OH^-]^2.19exp(-16.16/RT)

The seed formation and growth of α-ferric oxyhydroxide with aerial oxidative precipitation from aqueous solution of ferrous sulfate with KOH, NaOH, Na₂CO₃ and K₂CO₃ as precipitants have been studied by free pH drift experiment. It has been shown that all precipitants give same particle formation and growth path, and average particle length from KOH and NaOH as precipitants was about 1.5 times shorter than that of K₂CO₃ and Na₂CO₃. When initial mole ratio, (R_o=[Fe²⁺]_o/[OH^-]_o) of KOH was decreased the particle was grown oxyhydroxide seed growth from aqueous solution of ferrous sulfate with KOH has been studied. The influence of the air flow rate, reaction temperature and initial mole ratio, (R_o=[Fe²⁺]_o/[OH^-]_o), on the kinetics of seed growth are investigated by static pH experiment. The oxidation rate of seed growth increased with increase in the air low rate, reaction temperature and initial mole patio. The activation energy of seed growth is 16.16 KJ/mol and the rate equation of seed growth can be written as follows:

[References]

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[1] 설수덕, 성주경, 황용길, 대한화학회지, 21, 121 (1977)

[2] Guilin Y, Hongying O, Ruipeng L, CN 1033786 (1989)

[3] New Japan Steel and Chemical Co. Ltd., Japan Patent, 60090832 (1985)

[4] Masakatsu S, Shunichi E, Japan Patent, 60204629 (1985)

[5] Laijiu S, Yanchun C, Renmin G, Huaxue Shijie, 30, 178 (1989)

[6] Meiyun X, Keli Z, Youzu Y, Dong L, Huaxue Shijie, 33, 183 (1992)

[7] Yuefei Z, Xiandai Huagong, 9(34-36), 52 (1989)

[8] Czeslawa B, Przem. Chem., 62, 621 (1983)

[9] Helio N, Luis E, European Patent, 272548 (1988)

[10] Hidenobu K, Japan Patent, 63112427 (1988)

[11] 방계룡, 대한민국 특허 공개번호 89-008034 (1989)

[12] 김영삼, 대한민국 특허 공고번호 90-002547 (1990)

[13] 신희덕, 조동성, 오재현, 대한광산학회지, 25, 340 (1988)

[14] Patton TC, "Pigment Handbook," 341-345, Wiley-Interscience Publication (1976)

[15] Solomon DH, Hawthorne DG, "Chemistry of Pigments and Fillers," 100-107, A Wiley-Interscience Publication (1983)

[16] Bate G, "Ferromagnetic Materials," Vol. 2, 381-507, North-Holland Publishing Company (1980)

[17] Mackenzie RC, Miner. Mag., 32, 163 (1959)

[18] Feitknecht W, Michaelis W, Helv. Chim. Acta, 45, 212 (1962)

[19] Van Oosterhout GW, Acta Crystallogr., 13, 932 (1960)

[20] Atkinson RJ, Posner AM, Quirt JP, J. Inorg. Nucl. Chem., 30, 2371 (1968)

[21] Penniuman and Zoph, U.S. Patent, 1,327,061 (1920)

[22] Matijevic E, Accounts Chem. Res., 22, 14 (1981)

[23] Schwertmann U, "Iron Oxides in the Laboratory," Weinheim, VCH (1991)

[24] Kiyama M, Bull. Inst. Chem. Res., Kyoto Univ., 64, 4 (1986)

[25] Misawa T, Zairyo, 19, 537 (1970)

[26] Belsa MA, Mater. Sci. Forum, Trans. Tech Aadermannsdorf Switz., 28, 31 ~ 97 (1988)

[27] Kiyama M, Bull. Chem. Soc. Jpn., 46, 323 (1973)

[28] Hashimoto K, Sato T, Toda Y, Yogyo Kyokaishi, 86, 381 (1978)

[29] Park YD, Lee HH, Kim TO, J. Korean Ceram. Soc., 32, 1501 (1994)

[30] Sugimoto T, Matijevic E, J. Colloid Interface Sci., 74, 227 (1980)

[31] Kiyama M, Bull. Chem. Soc. Jpn., 47, 1646 (1974)

[32] Pelino M, Toro L, Petroni M, J. Mater. Sci., 24, 409 (1989)

[33] Yamaguchi T, Kimura T, J. Am. Ceram. Soc., 59, 333 (1976)

[34] Goss CJ, Miner. Mag., 51, 437 (1987)

[35] Kwon GW, Yoon BJ, HWAHAK KONGHAK, 34(3), 288 (1996)

[36] Lee JS, Rho S, Kim JD, HWAHAK KONGHAK, 27(5), 613 (1989)

[37] Domingo C, Rodriguez-Clemente R, Mater. Res. Bull., 26, 47 (1991)

[38] Domingo C, Solid State Ion., 59, 187 (1993)

[39] Clemente R, Colloids Surf. A: Physicochem. Eng. Asp., 79, 177 (1993)

[40] Fumin R,, Beijing Huagong Xueyuan Xuebao, Ziran Kexueban, 19, 50 ~ 56 (1992)

[41] Kotowski Therm. Treat. Radioact. Hazard. Chem., Mixed Med. Wastes, Proc. Incineration Conf., 11th, 81 ~ 85 (1992)

[42] Wenzhong L, Huagong Yejin, 11, 27 (1990)

[43] Misawa T, Hashimoto K, Corros. Sci., 14, 131 (1974)

[44] Park KY, Oh EK, Kim SG, Jang HD, HWAHAK KONGHAK, 34(4), 534 (1996)

[45] Park KY, HWAHAK KONGHAK, 34(2), 253 (1996)