Variation in ClO<sub>2</sub>/Cl<sub>2</sub> Ratio in the Chloride-Chlorate Process under Different Conditions

Bal Raj Deshwal; Hyung-Keun Lee

Journal of Industrial and Engineering Chemistry, Vol.10, No.4, 667-673, July, 2004

Export Citation

Variation in ClO₂/Cl₂ Ratio in the Chloride-Chlorate Process under Different Conditions

Bal Raj Deshwal, and Hyung-Keun Lee^{1, †}

Department of Chemistry, A.I.J.H.M. College, Rohtak - 124001 (Haryana), India
¹Flue Gas Treatment Center, Korea Institute of Energy Research, Daejeon 305-600, Korea

E-mail:

The chloride-chlorate process is a highly efficient, easy to operate, and cost effective tool for generating ClO₂, wherein the theoretical ClO₂/Cl₂ (η) ratio is 2. The present study attempts to investigate the optimal conditions for the best reaction yield in terms of chlorine dioxide production and minimal contamination of chlorine. The effects of the molar concentration of sulfuric acid, the temperature, and the chlorate/chloride (φ) ratio on the ClO₂/Cl₂ (η) ratio is examined. The experimental η-value ranged from 0.46 to as high as 3.4 under different conditions. A reaction mechanism compatible with the experimental observations is proposed, and the role that side reactions have on influencing the ClO₂/Cl₂ ratio is highlighted. A general equation is derived to express the ClO₂/Cl₂ ratio.

Keywords:ClO₂/Cl₂ ratio;chlorate/chloride ratio;side reaction;mechanism

[References]

Pryke DC, Reeve DW, TAPPI J., 80, 153 (1997)
Woodside V, Macleod KS, Pap. Trade J., 26, 137 (1953)
Jaszka DJ, Tonawanda NY, U.S. Patent, No. 3,950,500 (1976)
Cowley G, U.S. Patent, No. 4,250,159 (1981)
Ni Y, Wang X, J. Pulp Paper Sci., 23, J346 (1997)
Stockburger PJ, J. Pulp Paper Sci., 76, 99 (1993)
Norell M, Svedin BH, U.S. Patent, No. 3,978,517 (1990)
Zell MS, Fredette MCJ, U.S. Patent, No. 5,066,477 (1991)
Hoq MF, Indu B, Ernst ER, Gelbaum LT, Ind. Eng. Chem. Res., 31, 1807 (1992)
Burke M, Tenney J, Indu B, Hoq MF, Carr S, Ernst WR, Ind. Eng. Chem. Res., 32, 1449 (1993)
Engstrom J, Falgen H, U.S. Patent, No. 5,091,167 (1992)
Bigauskas TD, U.S. Patent, No. 5,366,714 (1994)
Rapson WH, Chem. Can., 18, 25 (1966)
Fredette MCJ, Cowley G, U.S. Patent, No. 4,414,193 (1983)
Rapson WH, Fredette MCJ, U.S. Patent, No. 4,534,952 (1985)
Tenney J, Shoaei M, Obijeski T, Ernst WR, Ind. Eng. Chem. Res., 29, 921 (1990)
Ernst WR, Shoaei M, Forney L, AIChE J., 34, 1927 (1998)
Deshwal BR, Lee HK, J. Hazard. Mater., B108, 173 (2004)
Aieta EM, Roberts PV, Hernandez M, J. Am. Water Works Assoc., 76, 64 (1984)
Tang TF, Gordon G, Anal. Chem., 52, 1430 (1980)
Vogel AI, Text Book of Quantitative Chemical Analysis; 5th Ed., p. 390, Longman, Inc., New York (1989)
Lenzi F, Rapson WH, Pulp Paper Mag. Can., 63, T442 (1962)
Hong CC, Rapson WH, Can. J. Chem. Eng., 46, 2053 (1968)
Taube H, Dodgen H, J. Am. Chem. Soc., 71, 3330 (1949)
Emmenegger F, Gordon G, Inorg. Chem., 6, 633 (1967)
Yin GH, Ni YH, Can. J. Chem. Eng., 76(5), 921 (1998)
Deshwal BR, Jo HD, Lee HK, Can. J. Chem. Eng., in press (2004)
Deshwal BR, Lee HK, J. Ind. Eng. Chem., submitted (2004)

[Referenced By]

[Related Articles]

[1] Pryke DC, Reeve DW, TAPPI J., 80, 153 (1997)

[2] Woodside V, Macleod KS, Pap. Trade J., 26, 137 (1953)

[3] Jaszka DJ, Tonawanda NY, U.S. Patent, No. 3,950,500 (1976)

[4] Cowley G, U.S. Patent, No. 4,250,159 (1981)

[5] Ni Y, Wang X, J. Pulp Paper Sci., 23, J346 (1997)

[6] Stockburger PJ, J. Pulp Paper Sci., 76, 99 (1993)

[7] Norell M, Svedin BH, U.S. Patent, No. 3,978,517 (1990)

[8] Zell MS, Fredette MCJ, U.S. Patent, No. 5,066,477 (1991)

[9] Hoq MF, Indu B, Ernst ER, Gelbaum LT, Ind. Eng. Chem. Res., 31, 1807 (1992)

[10] Burke M, Tenney J, Indu B, Hoq MF, Carr S, Ernst WR, Ind. Eng. Chem. Res., 32, 1449 (1993)

[11] Engstrom J, Falgen H, U.S. Patent, No. 5,091,167 (1992)

[12] Bigauskas TD, U.S. Patent, No. 5,366,714 (1994)

[13] Rapson WH, Chem. Can., 18, 25 (1966)

[14] Fredette MCJ, Cowley G, U.S. Patent, No. 4,414,193 (1983)

[15] Rapson WH, Fredette MCJ, U.S. Patent, No. 4,534,952 (1985)

[16] Tenney J, Shoaei M, Obijeski T, Ernst WR, Ind. Eng. Chem. Res., 29, 921 (1990)

[17] Ernst WR, Shoaei M, Forney L, AIChE J., 34, 1927 (1998)

[18] Deshwal BR, Lee HK, J. Hazard. Mater., B108, 173 (2004)

[19] Aieta EM, Roberts PV, Hernandez M, J. Am. Water Works Assoc., 76, 64 (1984)

[20] Tang TF, Gordon G, Anal. Chem., 52, 1430 (1980)

[21] Vogel AI, Text Book of Quantitative Chemical Analysis; 5th Ed., p. 390, Longman, Inc., New York (1989)

[22] Lenzi F, Rapson WH, Pulp Paper Mag. Can., 63, T442 (1962)

[23] Hong CC, Rapson WH, Can. J. Chem. Eng., 46, 2053 (1968)

[24] Taube H, Dodgen H, J. Am. Chem. Soc., 71, 3330 (1949)

[25] Emmenegger F, Gordon G, Inorg. Chem., 6, 633 (1967)

[26] Yin GH, Ni YH, Can. J. Chem. Eng., 76(5), 921 (1998)

[27] Deshwal BR, Jo HD, Lee HK, Can. J. Chem. Eng., in press (2004)

[28] Deshwal BR, Lee HK, J. Ind. Eng. Chem., submitted (2004)