Co-Mn-Br계 균일촉매를 이용한 2,6-Dimethylnaphthalene의 산화반응

김동범; 박승두; 차운오; 노항덕; 곽규대

Journal of the Korean Industrial and Engineering Chemistry, Vol.10, No.6, 863-870, October, 1999

Export Citation

Co-Mn-Br계 균일촉매를 이용한 2,6-Dimethylnaphthalene의 산화반응

Oxidation of 2,6-Dimethylnaphthalene by Co-Mn-Br Based Homogeneous Catalyst

김동범, 박승두, 차운오, 노항덕, 곽규대

초록

본 연구에서는 촉매로 Co-Mn-Br계를 사용하고, 상대적으로 온화한 반응조건에서 2,6-Dimethylnaphthalene(DMN)의 산화 반응 특성과 촉매가 반응에 미치는 영향을 고찰하였다. 이를 위해 2ℓ의 회분식 반응기를 이용하여 촉매의 농도를 조절하며 실험하였다. 먼저 반응시간에 따른 반응중간생성물의 농도변화를 분석하여 반응경로를 확인하였고, 그 결과 2-formyl-6-naphthoic acid, 2-methyl-6-naphthoic acid, 그리고 2-hydroxymethyl-6-methylnaphthalene이 반응중간물임을 확인할 수 있었다. 또한, 2,6-naphthalene dicarboxylic acid(NDA)의 수율은 Co와 Br의 농도에 많은 영향을 받는다는 것을 알 수 있었고, 제품의 품질 척도 중 하나님 color-b는 Mn의농도와 밀접한 관련이 있는 것으로 나타났으며, 용매연소는 Mn과 Br의 농도조절로 줄일 수가 있었다. 조촉매로 Ce/Cu 화합물을 첨가함으로 NDA의 수율을 증가시키고 용매연소를 줄이는 결과를 얻을 수 있었다.

The catalytic performance of Co-Mn-Br system was performed in the 2,6-dimethylnaphthalene(DMN) oxidation at relatively mild reaction conditions such as 160 ℃ and 6 kg/cm². Experiments were conducted using a 2L batch reactor with varying the concentrations of catalysts. The reaction route of DMN oxidation was considered by measuring the concentration of intermediate species. As the intermediate species, 2-formyl-6-naphthoic acid, 2-methyl-6-naphthoic acid and 2-hydroxymethyl-6-methylnaphthalene are found. It was found that the yield of 2,6-naphthalene dicarboxylic acid(NDA) is largely dependent on the Co and Br concentrations. In addition, it was observed that color-b was closely related with Mn concentration in this experimental range. The burning loss of solvent could be reduced by controlling the concentration of Mn and Br. Addition of small amount of Ce and Cu compounds led to increase the NDA yields and decrease the burning amount of solvent.

Keywords:2;6-dimethyl naphthalene(DMN);2;6-naphthalene dicarboxylic acid(NDA);Co-Mn-Br homogeneous catalyst;oxidation

[References]

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CHEM SYSTEMS, 2,6-Naphthalene Dicarboxylic Acid Precursors, 91S12 (1993)
Harper JJ, Kuhlmann GE, U.S. Patent, 5,183,933 (1991)
Saitou N, Hirota K, Hasebe R, Okuda N, Katsumi I, U.S. Patent, 5,144,066 (1991)
Broeker JL, Partenheimer W, U.S. Patent, 5,453,538 (1994)
Iwane H, Sugawara T, Kujira K, Szuki N, Sakata T, European Patent, 0600375 (1994)
Young DA, European Patent, 0361840 (1990)
Machide H, European Patent, 0721931 (1996)
靑柳三仁, 長谷川英雄, 生天目昭夫, 日本特許, 特開平 5-339203 (1993)
靑柳三仁, 長谷川英雄, 生天目昭夫, 日本特許, 特開平 6-65143 (1994)
Saitou N, Hirota K, Hasebe R, Okuda N, Katsumi I, U.S. Patent, 5,523,473 (1995)
Iwane H, Sugawara T, U.S. Patent, 5,175,352 (1992)
Matsude T, Sasakawa A, Hayashi S, Konai Y, European Patent, 0287279 (1988)
Hirose I, Amemiya T, Sakai T, European Patent, 0142719 (1985)
Iwane H, Sugawara T, European Patent, 0496264 (1992)
Hirose I, European Patent, 0204119 (1986)
Hayashi S, Matsuda T, Sasakawa A, Konai Y, GB Patent, 2,187,744 (1987)
矯本圭司, 矢田瀋, 日本特許, 特開平 6-211732 (1994)
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Streitwieser A, Heathcock CH, Introduction to Organic Chemistry, 3rd ed., 587, Macmillan, New York (1985)
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Yamgar RS, Pol UN, Dodwad SS, Asian J. Chem., 9, 195 (1997)
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[2] CHEM SYSTEMS, 2,6-Naphthalene Dicarboxylic Acid Precursors, 91S12 (1993)

[3] Harper JJ, Kuhlmann GE, U.S. Patent, 5,183,933 (1991)

[4] Saitou N, Hirota K, Hasebe R, Okuda N, Katsumi I, U.S. Patent, 5,144,066 (1991)

[5] Broeker JL, Partenheimer W, U.S. Patent, 5,453,538 (1994)

[6] Iwane H, Sugawara T, Kujira K, Szuki N, Sakata T, European Patent, 0600375 (1994)

[7] Young DA, European Patent, 0361840 (1990)

[8] Machide H, European Patent, 0721931 (1996)

[9] 靑柳三仁, 長谷川英雄, 生天目昭夫, 日本特許, 特開平 5-339203 (1993)

[10] 靑柳三仁, 長谷川英雄, 生天目昭夫, 日本特許, 特開平 6-65143 (1994)

[11] Saitou N, Hirota K, Hasebe R, Okuda N, Katsumi I, U.S. Patent, 5,523,473 (1995)

[12] Iwane H, Sugawara T, U.S. Patent, 5,175,352 (1992)

[13] Matsude T, Sasakawa A, Hayashi S, Konai Y, European Patent, 0287279 (1988)

[14] Hirose I, Amemiya T, Sakai T, European Patent, 0142719 (1985)

[15] Iwane H, Sugawara T, European Patent, 0496264 (1992)

[16] Hirose I, European Patent, 0204119 (1986)

[17] Hayashi S, Matsuda T, Sasakawa A, Konai Y, GB Patent, 2,187,744 (1987)

[18] 矯本圭司, 矢田瀋, 日本特許, 特開平 6-211732 (1994)

[19] 矯本圭司, 矢田瀋, 日本特許, 特開平 6-211733 (1994)

[20] Tanaka T, Inari M, European Patent, 0439007 (1991)

[21] Tanaka T, Inari M, European Patent, 0324342 (1989)

[22] Kamiya Y, Hama T, Kijima I, Bull. Chem. Soc. Jpn., 68, 204 (1995)

[23] 박상언, 조영도, 촉매, 33, 5 (1993)

[24] Amoco Chem. Corp. R&D Department, "Summary of Technical Information for the Manufacture of Terephhthalic Acid," Compiled by K.J. Abrams (1975)

[25] 김동범, 차운오, 곽규대, 한국공업화학회지, 7, 1204 (1996)

[26] Streitwieser A, Heathcock CH, Introduction to Organic Chemistry, 3rd ed., 587, Macmillan, New York (1985)

[27] Eastman Chemicals Division, Engineering Research Division, Process Chemistry Research Lab., Report No. 86-2242-650, Nov. 4 (1986)

[28] CEC/SKI Technical Meeting Report (1994)

[29] Anderson JM, Kochi JK, J. Am. Chem. Soc., 92, 2450 (1970)

[30] Matus I, Putyrskaya GV, "On the Decarboxylation of Acetic Acid during the Catalytic Oxidation of P-Xylene," Oxidation Communicationx 5, Nos 3-4, 349 (1983)

[31] Yamgar RS, Pol UN, Dodwad SS, Asian J. Chem., 9, 195 (1997)

[32] Ignaczak M, Dziegiec J, Kinet. Catal., 30, 898 (1990)

[33] Mohanty RK, Das M, Das AK, Indian J. Chem. A, 37, 34 (1998)