Pd/C촉매하 파라니트로아닐린 수고첨가에 의한 고순도 파라페닐렌디아민의 합성공정

조철군; 정광보

Journal of the Korean Industrial and Engineering Chemistry, Vol.10, No.8, 1210-1215, December, 1999

Export Citation

Pd/C촉매하 파라니트로아닐린 수고첨가에 의한 고순도 파라페닐렌디아민의 합성공정

Synthesis of High Purity p-Phenylenediamine from p-Nitroaniline by Catalytic Hydrogenation

조철군, 정광보

초록

Pd/C촉매가 부유되어 있는 3상 슬러리 반응기에서 원료 p-nitroaniline(PNA)를 수소 첨가시켜 고순도의 p-phenylenediamine(PPD)를 합성하는 최적 반응조건을 구하였다. 수소첨가 반응시 활성점에서 수소부족을 줄이고 불순물의 생성을 감소시킬 수 있도록, 기체-액체, 액체-촉매사이의 물질전달 저항을 최소화하고 표면반응속도가 율속할 수 있게 반응조건을 설정하였다. 이 반응조건은 온도 60℃, 압력 60∼70 psig, 촉매농도 12 g-cat/L일 때가 최적이었으며, 반응속도는 PNA 농도에 0차, 수소 반응압력에 1차를 각각 보여주었으며, 총괄반응속도식은 R_A=6.44×10⁶·H·P·m·exp(-4659/T)로 나타났다.

Optimum conditions of the hydrogenation of PNA to pure PPD were determined in a three-phase slurry reactor with suspended Pd/C catalyst particles. Minimization of mass transfer resistances at the interfaces of both gas-liquid and liquid-catalyst particles and control of overall reaction rate on catalyst surface leaded to decrease the hydrogen starvation on reaction active sites and to reduce the side reactions during hydrogenation. The optimum temperature, pressure, and catalysst concentration were confirmed to be in the range of 60℃, 60∼70 psig, and 1∼2 g-cat/L, respectively. Reaction rate was zero order with respect to the concentration of PNA and 1st order with respect to the pressure of hydrogen(P). Overall rate expression of the reaction was R_A=6.44×10⁶·H·P·m·exp(-4659/T) where H is constant, m is concentration of catalyst, and T is temperature.

Keywords:hydrogenation;PNA;PPD;slurry-reactor;Pd/C catalyst

[References]

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[1] Othmer K, "Encyclopedia of Chemical Technology," 2, John Wiley & Sons (1996)

[2] 조철군, 김종수, 한기도, "고순도 PPD 연구보고서," 한화그룹종합연구소 (1992)

[3] 일본화약(주) 정밀화학 연구부, "반응속도 및 제품품질의 검토," 수첨실험 12보 (1972)

[4] Yao HC, Emmett PH, J. Am. Chem. Soc., 81, 4125 (1959)

[5] Greenfield H, Uniroyal Incorporation, Section of Catalysis, 1038 (1969)

[6] Acres GJK, Cooper BJ, J. Appl. Chem. Biotech., 22, 769 (1972)

[7] Yum SB, Rhee HK, HWAHAK KONGHAK, 30(1), 125 (1992)

[8] Bird AJ, Thompson DT, Catal. Org. Synth., 61 (1980)

[9] Fogler HS, "Elements of Chemical Reaction Engineering," Prentice Hall (1986)

[10] Sherwood TK, Farkas EJ, Chem. Eng. Sci., 21, 573 (1966)

[11] Rajadhyksa RA, Karwa SL, Chem. Eng. Sci., 41, 7 (1986)

[12] Johnson Metthey Catalog, Hydrogenous Catalyst Technical Information (1991)