Kinetic analysis of catalytic hydrodechlorination process of polychlorinated biphenyls (PCBs)

被引:66
作者
Murena, F [1 ]
Schioppa, E [1 ]
机构
[1] Univ Naples Federico II, Dipartimento Ingn Chim, I-80125 Naples, Italy
关键词
catalytic hydrodechlorination; polychlorinated biphenyls; kinetic; Ni-Mo catalyst;
D O I
10.1016/S0926-3373(00)00157-0
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Catalytic hydrodechlorination (HDCl) of 2,3,4',6-tetrachlorobiphenyl and 2,3,3,5-tetrachlorobiphenyl has been studied in the presence of a sulphided Ni-Mo/gamma-Al2O3 catalyst. The reaction runs were carried out at constant temperature and pressure in a stirred batch reactor using hexadecane as the reaction medium. Temperature levels of T=250 degrees C and T=300 degrees C at a hydrogen pressure of P-H2 = 20 bar were tested. The results demonstrate that the HDCl process proceeds via an irreversible stepwise pattern. The kinetic constants of all observed intermediate HDCl steps were evaluated. The selectivity of HDCl reactions has been interpreted on the basis of electrophilic aromatic substitution mechanism. It shows that the HDCl rate is slower when carbon atoms adjacent to a substituted chlorine atom are bonded to other chlorine atoms. This depends on the inductive effect of chlorine atoms. It also shows that ortho-substitution is slower than meta- and para-substitution. In this case, both steric and electronic effects are probably relevant. (C) 2000 Published by Elsevier Science B.V.
引用
收藏
页码:257 / 267
页数:11
相关论文
共 21 条
[1]   FULL-SCALE HYDROTREATMENT OF POLYCHLORINATED-BIPHENYLS IN THE PRESENCE OF USED LUBRICATING OILS [J].
BRINKMAN, DW ;
DICKSON, JR ;
WILKINSON, D .
ENVIRONMENTAL SCIENCE & TECHNOLOGY, 1995, 29 (01) :87-91
[2]   CATALYTIC HYDROPROCESSING OF CHLOROPHENOLS [J].
CHON, S ;
ALLEN, DT .
AICHE JOURNAL, 1991, 37 (11) :1730-1732
[3]   CONVERSION OF CHLOROBENZENE OVER PALLADIUM AND RHODIUM CATALYSTS OF WIDELY VARYING DISPERSION [J].
COQ, B ;
FERRAT, G ;
FIGUERAS, F .
JOURNAL OF CATALYSIS, 1986, 101 (02) :434-445
[4]   Comparative study of activity and selectivity of transition metal sulfides in parallel hydrodechlorination of dichlorobenzene and hydrodesulfurization of methylthiophene [J].
Frimmel, J ;
Zdrazil, M .
JOURNAL OF CATALYSIS, 1997, 167 (01) :286-295
[5]   DETOXIFICATION OF ORGANIC WASTE LIQUIDS BY CATALYTIC-HYDROGENATION [J].
GIOIA, F .
JOURNAL OF HAZARDOUS MATERIALS, 1991, 26 (03) :243-260
[6]  
GIOIA F, 1994, J HAZARD MATER, V38, P277
[7]   CATALYTIC HYDROPROCESSING OF CHLORINATED BENZENES [J].
HAGH, BF ;
ALLEN, DT .
CHEMICAL ENGINEERING SCIENCE, 1990, 45 (08) :2695-2701
[8]   CATALYTIC HYDROPROCESSING OF CHLOROBENZENE AND 1,2-DICHLOROBENZENE [J].
HAGH, BF ;
ALLEN, DT .
AICHE JOURNAL, 1990, 36 (05) :773-778
[9]   DETERMINATION OF RATE CONSTANTS FOR COMPLEX KINETICS MODELS [J].
HIMMELBLAU, DM ;
JONES, CR ;
BISCHOFF, KB .
INDUSTRIAL & ENGINEERING CHEMISTRY FUNDAMENTALS, 1967, 6 (04) :539-+
[10]   HYDROGENATION AND RECYCLE OF ORGANIC WASTE STREAMS [J].
KALNES, TN ;
JAMES, RB .
ENVIRONMENTAL PROGRESS, 1988, 7 (03) :185-191