Co-oxidation effects of methanol and benzene on the decomposition of 4-chlorobiphenyl in supercritical water

G. Anitescu, V. Munteanu, L. L. Tavlarides

Research output: Contribution to journalArticlepeer-review

34 Scopus citations


The decomposition reactions of 4-chlorobiphenyl (4CB) are investigated at 25 MPa and 773 K in supercritical water (SCW) in the presence of methanol and then benzene both without and with oxygen (from H 2O 2/H 2O solutions) to understand the co-oxidation effects on PCB conversion and reaction products. The reactions of 4CB, delivered to a tubular reactor as solutions in methanol and benzene (3 g/L), are conducted isothermally under plug-flow regime, and GC-FID/TCD/MSD chromatographic methods are employed for product analysis. At similar oxygen/organic equivalence ratios (Φ I = 1.2 and Φ II = 1.3), global conversions of this simple PCB congener vary from 79 to 97% when delivered in methanol (I) and from 61 to 88% when benzene (II) has been used as co-solvent (2-24.5 s reaction time). Under the same initial oxygen concentration (0.144 mol/L; Φ I = 1.2 and Φ II = 0.5), molar conversions of 4CB in the latter system are even lower (48-72%). These results show the important role of methanol as reaction rate enhancer compared to benzene. Moreover, the identified reaction products of 4CB/MeOH and 4CB/C 6H 6 differ significantly in these systems, showing different reaction pathways. A dramatic increase in the number of reaction products has been observed in the presence of benzene compared to 4CB/MeOH reactions. Further, the more toxic dibenzofuran has been produced in the largest amount in the 4CB/C 6H 6 system and significant oligomerization of benzene/biphenyl also occurs. Even the most toxic dibenzo-p-dioxin was detected in amounts at the level of unreacted 4CB. These results clearly show the significance of the co-oxidation effects on PCB reaction rates, pathways, and products in SCW.

Original languageEnglish (US)
Pages (from-to)139-147
Number of pages9
JournalJournal of Supercritical Fluids
Issue number2
StatePublished - Feb 2005


  • GC-FID/TCD/MSD and IC analysis
  • Methanol and benzene as co-solvents and co-oxidants
  • PCBs
  • Supercritical water oxidation
  • Tubular flow reactor

ASJC Scopus subject areas

  • General Chemical Engineering
  • Condensed Matter Physics
  • Physical and Theoretical Chemistry


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