High-temperature liquid water: A viable medium for terephthalic acid synthesis

Jennifer B. Dunn, Phillip E. Savage

Research output: Contribution to journalArticle

31 Citations (Scopus)

Abstract

We report new information concerning the effect of oxygen concentration and catalyst concentration and identity [MnBr2, CoBr2, ZrBr4, and Mn(OAc)2] on the partial oxidation of p-xylene in dense water from 250 to 380 °C. Water is a more environmentally benign replacement for the acetic acid solvent used commercially. We used a 440 mL Hastelloy batch reactor for all experiments and monitored O2 consumption and product (including COx) formation. Increasing the catalyst concentration at 300 °C significantly increased terephthalic acid yields. MnBr2 was the most active catalyst of those we assessed. Increasing the initial O2 concentration beyond a modest excess did not significantly alter the terephthalic acid yield, but it increased the CO2 yield. Injecting supplemental O2 midreaction, however, did cause the terephthalic acid yield to increase. The highest terephthalic acid yields (>80%) occurred at 300 °C, [p-xylene]0 = 0.02 M, [O2]0 = 0.10 M, [Br] = 0.014 M, and t = 5-15 min. These yields are the highest reported to date from this reaction in high-temperature liquid water. Moreover, under these conditions and t = 15 min, COx yields were below 2% and reaction intermediates were not detected.

Original languageEnglish (US)
Pages (from-to)5427-5435
Number of pages9
JournalEnvironmental Science and Technology
Volume39
Issue number14
DOIs
StatePublished - Jul 15 2005

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liquid
Acids
Water
acid
Liquids
Xylene
Catalysts
catalyst
xylene
Reaction intermediates
water
Temperature
Batch reactors
Acetic acid
Acetic Acid
dense water
Oxygen
acetic acid
Oxidation
terephthalic acid

All Science Journal Classification (ASJC) codes

  • Chemistry(all)
  • Environmental Chemistry

Cite this

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abstract = "We report new information concerning the effect of oxygen concentration and catalyst concentration and identity [MnBr2, CoBr2, ZrBr4, and Mn(OAc)2] on the partial oxidation of p-xylene in dense water from 250 to 380 °C. Water is a more environmentally benign replacement for the acetic acid solvent used commercially. We used a 440 mL Hastelloy batch reactor for all experiments and monitored O2 consumption and product (including COx) formation. Increasing the catalyst concentration at 300 °C significantly increased terephthalic acid yields. MnBr2 was the most active catalyst of those we assessed. Increasing the initial O2 concentration beyond a modest excess did not significantly alter the terephthalic acid yield, but it increased the CO2 yield. Injecting supplemental O2 midreaction, however, did cause the terephthalic acid yield to increase. The highest terephthalic acid yields (>80{\%}) occurred at 300 °C, [p-xylene]0 = 0.02 M, [O2]0 = 0.10 M, [Br] = 0.014 M, and t = 5-15 min. These yields are the highest reported to date from this reaction in high-temperature liquid water. Moreover, under these conditions and t = 15 min, COx yields were below 2{\%} and reaction intermediates were not detected.",
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High-temperature liquid water : A viable medium for terephthalic acid synthesis. / Dunn, Jennifer B.; Savage, Phillip E.

In: Environmental Science and Technology, Vol. 39, No. 14, 15.07.2005, p. 5427-5435.

Research output: Contribution to journalArticle

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