Oxidative dehydrogenation of iso-butane to iso-butene I. Metal phosphate catalysts

Yusaku Takita, Ken Ichi Sano, Kazuo Kurosaki, Noboru Kawataa, Hiroyasu Nishiguchi, Masami Ito, Tatsumi Ishihara

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Abstract

Metal pyrophosphates catalyse the oxidative dehydrogenation of iso-butane to iso-butene at 450-550°C using a feed gas of 75 mol% iso-butane and 5% O2. Ni2P2O7 is the most selective catalyst with the iso-butene selectivity reaching to a maximum value of 82.2% at 550°C. Ag4P2O7 and Zn2P2O7 are also effective, but the iso-butene selectivities were slightly lower than that of Ni2P2O7. Pyrophosphates of Mg, Cr, Co, Mn, and Sn catalyse the oxidative dehydrogenation, but the iso-butene selectivity was 43.8-65.7% at the temperature where the maximum iso-butene yield is observed. The optimum oxygen concentration for iso-butene formation was 5-15 mol%, but the increase in O2 concentration did not increase the iso-butene selectivity. No adsorbed oxygen species was found by means of TPD. The lattice oxygen of the pyrophosphates began to react with H2 at 200-400°C. Reactivity of the lattice oxygen of pyrophosphates can be estimated from the value of ΔH0f for the corresponding oxide. More than 2 desorption peaks were observed in the TPD spectra of NH3 adsorbed on the pyrophosphates, and a linear correlation was found between the concentration of acid amount of the catalysts and the specific rate of iso-butene formation. This strongly suggests that the acidic sites play a key role in the iso-butene formation.

Original languageEnglish
Pages (from-to)49-56
Number of pages8
JournalApplied Catalysis A: General
Volume167
Issue number1
DOIs
Publication statusPublished - Feb 5 1998

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Butane
Dehydrogenation
Butenes
Phosphates
Metals
Catalysts
Diphosphates
Oxygen
Temperature programmed desorption
butane
butylene
Catalyst selectivity
Oxides
Desorption
Gases
Acids

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Process Chemistry and Technology

Cite this

Oxidative dehydrogenation of iso-butane to iso-butene I. Metal phosphate catalysts. / Takita, Yusaku; Sano, Ken Ichi; Kurosaki, Kazuo; Kawataa, Noboru; Nishiguchi, Hiroyasu; Ito, Masami; Ishihara, Tatsumi.

In: Applied Catalysis A: General, Vol. 167, No. 1, 05.02.1998, p. 49-56.

Research output: Contribution to journalArticle

Takita, Yusaku ; Sano, Ken Ichi ; Kurosaki, Kazuo ; Kawataa, Noboru ; Nishiguchi, Hiroyasu ; Ito, Masami ; Ishihara, Tatsumi. / Oxidative dehydrogenation of iso-butane to iso-butene I. Metal phosphate catalysts. In: Applied Catalysis A: General. 1998 ; Vol. 167, No. 1. pp. 49-56.
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abstract = "Metal pyrophosphates catalyse the oxidative dehydrogenation of iso-butane to iso-butene at 450-550°C using a feed gas of 75 mol{\%} iso-butane and 5{\%} O2. Ni2P2O7 is the most selective catalyst with the iso-butene selectivity reaching to a maximum value of 82.2{\%} at 550°C. Ag4P2O7 and Zn2P2O7 are also effective, but the iso-butene selectivities were slightly lower than that of Ni2P2O7. Pyrophosphates of Mg, Cr, Co, Mn, and Sn catalyse the oxidative dehydrogenation, but the iso-butene selectivity was 43.8-65.7{\%} at the temperature where the maximum iso-butene yield is observed. The optimum oxygen concentration for iso-butene formation was 5-15 mol{\%}, but the increase in O2 concentration did not increase the iso-butene selectivity. No adsorbed oxygen species was found by means of TPD. The lattice oxygen of the pyrophosphates began to react with H2 at 200-400°C. Reactivity of the lattice oxygen of pyrophosphates can be estimated from the value of ΔH0f for the corresponding oxide. More than 2 desorption peaks were observed in the TPD spectra of NH3 adsorbed on the pyrophosphates, and a linear correlation was found between the concentration of acid amount of the catalysts and the specific rate of iso-butene formation. This strongly suggests that the acidic sites play a key role in the iso-butene formation.",
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