Kinetics of citraconic anhydride formation via condensation of formaldehyde and succinates

Dushyant Shekhawat, Kirthivasan Nagarajan, James E. Jackson, Dennis J. Miller

Research output: Contribution to journalArticle

  • 2 Citations

Abstract

Formation of citraconic anhydride via condensation of succinic acid and its derivatives with formaldehyde is carried out over γ-alumina catalyst in a continuous fixed-bed reactor. Dimethyl succinate and Formalin (37 wt % formaldehyde, 10 wt % methanol in water) are the preferred feed materials for the reaction; catalyst activity is sustained with Formalin relative to that with other formaldehyde sources such as trioxane or Formcel, because the water in Formalin inhibits coke formation. With this feed combination, a total citraconate yield of 31% of theoretical with 72% selectivity is achieved at a weight hour space velocity of 0.9 kg of succinate/kg of catalyst/h, a succinate to formaldehyde molar feed ratio of 1:2, and a temperature of 380 °C. The reaction is free from mass transfer limitations at these conditions. A kinetic model is presented that describes product distributions and reactant conversion as a function of space velocity and temperature. The reaction system is part of an overall process to produce itaconic acid from renewable resource-based succinic acid.

LanguageEnglish (US)
Pages611-617
Number of pages7
JournalOrganic Process Research and Development
Volume6
Issue number5
DOIs
StatePublished - Sep 2002

Profile

Succinates
anhydrides
formaldehyde
Formaldehyde
Condensation
condensation
Succinic Acid
Kinetics
kinetics
catalysts
acids
coke
water
mass transfer
beds
resources
Coke
methyl alcohol
aluminum oxides
selectivity

ASJC Scopus subject areas

  • Drug Discovery
  • Organic Chemistry

Cite this

Kinetics of citraconic anhydride formation via condensation of formaldehyde and succinates. / Shekhawat, Dushyant; Nagarajan, Kirthivasan; Jackson, James E.; Miller, Dennis J.

In: Organic Process Research and Development, Vol. 6, No. 5, 09.2002, p. 611-617.

Research output: Contribution to journalArticle

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abstract = "Formation of citraconic anhydride via condensation of succinic acid and its derivatives with formaldehyde is carried out over γ-alumina catalyst in a continuous fixed-bed reactor. Dimethyl succinate and Formalin (37 wt {\%} formaldehyde, 10 wt {\%} methanol in water) are the preferred feed materials for the reaction; catalyst activity is sustained with Formalin relative to that with other formaldehyde sources such as trioxane or Formcel, because the water in Formalin inhibits coke formation. With this feed combination, a total citraconate yield of 31{\%} of theoretical with 72{\%} selectivity is achieved at a weight hour space velocity of 0.9 kg of succinate/kg of catalyst/h, a succinate to formaldehyde molar feed ratio of 1:2, and a temperature of 380 °C. The reaction is free from mass transfer limitations at these conditions. A kinetic model is presented that describes product distributions and reactant conversion as a function of space velocity and temperature. The reaction system is part of an overall process to produce itaconic acid from renewable resource-based succinic acid.",
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