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.

    Original languageEnglish (US)
    Pages (from-to)611-617
    Number of pages7
    JournalOrganic Process Research and Development
    Volume6
    Issue number5
    DOIs
    StatePublished - Sep 2002

    Profile

    formaldehyde
    Succinates
    Anhydrides
    Formaldehyde
    Succinic Acid
    catalysts
    acids
    anhydrides
    condensation
    kinetics
    water
    temperature
    Temperature
    Water
    Acetyl-CoA Hydrolase
    Acetanilides
    Afferent Loop Syndrome
    Dye Dilution Technique
    Kinetics
    coke

    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

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

    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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    AU - Shekhawat,Dushyant

    AU - Nagarajan,Kirthivasan

    AU - Jackson,James E.

    AU - Miller,Dennis J.

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    N2 - 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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