An improved approach for cyclic acetals from glycerol

Xi Hong, Aspi K. Kolah, Carl T. Lira, Dennis J. Miller

    Research output: Chapter in Book/Report/Conference proceedingConference contribution

    • 2 Citations

    Abstract

    The production of biodiesel from plant triglycerides leads to formation of byproduct glycerol, a versatile feedstock for producing chemicals such as propylene glycol and epichlorohydrin. It is well known that glycerol can be converted into cyclic acetals via condensation with aldehydes; for example, 2-methyl-4-hydroxymethyl-1,3-dioxolane and 2-methyl-5-hydroxy-1,3-dioxane are formed via reaction of glycerol with acetaldehyde. These compounds have desirable properties as fuel additives via improving pour point and viscosity of biodiesel, and reducing particulate emissions from fuel combustion. Glycerol acetals can be synthesized directly with aldehydes or by transacetalization with another acetal compound. In this paper, we present results of glycerol acetal synthesis using 1,1-diethoxyethane (DEE). Reaction kinetics and equilibria, along with physical property data such as reactant miscibility, have been studied at different reaction temperatures, reactant molar ratios, and Amberlyst-15 cationic exchange resin catalyst loadings. A kinetic model describing the reaction is presented; results are compared with acetal formation via direct condensation with acetaldehyde. Results show that acetal formation with 1,1-diethoxyethane is faster and proceeds further to completion than reaction of glycerol with acetaldehyde. In addition, the reaction of 1,1-DEE produces ethanol as a product, thus making the system water-free. However, the disadvantage of transacetalization with 1,1-DEE is that it requires the extra step of making 1,1-DEE from ethanol and acetaldehyde (although the ethanol can be recycled in the process). Based on the comparison of the reaction parameters, the conceptual design of a continuous process to make cyclic glycerol acetals using 1,1-DEE will be presented.

    Original languageEnglish (US)
    Title of host publicationAIChE Annual Meeting, Conference Proceedings
    StatePublished - 2009
    Event2009 AIChE Annual Meeting, 09AIChE - Nashville, TN, United States

    Other

    Other2009 AIChE Annual Meeting, 09AIChE
    CountryUnited States
    CityNashville, TN
    Period11/8/0911/13/09

    Profile

    Glycerol
    Acetaldehyde
    Ethanol
    Biodiesel
    Aldehydes
    Condensation
    Dye Dilution Technique
    Fuel additives
    Particulate emissions
    Conceptual design
    Glycols
    Reaction kinetics
    Feedstocks
    Propylene
    Byproducts
    Resins
    Solubility
    Physical properties
    Viscosity
    Catalysts

    ASJC Scopus subject areas

    • Chemical Engineering(all)
    • Chemistry(all)

    Cite this

    Hong, X., Kolah, A. K., Lira, C. T., & Miller, D. J. (2009). An improved approach for cyclic acetals from glycerol. In AIChE Annual Meeting, Conference Proceedings

    An improved approach for cyclic acetals from glycerol. / Hong, Xi; Kolah, Aspi K.; Lira, Carl T.; Miller, Dennis J.

    AIChE Annual Meeting, Conference Proceedings. 2009.

    Research output: Chapter in Book/Report/Conference proceedingConference contribution

    Hong, X, Kolah, AK, Lira, CT & Miller, DJ 2009, An improved approach for cyclic acetals from glycerol. in AIChE Annual Meeting, Conference Proceedings. 2009 AIChE Annual Meeting, 09AIChE, Nashville, TN, United States, 8-13 November.
    Hong X, Kolah AK, Lira CT, Miller DJ. An improved approach for cyclic acetals from glycerol. In AIChE Annual Meeting, Conference Proceedings. 2009.

    Hong, Xi; Kolah, Aspi K.; Lira, Carl T.; Miller, Dennis J. / An improved approach for cyclic acetals from glycerol.

    AIChE Annual Meeting, Conference Proceedings. 2009.

    Research output: Chapter in Book/Report/Conference proceedingConference contribution

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    abstract = "The production of biodiesel from plant triglycerides leads to formation of byproduct glycerol, a versatile feedstock for producing chemicals such as propylene glycol and epichlorohydrin. It is well known that glycerol can be converted into cyclic acetals via condensation with aldehydes; for example, 2-methyl-4-hydroxymethyl-1,3-dioxolane and 2-methyl-5-hydroxy-1,3-dioxane are formed via reaction of glycerol with acetaldehyde. These compounds have desirable properties as fuel additives via improving pour point and viscosity of biodiesel, and reducing particulate emissions from fuel combustion. Glycerol acetals can be synthesized directly with aldehydes or by transacetalization with another acetal compound. In this paper, we present results of glycerol acetal synthesis using 1,1-diethoxyethane (DEE). Reaction kinetics and equilibria, along with physical property data such as reactant miscibility, have been studied at different reaction temperatures, reactant molar ratios, and Amberlyst-15 cationic exchange resin catalyst loadings. A kinetic model describing the reaction is presented; results are compared with acetal formation via direct condensation with acetaldehyde. Results show that acetal formation with 1,1-diethoxyethane is faster and proceeds further to completion than reaction of glycerol with acetaldehyde. In addition, the reaction of 1,1-DEE produces ethanol as a product, thus making the system water-free. However, the disadvantage of transacetalization with 1,1-DEE is that it requires the extra step of making 1,1-DEE from ethanol and acetaldehyde (although the ethanol can be recycled in the process). Based on the comparison of the reaction parameters, the conceptual design of a continuous process to make cyclic glycerol acetals using 1,1-DEE will be presented.",
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