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Crystallization Behavior of Fatty Acid Methyl Esters

  • Original Paper
  • Published:
Journal of the American Oil Chemists' Society

Abstract

Biodiesel from most agricultural feedstocks has flow properties that are prone to startup and operability problems during cold weather. Biodiesel from soybean oil is generally a mixture of long-chain fatty acid alkyl esters composed of 0.15–0.20 mass fraction saturated esters (melting point [MP] ≫ 0 °C) mixed with unsaturated esters (MP < 0 °C). This work investigates the crystallization properties of two saturated fatty acid methyl esters (FAME) commonly found in biodiesel from soybean oil. Differential scanning calorimetry (DSC) heating and cooling scans of methyl palmitate (MeC16), methyl stearate (MeC18) and methyl oleate (MeC18:1) in pure form were analyzed. Crystallization behavior in ternary FAME mixtures was inferred by the application of thermodynamic models based on ideal solution and freezing-point depression theories. Activity coefficients for MeC16 and MeC18 in MeC18:1 solvent were determined by analyzing DSC cooling curves for binary FAME mixtures. Eutectic points were predicted by both models. Crystallization onset temperatures inferred from freezing point depression theory were more accurate than those for ideal solutions with respect to a direct DSC cooling curve analysis of corresponding ternary mixtures. This work shows that the crystallization onset temperature (cloud point) of biodiesel may be predicted by freezing-point depression theory if the activity coefficients of the component FAME are known.

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Abbreviations

CP:

Cloud point of diesel fuels (°C or K)

DSC:

Differential scanning calorimeter

FAME:

Fatty acid methyl ester(s)

FP:

Freezing point onset temperature of pure component (°C or K)

MeC16:

Palmitic acid methyl ester

MeC18:

Stearic acid methyl ester

MeC18:1:

Oleic acid methyl ester

MP:

Melting point onset temperature of pure component (°C or K)

SD:

Standard deviation of mean value

C p, \( C_{\text{p}}^{\text{L}} \), \( C_{\text{p}}^{\text{S}} \) :

heat capacity of pure component (kJ/mol-K); “L” = liquid, “S” = solid

ΔC p :

differential heat capacity \( [C_{\text{p}}^{\text{L}} - C_{\text{p}}^{\text{S}} ] \) (kJ/mol-K)

g S :

osmotic coefficient of solvent (calculated from Eq. 2)

\( g_{\text{S}}^{\text{H}} \) :

osmotic coefficient of solvent calculated assuming ΔC p = 0

ΔH fus :

enthalpy of fusion (kJ/mol)

ΔH m :

enthalpy of melting (kJ/mol)

P H :

temperature of minimum heat flow of melting peak on DSC curve (°C)

P F :

temperature of maximum heat flow of freezing peak on DSC curve (°C)

R g :

gas constant = 8.3144 J/mol K

T :

temperature (°C or K)

T f :

crystallization onset temperature of FAME mixture (°C or K)

\( T_{\text{f}}^{[1]} ,T_{\text{f}}^{[2]} \) :

T f calculated from Eq. 1 or 2 (°C or K)

\( T_{\text{f}}^{\text{DSC}} \) :

crystallization onset temperature of ternary FAME mixture measured by DSC (°C or K)

x, x i :

mole fraction of species “i” in a mixture; i = 1 for MeC16, 2 for MeC18, S for MeC18:1

y, y i :

mass fraction of species “i” in a mixture (g/g); i = 1 for MeC16, 2 for MeC18

δT f :

absolute deviation between T f values calculated from theory and measured directly from DSC cooling curves [\( [|\{ T_{\text{f}}^{[1]} {\text{ or T}}_{\text{f}}^{[2]} \} - T_{\text{f}}^{\text{DSC}} |] \) (°C or K)

γ, γ i :

activity coefficient of species “i” in liquid phase, calculated from Eq. 2; i = 1 for MeC16, 2 for MeC18

\( \gamma _{i}^{\text{H}} \) :

activity coefficient of species “i” in liquid phase, calculated from Eq. 2 assuming ΔC p = 0; i = 1 for MeC16, 2 for MeC18

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Acknowledgments

Technical assistance on this project was provided by K. Ascherl, H. Khoury, R. Sanders and K. Steidley. In addition, G. Suppes and R. Fillieres provided consultation on the development of experimental studies and the interpretation of results.

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Authors and Affiliations

  1. Food and Industrial Oils Research, United States Department of Agriculture (USDA), Agricultural Research Service (ARS), National Center for Agricultural Utilization Research, Peoria, IL, USA

    Robert O. Dunn

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Correspondence to Robert O. Dunn.

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The use of trade, firm, or corporation names in this publication is for the information and convenience of the reader. Such use does not constitute an official endorsement or approval by USDA or ARS of any product or service to the exclusion of others that may be suitable.

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Dunn, R.O. Crystallization Behavior of Fatty Acid Methyl Esters. J Am Oil Chem Soc 85, 961–972 (2008). https://doi.org/10.1007/s11746-008-1279-x

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