Methodology

 Process Flow of the Production of Methyl Esters from Vegetable Oil

 Methods/Procedures of Analysis

In the process vegetable oil was trans-esterifies in the reactor, followed by downstream

purification, which consisted of: methanol recovery by distillation; glycerol separation; and

methyl-ester purification by distillation. The final purity of the methyl-ester product was

quantified by reporting the product stream composition, which was determined by

thermodynamic calculations in ASPEN. Mono-and di-glycosides were neglected as reaction

intermediates. Plant capacity, unit block operating conditions, and chemical components (except

the catalyst) were selected based on heterogeneous acid catalyst (Styrene divinely benzene

copolymer) simulation. For the present simulation styrene divinely benzene copolymer was

chosen as the catalyst, as it has been shown to effectively catalyze both the trans-esterification

and esterification reactions by Kucek KT et al. and Pinto AC et al. Although the properties for

triolein were available in the ASPEN data banks, different values of the boiling point and critical

temperature were obtained from the literature and used to re-estimate the Antoine’s vapor

pressure coefficients since initial estimates and the results were unsatisfactory. The NRTL (Non-

Random Two-Liquid) model was selected as the thermodynamic model.

The non-random two-liquid model is an activity coefficient model that correlates the activity

coefficients yi of a compound i with its mole fractions xi in the liquid phase concerned. It is

frequently applied in the field of chemical engineering to calculate phase equilibria. The concept

of NRTL is based on the hypothesis of Wilson that the local concentration around a molecule is
different from the bulk concentration. This difference is due to a difference between the

interaction energy of the central molecule with the molecules of its own kind Uii and that with

the molecules of the other kind Uij. The energy difference also introduces a non-randomness at

the local molecular level. The NRTL model belongs to the so-called local-composition models.

NRTL method is not thermodynamically consistent due to the assumption that the local

composition around molecule i is independent of the local composition around molecule j.

Since no kinetic data were available for the styrene divinely benzene copolymer reaction, the

reactor was modeled as a stoichiometry reactor representing a packed bed reactor, eliminating

the catalyst removal step. The conversion was set at 90%. It was assumed that no side reactions

involving glycerol occurred. Additionally, since the reactor is modeled as a batch reactor,

including such parameters would not have affected the results.

 Citation of Sources

The study cited different literatures for the necessary information for the production of

biodiesel. Plant capacity, unit block operating conditions, and chemical components (except the

catalyst) are obtained from Distribution of methanol and catalysts between biodiesel and glycerin

phases by Chiu CW et al. The operating values and calculated data of each component are

acquired from literatures: Perry’s chemical engineers’ handbook, New multi-phase catalytic

systems based on tin compounds active for vegetable oil transesterification reaction, Optimal

control of biodiesel production in a batch reactor and Biodiesel production from various

feedstocks and their effects on the fuel properties. The reaction rate constant, k, was taken from.

Cooling water flow rate, Fc, overall heat transfer coefficient times transfer area, UA, products
and reactants values are obtained from Dynamics and control of a biodiesel Transesterification

reactor, Chemical Engineering and Technology.

Catalyst characteristics such as density and porosity have not been included in the reaction

scheme since they have not been reported in the literature and are likely to change with each

method of synthesis.

Reference:

https://ipfs.io/ipfs/QmXoypizjW3WknFiJnKLwHCnL72vedxjQkDDP1mXWo6uco/wiki/Non-

Random_Two_Liquid_model.html