This spreadsheet is used to study reaction kinetics of Biodiesel Production.

The
kinetic model used in this spreadsheet is Komer's Model (2002) which is extended by
Timothy Lawrence (2005) to include the effect of temperature to the the rate
constants. The description of the Komer's Model is provided in sheet 'Model
Description'.

All calculations are done in sheet 'Main Calculations'. They consists of 5 sequential
steps as follows:
1. User supplies operating temperature of the reaction. This spreadsheet will estimate
the normalized rate constants using Arhenius Equation based on Activation Energies
(Ea) and Arhenius Pre factors (A) provided in sheet 'Data of Ea&A'.
2. User then needs to supply their own p, n, and desired E (p is initial molar ratio of
catalyst to TG (Triglycerides), n is initial molar ratio of alcohol to TG, and E is end
product normalized concentration of alkyl ester which is the biodiesel product). This
spreadsheet is then able to estimate end product normalized concentrations of TG,
DG (Diglycerides), MG (Monoglycerides), G (Glycerol), ROH (alcohol), OH
(catalyst), and A (soap).
3. User then supplies the properties of their reactants (rho_TG, MW_TG, rho_ROH,
and MW_ROH) to let this spreadsheet to calculate the required reactant and catalyst
concentrations.
4. This spreadsheet will then calculate time of reaction (time when equilibrium is
reached) based on calculated normalized TG using formula in sheet 'Data of Ea&A'.
5. The last step is the calculation of end product actual concentrations based on
calculated normalized concentrations.

References:
1. Ishchuk, S.Yu et al (1992), “Kinetics of saponification of hydrogenated castor oil
by lithium hydroxide”, Chemistry and Technology of Fuels and Oils, 28(1-2): 48-50.
2. Komers, K. et al (2002), “Kinetics and mechanism of the KOH - catalyzed
methanolysis of rapeseed oil for biodiesel production”, European Journal of Lipid
Science and Technology, 104(11): 728-737.
3. Noureddini, H. and Zhu, D. (1997), “Kinetics of transesterification of soybean oil”,
Journal of the American Oil Chemists Society, 74(11): 1457-1463.
4. TURNER, TIMOTHY LAWRENCE (2005). "Modeling and Simulation of
Reaction Kinetics for Biodiesel Production". Graduate Faculty of North Carolina
State University.

Prepared by : Muhamad Nizar

1. Calculation of rate constants based on specified operating temperature (T)

R (cal/mol/K) T (oC) T (K)

1.987215583 22.75 295.9 1. Input data in yellow cells
2. Calculated data are in green cells
Rate constants Value
k2' 5.9489 L/mol s
k2r' 2.9800 L/mol s
k4' 9.3991 L/mol s
k4r' 7.3110 L/mol s
k6' 15.1800 L/mol s
k6r' 0.6982 L/mol s
k8 0.0133 L/mol s
k9 0.3436 L/mol s
k10 0.7474 L/mol s
k11 0.4654 L/mol s

2. Calculation of end product normalized concentrations (unitless)

Komers normalizes the remaining species by the initial concentrations of triglyceride

and alcohol, as follows:
TG = [TG]/a
a = [TG]o
DG = [DG]/a
MG = [MG]/a
G = [G]/a
A = [A]/a
OH = [OH-]/a
W = [H2O]/a
ROH = [ROH]/b
b = [ROH]o
E = [E]/b
The following balance equations also apply:

TG + DG + MG + G = 1
ROH + E = 1
OH + A = p
p = [OH-]o / [TG]o
nE + 3TG + 2DG + MG + A = 3
n = [ROH]o / [TG]o

Using equilibrium relations, Komers was able to develop an algebraic solution for the end product
concentrations.
Assuming that all reactions have reached equilibrium, we calculate equilibrium constants:

K2' 1.9963
K4' 1.2856
K6' 21.7417

Define
p 0.1225
n 2.0883
E 0.7687

We obtain
<-- this value is adjusted
TG 0.2982 until value of balance ~ 1
DG 0.1791
MG 0.0693
G 0.4533
balance 1

We then also obtain based on balance equations:

A 0.0725
ROH 0.2313
OH 0.0500
3. Calculation of required reactant and catalyst concentrations

Specify:
rho_TG 0.925 g/ml <-- this value is depended on type of oil/fat used
MW_TG 882.82 g/mol <-- this value is depended on type of oil/fat used
rho_ROH 0.791 g/ml <-- this value is depended on type of alcohol used
MW_ROH 32.04 g/mol <-- this value is depended on type of alcohol used

We then calculate:
[TG]_pure 1.0478 mol/L
[ROH]_pure 24.6879 mol/L
[TG]o = a 0.9625 mol/L
[ROH]o = b 2.0099 mol/L
[OH-]o 0.1179 mol/L <--- this is the concentration of required catalyst

4. Calculation of time of reaction based on calculated normalized TG

time of reaction 142.3101 s 2.3718 min

5. Calculation of end product actual concentrations based on calculated normalized

concentrations

[TG] 0.2870 mol/L

[DG] 0.1724 mol/L
[MG] 0.0667 mol/L
[G] 0.4363 mol/L
[A] 0.0698 mol/L
[OH-] 0.0481 mol/L
[ROH] 0.4649 mol/L
<-- this is calculated using the same approach as
[H2O] 55.4939 mol/L [TG]_pure is calcucated
[E] 1.5450 mol/L <-- this is the Biodiesel