Reactor Sizing Since the primary purpose of a reactor is to provide desirable conditions for reaction, the reaction rate

per unit volume of reactor is important in analysing or sizing a reactor. For a given production rate, it determines the reactor volume required to effect the desired the transformation. The sizing of a chemical reactor for the production of biodiesel required the modelling of the complex series of reversible reactions which have been reported by Freedman et. al. Poljansek et. al. reported on the production of biodiesel by transesterification of large branched triglycerides (TG) into smaller, generally straight-chain molecules of alkyl (most often methyl) esters in the presence of a catalyst. Diand monoglycerides (DG and MG) are intermediates and glycerol (G) is the side product. The three reactions are consecutive and reversible and these reactions are shown below in figure 1.

Figure 1: Reaction scheme of triglyceride transesterification to glycerol and alkyl ester (Poljansek et. al. (year unknown))

Reactor sizing focuses on finding the volume of the reactor at a certain conversion and volumetric flowrate. It has been reported in literature that for continious flow systems, the conversion usually increases with increasing volume therefore conversion is a function of reactor volume. From first principles, the reactor volume equation has been derived to be:

Where: FA0 is the molar flow rate of species A fed to the reactor operated at steady state (mol/h) X is the conversion of the reactor rA is the rate of reaction in terms of component A From the above knowledge of sizing a chemical reactor from the rate of reaction as a function of conversion, the chemical reactors in the biodiesel production were sized. To fully understand the process reaction of biodiesel, the kinetics of the reactions is therefore very significant to study first. Work on chemical kinetics specific to biodiesel production began with Freedman and colleagues at USDA in the early 1980s (Freedman 1984, 1986). In Freedmans model, the overall reaction:

Freedman investigated transesterification of soy oil using butanol and methanol, with molar ratios of alcohol to oil of 30:1 and 6:1, at temperatures ranging from 20 C to 60 C. With butanol, he found the forward reactions to be second order at 6:1 and pseudo-first order at 30:1. With methanol, he found the forward reactions to be fourth order at 6:1, implying the shunt reaction, and pseudo-first order at 30:1. All reverse reactions were found to be second order. In 1997, Noureddini et. al of the University of Nebraska again studied the kinetics of transesterification of soybean oil. They used the same reaction model proposed by Freedman. However, they took measurements at differing mixing intensities, as measured by the Reynolds number of the stirrer. Noureddini et. al. reported that the shunt reaction reported by Freedman et. al. is not necessary, therefore in this paper, the reaction constants will be taken from Noureddini et. al. Below are the activation energies as well as reaction rate constants as reported by Noureddini et. al. The reaction rate constants at 60 OC were estimated using the activation energies from the equation:
o o

Table 1: Rate Consatnts and Activation Energies Noureddini et. al. (1997)

Triglyceride can be shown below to react with methanol to produce diglycerides, the diglycerides react with another methanol molecule to produce monoglycerides and then these react with a third methanol molecule to produce glycerol. At each of these three stages, a molecule of Biodiesel is produced so that, overall, three molecules of methanol are needed to produce three molecules of ester and one molecule of glycerol. Each of these reactions is reversible with a different rate constant (kn) denoting that the forward and reverse reactions take place at different rates. The reactions are all known to be second order (or pseudo-second order) so that we can express the rate of disappearance/appearance of the various components in a series of differential equations (Noureddini et. al. (1997).

Figure 2: Reactions and Rate equations controlling the transesterification reaction (Noureddini et. al (1997))

Reactor sizing focuses on finding the volume of the reactor at a certain conversion and volumetric flowrate. It has been reported in literature that for continious flow systems, the conversion usually increases with increasing volume therefore conversion is a function of reactor volume. From first principles, the reactor volume equation has been derived to be:

Where: FA0 is the molar flow rate of species A fed to the reactor operated at steady state (mol/h) X is the conversion of the reactor rA is the rate of reaction in terms of component A From the above knowledge of sizing a chemical reactor from the rate of reaction as a function of conversion, the chemical reactors in the biodiesel production were sized. FA0 and X are known except rA therefore calculations are needed. Since there are a number of reactions in series both giving biodiesel, both having different rates, therefore there is a need to assume the rate limiting step which is the slowest reaction and that will be the reaction that control the overall reaction.

From the reactions above, the rate of reactions are given below [ ([ Where [ ([ Where [ ([ ][ ] ][ ] [ [ ][ ] ][ ] ) [ ([ ][ ] ][ ] [ ][ ] [ ][ ] ) ][ ] ][ ] [ [ ][ ] ][ ] ) [ ([ ][ ] ][ ] [ [ ][ ] ][ ] ) ][ ] ][ ] [ [ ][ ] ][ ] )

Global reactions are not usually well represented by mass action kinetics because the rate results from the combined effect of several simultaneus elementary reactions that underline the global reaction. The elementary steps include short-lived and unstable intermidiate components such as free radicals, ions, molecules, transition complex e.t.c (Perry 7-14, 2008). The reason many global reactions between stable reactants and products have complex mechanism is that these unstable reactants intermidiates have to be produced in order for the reaction to proceed at reasonable rates. Often simplifying assumptions are valid over limited ranges of compositions, temperature and pressure. These assumptions can fail completely-in that case the full elementary reaction network has to be considered, and no closed-form kinetics can be derived to represent the complex system as a complex reaction (Perry 7-14, 2008). Assuming the third reaction to be rate limiting step because the third reaction was reported by Nouriddini to be the slowest and reduces as the temperature increase. Therefore this means that rTG/k1 and rDG/k3 are relatively very small (approximately zero) while rMG/k5 is large. Now we need to express the third rate law interms of measurable concentration. [ [ ] [ ] ][ ] [ ] [ ][ ] [ ] [ ][ ] [ ]

][ ] [ ]

][ ] [ ]

][ ] [ ]

[ ][ ] )

Figure 3: Reactor 1

Substituing values in the previously derived equation to find r, it was then substituted in

And a volume of 0.1m3 was found. Since the entire design of the whole process is based on a design illustrated in Apostolakou et. al. (2009) as the base case. Apostolakou et. al. (2009) suggested a reactor volume to be calculated using an equation: with the residance time, Q as the volumetric flowrate of all streams and V as the reactor volume. Using this method, a volume of 4m3 was found. Another method to find the volume of the reactor was using the method illustrated in Fogler (2006) where volume of the reactor is calculated from the space time equation shown below:

Were V is the reactor volume, and v0 is the input volumetric flowrate and T as the space time. Space time is the the time it takes for the fluid to enter the reactor completely (Fogler, 2006), it is also called the holding up time or mean residance time. In absence of dispersion, space time is the time the molecules spends in the reactor. In this design, the residance time is 1 hour therefore the volume of the reactor is 3.29 m3. Reactor 2

Using the equation

, the volume of the reactor was found to be 4m3 as well and using

The volume was found to be 3m3 as well. Using the rate laws, the volume calculated as illustrated in reactor 1 sizing is 4.8m3. Agitation The reason why the reactor has an agitator is because of the following reasons: 1. The rate of transesterification depends on the agitation rate or directly proportional to the Reynolds number (Nouriddini, 1998) 2. Blending the two miscible liquids 3. Increase the heat transfer between The two reactors have the same volume that means the two tanks are identical. Therefore the calculations are made for one reactor. Generally, liquids are agitated in a cylindrical vessel which can either be closed or open to the air.