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Chemistry of Biodiesel Production

By Jason M. Keith, Department of Chemical Engineering, Michigan Technological University.

Introduction There has been increasing emphasis on the production of liquid fuels from renewable sources. Biodiesel has been proposed as one of those fuels because its production can be carbon-neutral and its use can help achieve energy independence. Most of the biodiesel produced in the United States is made from soybean oil. In this process, soybean oil (which is composed mostly of the triolein triglyceride) is mixed with an alcohol (typically methanol) and a catalyst (typicallysodium hydroxide or potassium hydroxide). With this feedstock, the reaction that produces methyl oleate (biodiesel) and glycerol by-product is: Triolein + 3 methanol 3 methyl oleate + glycerol The chemicals involved in this reaction (and their properties) are shown below. Triolein: density 0.9 g/cm and molecular weight 885.46 g/mol (note that in the structure below, R = C17H33, which is a hydrocarbon with one double bond near the middle of the chain)

Methanol: density 0.79 g/cm and molecular weight 32 g/mol CH3OH Methyl oleate: density 0.88 g/cm and molecular weight 296.5 g/mol

Glycerol: density 1.26 g/cm and molecular weight 92.1 g/mol

After the batch reaction has taken place, the reactor contains biodiesel product, glycerol by-product, and any unused reactants. The biodiesel phase and the glycerol phase have different densities and can be separated easily. The remaining biodiesel phase will contain water, methanol, some glycerol, and the hydroxide catalyst. The catalyst in this phase is neutralized easily by adding acid. Then the solution is washed with water to remove any impurities. Finally, the biodiesel is dried to remove the water. The glycerol phase also is treated, mainly to recycle the excess methanol; this is necessary to keep the biodiesel production costs low. This article will focus on the reactions that occur within the batch reactor. It is important to know the feedstock required to obtain a certain amount of biodiesel and estimate the fuel production from a reactor of a specific size. Determining the Amount of Chemicals Formed in the Batch Reactor Suppose that 1000 L of soybean oil is mixed with 150 L of methanol. If the conversion of triolein cannot exceed 70% of the methanol feedstock, is this enough to react all of the soybean oil? What are the moles, masses (in kilograms), and volume (in liters) of each chemical after the reaction is complete? To answer these questions, refer to Tables 1 through 3, below. Since the chemical reactions are always in terms of moles, it is necessary to use the density and molecular weight to convert liters into moles. For triolein, there is:

Also,

Similarly, for methanol, there is:

Also,

These numbers are shown in Table 1. Table 1: Feed Conditions Chemical Triolein Methanol Volume (L) 1000 150 Mass (kg) 900 118.5 Moles (mol) 1016.4 3703.1

Even though the chemical reaction suggests that 3 moles of methanol is needed to react with 1 mole of triolein, experiments have shown that the amount of methanol that reacts is limited to a certain fraction of the feed methanol. For the purposes of this article, it is assumed that this is 70%. Thus, the number of moles of triolein that reacts cannot exceed 3703.1(0.70) = 2592.2 mol. As a result, the triolein that reacts is one-third of this amount, or 864.1 mol. These numbers are shown in Table 2, along with the final moles of each of the chemicals involved. Table 2: Reaction Conditions Chemical Triolein Methanol Methyl oleate Glycerol Initial Moles 1016.4 3703.1 0 0 Reaction Moles 864.1 2592.2 2592.2 864.1 Final Moles 152.3 1110.9 2592.2 864.1

Finally, the molecular weight and density can be used to determine the final mass and volume of all of the chemicals. For triolein, there is:

Also,

Similarly, for methanol there is:

Also,

For the biodiesel (methyl oleate) product, there is:

Also,

Finally, for the glycerol by-product, there is:

Also,

Table 3 Lists the final conditions. Table 3: Final Conditions Chemical Triolein Methanol Methyl oleate Glycerol Moles (mol) 152.3 1110.9 2592.1 864.1 Mass (kg) 134.9 35.5 768.6 79.6 Volume (L) 149.8 45.0 873.4 63.2

Thus, for this system there is not enough methanol to convert all the triolein into biodiesel. The minimum amount of methanol needed is equal to 1016.4 3/0.7 = 4356 mol = 139.4 kg = 176.4 L. Fuel Station: Determining the Biodiesel Requirements Consider a 15,000-L chemical reactor. What are the volumes of triolein and methanol that should be fed to the reactor? Also, if this is blended (by volume) as 20% biodiesel and 80% conventional diesel fuel, how many gallons of fuel can be made from this reactor?

In this situation, it is desirable to minimize the unreacted methanol. In the example above, it was shown that for 1000 L of triolein, 176.4 L of methanol is the minimum feedstock needed. Scaling up these numbers leads to the following calculation:

The triolein supplied is thus

Also,

The reacted biodiesel is three times this amount: 38,900 mol. This corresponds to 11,527 kg = 13,100 L. In a 20% blend, this is 65,500 L = 17,300 gallons of biodiesel.