BIODIESEL PRODUCTION BY REACTIVE DISTILLATION

Matallana, L. G1; Gutirrez, L, F.1, Cardona, C, A.1* 1 National University of Colombia at Manizales Abstract. Fossil fuels demand to meet energy requirements, is increasing every day and oil reserves are
reducing dramatically. For this reason, the production of renewable fuels has acquired great importance in the last years in order to satisfy these energy necessities. The biodiesel makes part of this kind of fuels. However, currently there are problems in its separation and purification. Therefore, new alternatives are needed to be explored like non-conventional separation processes among which reactive distillation can be considered. Recently the esterification of lauric acid with 2-ethyl hexanol and methanol by reactive distillation was reported. However these reports are totally based on experiments without a good analysis of the process technology. In this paper theoretically the possibility of producing the corresponding ester with oleic acid and lauric acid is investigated. In a first stage of this work, a physical chemical analysis of involved components in the system was achieved using tools of classical equilibrium thermodynamics for the determination of topological characteristics of concentration simplex. Then, an analysis of statics was made to determine the limiting stable steady states of maximal conversion for these esterification reactions. This analysis allows drawing tentative trajectories for the reactive distillation in order to define the more adequate process flow sheet. Considering the above mentioned, a simulation taking into account a equilibrium model was performed utilizing the packages Aspen Plus and PRO/II. This study was based on the fundamentals of thermodynamic - topological analysis which is an excellent tool for the design of reactive distillation processes.

Keywords: Reactive distillation, Biodiesel, Analysis of the Statics.

1. Introduction
The diesel fuel derived from petroleum has played an important role in the industrial development. Its low cost causes it to be used to mobilize the charge transport, the transport of passengers the big cities and in the generation of electrical energy. However, it is a non-renewable resource, the gases of its combustion generate high environmental danger. That is why in the last decade an alternative for obtaining diesel has been looked for. For this reason a series of investigators try to obtain biodiesel by transesterification of vegetables oils with alcohol (Srivastava and Prasad, 2000). Biodiesel is a biodegradable ester that does not contain dangerous agent as sulphur. In addition, the plants from which the vegetable oils are produced, capture more CO2 from the atmosphere than the amount that these oils release during their combustion. In this work studied at theoretical level the viability of the obtaining of biodiesel from lauric acid with methanol and 2-ethyl hexanol by reactive distillation, as a first approach to design complex tranesterification reactions using vegetables oils. For this a short cut method was used (analysis of the stactics) that allows to synthesize the technological scheme of the process. Reactive distillation process was simulated by ASPEN PLUS simulator.

2. Reactive Distillation
The reactive distillation is a hybrid process that combines the reaction and separation in a single equipment. The product is retired at the same it is formed. This characteristic does possible to over come the equilibrium
*

To whom all correspondence should be addressed.

Address: National University of Colombia at Manizales. Carrera 27, No. 64 - 60 of. 505 E-mail: ccardona@nevado.manizales.unal.edu.co

thermodynamic of the reaction, reaching best conversions and selectivities (Pai et al, 2002; Pisarenko et al, 2001). Some works exits in which the production of biodiesel by reactive distillation is reported, as the one developed by Omata (Omata et al, 2003). However, no one of these works have carried out the analysis of the statics to define if results obtained in the simulation can be significant. This analysis, proposed and developed by Pisarenko et al. (2001), Zharov et al. (1975), Serafimov et al (1973, 1975) Cardona et al. (2003), allows determining the possible limitant stable states with maximal conversion. The analysis provides the most appropriate qualitative technological scheme to meet the requirements and specifications of the process. This is obtained with little initial information. This procedure is based on the principle of the thermodynamics and the phase equilibrium. The possible separation of pseudo-initial mixtures is determined by evaluates the stable states of the process. Then, it is possible to determine: The optimal relation distillate/bottom (P/W), the composition of feeding and the possible zone of reaction. All the calculation are made assuming / regime, that means that the tower operates to infinite reflux and infinite efficiency (infinite number of stages).

3. Analysis of the Distillation Diagram Structure for Reactive System

For all the reaction systems, UNIFAC model was used for the calculation for activities and Hayden OConnell equations for fugacities (considering that the system, methyl laureate and 2-ethylhexyl laureate production is reactive). The fallowing esterificacion of lauric acid with methanol for methyl laureate production is described by reaction:

C12 H 24 O2 + CH 3OH C13 H 26 O2 + H 2 O

The characterization of fixed points corresponding to this reaction can be observed in table 1.
Table 1. Stability of fixed points (Methyl laureate production)

Component Lauric Acid Methanol Methyl laureate Water

Boiling Point (K) 571.78 337.68 540.39 373.15

Type of Fixed Point Stable Node (the curves arrive at this point) Unstable node (the curves leave this point) Saddle (the curves only approach but they do not arrive at this point ) Saddle (the curves only approach but they do not arrive at this point )

The esterification of lauric acid with 2-ethyl hexanol production, is described by the fallowing reaction:

C12 H 24 O2 + C8 H 18 O C 20 H 40 O2 + H 2 O

The characterization of fixed points is show in table 2:

Table 2. Stability of fixed points (2-ethylhexyl laureate production)

Component Lauric Acid 2-ethyl hexanol 2-ethylhexyl laureate Water Az 2-ethyl hexanol - water

Boiling Point (K) 571.78 457.76 607 373.15 372.25

Type of Fixed Point Saddle (the curves only approach but they do not arrive at this point ) Saddle (the curves only approach but they do not arrive at this point ) Unstable node (the curves leave this point) Saddle (the curves only approach but they do not arrive at this point ) Stable Node (the curves arrive at this point)

The existent of only one distillation region can be concluded from figure 1. For the case of a direct separation (formulated distilled), there is one distillation subregion. When drawing up balance lines between the methanol (the most volatile component) and any point with quaternary composition (the feed), the corresponding bottons have a ternary composition (lauric acid methyl laureate water). For an indirect separation there is one distillation subregion. When drawing up lines of balance between the lauric acid (the less volatile component of the system) and any point of quaternary feed, the corresponding distillate always will have a ternary composition (methanol water methyl laureate). For 2-ethyl hexyl laureate production is possible to conclude that exits only one distillation region too. For a direct separation, there are two ditillation subregions. The first subregion is lauric acid, 2-ethyl hexanol and 2ethyl laureate and the second subregion is lauric acid, water and 2-ethyl laureate. For a indirect separation, only one subregion of distillation was found: Lauric acid, 2-ethyl haxanol and water (see figure 1b)
Methanol

2-ethyl hexanol

Lauric Acid

Water

Lauric Acid

Water

Methyl laureate

2-ethylhexyl Laureate

Fig. 1. Distillation diagram structure of the system (a. Methyl laureate production, b. 2-ethylhexyl laureate)

3. Chemical Interaction Manifold (CIM)

For this drawing up of the lines or ways of reaction, the reaction pole must be fond through the fallowing equation:

Np L1 = L2 N N p r
Where:

(1)

L1 Necessary distance to find pole. L2 Distance from the stoichiometric feeding to the point of product formation. Np Number of product moles. Nr Number of reactants moles. Once located this point, we draw up lines form the point of maximal conversion to another coordinated within the reaction plane, thus being defined the different ways or lines of attacking (Serafimov, et al. 1973). For methyl laureate production process, stoichiometric total coefficient is 0 (Eq. 1) and, for this reason, the chemical interaction lines are parallel through the concentrational simplex (Figure 2). In the same way, for 2ethylhexyl laurete production process, the chemical interaction lines are parallel through the concentrational simplex (figure 2b).

Methanol

2-ethyl hexanol

Lauric Acid

Water

Lauric Acid

Water

Methyl Laureate

2-ethylhexyl Laureate

Fig. 2. Chemical Interaction Manifold. (a. Methyl laureate production, b. 2-ethylhexyl laureate)

4. Determination of P/W Dependence

For each one of the pseudo initial mixtures, a value of P/W ratio for the different types of separation is determined through the corresponding balance line (line whose initial point in the simplex composition

corresponds to the composition of the flow of the formulated product distilled or bottoms and the conjugated corresponds to the extreme boiling point). The values of P and W are found through the use of Eq 2:

P XW X * = W XDX*
P = Flow of distillate W = Flow of bottoms. XW = Composition of bottoms products XD = Composition of top products. X* = Composition of pseudo initial mixture

(2)

Only the lines of balance and, therefore, P/W relations for a stochiometric feed were drawing in figure 3. Where, direct and indirect separations for methyl laureate production that are show in figures 3a and 3b respectively. Nad for 2-ethyl hexyl laureate production that can be observed in figures 3c and 3d.

a.

Methanol

b.

Methanol

Lauric Acid

Water

Lauric Acid

Water

Methyl Laureate 2-ethyl hexanol

Methyl Laureate 2-ethyl hexanol

c.

d.

Lauric Acid

Water

Lauric Acid

Water

2-ethylhexyl laureate

2-ethylhexyl laureate

Fig. 3. a. Direct Separation b. Indirect separation (Methyl laureate production). c. Direct Separation d. Indirect separation (2-ethylhexyl laureate production).

Table 2. P/W dependence. Methyl Laureate production. Direct Separation, stochiometric feed.

Lauric Acid 0.50 0.45 0.40 0.35 0.30 0.25 0.20 0.15 0.10 0.05 0

Methanol 0.50 0.45 0.40 0.35 0.30 0.25 0.20 0.15 0.10 0.05 0

Methyl Laureate 0 0.05 0.10 0.15 0.20 0.25 0.30 0.35 0.40 0.45 0.50

Water 0 0.05 0.10 0.15 0.20 0.25 0.30 0.35 0.40 0.45 0.50

P
1

Relation P/W
SI

0.81 0.65 0.42 0.33 0.24 0.13 0.11 0.05 0 0.53

0,9

P/W

0,6

0,3
SII

0 Pseudo Initial Concentration

1 2 3 4 5 6 7 8 9 10 11

Table 3. P/W dependence. 2-ethylhexyl Laureate production. Direct Separation, stochiometric feed.

Lauric Acid 0.50 0.45 0.40 0.35 0.30 0.25 0.20 0.15 0.10 0.05 0

Methanol

Methyl Laureate

Water

P
0

W
1,2 1 0,8 P/W 0,6 0,4 0,2 0

Relation P/W

0.50 0.45 0.40 0.35 0.30 0.25 0.20 0.15 0.10 0.05 0

0 0.05 0.10 0.15 0.20 0.25 0.30 0.35 0.40 0.45 0.50

0 0.05 0.10 0.15 0.20 0.25 0.30 0.35 0.40 0.45 0.50

0.07 0.18 0.35 0.62 1.01 0.76 0.67 0.60 0.57 0

SI

SII

1 2 3 4 5 6 7 8 9 10 11 Pseudo Initial Concentration

5. Practical Estimation feasibility for limiting steady states (LSS)

To analyze the practical possibility of the LSS, each one of the corresponding trial trajectories must fulfil the following conditions: I. They are developed in all the concentrational simplex II. A segment of the trial trajectory is at least in the zone of direct reaction (Figure 8 and 9).

Methanol

2-ethyl hexanol

Lauric Acid

Water

Lauric Acid

Water

Methyl Laureate

2-ethylhexyl laureate

Fig. 4. Trial Trajectory direct separation stoichiometric feed

In the tables 2 and 3 can see the stables states for methyl laureate and 2-ethylhexyl laureate production. Show it a stable state of maximal P/W ratio (SI see Table 2 and 3). However, the most feasible stable state for these cases is the stable state with minimal P/W ratio and maximal conversion (SII see Table 2 and 3), that fulfil with necessary and sufficient condition above exposed. For the analysis of the trial trajectories, a point with smaller conversion was taken for both cases, otherwise none of the previous ones would fulfil the condition for being developed in all the simplex of concentrations, in addition the segment to the trajectory that is located in the zone of direct reaction is situated in all the limit and as consequence would be needed an infinite volume of reaction. For the studied systems (methyl laureate and 2-ethylhexyl laureate production), the viability of the limitants stable status occur to direct separation with stoichiometric feed (see figure 4).

6. Simulation
The columns were simulated using Aspen Plus, which used rigorous algorithms for reactive distillation calculations. The generalities and conditions are summarized next: Reaction in liquid phase and modeling with chemical equilibrium. For the calculate of distribution coefficients (Ki) was use a model with activity and fugacity coefficients evaluate by UNIFAC and Hayden OConnel equation, respectively. The simulation was carried out taking as base the obtained results in the analysis of the statics and each one of the relevant variables for the reactive column simulation.

Table 4. Specifications simulated reactive distillation column

Specifications Number of stages Reaction Section stages Rectification section stages Stripping section Stage feed Stage feed Column pressure: constant pressure along the column Reactive Feed temperature: Reflux relation: ReactivefFeed (kgmol/h): Equilibrium chemical constant

Methyl laureate 20 5-15 1-5 15-20 Lauric acid : 5 Methanol: 15 101.325 kPa 30C 3.5 50 for each reactive Constant reports by Omota et al (2003)

2-ethyl hexyl laureate 14 7-8 3-6 9-14 lauric acid: 3 2-etyl hexanol: 9 32 kPa 30C 3 50 for each reactive Constant reports by Omota et al (2003)

1 0.9 0.8 0.7 Liquid Composition 0.6 0.5 0.4 0.3 0.2 0.1 0 2 4 6 8 10 N 12 14 16 18 20 Temperature (K) Lauric Acid methanol Methyl Laureate water

560 540 520 500 480 460 440 420 400 380 360 0 2 4 6 8 10 N 12 14 16 18 20

Fig. 5. Concentrations and temperature Profiles for Methyl Laureate Production

1 0.9 0.8 0.7 Liquid Composition
Temperature (K) 480

Lauric Acid 2-ethyl hexanol 2-ethylhexil Laureate water

470 460 450 440 430 420 410 400 390

0.6 0.5 0.4 0.3 0.2 0.1 0 2 4 6 N 8 10 12 14

380

6 N

10

12

14

Fig. 6. Concentrations and temperature Profiles for 2-ethylhexyl laureate production

The concentration and temperature profiles are showed in figures 5 and 6 for methyl laureate and 2ethylhexyl laureate production respectively. In both cases the reactives were consumed totally reached a product purity closed to 98%.

7. Conclusions
Of the statics allowed determining the feasibility of implementing the reactive distillation processes. In this case, it was verified that the analysis of the statics is a powerful tool that lets to know if a process is viable. The outlined hybrid process (reactive distillation), is completely valid, since it is expandable to the transesterification reaction. The configurations obtained by short-cut and rigorous method are agreed totally. To pressure of 101.325 kPa, the column temperature profiles are so high for 2-ethylhexyl laureate production. For this was necessary to operate the column at 32 kPa for diminish the temperature profile and avoid some possible complications as deactivation catalyst and breakdown of involved components.

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Acknowledgments
The authors wish to express their acknowledgments to the National Institute for the Development of Science and Technology of Colombia, Colciencias, the National University of Colombia at Manizales.