**4. Fatty acid alkyl ester derivatives**

Industrially, mono-alkyl fatty acid esters can be prepared by reacting fat and oil triglycerides with an alcohol using akaline-catalyzed interesterification (alcoholysis) or from the direct esterification of fatty acids (Farris, 1979; Sonntag, 1982). Although a variety of alcohols can be utilized, fatty acid methyl esters (FAME) prepared using methanol are most common based on price and availability. These fatty acid esters not only serve as specialty chemicals but are also used extensively in various oleochemical processes as intermediates to produce fatty alcohols, alkanolamides, and -sulfonated methyl esters (Gervajio, 2005; Gunstone et al., 2007a). Additionally, fatty acid esters, particularly fatty acid methyl esters, are used extensively for the burgeoning biodiesel industry (mono-alkyl esters of long-chain fatty acids derived from vegetable oils or animal fats).

#### **4.1 Distillation**

128 Distillation – Advances from Modeling to Applications

(°C) Rotor Distillate Residue Distillate (g/min) Residue Distillate Low flow rate 175 174 29.3 0.9 19.2 1.01 0.05 12 1 200 201 29.4 2.4 15.9 0.92 0.15 12 1 225 226 29.8 2.7 12.9 0.78 0.21 12 1 250 249 29.9 3.6 9.5 0.66 0.38 12 1 275 274 29.8 5.2 9.5 0.74 0.55 12 4 300 299 30.1 3.0 3.3 0.32 0.91 12 5 325 322 30.2 8.1 6.2 0.72 1.31 12 6 High flow rate 175 174 29.7 4.0 39.9 2.20 0.10 12 3 200 198 29.5 7.6 34.2 2.09 0.22 13 1 225 225 30.2 7.5 31.0 1.93 0.24 14 3 250 248 30.5 8.7 18.7 1.37 0.47 14 4 275 274 29.7 8.2 20.2 1.42 0.41 14 4 300 299 30.4 13.8 21.9 1.79 0.63 14 6

Split

Low Flow Rate

High Flow Rate

ratio Gardner color

point Temperature (°C) Isolated mass (g) Rate

Table 6. Effect of Myer Lab 3 distillation parameters on split and color

40

60

Monoestolide (%)

80

100

160 200 240 280 320

Fig. 14. Effect of rotor temperature on monoestolide composition in distillate fraction

material for cosmetic applications where product color is an important factor.

Temperature (o

Higher temperatures show degradation in color values as a result of co-distillation and splatter from the color bodies found in the polyestolide fraction. This color improvement from the starting material (Gardner color of 12) should greatly enhance the value of this

C)

Set

With regards to distillation, mono-alkyl fatty acid esters have several significant advantages when compared to the distillation of fatty acids (Budde, 1968; Farris, 1979). Because the acid moiety is in the ester form, the fatty acid esters are less corrosive. Therefore, expensive corrosion resistant equipment may not be necessary. Since the ester group cannot participate in hydrogen bonding the esters have lower boiling points, are oftentimes easier to fractionate, and require less energy for their fractionation, Table 2. As can be seen from Table 2, the esters tend to boil approximately 30°C below their corresponding fatty acids. As a result of the two aforementioned properties, the esters are also less susceptible to color formation, decarboxylation and degradation during the distillation. Finally, the fatty acid methyl esters are more ameneable to fractional distillation and separation since they follow Raoult's law more closely than their corresponding fatty acids, which show significant deviation from Raoult's law making it difficult to fractionally distill and separate fatty acids differing by two carbon atoms in chain length (Budde, 1968; Markley, 1964).

Careful control of the distillation parameters allows the advantages inherent to the fatty acid esters to be exploited and used advantageously especially when attempting to fractionate thermolabile materials such as highly unsaturated esters derived from marine oils. Fractional distillation has been performed for some time on a variety of saturated and highly unsaturated fatty acid ester mixtures at reduced pressures on the laboratory scale as a method to purify fatty acid esters. Early reports examined the separation of various fatty acid methyl esters of corn (Baughman & Jamieson, 1921), sunflower (Baughman & Jamieson, 1922b), soybean (Baughman & Jamieson, 1922a), and menhaden oils (Brown & Beal, 1923) by fractional distillation into their various components. Later spinning band columns improved distillation fractionation; for example, Weitkamp (1945) reported the isolation of 32 compounds into four main compound classes (fatty acids, 2-hydroxy acids, and two types of branched iso and anteiso acids) from wool wax by distilling fatty acid methyl esters. Privett and coworkers (1959) distilled several fractions of methyl esters derived from pork liver lipids. Fractional distillation of unsaturated C20 esters from rapeseed (Haeffner, 1970) and herring oil methyl esters (Ackman et al., 1973) have also been reported. Methyl docosahexaenoate (C22:6) was fractionated from a fatty acid methyl ester mixture derived from tuna oil using spinning band distillation at a pressure of 0.025-0.030 mm Hg (Privett et al., 1969). Unique to this method, an amplified distillation process was used, wherein a mixture of carrier components based on long chain acetates (3 g myristyl, 7 g palmitoleyl, 7

Distillation of Natural Fatty Acids and Their Chemical Derivatives 131

ethyl, propyl, butyl esters, etc. might be used for either B100 or blending applications. Because various esters may be used and these higher esters likely have boiling points higher than the methyl esters, focus on the distillation characteristics of these fatty acid esters with regards to biodiesel specifications are important. Accordingly, Schober and coworkers (2010) have examined the distillation characteristics for a series of fatty acid ethyl esters derived from various feedstock following ASTM D1160 specifications. They found the ethyl esters exceeded the maximum limit set for in the ASTM specifications which has important

Reactive distillation has been known since the 1920's but has gotten renewed interest in recent years. The complexities of reactive distillation have been thoroughly reviewed (Malone & Doherty, 2000; Sharma & Singh, 2010; Taylor & Krishna, 2000). Reactive distillation is the simultaneous implementation of reaction and distillation within a single column unit, whereby the reactants are converted to products in a reaction zone in the presence of catalyst with simultaneous distillation of the products and recycling of unused reactants to the reaction zone (Doherty & Buzad, 1992; Kiss et al. 2008, Malone & Doherty, 2000; Omota et al., 2001; Omota et al., 2003ab; Sharma & Singh, 2010; Taylor & Krishna, 2000). A diagram comparing a conventional reaction and distillation process to a reactive

Briefly, as seen in Fig 15a., the reaction in the presence of catalyst takes place in a separate reactor. The crude products are transferred to a sequence of distillation columns are required to produce pure C and D by the conventional process. The unreacted components, A and B, are recycled back to the reactor. In contrast, Fig 15b shows that by combining the reaction and distillation operations, A and B continuously react in the reaction zone while products C and D are removed from A and B in the rectifying and stripping sections at the top and bottom, respectively (Taylor, & Krishna, 2000). This technique can reach 100% conversion and potentially minimize operational and equipment costs and decrease waste energy. Reactive distillation is especially suited for the chemical reactions limited by thermodynamic and equilibrium constraints, since one or more of the products of the reaction are continuously separated from the reactants (Kiss, 2011; Nguyen & Demirel,

With regards to fatty acid ester production and purification, and more specifically to large scale production of biodiesel, it would appear that reactive distillation could provide an efficient and integrated approach to obtain the desired fatty acid esters. However, to date most studies have focused on computer aided modeling, simulation and economics of reactive distillation to produce fatty acid alkyl esters (Bhatia et al., 2007; Kiss, 2011; Kiss et al., 2006; Nguyen & Demirel, 2011; Omota et al., 2001; Omota et al., 2003ab) while more recent experimentally based studies are not as prevalent (Bhatia et al., 2006; He et al., 2006;

Steinigeweg and Gmehling (2003) reported the development of a reactive distillation process for the pilot plant production of decanoic acid methyl esters. The reaction was catalyzed heterogeneously using a strong acidic ion-exchange resin and supported by structured corrugated wire mesh sheets (Katapak-S) in the columns and reaction parameters such as

implications for higher esters to be used as biodiesel.

**4.2 Reactive distillation** 

2011).

distillation process is shown in Fig. 15.

Silva et al., 2010; Steinigeweg & Gmehling, 2003).

g oleyl, 5 g of 11-eicosenoyl, and 3 g erucyl acetates) was employed to facilitate the fractionation of minor components and minimize artifacts arising from C22:6 methyl ester degradation by keeping the distillation temperature from rising sharply during fractionation. The carrier acetates were present in two-to three-fold excess over the fatty acid methyl esters and were chosen to have a range of boiling points covering that of the sample, not form azeotropes and could be separated easily with any sample components. Distillation gave fractions containing mixtures of the enriched methyl esters and acetates. These separate fractions containing the desired methyl esters and carrier acetates were then saponified to give long chain alcohols (from carriers) which were extracted from the soaps as nonsaponifiable matter. The sodium acetate was converted to acetic acid by acidification and separated from the desired fatty acids by extraction with distilled water. By this method a cut of tuna oil containing 84% C22:6 was obtained.

The development of molecular distillation techniques characterized by short exposure of the sample to high temperatures, short path length for the distillate, and high vacuum led to better column efficiencies. Many reports on the molecular distillation of fatty acid esters from sunflower and soybean esters (Pramparo et al., 2005), rapeseed fatty acid esters and tocopherols (Jiang et al., 2006), eicosapentaenoic (EPA) and docosahexaenoic acid ethyl esters (Brevik et al., 1997), and squid visceral oil ethyl esters (Liang & Hwang, 2000; Rossi et al., 2011) have been reported. Vázquez and Akoh (2010) reported a detailed study on the fractionation of short and medium chain fatty acid ethyl esters via short-path distillation that were obtained from a blend of coconut oil and dairy fat. They examined feed rates, temperatures, and single or multiple steps. They were able to obtain fractions containing a high purity of specific fatty acid ethyl esters with a desired composition and yield.

On an industrial scale, a recent set of patents describe a continuous process (~2,000 kg/h) whereby fractional distillation of palm kernel fatty acid methyl esters is done to produce technical grade oleic acid methyl esters (~75 wt%) containing low levels of saturated methyl palmitate (< 5 wt%) and methyl stearate (<2 wt%) (Heck et al., 2000; Heck et al., 2005). This method avoids additional crystallization steps currently used by other processes. The resulting enriched methyl oleate fraction could then be reduced to obtain the corresponding unsaturated fatty alcohols. In this process, the starting palm kernel methyl esters are first fractionally distilled to separate the C8-C14 esters from the C16-C18 esters. The bottom C16- C18 ester fraction is subsequently fractionally distilled to separate the C18 esters (saturated and unsaturated) from the C16 esters. Finally, the C18 esters are fractionally distilled to obtain an enriched C18 unsaturated fraction (methyl oleate) while reducing the saturated C18 ester (methyl stearate) to less than 2 wt%.

A 1999 patent describes the large scale fractional distillation of rapeseed methyl esters, among other fats and oil esters, to obtain a colorless fraction enriched in C22 (behenic) methyl esters with low acid value and purity of at least 86 wt% (Kenneally et al., 1999). The starting rapeseed methyl esters composition was C16-3.5%, C18-38.0%, C20-9.7%, C22- 47.4%, C24-1.4%. Batch fractional distillation at 232-274°C of the rapeseed methyl esters using a packed column with 10 theoretical stages, overhead condenser, receiver, and vacuum pump operating between 5-25 mm Hg gave a 32% yield of the C22 methyl ester cut containing 92.6% C22 and 1.8% C18.

The explosive growth of the biodiesel industry has focused attention on mono-alkyl esters of long-chain fatty acids. Typically, biodiesel is comprised of fatty acid methyl esters, although ethyl, propyl, butyl esters, etc. might be used for either B100 or blending applications. Because various esters may be used and these higher esters likely have boiling points higher than the methyl esters, focus on the distillation characteristics of these fatty acid esters with regards to biodiesel specifications are important. Accordingly, Schober and coworkers (2010) have examined the distillation characteristics for a series of fatty acid ethyl esters derived from various feedstock following ASTM D1160 specifications. They found the ethyl esters exceeded the maximum limit set for in the ASTM specifications which has important implications for higher esters to be used as biodiesel.

#### **4.2 Reactive distillation**

130 Distillation – Advances from Modeling to Applications

g oleyl, 5 g of 11-eicosenoyl, and 3 g erucyl acetates) was employed to facilitate the fractionation of minor components and minimize artifacts arising from C22:6 methyl ester degradation by keeping the distillation temperature from rising sharply during fractionation. The carrier acetates were present in two-to three-fold excess over the fatty acid methyl esters and were chosen to have a range of boiling points covering that of the sample, not form azeotropes and could be separated easily with any sample components. Distillation gave fractions containing mixtures of the enriched methyl esters and acetates. These separate fractions containing the desired methyl esters and carrier acetates were then saponified to give long chain alcohols (from carriers) which were extracted from the soaps as nonsaponifiable matter. The sodium acetate was converted to acetic acid by acidification and separated from the desired fatty acids by extraction with distilled water. By this method

The development of molecular distillation techniques characterized by short exposure of the sample to high temperatures, short path length for the distillate, and high vacuum led to better column efficiencies. Many reports on the molecular distillation of fatty acid esters from sunflower and soybean esters (Pramparo et al., 2005), rapeseed fatty acid esters and tocopherols (Jiang et al., 2006), eicosapentaenoic (EPA) and docosahexaenoic acid ethyl esters (Brevik et al., 1997), and squid visceral oil ethyl esters (Liang & Hwang, 2000; Rossi et al., 2011) have been reported. Vázquez and Akoh (2010) reported a detailed study on the fractionation of short and medium chain fatty acid ethyl esters via short-path distillation that were obtained from a blend of coconut oil and dairy fat. They examined feed rates, temperatures, and single or multiple steps. They were able to obtain fractions containing a

high purity of specific fatty acid ethyl esters with a desired composition and yield.

On an industrial scale, a recent set of patents describe a continuous process (~2,000 kg/h) whereby fractional distillation of palm kernel fatty acid methyl esters is done to produce technical grade oleic acid methyl esters (~75 wt%) containing low levels of saturated methyl palmitate (< 5 wt%) and methyl stearate (<2 wt%) (Heck et al., 2000; Heck et al., 2005). This method avoids additional crystallization steps currently used by other processes. The resulting enriched methyl oleate fraction could then be reduced to obtain the corresponding unsaturated fatty alcohols. In this process, the starting palm kernel methyl esters are first fractionally distilled to separate the C8-C14 esters from the C16-C18 esters. The bottom C16- C18 ester fraction is subsequently fractionally distilled to separate the C18 esters (saturated and unsaturated) from the C16 esters. Finally, the C18 esters are fractionally distilled to obtain an enriched C18 unsaturated fraction (methyl oleate) while reducing the saturated

A 1999 patent describes the large scale fractional distillation of rapeseed methyl esters, among other fats and oil esters, to obtain a colorless fraction enriched in C22 (behenic) methyl esters with low acid value and purity of at least 86 wt% (Kenneally et al., 1999). The starting rapeseed methyl esters composition was C16-3.5%, C18-38.0%, C20-9.7%, C22- 47.4%, C24-1.4%. Batch fractional distillation at 232-274°C of the rapeseed methyl esters using a packed column with 10 theoretical stages, overhead condenser, receiver, and vacuum pump operating between 5-25 mm Hg gave a 32% yield of the C22 methyl ester cut

The explosive growth of the biodiesel industry has focused attention on mono-alkyl esters of long-chain fatty acids. Typically, biodiesel is comprised of fatty acid methyl esters, although

a cut of tuna oil containing 84% C22:6 was obtained.

C18 ester (methyl stearate) to less than 2 wt%.

containing 92.6% C22 and 1.8% C18.

Reactive distillation has been known since the 1920's but has gotten renewed interest in recent years. The complexities of reactive distillation have been thoroughly reviewed (Malone & Doherty, 2000; Sharma & Singh, 2010; Taylor & Krishna, 2000). Reactive distillation is the simultaneous implementation of reaction and distillation within a single column unit, whereby the reactants are converted to products in a reaction zone in the presence of catalyst with simultaneous distillation of the products and recycling of unused reactants to the reaction zone (Doherty & Buzad, 1992; Kiss et al. 2008, Malone & Doherty, 2000; Omota et al., 2001; Omota et al., 2003ab; Sharma & Singh, 2010; Taylor & Krishna, 2000). A diagram comparing a conventional reaction and distillation process to a reactive distillation process is shown in Fig. 15.

Briefly, as seen in Fig 15a., the reaction in the presence of catalyst takes place in a separate reactor. The crude products are transferred to a sequence of distillation columns are required to produce pure C and D by the conventional process. The unreacted components, A and B, are recycled back to the reactor. In contrast, Fig 15b shows that by combining the reaction and distillation operations, A and B continuously react in the reaction zone while products C and D are removed from A and B in the rectifying and stripping sections at the top and bottom, respectively (Taylor, & Krishna, 2000). This technique can reach 100% conversion and potentially minimize operational and equipment costs and decrease waste energy. Reactive distillation is especially suited for the chemical reactions limited by thermodynamic and equilibrium constraints, since one or more of the products of the reaction are continuously separated from the reactants (Kiss, 2011; Nguyen & Demirel, 2011).

With regards to fatty acid ester production and purification, and more specifically to large scale production of biodiesel, it would appear that reactive distillation could provide an efficient and integrated approach to obtain the desired fatty acid esters. However, to date most studies have focused on computer aided modeling, simulation and economics of reactive distillation to produce fatty acid alkyl esters (Bhatia et al., 2007; Kiss, 2011; Kiss et al., 2006; Nguyen & Demirel, 2011; Omota et al., 2001; Omota et al., 2003ab) while more recent experimentally based studies are not as prevalent (Bhatia et al., 2006; He et al., 2006; Silva et al., 2010; Steinigeweg & Gmehling, 2003).

Steinigeweg and Gmehling (2003) reported the development of a reactive distillation process for the pilot plant production of decanoic acid methyl esters. The reaction was catalyzed heterogeneously using a strong acidic ion-exchange resin and supported by structured corrugated wire mesh sheets (Katapak-S) in the columns and reaction parameters such as

Distillation of Natural Fatty Acids and Their Chemical Derivatives 133

Using a laboratory scale continuous flow reactive distillation apparatus, He, Singh, & Thompson, (2006) examined a combined process which used a conventional pre-reactor coupled to a reactive distillation column to convert canola oil into its corresponding fatty

Fig. 16. Schematic of reactive distillation reactor system used to convert canola oil into its

Reaction parameters such as methanol:canola oil, feed rate of canola oil and potassium hydroxide catalyst, and temperature were examined for runs with and without the prereactor. A 95% conversion with a 94% yield (esters contained 1.1%, 2.0%, and 2.0% mono-, di-, and triglyceride, respectively) was obtained using a column temperature of 65°C and a 4:1 methanol:canola oil molar ratio with the pre-reactor. They were able to reduce reaction times 10 to 15 times while also reducing methanol consumption by 66% over conventional

Recently, Brazilian researchers used a pre-reactor (with sodium hydroxide catalyst) coupled to a reactive distillation column in a semi-batch system to examine the preparation of fatty acid methyl esters from soybean oil and bioethanol (Silva et al., 2010). They used experimental design to optimize the catalyst concentration (from 0.5 wt% to 1.5 wt %) and the ethanol/soybean oil molar ratio (from 3:1 to 9:1). The reactive column reflux rate was 83 ml/min, and the reaction time was 6 min. Their best conversion to esters was 98.18 wt% with 0.65 wt% of sodium hydroxide, ethanol/soybean oil molar ratio of 8:1, and reaction time of 6 min. The reaction time of 6 min means: 1 min in the pre-reactor and 5 min in the

A recently patent published application demonstrated a process to produce mixed fatty acid esters with a variety of heterogeneous catalysts. Again, a pre-reactor coupled to a reactive distillation column was used (Asthana et al., 2009). Crude fatty acid methyl esters are first prepared in the pre-reactor much like a conventional biodiesel process. After a crude separation of glycerol and other components the fatty acid methyl esters are transferred to the reactive distillation column where they undergo further reaction with different alcohols

corresponding fatty acid methyl esters (He et al., 2006)

acid methyl esters, Fig. 16.

biodiesel processes.

reactive distillation column.

Fig. 15. Scheme comparing the reaction sequence where A and B are reactants and C and D are the desired products. (a) conventional reactor and distillation process; (b) reactive distillation column. Adapted from Taylor & Krishna (2000)

reflux ratio and reactant ratios were examined (Steinigeweg & Gmehling, 2003). They found that a low reflux ratio of 0.01, a (1:2) decanoic acid:methanol in feed stream, distillate to feed ratio of (1:2), 393K and 3 bar resulted in good fatty acid conversion to the corresponding methyl decanoate. Recently, computer simulation for the esterification of decanoic acid with methanol using reactive distillation has been carried out by Machado and coworkers (2011) using the experimental data obtained Steinigeweg and Gmehling (2003) to validate their models. Furthermore, Machado and coworkers modeled experimental results obtained for the esterification of oleic acid with methanol (Silva et al., 2010; Kiss et al., 2006) and lauric acid with ethanol (De Pietre et al., 2010). They found good agreement between their modeling and the experimentally determined esters found in the literature and predict conversions above 98%.

Bhatia and coworkers performed a thorough study on the esterification of palmitic acid with isopropanol in a reactive distillation column using zinc acetate supported on functionalized silica gel as a catalyst in Katapak-SP structured packing (Bhatia et al., 2006). The column performance was evaluated by varying the operating parameters such as feed flow rate, reboiler temperature, palmitic acid feed composition, palmitic acid feed temperature, molar ratio of isopropanol feed to palmitic acid feed and reflux ratio. From their work they proposed a technically optimized reactive distillation process for the production of isopropyl palmitate.

Fig. 15. Scheme comparing the reaction sequence where A and B are reactants and C and D are the desired products. (a) conventional reactor and distillation process; (b) reactive

reflux ratio and reactant ratios were examined (Steinigeweg & Gmehling, 2003). They found that a low reflux ratio of 0.01, a (1:2) decanoic acid:methanol in feed stream, distillate to feed ratio of (1:2), 393K and 3 bar resulted in good fatty acid conversion to the corresponding methyl decanoate. Recently, computer simulation for the esterification of decanoic acid with methanol using reactive distillation has been carried out by Machado and coworkers (2011) using the experimental data obtained Steinigeweg and Gmehling (2003) to validate their models. Furthermore, Machado and coworkers modeled experimental results obtained for the esterification of oleic acid with methanol (Silva et al., 2010; Kiss et al., 2006) and lauric acid with ethanol (De Pietre et al., 2010). They found good agreement between their modeling and the experimentally determined esters found in the literature and predict

Bhatia and coworkers performed a thorough study on the esterification of palmitic acid with isopropanol in a reactive distillation column using zinc acetate supported on functionalized silica gel as a catalyst in Katapak-SP structured packing (Bhatia et al., 2006). The column performance was evaluated by varying the operating parameters such as feed flow rate, reboiler temperature, palmitic acid feed composition, palmitic acid feed temperature, molar ratio of isopropanol feed to palmitic acid feed and reflux ratio. From their work they proposed a technically optimized reactive distillation process for the production of

distillation column. Adapted from Taylor & Krishna (2000)

conversions above 98%.

isopropyl palmitate.

Reaction Sequence: A + B C + D

Using a laboratory scale continuous flow reactive distillation apparatus, He, Singh, & Thompson, (2006) examined a combined process which used a conventional pre-reactor coupled to a reactive distillation column to convert canola oil into its corresponding fatty acid methyl esters, Fig. 16.

Fig. 16. Schematic of reactive distillation reactor system used to convert canola oil into its corresponding fatty acid methyl esters (He et al., 2006)

Reaction parameters such as methanol:canola oil, feed rate of canola oil and potassium hydroxide catalyst, and temperature were examined for runs with and without the prereactor. A 95% conversion with a 94% yield (esters contained 1.1%, 2.0%, and 2.0% mono-, di-, and triglyceride, respectively) was obtained using a column temperature of 65°C and a 4:1 methanol:canola oil molar ratio with the pre-reactor. They were able to reduce reaction times 10 to 15 times while also reducing methanol consumption by 66% over conventional biodiesel processes.

Recently, Brazilian researchers used a pre-reactor (with sodium hydroxide catalyst) coupled to a reactive distillation column in a semi-batch system to examine the preparation of fatty acid methyl esters from soybean oil and bioethanol (Silva et al., 2010). They used experimental design to optimize the catalyst concentration (from 0.5 wt% to 1.5 wt %) and the ethanol/soybean oil molar ratio (from 3:1 to 9:1). The reactive column reflux rate was 83 ml/min, and the reaction time was 6 min. Their best conversion to esters was 98.18 wt% with 0.65 wt% of sodium hydroxide, ethanol/soybean oil molar ratio of 8:1, and reaction time of 6 min. The reaction time of 6 min means: 1 min in the pre-reactor and 5 min in the reactive distillation column.

A recently patent published application demonstrated a process to produce mixed fatty acid esters with a variety of heterogeneous catalysts. Again, a pre-reactor coupled to a reactive distillation column was used (Asthana et al., 2009). Crude fatty acid methyl esters are first prepared in the pre-reactor much like a conventional biodiesel process. After a crude separation of glycerol and other components the fatty acid methyl esters are transferred to the reactive distillation column where they undergo further reaction with different alcohols

Distillation of Natural Fatty Acids and Their Chemical Derivatives 135

Brevik, H., Haraldsson, G.G., & Kristinsson, B. (1997). Preparation of highly purified

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from 2-8 carbon atoms to give a fatty acid alkyl ester mixture upon exiting the reactive distillation column.

Although the results described above are promising and represent good first steps toward implementation of reactive distillation for fatty acid ester production, as concluded by Taylor and Krishna in their 2000 review on reactive distillation, and with particular focus towards production and separation of fatty acid esters, they state:

…There is a crying need for research in this area. It is perhaps worth noting here that modern tools of computational fluid dynamics could be invaluable in developing better insights into hydrodynamics and mass transfer in RD columns. Besides more research on hydrodynamics and mass transfer, there is need for more experimental work with the express purpose of model validation…

There remains more work to be done in the use of reactive distillation to produce and purify fatty acid alkyl esters.

#### **5. References**


from 2-8 carbon atoms to give a fatty acid alkyl ester mixture upon exiting the reactive

Although the results described above are promising and represent good first steps toward implementation of reactive distillation for fatty acid ester production, as concluded by Taylor and Krishna in their 2000 review on reactive distillation, and with particular focus

…There is a crying need for research in this area. It is perhaps worth noting here that modern tools of computational fluid dynamics could be invaluable in developing better insights into hydrodynamics and mass transfer in RD columns. Besides more research on hydrodynamics and mass transfer, there is need for more experimental work with

There remains more work to be done in the use of reactive distillation to produce and purify

Ackelsberg, O.J. (1958). Fat splitting. *J. Am. Oil Chem. Soc.* Vol.35, pp. 635-640, ISSN 0003-

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**6** 

*Austria* 

**Changes in the Qualitative and** 

**Quantitative Composition of Essential** 

**Oils of Clary Sage and Roman Chamomile** 

**During Steam Distillation in Pilot Plant Scale** 

Susanne Wagner, Angela Pfleger, Michael Mandl and Herbert Böchzelt *Joanneum Research Forschungsgesellschaft mbH Graz, Resources, Institute of Water, Energy and Sustainability, Department for Plant Materials Sciences and Utilisation* 

Clary sage (*Salvia sclarea* L.*)* from the genus Salvia is a biennial or short-living herbaceous perennial plant. Its leaves are united to a basal rosette in the first year, 12 to 25 cm long and 7 to 15 cm wide, ovate, cordate at the base, obtuse and long-stemmed. All the leaves are reticulate-rugose and hairy on both sides. The flowers seem loose to fairly dense, often branched paniculate. They reach approximately 2 cm and the large heart-shaped bracts are long, tapering and purple in early stages, later greenish white. Blossom: June or July to August. The seeds are 2 to 3 mm long nuts. Its native regions are the northern Mediterranean

**1. Introduction** 

Fig. 1. Clary sage

Stauffer, C. (1996). *Fats & Oils*. Eagan Press, ISBN 0-913250-90-2. St. Paul, Minnesota, USA.

