Oleic acid, esterification with

Tesser, R., Di Serio, M., Guida, M., Nastasi, M., and Santacesaria, E. 2005. Kinetics of oleic acid esterification with methanol in the presence of triglycerides. Ind. Eng. Chem. Res., 44,7978-7982. 

Figure 1. Acid-catalyzed oleic acid esterification with alkyl alcohols. O O...

Figure 4. Typical chromatogram of oleic acid esterification with ethyl alcohol.

Figure 8. Effect of temperature on HPW-catalyzed oleic acid esterification with...

Figure 12. Effect of the tin catalyst nature on the oleic acid esterification with ethyl alcohol. Reaction conditions oleic acid (1.0 mmol) ethyl alcohol (155.0 mmol) catalyst (50 mg) 60°C.

The solubility of catalyst was also a key feature in these reactions for instance, the solid tin oxides (SnO and Sn02) were equally inactive on the oleic acid esterification with ethyl alcohol, certainly, due to its almost complete insolubility (Figure 12). 

The efficiency of tin bromide catalyst was assessed in oleic acid esterification with difierent alcohols and the kinetic curves are displayed in Figure 13 [27]. It was observed that both steric hindrance as well as the carbon chain of alcohol affect drastically the final yielding of reactions. 

Figure 13. SnBr2-catalyzed oleic acid esterification with different alcohols [27]. Reaction conditions alcohol oleic acid SnBr2 molar ratio equal to 170 1 0,1 temperature 60°C.

FIGURE 8.4 Effect of solvent removal and the stepwise addition of fructose on the percent conversion of saccharide (a) and on the solubility of fructose (b) for lipase-catalyzed fructose-oleic acid esterification. ( ) Fructose was added to 50 mmol oleic acid and 13.4 g tert-butanol in 5 mmol increments for 2-h cycles until the net amount of fructose added was 25 mmol tert-butanol underwent free evaporation for up to 10 h, at which time, the reaction was stopped, solvent was removed completely by rotary evaporation, then the reaction was continued. (A) Fructose (25 mmol) was added at time 0 to 50 mmol of oleic acid and 13.4 g (46.9 wt.% fructose-free basis) tert-butanol solvent freely evaporated away throughout at a rate of 0.47 g per h. Both reactions were operated in stirred batch mode using approximately 0.5 g immobilized C. antarctica lipase, (Chirazyme L-2, s.-f, c2, Lyo., Boehringer-Mannheim, Indianapolis, IN), a stir rate of 450 rev min and a reaction temperature of 65°C. (From Walde, P. et al., Chem. Phys. Lipids, 53, 265-288, 1990. With permission.)... 

A membrane reactor using a H-ZSM5 membrane was used by Bernal et al. [3.42] to carry out the esterification reaction of acetic acid with ethanol. An equimolar etha-nol/acetic acid liquid mixture was fed in the membrane interior, while He gas was used as an inert sweep on the shell-side. In this particular application the membrane, itself, provides the catalysis for the reaction. NaA and T-type zeolite membranes have been utilized for esterification reactions in a PVMR and in a vapor permeation membrane reactor (VPMR) by Tanaka et al [3.43, 3.44]. Both membranes are hydrophilic and show good separation characteristics towards a number of alcohols. The NaA membrane was used to study the oleic/acid esterification in a vapor permeation membrane reactor (VPMR) at 383... 

Fig. 2 Lower-temperature esterification process allows for the production of gram-scale quantities of (a) y-Fe203, (b) Mn203, (c) CoO and (d) ZnO nanocrystals, whose shapes (e) are due to oleic acid interactions with the polar crystal planes. Reproduced with permission from ref. 16. Copyright 2014 American Chemical Society. ...

Esterification reactions of fatty acids with alcohols are well-known class of liquid-phase reactions of great industrial interest due to the wide practical importance of fatty esters ingredients of different commercial products. Herein, we describes acid-catalyzed oleic acid esterification reactions with alkyl alcohols without a solvent. The use of alkyl oleate esters has increased in the past few years and its applications include cosmetics, pharmaceuticals, food additives, and high- pressure lubricants [1]. 

A comparison of H3PW12O40 (HPW) and SnCl2 catalytic activity against sulfuric acid and />-tolenesulfonic acid (PTSA) in the oleic acid esterification reactions with ethyl alcohol was made by us and the resulting kinetic curves are shown on Figure 6. 

Figure 6. Kinetic curves of oleic acid esterification reactions with ethyl alcohol.

The HPW and SnCl2 catalytic activity on oleic acid esterification who was added to the WCO (waste cooking oil) samples was also evaluated. Soybean oil samples containing oleic acid ca. 10 mmol) were prepared and the SnCl2 catalyst activity was then evaluate in the esterification reaction with ethyl alcohol (Figure 7). 

Recently, we have reported some preliminary results of SnCl2-catalyzed oleic acid esterification reaction with ethyl alcohol esterification with this recycle procedure [24], The similar way, the literature has reported a simple procedure for recycling of HPW catalyst after FFA esterification reactions [25]. 

The esterification of -butyl alcohol and oleic acid with a phenol—formaldehydesulfonic acid resin (similar to amberHte IR-100) is essentially second order after an initial slow period (52). The velocity constant is directiy proportional to the surface area of the catalyst per unit weight of reactants. 

Microemulsion media can be adopted for biotransformations lipases have been used and large difference in rates of esterification, e.g. I-pentanol vs 2-pentanol with oleic acid, have been observed (Stamatis et al., 1993). 

Experimental procedure for the enzymatic esterification of oleic acid with... 

In a first experiment, the esterification of oleic acid with 1-butanol catalysed by a Rhizomucor miehei lipase was investigated (Scheme 4.3). Lipases usually function at the water/organic interface, which make them extremely suitable for use in the CCS. 

There are a few reported cases of esterases that catalyze not only hydrolysis but also the reverse reaction of ester formation, in analogy with the global reaction described for serine peptidases (Fig. 3.4). Thus, cholesterol esterase can catalyze the esterification of oleic acid with cholesterol and, more importantly in our context, that of fatty acids with haloethanols [54], Esterification and transesterification reactions are also mediated by carboxyleste-rases, as discussed in greater detail in Sect. 7.4. 

CRL, HLL AOT-isooctane Regioselective esterification of butane-1,3-diol with oleic acid [32]... 

Esterification between oleic acid and oleyl alcohol, catalyzed by the Mucor miehei immobihzed hpase in a batch-stirred tank reactor with supercritical carbon dioxide as solvent produced higher reaction rates at supercritical conditions than in the solvent-free system (Knez et al., 1995). 

Esterification of oleic acid with methanol Sulfonic macroporous ion exchange resin Increased activity Vieville et al. (1993, 1994)... 

Knez and Habulin (1992) Batch Esterification of oleic acid with oleyl alcohol Lipozyme IM... 

Miller et al. (1991) demonstrated the effect of increased hydrolysis once an optimal amount of water has been added when they studied the inter-esterification of the triglycerides trilaurin and myristic acid. The observed rate of inter-esterification decreased to approximately one-third of its original rate when the water content was reduced from 1.75 (grams water per kilogram carbon dioxide) to zero. They also showed that the amount of hydrolysis increased about 10% as the water content increased. Knez et al. (1998) also found that the addition of small amounts of water increased the conversion rate when they studied the esterification of oleic acid with oleyl alcohol. 

The molar ratio of methanol to fatty acids is also an important parameter that controls the reaction. Figure 6 shows the obtained yields of methyl esters from oleic acid, a model of fatty acids, treated at various molar ratios of methanol to fatty acid. Interestingly, compared with the transesterification reaction shownby the dashed line (13), methyl esterification proceeded more at the lower molar ratio, and it is apparent that at a molar ratio of 3, oleic acid was mostly converted to its methyl ester. This result is important in designing the production process, since a reaction with a low molar ratio requires less energy for the process. 

Calculate AH°S for the esterification of oleic acid with methanol using the appropriate heats of formation for the compounds. 

For the esterification of terephthalic acid with ethylene glycol at 473 K, SO /TiCh calcined at 773 K is much more active than SiC -A Ch as shown in Fig. 6 [60]. The SO /TiCh showed a maximum activity when calcined at 573 K for the esterification of oleic acid with glycerol and of propionic acid with butanol at 403 K [61], where the active sites were attributed to Bronsted acid sites from a correlation between the activity and the Bronsted acidity. The esterification of phthalic anhydride with 2-ethylhexanol to form dioctyl phthalate is also efficiently catalyzed by solid super-acids, the selectivity being more than 90% [62]. The... 

Interestingly, for maximum TAG synthesis, a preference was shown for palmitoyl-CoA as substrate for the initial acylation of glycerol-3-phosphate (Kinsella and Gross, 1973), apparently accelerating the rate of supply of substrate as acceptor for de novo-synthesized fatty adds, whereas oleic acid reduced total de novo synthesis, apparently by competing with butyryl CoA for the esterification of diacylglycerol (Hansen and Knudsen, 1987). 

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