• Clean Technology
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• v.18 no.1
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• pp.102-110
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• 2012

In this study, the production of bio-diesel from animal oil by esterification and trans-esterification was investigated. There were three different extraction methods for oil extraction from raw animal fat. Heterogeneous catalysts such as Amberlyst-15 and Amberlyst BD-20 and a homogeneous catalyst such as sulfuric acid were used for esterification. Among three catalysts, the removal efficiency of Free Fatty Acid (FFA) was the highest in sulfuric acid. Response surface method was carried out to find the optimal esterification condition of sulfuric acid and methanol. After the esterification under the optimal condition, this animal fat was used for the trans-esterification. Animal oil used for trans-esterification was below 1% of FFA content and 0.09% of water content. The catalysts for trans-esterification were KOH, NaOH and $NaOCH_3$. To investigate the effects of catalyst type and amount on trans-esterification, The amount of catalyst were changed with 0.3, 0.6 and 0.9 wt%. The molar ratio of methanol/oil was changed with 4, 6, 9 and 12. The amount of catalyst was fixed to 0.8 wt%. The KOH catalyst showed the highest FAME conversion for trans- esterification, and the optimal methanol/oil weight ratio was 6. In the experiments of various catalysts and methanol molar ratios, the highest content of FAME is 96%. However, this FAME content was below Korean bio-diesel standard which is 96.5% of FAME content. After distillation, FAME content increased to 98%.

• Korean Chemical Engineering Research
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• v.45 no.3
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• pp.286-290
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• 2007

The esterification efficiency of several ionic liquids has been investigated to determine the feasibility for the conversion of free fatty acids to alkylester. Five ionic liquid catalysts having strong acidity, BPC[$AlCl_3$], BMIM[$Bf_4$], BMIM[$Pf_6$], EMIM[$Ntf_2$], BMIM[Otf], have been employed in this work. BPC[$AlCl_3$] has the highest esterification efficiency among the ionic liquid catalysts. Over 90% conversion efficiency has been achieved in the esterification of the simulated used cooking oil by BPC[$AlCl_3$] with two hours reaction time. Since BPC[$AlCl_3$] has several advantages such as high esterification activity, ease of separation from reaction mixture and reusability after treatment procedure, it will be a promising catalyst for the conversion of free fatty acids to esters in waste fats.

• Biotechnology and Bioprocess Engineering:BBE
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• v.7 no.2
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• pp.76-84
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• 2002

On-line conversion estimation of enzymatic esterification reactions in solvent-free media was investigated. In principle, conversion to ester can be determined from the amount of water produced by the reaction, because water is formed as a by-product in a stoichiometric manner. In this study, we estimated the water production rate only from some measurements of relative humidity and water balances without using any analytical methods. In order to test the performance of the on-line conversion estimation, the lipase-catalyzed esterification of n-capric acid and n-decal alcohol in solvent-free media was performed whilst controlling water activity at various values. The reaction conversions estimated on-line were similar to those determined by offline gas chromatographic analysis. However, when the water activity was controlled at higher values, discrepancies between the estimated conversion values and the measured values became significant. The deviation was found to be due to the inaccurate measurement of the water content in the reaction medium during the initial stages of the reaction. Using a digital filter, we were able to improve the accuracy of the on-line conversion estimation method considerably. Despite the simplicity of this method, the on-line estimated conversions were in good agreement with the off-line measured values.

• Journal of Institute of Control, Robotics and Systems
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• v.11 no.6
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• pp.550-557
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• 2005

The multivariate statistical analysis methods, using both multiple linear regression(MLR) and partial least square(PLS), have been applied to predict the reactor properties and the product quality of a direct esterification reactor for polyethylene terephthalate(PET) synthesis. On the basis of the set of data including the flow rate of water vapor, the flow rate of EG vapor, the concentration of acid end groups of a product and other operating conditions such as temperature, pressure, reaction times and feed monomer mole ratio, two multi-variable analysis methods have been applied. Their regression and prediction abilities also have been compared. The prediction results are critically compared with the actual plant data and the other mathematical model based results in reliability. This paper shows that PLS method approach can be used for the reasonably accurate prediction of a product quality of a direct esterification reactor in PET synthesis process.

• Bulletin of the Korean Chemical Society
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• v.34 no.4
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• pp.1160-1164
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• 2013

The solid super acid catalyst $SO{_4}^{2-}$/$ZrO_2$ was prepared by impregnation method using $ZrO_2$ as the catalyst support. Catalyst forming was taken into consideration in order to separate catalyst from the mixture of cellulose acetate propionate (CAP). $Al_2O_3$ and sesbania gum powder were selected as binding agent and auxiliary agent respectively. The catalytic properties were evaluated through esterification of cellulose with acetic anhydride, propionic anhydride and characterized by XRD, FTIR and $NH_3$-TPD. In this paper, the effects of concentration of $H_2SO_4$ impregnated, calcination temperature, esterification temperature and esterification time on the yield, acyl content and viscosity of CAP were investigated. The results showed that $SO{_4}^{2-}/ZrO_2$ successfully catalyzed CAP synthesis over catalysts impregnated in 0.75 mol/L $H_2SO_4$ and calcined at $500^{\circ}C$. The yield, acetyl content and propionyl content of CAP reached the maximum value of 105.3%, 29.9% and 25.8% reacted at $50^{\circ}C$ for 8 h.

• Journal of the Korean Society of Safety
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• v.24 no.4
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• pp.40-46
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• 2009

The early identification of thermal hazards associated with a process such as the heats of reaction, exothermic decompositions, and the understanding of thermodynamics before any large scale operations are undertaken. The evaluation of reaction factors and thermal behavior on esterification process in manufacture of concrete mixture agents are described in the present paper. The experiments were performed in the differential scanning calorimetry(DSC), C 80 calorimeter, and thermal screening unit($TS^u$). The aim of the study was to evaluate the thermal stability of single material and mixture in esterification process. We provided the thermal data of chemical materials to present safe operating conditions through this study.

• Biotechnology and Bioprocess Engineering:BBE
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• v.11 no.3
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• pp.211-214
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• 2006

Immobilized Candida antarctica lipase was used to catalyze the separation of ketoprofen into its components by means of esterification followed by the enzymatic hydrolysis of the ester product. In this study, ketoprofen underwent esterification to ethanol in the presence of isooctane. When the reaction was complete, 58.3% of the ketoprofen had been transformed into an ester. The ketoprofen remaining in solution after the reaction was complete consisted primarily of its S-enantiomer (83.0%), while the 59.4% of the ketoprofen component of the ester consisted of its R-enantiomer. We then subjected the ester product to enzymatic hydrolysis in the presence of the same enzyme and produced a ketoprofen product rich in the R-enantiomer; 77% of this product consisted of the R-enantiomer when 50% of the ester had been hydrolyzed, and 90% of it consisted of the R-enantiomer when 30% of the ester had been hydrolyzed. By contrast, the R-enantiomer levels only reached approximately 42 and 65%, respectively, when 50 and 30% of the racemic ester was hydrolyzed under the same conditions.

• Clean Technology
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• v.19 no.3
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• pp.313-319
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• 2013

To produce biodiesel efficiently from fish oil containing 4% free fatty acid, esterification and trans-esterification were carried out with Vietnam catfish oil, which was kindly provided from GS-bio company. Heterogeneous solid acid catalysts such as Amberlyst-15 and Amberlyst BD-20 and sulfuric acid as homogeneous acid catalyst were used for the esterification of free fatty acids in the fish oil. Sulfuric acid showed the highest removal efficiency of free fatty acid and the shortest reaction time among three acid catalysts. The base catalysts for trans-esterification such as KOH, $NaOCH_3$ and NaOH were compared with each other and KOH was determined to be the best transesterification catalyst. Some solid material, which assumed to be saponified product from glycerol and biodiesel, were observed to form in the fish oil biodiesel when using $NaOCH_3$ and NaOH as the transesterification catalyst. The initial acid value of fish oil was proven to have a negative effect on biodiesel conversion. Of the three catalysts, KOH catalyst transesterification was shown to have high content of FAME and the optimal ratio of methanol/oil ratio was identified to be 9:1.

• Applied Chemistry for Engineering
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• v.16 no.2
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• pp.243-249
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• 2005

Esterification of lactic acid with alcohols catalyzed by Amberlyst-type ion exchange resins and sulfuric acid was carried out in a batch reactor with total /or partial recycle of distilled condensates, respectively. The esterification of lactic acid in the total-recycling reactor (n-butanol/lactic acid = 4, $100^{\circ}C$) was promoted by decreasing the residual water and increasing the mole ratio of n-butanol/lactic acid. Also, it was confirmed that methanol with simple structure and tert-butanol with superior substitution reactivity were more effective in increasing the conversion of esterification reaction, compared to ethanol, n-butanol, and iso-butanol. In a partial-recycling reactor (n-butanol/ammonium lactate = 4, $115^{\circ}C$), the conversion of ammonium lactate into butyl lactate with 1.0 wt% Amberyst-type resins was higher in comparison to that with 0.2 mol $H_2SO_4$ (per 1.0 mol ammonium lactate). The esterification was gradually occurred during the initial stage of reaction in the presence of solid catalyst, whereas the initial addition of $H_2SO_4$ did not affect the initial rate of esterification reaction because of ammonium sulfate formation by the neutralizing reaction of ammonium lactate with sulfuric acid.

• Bulletin of the Korean Chemical Society
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• v.31 no.8
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• pp.2361-2367
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• 2010

$TiO_2-ZrO_2$ was prepared with surfactant through a sol-gel method. Catalysts containing 5 - 35% $H_3PO_4$ were prepared using these oxides. Subsequently the catalytic performance of prepared catalysts was determined for liquid phase esterification of aromatic acids. $H_3PO_4/TiO_2-ZrO_2$ has been used as catalyst to synthesize various novel esters by esterification of some aromatic acids with aliphatic alcohols (2-propanol, 1-butanol, iso butanol, 3-pentanol, 1-hexanol, heptanol, cyclo heptanol, octanol and decanol). Under optimized conditions, maximum yields and selectivity (100%) to the corresponding ester, was obtained by using 25 wt % $H_3PO_4/TiO_2-ZrO_2$ as catalyst. The Catalyst can be easily recycled after reaction and can be reused without any significant loss of activity/selectivity performance. No by-product formation, high yields, short reaction times, mild reaction conditions, operational simplicity with reusability of the catalyst are the salient features of the present synthetic protocol. The reaction was carried out under solvent-free condition.