transesterification
Dotaz
Zobrazit nápovědu
A new method for the preparation of anhydrous ethyl ester of lactic acid was studied. The selected method is based on catalytic transesterification of lactic acid oligomers, which were prepared for this purpose by autocatalytic oligomerization of lactic acid. In this work, a kinetic model for the case of catalytic alcoholysis of oligoesters was derived assuming a first-order reaction and equimolar content of reactants in the reaction mixture. The model makes it possible to obtain the values of the reaction rate and equilibrium constants and the equilibrium alcohol concentration by regression analysis at one time. The model was verified by measuring the rate of consumption of ethanol over the time at various reaction temperatures with anhydrous FeCl₃ as the catalyst. The reaction was studied at overpressure under autogenous conditions in the temperature range of 100⁻180 °C. For the catalyst concentration of 1 mol %, the activation energy value was 64.35 kJ·mol-1. The dependence of equilibrium composition and rate constant on the temperature was obtained. The derived model is generally applicable to all first-order equilibrium reactions. The presumption is that the forward and reverse reactions are of the same order and have the same stoichiometry and equivalent amounts of reactants at the beginning of the reaction.
The successfulness of a lipase-catalyzed industrial process depends on a proper lipase selection. In this work, an alternative screening platform for industrially important biotransformations catalyzed by microbial lipases was proposed. Thus, the reactivity of sixty lipase activities from spore-forming microorganisms towards hydrolytic and transesterification reactions by using p-nitrophenyl palmitate as a chromogenic acyl donor substrate was explored. Only three biocatalysts were capable of catalyzing all reactions tested. Fourteen biocatalysts did not show hydrolytic activity at all; however, they displayed transesterification activities using ethanol, starch, low-methoxyl (LM) pectin, high-methoxyl (HM) pectin, or vitamin C as acyl acceptors. Using heat-treated biocatalysts, hydrolytic activities were not highly correlated with the corresponding transesterification activities using ethanol (r = -0.058, p = 0.660), starch (r = 0.431, p = 0.001), LM pectin (r = -0.010, p = 0.938), HM pectin (r = 0.167, p = 0.202), and vitamin C (r = -0.048, p = 0.716) as acyl acceptor. In addition, to the best of our knowledge, several transesterification activities produced from microorganisms of the genus Bacillus, Brevibacillus, Lysinibacillus, Geobacillus, or Sporosarcina were reported for first time. Finally, the global lipase market was presented and segmented by date, application, geography and player highlighting the commercial contribution of microbial lipases.
- MeSH
- biotransformace MeSH
- esterifikace MeSH
- hydrolýza MeSH
- katalýza MeSH
- lipasa * metabolismus MeSH
- Publikační typ
- časopisecké články MeSH
Lipases from Geotrichum candidum 4013 (extracellular lipase and cell-bound lipase) were immobilized by adsorption on chitosan beads. The enzyme preparations were tested in the synthesis of ester prodrugs from racemic 9-(2,3-dihydroxypropyl)adenine in dimethylformamide with different vinyl esters (acetate, butyrate, decanoate, laurate, palmitate). The transesterification activities of these immobilized enzymes were compared with commercially available lipases (lipase from hog pancreas, Aspergillus niger, Candida antarctica, Pseudomonas fluorescens). Lipase from Candida antarctica was found to be the most efficient enzyme regarding chemical yield of the desired products, while transesterification by lipase from Aspergillus niger resulted in lower yields.
- MeSH
- adenin * analogy a deriváty chemická syntéza chemie MeSH
- chitosan chemie MeSH
- enzymy imobilizované chemie metabolismus MeSH
- esterifikace MeSH
- estery chemie MeSH
- Geotrichum enzymologie MeSH
- lipasa chemie izolace a purifikace MeSH
- prekurzory léčiv * chemická syntéza chemie MeSH
- Publikační typ
- časopisecké články MeSH
- práce podpořená grantem MeSH
The effects of phase separation temperatures (5-90°C) on losses of higher fatty acid (C(16) and C(18)) ethyl esters in the glycerol phase were investigated. Losses of ethyl esters produced from ethanolysis of rapeseed oil were 30-60% higher when NaOH rather than KOH was used as homogeneous catalyst. The losses decreased with an increase in separation temperature, resulting in an increase in the yield of the ester phase. The concentration of impurities (e.g. alkali metals, free glycerol and glycerides) in the ester phase increased with increasing separation temperature due reversible transesterification and reciprocal solubility of the compounds. Carbonates formed during neutralization of the catalysts are also transesterification catalysts and they cause reverse reaction. The ethyl ester bound in the glycerol phase during NaOH-mediated catalysis can be extracted by heating the separated glycerol phase to 60-90°C. The ester yield is increasing with increasing separation temperature, however with decreasing quality.
This paper deals with the effect of water and catalyst (KOH) amount on the quantity and quality of transesterification products of rapeseed oil by methanol, the methyl ester phase (i.e. yield, conversion), and the side-product, the glycerol phase (i.e. density, viscosity, the mass fraction of glycerol, esters, soaps). The dependencies were described by statistical models. The transesterification was carried out at constant reaction conditions (90 min reaction time, 400 rpm, 60 degrees Celsius). Twelve experiments with the independent factors, amount of potassium hydroxide (0.65-0.9 mg per gram of oil) and total amount of water (0.24-1.42 mg per gram of oil) naturally present in the reaction components or formed by the neutralisation reaction of free fatty acids and of added water. The data were analyzed by linear regression with respect to regression triplet (complex critical analysis of the model, data and regression method). The analysis resulted in a set of linear and/or quadratic models consisting of statistically proven terms at a statistical significance level of 0.05 and demonstrated that ester in the glycerol phase increases with increasing amount of soaps.
- MeSH
- biomechanika MeSH
- chemická frakcionace MeSH
- chemické modely MeSH
- draslík farmakologie MeSH
- esterifikace účinky léků MeSH
- estery metabolismus MeSH
- glycerol farmakologie MeSH
- hydrogenuhličitany farmakologie MeSH
- hydrolýza účinky léků MeSH
- hydroxidy farmakologie MeSH
- methan metabolismus MeSH
- mýdla MeSH
- oleje rostlin metabolismus MeSH
- sloučeniny draslíku farmakologie MeSH
- uhličitany farmakologie MeSH
- viskozita účinky léků MeSH
- voda farmakologie MeSH
- Publikační typ
- časopisecké články MeSH
- práce podpořená grantem MeSH
Biodiesel is a mixture of esters of fatty acids (most often palmitic, stearic and oleic) and lower alcohols (in our work butanol) produced by transesterification. It is a renewable source of energy, prepared from triacylglycerides, which are contained in vegetable oils and animal fats. This work focuses on alkaline catalyzed transesterification of rapeseed oil with butanol and comparison of two catalysts (potassium hydroxide and potassium tert-butoxide). In industry is usually transesterification of rapeseed oil carried out like reaction catalyzed by potassium hydroxide. Potassium hydroxide have high content of K2CO3, KHCO3 and water. Moreover water is formed by neutralization of potassium hydroxide with free fatty acids contained in oil. In cause of tert-butoxide catalyzed reaction, it is not possible because tert-butoxide have not a OH- aniont, which is needed for water forming. The influence of various conditions (addition of water, temperature of separation, intensity of stirring and type of catalyst) on butanolysis process was studied for both catalysts. For both catalysts dependence of conversions on time were plotted. When tert-butoxide was used, satisfactory phase separation was not achieved. The only way was separation of hot crude reaction mixture without adding water. Ester formed by this method had high content of free glycerol and soaps, but reached higher conversion. The best results were obtained with KOH and subsequent separation of cold crude reaction mixture with the addition of water and slow stirring. The difference between reactions catalyzed by potassium hydroxide and potassium tert-butoxide was described.
- MeSH
- biopaliva * MeSH
- butanoly * MeSH
- hydroxidy * MeSH
- katalýza MeSH
- kyseliny mastné mononenasycené MeSH
- olej z řepky MeSH
- oleje rostlin MeSH
- sloučeniny draslíku * MeSH
- zvířata MeSH
- Check Tag
- zvířata MeSH
- Publikační typ
- časopisecké články MeSH
The paper describes transesterification of oil by methanol with use of cosolvents such as ethyl acetate, tetrahydrofuran, hexane, acetone and diethyl ether at catalyst homogeneous (potassium hydroxide) and heterogeneous (mixed oxides). The cosolvents dissolve oil and methanol to form a single (homogeneous) phase, which increases the reaction rate. Therefore, the biodiesel production will be environmentally friendly because less energy is consumed, which increases sustainability. The whole binodal curve of ternary plots of oil, methanol and cosolvent was determined to find the molar ratio, in which the reaction mixture forms a single phase. The ethyl acetate and tetrahydrofuran have relatively small heterogeneous region, because of the similarity of their electric dipole moment with methanol. After transesterification, the detailed analysis of ester and also glycerol phase was carried out. For homogeneous catalyst, the highest esters content in the ester phase was achieved with tetrahydrofuran. For heterogeneous catalyst, the ester content was lower with cosolvent than without cosolvent, probably due to dilution of reaction components by cosolvent or bonding of cosolvent to the active sites of the catalyst.
- MeSH
- biopaliva * MeSH
- esterifikace MeSH
- estery * MeSH
- katalýza MeSH
- methanol MeSH
- oleje rostlin MeSH
- Publikační typ
- časopisecké články MeSH
The potential of new trimetallic (Ce, Cu, La) loaded montmorillonite clay catalyst for synthesizing biodiesel using novel non-edible Celastrus paniculatus Willd seed oil via two-step transesterification reaction has been reported along with catalyst characterization. Transesterification reaction was optimized and maximum biodiesel yield of 89.42% achieved under optimal operating reaction states like; 1:12 oil to methanol ratio, 3.5% of catalyst amount, 120 °C of reaction temperature for 3 h. The predicted and experimental biodiesel yields under these reaction conditions were 89.42 and 89.40%, which showing less than 0.05% variation. Additionally, optimum biodiesel yield can be predicted by drawing 3D surface plots and 2D contour plots using MINITAB 17 software. For the characterization of the obtained biodiesel, analysis including the GC/MS, FT-IR, 1H NMR and 13C NMR were applied. The fuel properties of obtained biodiesel agrees well with the different European Union (EU-14214), China (GB/T 20828), and American (ASTM-951, 6751) standards.
- MeSH
- bentonit * MeSH
- biopaliva * analýza MeSH
- esterifikace MeSH
- katalýza MeSH
- oleje rostlin analýza MeSH
- spektroskopie infračervená s Fourierovou transformací MeSH
- Publikační typ
- časopisecké články MeSH
- Geografické názvy
- Čína MeSH
