Encapsulation of lipases on coordination polymers and their catalytic performance in glycerolysis and esterification

In this study,lipases of CALB(Candida antarctica lipase B),TLL(Thermomyces lanuginosa lipase),RML(Rhizomucor miehei lipase),CALA(Candida antarctica lipase A)and LU(Lecitase?Ultra)were encapsulated into the nucleotidehybrid metal coordination polymers(CPs)for diacylglyerols(DAG)preparation.Guanosine 5'-monophosphate(GMP)and adenosine 5'-monophosphate(AMP)were used as coordinating molecules,and metal ions of Fe^(3+),Ba^(2+),Mn^(2+),Ni^(2+)and Cr^(3+)were applied to prepare matrix.Results indicated that,besides Ba^(2+)with AMP,all other metal ions can coordinate with AMP and GMP to generate CPs.In addition,the AMP/Ni was amorphous when standing temperature was 4℃,while it was crystalline when standing temperature was from 30 to 180℃.DAG content from 47.55%to 64.99%was obtained from glycerolysis by CALB@GMP/Ba,RML@GMP/Ba,TLL@GMP/Ba,RML@GMP/Mn and TLL@GMP/Mn.Additionally,CALB@GMP/Fe showed selectivity towards DAG formation in the esterification and DAG content up to 61.88%was obtained.

Enzymatic Glycerolysis of Chinese Vegetable Tallow Fraction by Lipase and Study of the Mechanism

Glycerolysis of Chinese vegetable tallow (CVT) fraction was investigated using a 1,3-specific lipase from Rhizopus arrhizus as catalyst. Based upon a binary gradient HPLC with an evaporative light-scattering detector (ELSD), the contents of free fatty acids (FFA), monoglycerides (MG), diglycerides(DG) and triglycerides (TG)with their positional isomers during the glycerolysis were determined. The effects of water content and the ratio of glycerol to oil on the product distribution of glycerolysis were studied. Under the optimum reactant conditions:250 units lipase per gram oil at 37 ℃ with 1:2 molar ratio of oil to glycerol in a solvent-free system, after 24 h reaction, the product consisted of 7.2% TG, 25.6% MG, 56.1% DG and 4.9% FFA (all by mass). Furthermore, the mechanism of glycerolysis was discussed in detail.

Kinetic study and kinetic parameters of lipase-catalyzed glycerolysis of sardine oil in a homogeneous medium

The production of polyunsaturated fatty acids （PUFAs） concentrates by enzymatic catalysis has gained interest due to their stereospecificity and the milder conditions employed compared to the use of inorganic catalysts. The enzymatic glycerolysis of sardine oil by Lipozymeò435 to get PUFA concentrates in the forms of di‐and monoacylglycerols （DAGs, MAGs） in an optimized amount of tert‐butanol as the organic solvent was studied. First, mass transfer limitation of the reaction sys‐tem was analyzed. The effects of different operating variables such as lipase loading, temperature and feed composition were investigated. A semi‐empirical kinetic model based on the reversible elementary reactions of glycerolysis and hydrolysis of the glycerides was employed to correlate the experimental kinetic data. A molar ratio glycerol：oil of 3：1 was the optimum, which produced more than 84 wt%of MAG at 323 K. A comparison with other glycerolysis systems was performed using MAG yield, reaction rate and significance of kinetic parameters.

Low Temperature Glycerolysis as a High FFA Pre-Treatment Method for Biodiesel Production

A novel low temperature glycerolysis process for lowering free fatty acid (FFA) in crude jatropha oil for alkali catalyzed transesterification has been developed. The response surface methodology (RSM) based on central composite design was used to model and optimize the glycerolysis efficiency under three reaction variables namely;reaction time, temperature and glycerol to oil mass ratio. The optimum conditions for highest glycerolysis efficiency of 98.67% were found to be temperature of 65℃, reaction time of 73 minutes and 2.24 g/g glycerol to oil mass ratio. These conditions lower the high free fatty acid of crude jatropha oil from 4.54% to 0.0654% which is below 3% recommended for alkali catalyzed transesterification. The pre-treated crude jatropha oil was then transesterified by using homogeneous base transesterification resulting to a conversion of 97.87%. The fuel properties of jatropha biodiesel obtained were found to be comparable to those of ASTM D6751 and EN 14214 standards. The process can also utilize the crude glycerol from the transesterification reaction, hence lowering the cost of biodiesel. The glycerolysis is easier implemented than acid esterification thereby avoiding the need for neutralization and alcohol removal step.

Economic Analysis of Biodiesel and Glycerol Carbonate Production Plant by Glycerolysis

Techno-economic analysis of an indirect use of carbon dioxide within the route of glycerolysis of glycerol with urea is investigated. The results show that the net present value of the biodiesel-glycerol carbonate production by glycerolysis is higher than the biodiesel-glycerol carbonate production by direct carboxylationat at the end of the 12-year operation with similar capacities. The stochastic model has predicted that using glycerolysis route for the synthesis of glycerol carbonate production might increase the probability of getting positive net present value by about 15%.

Enzymatic preparation of mono-and diacylglycerols:A review

Monoacylglycerols(MAGs) and diacylglycerols(DAGs) are partial glycerides widely used in food industry. They are safe and non-toxic food emulsifiers, especially for MAGs. MAGs account for approximately 75% of the total emulsifiers in food industry worldwide. DAGs are recognized as functional cooking oils, they can suppress body fat accumulation and postprandial serum triacylglycerols(TAGs) level. The traditional production of MAGs and DAGs is based on the chemical method, which requires high reaction temperature usually up to 200–260 ℃. Such high temperature is not suitable for oil containing heat sensitive polyunsaturated fatty acids. Enzymatic approach has been received increasing attentions. Enzymatic production of partial glycerides to replace chemical processes has been in industry, particularly for DAGs production as the products have been claimed as a functional and nutritional oil. Enzyme technology for the processing of oils and fats has been moved to industry step by step and case by case during the last 20 years. More and more applications are particularly moving into bulky oils and fats processing. At the same time, the cost of enzymes as a commercial product is reducing steadily. This review summarized the recent 15 years advances on the the enzymatic preparation of MAGs and DAGs. The critical process parameters under different reaction routes were presented and emphasized. The reaction media not only increased the homogeneity of the reaction system, but also shifted the reaction equilibrium towards the target product generation, and this part was stated in detail. In addition, the patent evaluation was included, and the application of MAGs and DAGs was covered.

Pre-Treatment of High Free Fatty Acids Oils by Chemical Re-Esterification for Biodiesel Production—A Review

Non edible oil sources have the potential to lower the cost of biodiesel. However, they usually contain significant high amounts of free fatty acids (FFA) that make them inadequate for direct base catalyzed transesterification reaction (where the FFA content should be lower than 3%). The present work reviews chemical re-esterification as a possible method for the pre-treatment of high FFA feedstock for biodiesel production. The effects of temperature, amount of glycerol, type and amount of catalyst have been discussed. Chemical re-esterification lowers FFA to acceptable levels for transesterification at the same time utilizing the glycerol by product from the same process. Further researches have been proposed as a way forward to improve the process kinetics and optimization so as to make it more economical.