Hydrolysis Of Vegetable Oils Research Articles

The evaluation of the performance of rice husk and rice straw as potential matrix to obtain the best lipase immobilized system: creating wealth from wastes

India generates 126.6 and 42 million tons of Rice straw (RS) and Rice husk (RH) annually, respectively. These agro-processing wastes feedstock are dumped in landfills or burnt, releasing toxic gases and particulate matter into the environment. This paper explores the valorization of these wastes feedstock into sustainable, economic products. We compare these wastes as matrices for lipase immobilization. These matrices were characterized, different parameters (pH, temperature, ionic strength, and metal ion cofactors) were checked, and the selected matrix was analyzed for reusability and hydrolysis of vegetable oils. Lipase immobilized Rice straw (LIRS) showed the highest activity with 72.84% protein loading. Field emission scanning electron microscopy (FESEM) demonstrated morphological changes after enzyme immobilization. FTIR showed no new bond formation, and immobilization data was fitted to Freundlich adsorption isotherm (with K = 12.18 mg/g, nF = 4.5). The highest activity with protein loading, 91.05%, was observed at pH 8, 37 °C temperature, 50 mM ionic strength, and lipase activity doubled in the presence of Mg2+ ions. The LIRS retained 75% of its initial activity up to five cycles and efficiently hydrolyzed different oils. The results reflected that the LIRS system performs better and can be used to degrade oily waste.

Metal-organic framework based on iron and terephthalic acid as a multiporous support for lipase Burkholderia lata LBBIO-BL02 and its potential for biocatalysis

Metal-organic frameworks (MOFs) are versatile materials because they have a large internal surface area and tuneable pores, making them suitable for enzyme immobilization. In this study, we prepared a typical microporous Fe-BDC MOF through a thermal treatment to produce additional meso and macropores interconnected to each other, capable of immobilizing the Burkholderia lata LBBIO-BL02 (BLL) lipase by entrapment and physical adsorption. The immobilization efficiency (E) was 90%, and the activity retention (R) was 400% (pNPP hydrolysis). The immobilized lipase (BLL@BDC) also showed excellent activity in the hydrolysis of vegetable oils in aqueous medium, achieving up to 3,200 U g−1 for olive oil, as well as high stability in organic solvents, especially for polar ones, such as iso-propanol (101.5 ± 2.6%), ethanol (103.0 ± 6.0%) and acetone (107.7 ± 8.3%). The results indicate that the multiporous Fe-BDC MOF is a promising support for lipase immobilization and further application in biocatalysis performed in organic media.

Production and Characterization of Whole-Cell Rhizopus oryzae CCT3759 to be Applied as Biocatalyst in Vegetable Oils Hydrolysis

The present study aims to produce a mycelium-bound lipase of the fungus Rhizopus oryzae CCT3759 by submerged fermentation in order to be applied as biocatalyst in the hydrolysis of different vegetable oils. Optimal cultivation conditions have been achieved in a medium containing olive oil as inducer for 72 h of fermentation, thus obtaining 30.5 g/L of dry biomass concentration and hydrolytic activity of 389.1 U/g, which corresponds to a total lipase activity around of 12,000 U/L. Maximum hydrolytic activity was observed at pH 6.0 and 40 °C. Kinetic parameters concerning apparent Michaelis–Menten constant (Km = 50.5 mM) and maximum reaction rate (Vmax = 815.4 µmol/g min) have been determined in olive oil emulsion hydrolysis. Thermal stability tests revealed that the enzyme retained 75% of its initial activity after 4 h at 50 °C, whose thermal inactivation constant (Kd) and half-life (t1/2) was 0.073 h−1 and 9.4 h, respectively. The effect of biocatalyst concentration, expressed as activity units—U (200 and 400 U), on the hydrolysis of vegetable oils was investigated under fixed conditions: oil/buffer mass ratio of 25% (m/m), 100 mM buffer sodium phosphate pH 6.0, 40 °C and the mechanical stirring frequency of 600 rpm. As expected, increasing the initial activity from 200 to 400 U leads to higher values of initial reaction rates and hydrolysis percentage. However, initial reaction rate values were similar for six different vegetable oils due to the high accessibility of the lipase to the substrate under such experimental conditions. A complete hydrolysis of olive, cottonseed, sunflower and canola oils has been achieved after 26–30 h of reaction using 400 U of activity. These results suggest a promising application of the produced biocatalyst in the production of free fatty acids, an important class of compounds for oleochemical industries.

Amano Lipase PS from Burkholderia cepacia- Evaluation of the Effect of Substrates and Reaction Media on the Catalytic Activity

: Lipases in the native or immobilized form have commonly been used as catalysts in the chemical and pharmaceutical industry. One of the widely available enzyme catalysts on the market is lipase from Burkholderia cepacia (BCLs), previously called Pseudomonas cepacia (PCLs). This enzyme is applied, among others, in the stereoselective acylation of molecules to achieve chiral pure enantiomers of drugs or their building blocks. In this study, Amano lipase PS (APS-BCL), which is a commercial lipase from Burkholderia cepacia (BC) was tested. The lipolytic activity of APS-BCL by hydrolysis of vegetable oils and enantioselective activity of APS-BCL by the kinetic resolution of (R,S)-1-phenylethanol with using isopropenyl acetate as an acyl donor were evaluated. An effect of reaction media with different logP values (t-butyl methyl ether, dichloromethane, diisopropyl ether, toluene, cyclohexane, n-hexane, isooctane and n-heptane) on the enantioselective activity of lipase was also studied. The high value of the enantiomeric ratio (E =308.5) with the utilization of isopropenyl acetate was achieved. Whereas, the best reaction medium turned out to be diisopropyl ether, C =47.9%, eep =98%, ees =90%, after 24 h of incubation. Moreover, the influence of ω6/ω9 polyunsaturated fatty acids (PUFAs) ratio in commercial (peanut, camelina, rape, pumpkin seed, walnut, sesame, avocado, rice, corn, black cumin, hemp, safflower, grape seed) oils was investigated for the lipase activity. For the first time, the cut-off limit of ω6/ω9 ratio was proposed. The ratio equal to or higher than 2.3 allows achieving higher lipolytic activity.

Preparation of Fatty Acid and Monoglyceride from Vegetable Oil.

Fatty acid and monoglyceride are examples of lipid compounds that can be founded in vegetable oils. The fatty acid has an important role in the human diet, lubricants, detergents, cosmetics, plastics, coatings, and resin. Monoglyceride has a wide function in the food industry in particular as natural emulsifier, pharmaceuticals, cosmetics, antioxidant, and antibacterial. Therefore, isolation and preparation of fatty acid and monoglyceride are the crucial step. This article focuses on providing the chemical reaction paths of isolation fatty acid and synthesis of monoglyceride from vegetable oils. Fatty acids could be isolated by Colgate-Emery steam hydrolysis, hydrolysis of vegetable oils using inorganic base catalyst or lipase, and base-catalyzed hydrolysis of pure fatty acid methyl ester. There are three steps in the synthesis of pure fatty acid methyl ester which are neutralization, transesterification, and fractional distillation. There are four reactions paths in preparing monoglyceride from vegetable oils. They are glycerolysis, ethanolysis using lipase enzyme (sn-1,3), esterification of fatty acid with glycerol in the presence of inorganic acid catalyst or lipase, transesterification of fatty acid methyl ester with glycerol, transesterification of fatty acid methyl ester with protected glycerol (1,2-O-isopropylidene glycerol), and deprotection using an acid resin (Amberlyst-15).

Techno-economic evaluation of two alternative processes for production of green diesel from karanja oil: A pinch analysis approach

Hydrodeoxygenation (HDO) of vegetable oil is a potential technology for the production of green diesel for direct application in unmodified combustion engines. This study provides the conceptual process design for HDO of karanja oils by two different routes: (i) direct HDO of vegetable oils (direct HDO) and (ii) HDO of fatty acids derived from hydrolysis of vegetable oils (two-step HDO). Pinch analysis was carried out to obtain energy targets and the maximum level of heat recovery and to design the heat exchange network. An economic analysis was then performed using USD 0.5 per kg as the retail price of karanja oil. The production costs of green diesel were estimated as USD 0.84 per kg and USD 0.798 per kg for direct and two-step HDO, respectively, for an optimum plant capacity of 0.12 × 106 metric ton per annum of karanja oil. The analysis was further extended to understand various cost-contributing factors and the effect of feedstock and the price of co-products on the manufacturing costs of green diesel. A discounted cash flow analysis was carried out to determine the minimum selling price of green diesel.

Production of omega 3, 6, and 9 fatty acids from hydrolysis of vegetable oils and animal fat with Colletotrichum gloeosporioides lipase.

Hydrolysis of vegetable oils (Olive, corn, peanut, sesame, flaxseed, soy, canola, garlic, sunflower, almond, castor bean oils) and beef marrow bone oil by Colletotrichum gloeosporioides lipase was studied. The enzyme was capable of generating free fatty acids from all oils tested. The higher hydrolytic activity of the enzyme was towards olive (18.0IU) and soybean (17.8IU) oils. The average percentage of essential fatty acids generated from hydrolysis of the oils was 32.92% of omega 9 (as oleic acid C18:1), 26.24% of omega 6 (linoleic C18:2), and 5.86% of omega 3 (such as α-linolenic acid C18:3). Comparison between chromatographic profile of the oils and its enzymatic hydrolysate showed a good equivalence, stressing the applicability of these vegetable substrates under the action of lipase from C. gloeosporioides produce essential fatty acids, being more efficient production of α-linolenic acid from flaxseed oil, linoleic acid from sunflower oil, and oleic acid from olive.

Determination of Yield of Enzymatic Hydrolysis of Vegetable Oils by Near-Infrared Spectroscopy

Determination of Yield of Enzymatic Hydrolysis of Vegetable Oils by Near-Infrared Spectroscopy

Experimental and theoretical study of the influence of water on hydrolyzed product formation during the feruloylation of vegetable oil.

Feruloylated vegetable oil is a valuable green bioproduct that has several cosmeceutical applications associated with its inherent anti-oxidant and ultraviolet-absorption properties. Hydrolyzed vegetable oil by-products can influence product quality and consistency. The formation of by-products by residual water in the enzymatic synthesis of feruloylated vegetable oil was investigated using chemical theory and experimental studies by monitoring the reaction over a 22-day period. The hydrolysis of vegetable oil is thermodynamically favored over the hydrolysis of the ethyl ferulate starting material. These results suggest that hydrolyzed vegetable oil products will be experimentally observed in greater concentrations compared to hydrolyzed ethyl ferulate products. Quantum chemical studies identified several reaction mechanisms that explain the formation of side products by water, suggesting that residual water influences product quality. Efforts to reduce residual water can improve product consistency and reduce purification costs. Published 2016. This article is a U.S. Government work and is in the public domain in the USA.

IMMOBILIZATION OF LIPASE BY ENCAPSULATION IN SILICA AEROGEL

Lipase from Burkholderia cepacia was immobilized in a silica matrix and dried in high pressure carbon dioxide media (aerogel). The protic ionic liquid (PIL) was used in the immobilization process by encapsulation. The objective of this work was to evaluate the influence of the drying technique using supercritical carbon dioxide in biocatalysts obtained through the sol-gel technique by evaluating temperature and pressure and, after selecting the best drying conditions, to investigate the application of the technique for the biocatalyst using ionic liquid as an additive in the immobilization process. The results for immobilized biocatalysts showed that the best conditions of pressure and temperature were 100 bar and 25 oC, respectively, giving a total activity recovery yield of 37.27% without PIL (EN) and 44.23% with PIL (ENLI). The operational stability of the biocatalysts showed a half-life of 11.4 h for ENLI and 6 h for EN. Therefore, solvent extraction using supercritical CO2, besides shortening drying time, offers little resistance to the immobilization of lipases, since their macropores provide ample room for their molecules. The use of the ionic liquid as an additive in the process studied for the immobilization of enzymes produced attractive yields for immobilization and therefore has potential for industrial applications in the hydrolysis of vegetable oils.

Thermal stability of fatty acids in subcritical water

In this work, hydrolytic reaction conditions of various temperatures (300–370°C) and times (0–30min) at a constant pressure of 20MPa were applied to the thermal decomposition of three kinds of fatty acids (FAs), stearic acid, oleic acid, and linoleic acid, in subcritical water. The degradation characteristics were investigated from the derived data, and the thermal stability of FAs in subcritical water was estimated. The primary reactions we observed were isomerization and pyrolysis of FAs. The main pathway of degradation was deduced by analyzing the contents of pyrolyzed products. We found that more saturated FAs have greater thermal stability in subcritical water. All FAs remained stable at 300°C or below. Based on these results, we recommend that hydrolysis of vegetable oils and fats using subcritical water should be carried out below 300°C (at 20MPa) and for less than 30min to obtain high-yield FA production.

Application of Benzyl Ester of Modified Vegetable Oils as Rubber Processing Oils

Benzyl esters of fatty acids based on three types of vegetable oils (i.e., coconut, palm, and soybean oils) were in-house prepared. They were used as alternative rubber processing oil to replace conventional aromatic oil which has been banned by European community since December 2009. Fatty acids were first prepared by hydrolysis of vegetable oils and thereafter esterified with benzyl alcohol in the presence of sulfuric acid as a catalyst. The reaction based on molar ratio of fatty acid:benzyl alcohol:sulfuric acid was set at 1.5:1.0:0.05 gave yield of benzyl esters higher than 80%. Rubber compounds containing different types of benzyl ester were prepared according to the standard formulation of ASTM 3184. It was found that the processing oil in the form of benzyl esters is possible to use instead of aromatic oil in rubber formulation. Various parameters and properties include mixing energy, Mooney viscosity, curing, mechanical and dynamic mechanical properties of rubber compounds and vulcanizates have been investigated.

Restriction of linoleic acid inhibition of methanization of piggery wastewater and enhancement of its mineralization by adding calcium ions

BACKGROUND: Linoleic acid, which is a major derivative generated from hydrolysis of vegetable oils, is often found at high concentration in food processing and kitchen wastes. This fatty acid could be introduced into an anaerobic system treating piggery wastewater via co-digestion strategy. In this study, the effect of CaCl2 on the inhibitory behavior of linoleic acid in the anaerobic digestion of piggery wastewater was investigated. RESULTS: Linoleic acid exerted strong inhibitory effects on methanization of piggery wastewater with IC50 of 376 mg L−1 and 568 mg L−1 for ISR (inoculum substrate ratio) 0.38 and 2.0, respectively. Among tested cations (Na+, Mg2+, Ca2+, Al3+ and Fe3+), only Ca2+ effectively reversed linoleic acid inhibition. In addition, it was found that CaCl2 restricted linoleic acid inhibition only when it was added before or immediately after linoleic acid addition. Without CaCl2, linoleic acid was stoichiometrically transformed to oleic acid, which persisted for a prolonged period. In the presence of CaCl2, however, linoleic acid was completely converted to methane without accumulation of oleic acid. It was also found that oleic acid was self-inhibitory to its oxidation to acetate, and CaCl2 removed this inhibition. CONCLUSION: From these findings, it was concluded that calcium ion not only mitigated linoleic acid inhibition in the anaerobic digestion of piggery wastewater, but also enhanced its mineralization to methane. Copyright © 2010 Society of Chemical Industry

Hydrolysis of vegetable oils and fats to fatty acids over solid acid catalysts

Solid Fe-Zn double-metal cyanide (DMC) complexes exhibit high catalytic activity for hydrolysis of edible and non-edible vegetable oils and animal fat. In a batch reaction, complete conversion of vegetable oil triglycerides to fatty acids with selectivity greater than 73 wt% was obtained at temperatures as low as 463 K, autogenous pressure and with 5 wt% of catalyst. Catalytic activity of DMC was superior to Amberlyst™70, SAPO-11, H-β, HY, MoO x /Al 2O 3 and sulfated zirconia. Rates of hydrolysis were greatly enhanced when solvents (tetrahydrofuran or N, N-dimethylformamide), phase transfer agents (tetrapropyl ammonium bromide) and products (a mixture of mono-/diglycerides and fatty acids) or fatty acid was added to the feed. Surface hydrophobicity which enables high wettability and activation of glycerides on active, acidic sites of reusable DMC is attributed to be the major cause for its superior catalytic activity.

Continuous Flow Hydrolysis of Sunflower Oil for Biodiesel

Free fatty acids are an important intermediate for several industrial applications, particularly for production of biodiesel via methanolysis. The use of subcritical water as both solvent and reactant for the hydrolysis of vegetable oil to generate fatty acids has recently been proven to be a successful medium for hydrolysis without employing acid or alkali catalysts, while allowing for a simple process and high yield. Continuous flow hydrolysis of sunflower oil in subcritical water to obtain FFA was investigated in a tubular reactor at 10 to 20 MPa, 270 to 350°C and water/oil ratios of 80:20 and 50:50 v:v%. The rate of the hydrolysis was enhanced significantly by increasing reaction temperature end decreasing the water/oil ratio.

Instantaneous characterization of vegetable oils via TAG and FFA profiles by easy ambient sonic-spray ionization mass spectrometry

A fast and reliable method is presented for the analysis of vegetable oils. Easy ambient sonic-spray ionization mass spectrometry (EASI-MS) is shown to efficiently desorb and ionize the main oil constituents from an inert surface under ambient conditions and to provide comprehensive triacylglyceride (TAG) and free fatty acid (FFA) profiles detected mainly as either [TAG + Na](+) or [FFA-H](-) ions. EASI(+/-)-MS analysis is simple, easily implemented, requires just a tiny droplet of the oil and is performed without any pre-separation or chemical manipulation. It also causes no fragmentation of TAG ions hence diacylglyceride (DAG) and monoacylglyceride (MAG) profiles and contents can also be measured. The EASI(+/-)-MS profiles of TAG and FFA permit authentication and quality control and can be used, for instance, to access levels of adulteration, acidity, oxidation or hydrolysis of vegetable oils in general.

Potential effect of the membrane potting on the long-term performance during hydrolysis of edible oil

For both the hydrolysis of vegetable oils and the esterification of glycerol and fatty acids hollow fibre membrane bioreactors are developed. In these bioreactors, hydrophilic membranes are used as immobilization carrier for the enzyme as well as phase separator. In this paper, the membrane reactor is scaled up from a 0.8 m 2 lab scale module to a 22.5 m 2 bench scale unit. In spite of cleaning, hardly any oil flow was possible through the fibre lumen within 3 months of operation. To study these phenomena, a series of lab scale experiments hydrolyzing sunflower oil was performed. During 40 days the cross-sectional area of the fibres decreased to 20% of its initial value. As a result, the hydrolysis activity of the bioreactor decline for 94%. Two possible fibre blocking mechanisms could be eliminated: enzyme coagulation and substrate/product polymerization. We found that fibre blocking was caused by swelling of the polyurethane potting. Swelling led to a decrease of the available volume for the membrane fibres embedded in the polyurethane potting, hence the flow resistance in the lumen increased. Potting material immersed in short chain fatty acids gave a more rapid swelling than immersed in longer chain fatty acids. Similar to this, in a reactor running with a short tail fatty acid, oil flow was not possible any more after 5 days, while the use of oleic acid gave no fibre blocking, on the same time scale. In many types of hollow fibre membrane modules, polyurethane is used as potting resin. The use of these modules in membrane bioreactors or in any other two-phase membrane system could lead to flow problems.

Hydrolysis of Vegetable Oils in Sub- and Supercritical Water

Water, in its subcritical state, can be used as both a solvent and reactant for the hydrolysis of triglycerides. In this study, soybean, linseed, and coconut oils were successfully and reproducibly hydrolyzed to free fatty acids with water at a density of 0.7 g/mL and temperatures of 260−280 °C. Under these conditions the reaction proceeds quickly, with conversion of greater than 97% after 15−20 min. Some geometric isomerization of the linolenic acids was observed at reaction temperatures as low as 250 °C. Reactions carried out at higher temperatures and pressures, up to the critical point of water, produced either/or degradation, pyrolysis, and polymerization, of the oils and resultant fatty acids.

Hydrolysis of vegetable oils and triglycerides by thermotolerant and zoopathogenic species of Aspergillus from Nigerian palm produce.

The ability of Aspergillus fumigatus Fres. and Aspergillus nidulans (Eidam) Wint obtained from Nigerian palm produce to degrade vegetable oils and triglycerides and the production and activity of their extracellular lipases were studied. Both species readily hydrolysed palm oil and palm kernel oil among others liberating free fatty acids in the process. Good growth with mycelia production of both fungi were also recorded on the triglycerides used as sources of carbon at 37 degrees C with the best results obtained on palmitic and oleic acids, the predominant fatty acids in palm oil. Extracellular lipases were detected in the culture filtrates of both fungi within 48 h of incubation on an oat-meal chaff medium at 37 degrees C. Peak enzyme production occurred within the 10-day incubation period. The lipases of both fungal species were most active at a pH of 5.6 and a temperature of 45 degrees C. The best glyceride for assaying the lipase activities of these fungi was trihexanoin while palm oil was a better vegetable oil than the conventional groundnut oil used for the same purpose. Because of the zoopathogenic nature of these fungi, attention is drawn to the potential health risks which their presence on the palm products where they were obtained pose to the consumers.

Note on Hydrolysis of Vegetable Oils by Emulsion of Ricinus communis

Note on Hydrolysis of Vegetable Oils by Emulsion of <i>Ricinus communis</i>