Comparison between conventional and ultrasonic preparation of beef tallow biodiesel

Tallow is biodiesel feedstock that, due to its highly centralized generation in slaughter/processing facilities and historically low prices, may have energetic, environmental, and economic advantages that could be exploited. Transesterification of fatty acids by means of ultrasonic energy has been used for biodiesel production from different vegetable oils. However, application of ultrasonic irradiation for biodiesel production from beef tallow has received little attention. In this work, the transesterification of beef tallow with methanol was performed in the presence of potassium hydroxide as a catalyst using ultrasound irradiation (400 W, 24 kHz). The reaction time, conversion and biodiesel quality were compared with that seen in conventional transesterification. The results indicated that the reaction conversion and biodiesel quality were similar; however, the use of ultrasonic irradiation decreased the reaction time, showing that this method may be a promising alternative to the conventional method.     

Solid phase enzymatic glycerolysis of beef tallow resulting in a high yield of monoglyceride

A mixture of mono-, di- and triglycerides was obtained when beef tallow was reacted with glycerol using lipase enzyme as a catalyst. The reaction was carried out batchwise in a small vessel with agitation by magnetic stirring. The yield of monoglyceride (MG) was greatly influenced by the reaction temperature—at higher temperatures (48–50°C) a yield of approximately 30% MG was obtained, while at lower temperatures (38–46°C) a yield of approximately 70% MG was obtained. A sharp transition was observed between the high and low yield equilibrium states. The temperature at which this transition occurred is called the critical temperature (T_c) and was found to be 46°C in the case of tallow. During the course of the reaction, when approximately 40% MG had been synthesized, the reaction mixture became solid but the reaction continued until approximately 70% MG had been synthesized. A yield of 70% MG also was obtained with tallow at 42°C when a glycerol/tallow mole ratio ranging from 1.5 to 2.5 was used. The free fatty acid content at equilibrium depended on the water concentration in the glycerol phase and varied from 0.5% to 11.0% when the water content ranged from 0.6% to 12.5%. Above 8% water content, the yield of MG was reduced. Of the commercially available lipases that were investigated, lipase fromPseudomonas fluorescens orChromobacterium viscosum resulted in the highest yield of MG.     

超临界流体萃取技术的应用及研究进展

超临界流体萃取技术近年来被广泛应用于中草药、食品、香料、化工及环境保护等领域。介绍了超临界流体萃取技术与传统的萃取方法相比所具备的优势及其发展前景。     

Pilot-scale supercritical carbon dioxide extraction and fractionation of wheat germ oil

There is a need for the development of new processing techniques to facilitate vegetable oil extraction and refining while sustaining the nutritional components naturally present in edible oils and reducing the adverse impact of oil processing on the environment. In this study supercritical carbon dioxide (SC−CO₂) extraction and fractionation techniques were examined as alternative methods to obtain wheat germ oil (WGO) of high quality and purity. It was shown that the SC−CO₂ extraction technique is effective in extraction of WGO. There was no significant difference in the FA composition of SC−CO₂- and hexane-extracted WGO. Both hexane-and SC−CO₂-extracted WGO were rich in α-tocopherol. Moisture content of the SC−CO₂-extracted oil was higher than that of the hexane-extracted oil. Solvent/feed ratio had a significant effect on the SC−CO₂ extraction yields. This study demonstrated that supercritical fluid fractionation was a viable process to remove FFA efficiently from both hexane-and SC−CO₂-extracted WGO while retaining bioactive oil components in the final product.     

超临界气体提取技术进展

讨论了超临界气体提取技术中气体的选择原则、提取装置的现状及其应用中工艺条件的选定,并对国内的研究工作提出了建议。     

超临界萃取法制备辣椒红色素

将原料干红辣椒采用溶剂法提取出辣椒树脂中间产品,并以其为原料进行了超临界CO2制备辣椒红色素的实验研究。通过对超临界萃取压力、温度、时间与装料系数的相关实验研究,确定出超临界CO2萃取法制备辣椒红色素的工艺条件。研究结果表明,最优工艺参数为:萃取压力20 MPa,萃取温度35℃,萃取时间6 h,装料系数0.7。制取的辣椒红色素产品符合中国国家标准,主要指标色价、己烷残留等均优于国标要求。     

Application of full factorial design and Doehlert matrix for the optimisation of beef tallow methanolysis via homogeneous catalysis

The transesterification of triglycerides by means of alkaline catalysts is the most widely used route for biodiesel production and reaction optimisation by multivariate methods has been used for biodiesel production from different vegetable oils. However, the application of simultaneous optimisation for biodiesel production from beef tallow has received little attention. In an effort to optimize the beef tallow biodiesel production, a combination of the full factorial design and the Doehlert matrix was applied, and the effects of temperature, reaction time, catalyst concentration and alcohol:tallow molar ratio and their reciprocal interactions were assessed. The response variables under study were purity and yield of the final biodiesel product. In the selected condition [alcohol:tallow molar ratio (M) = 7.5:1, catalyst:tallow mass ratio (C) = 1.5%, reaction time (t) = 20 min and temperature = 50 °C], the conversion yield of tallow biodiesel was 88.4% and the purity was 99.4%. The final biodiesel obtained was analysed and showed to have good quality characteristics.     

超临界CO_2流体萃取植物油的实验研究

建立了一套超临界流体萃取实验装置,就大豆和花生两种植物油超临界流体萃取进行了较为详细的实验研究.在探讨了压力、温度、颗粒度、空隙率以及时间等对萃取率的影响之后,获得了指导实际生产的最佳工艺参数条件.     

Fractionation of whey protein isolate with supercritical carbon dioxide-process modeling and cost estimation

An economical and environmentally friendly whey protein fractionation process was developed using supercritical carbon dioxide (sCO₂) as an acid to produce enriched fractions of α-lactalbumin (α-LA) and β-lactoglobulin (β-LG) from a commercial whey protein isolate (WPI) containing 20% α-LA and 55% β-LG, through selective precipitation of α-LA. Pilot-scale experiments were performed around the optimal parameter range (T = 60 to 65 °C, P = 8 to 31 MPa, C = 5 to 15% (w/w) WPI) to quantify the recovery rates of the individual proteins and the compositions of both fractions as a function of processing conditions. Mass balances were calculated in a process flow-sheet to design a large-scale, semi-continuous process model using SuperproDesigner® software. Total startup and production costs were estimated as a function of processing parameters, product yield and purity. Temperature, T, pressure, P, and concentration, C, showed conflicting effects on equipment costs and the individual precipitation rates of the two proteins, affecting the quantity, quality, and production cost of the fractions considerably. The highest α-LA purity, 61%, with 80% α-LA recovery in the solid fraction, was obtained at T = 60 °C, C = 5% WPI, P = 8.3 MPa, with a production cost of $8.65 per kilogram of WPI treated. The most profitable conditions resulted in 57%-pure α-LA, with 71% α-LA recovery in the solid fraction and 89% β-LG recovery in the soluble fraction, and production cost of $5.43 per kilogram of WPI treated at T = 62 °C, C = 10% WPI and P = 5.5 MPa. The two fractions are ready-to-use, new food ingredients with a pH of 6.7 and contain no residual acid or chemical contaminants.     

Combined extraction processes of lipid from Chlorella vulgaris microalgae: microwave prior to supercritical carbon dioxide extraction

Extraction yields and fatty acid profiles from freeze-dried Chlorella vulgaris by microwave pretreatment followed by supercritical carbon dioxide (MW-SCCO(2)) extraction were compared with those obtained by supercritical carbon dioxide extraction alone (SCCO(2)). Work performed with pressure range of 20-28 Mpa and temperature interval of 40-70 °C, gave the highest extraction yield (w/w dry weight) at 28 MPa/40 °C. MW-SCCO(2) allowed to obtain the highest extraction yield (4.73%) compared to SCCO(2) extraction alone (1.81%). Qualitative and quantitative analyses of microalgae oil showed that palmitic, oleic, linoleic and α-linolenic acid were the most abundant identified fatty acids. Oils obtained by MW-SCCO(2) extraction had the highest concentrations of fatty acids compared to SCCO(2) extraction without pretreatment. Native form, and microwave pretreated and untreated microalgae were observed by scanning electronic microscopy (SEM). SEM micrographs of pretreated microalgae present tearing wall agglomerates. After SCCO(2), microwave pretreated microalgae presented several micro cracks; while native form microalgae wall was slightly damaged.     

Safety of oleochemical products derived from beef tallow or bone fat regarding prions

Bovine bone fat and beef tallow are widely used as raw material for oleochemical processes. Due to high temperature and pressure these processes are supposed to have an excellent inactivation potential for prions, i.e. the agent of BSE and other transmissible spongiform encephalopathies. To experimentally prove the destruction of the pathogenic prion protein aggregates under technically relevant conditions, oleochemical processes were emulated in the laboratory in reduced scale. Fat samples were spiked with highly infectious ex vivo prion rods and aliquots were taken before and after the processes. From these aliquots, undegraded prion protein was precipitated and determined by a sensitive Western blot assay. Degradation factors of 2 ?10³ ‐ 10⁴ for catalytic fat hydrogenation and 10⁷ for fat hydrolysis represent acceptable safety limits. With these experimental prion protein degradation factors the risk of human exposure to oleochemical products of bovine origin can be assessed. Assuming worst‐case scenarios, the annual risk for human consumption of hydrogenated beef tallow is less than 6.8 x 10^‐7 and for skin application of fatty acid derivatives is less than 7.0 x 10^‐10. Both values are smaller than the background risk of contracting sporadic Creutzfeldt‐Jakob disease (1 x 10^‐6 per annum).     

Analysis oftrans-18:1 isomer content and profile in edible refined beef tallow

Thetrans 18:1 acid content and profile for several samples of edible refined beef tallow were determined monthly over a period of one year. For this purpose, gas-liquid chromatography was combined with silver-ion thin-layer chromatography. The mean content oftrans-18:1 isomers was 4.9±0.9% (n=10) of total fatty acids with a minimum of 3.4% and a maximum of 6.2%. The distribution profile of individual isomers was also established. As in other ruminant fats (milk fat, meat fat), the main isomer is vaccenic (trans-11 18:1) acid. Other isomers, with their ethylenic bonds between positions 6 and 16, were found in lesser amounts. However, some slight but definite differences exist between beef tallow and cow milk fat. The relative proportion of vaccenic acid is higher in the former than in the latter. However, the distribution pattern oftrans-18:1 isomers in beef tallow closely resembles that in beef meat fat (lean part).     

胆甾醇在超临界CO2中的溶解度测定与关联

利用动态法测定了胆甾醇在超临界CO2中的溶解度。在10—30 MPa,313—343 K下,胆甾醇的溶解度摩尔分率为10-6—10-4。引入与密度有关的混合规则,将二元交互参数表示为密度的函数,采用PR状态方程,关联胆甾醇在超临界CO2中的溶解度。改进后的溶解度模型克服了采用经典混合规则的PR方程不能很好地关联胆甾醇大分子物质的缺陷,大大提高了关联精度。     

Continuous fractionation of used frying oil by supercritical CO<Subscript>2</Subscript>

Fractionation by supercritical carbon dioxide (SC−CO₂) might be a way to purify used frying oils, since a selective separation of the oil components based on their polarity and M.W. can be attained. In this work, we studied the purification of peanut oil used for frying by SC−CO₂ continuous fractionation in a packed column. The influence of pressure (15–35 MPa) and temperature (25–55°C) on the yield and on the composition of products was determined. The composition of the top and bottom products was evaluated by using size-exclusion chromatography and other accepted chemical methods. Process conditions were selected to separate TG from degraded compounds. Experimental results indicated that the operating conditions leading to maximal TG recovery in the extract were 35 MPa, 55°C, and a solvent-to-feed ratio of 53. By operating at these conditions, it was possible to recover 97% of the TG placed on the column and about 52% by weight of the used frying oil. The composition of the purified top stream was very similar to that of fresh frying oil.     

超临界萃取对中草药有效成分分离的最新进展

本文从超临界技术的发展,原理及其特点、难点和简单工艺流程等几方面做了介绍,综述了超临界流体萃取在中草药有效成分分离提取中的最新进展,评价了该技术的优缺点,并对今后的超临界技术萃取中草药有效成分的发展趋势进行了展望。     

Titania aerogels prepared by low-temperature supercritical drying. Influence of extraction conditions

Titania aerogels with meso- to macroporosity and high specific surface area were prepared by varying the conditions of semicontinuous extraction of methanolic titania gels with CO₂. The conditions varied were extraction temperature, extraction duration, and CO₂ in liquid or supercritical state. The resulting titania aerogels were characterised by means of nitrogen physisorption, X-ray diffraction, thermal analysis and transmission electron microscopy. All uncalcined aerogels contained significant amounts of organic residues (12–14 wt% elemental carbon), and remained X-ray amorphous during calcination in air up to 673 K. Thermoanalytical studies showed that crystallization generally occurred in the range 730–745 K. The variation of the extraction temperature at either constant density or pressure of CO₂, the use of either liquid or supercritical CO₂, and the duration of extraction greatly influenced surface area, pore size distribution, and pore volume. The highest specific surface area (623 m² g^–1) and nitrogen pore volume (4.0 cm³ g^–1) were obtained, if the density of supercritical CO₂ corresponded to that of methanol at the lowest temperature applied (313 K). The studies indicate that textural properties can be varied over a wide range by choosing appropriate extraction conditions.     

超临界CO_2萃取青皮挥发油的工艺研究

采用正交实验法对超临界CO2萃取中药青皮挥发油的最佳工艺条件进行优选。以挥发油得率为考察指标,探讨了萃取压力、萃取温度、萃取时间三因素在不同水平下对青皮挥发油得率的影响,并与水蒸气蒸馏法进行了比较。研究表明,萃取压力对挥发油得率有显著影响,萃取温度及时间影响不显著,各因素作用主次关系为:压力>温度>时间。优选得到的最佳工艺为:萃取压力25 MPa,萃取温度35℃,萃取时间1.5 h,得率为1.3197%,比水蒸气蒸馏法提高2.4倍,时间减少78.57%。超临界CO2萃取收率高、耗时短、品质好。     

饱水竹木漆器的超临界CO_2脱水干燥研究

用超临界CO2对战国时代的饱水竹木漆器（含水率大于200%）进行脱水干燥。结果表明,超临界CO2脱水干燥的最优工艺条件为：干燥温度50℃,压力25 MPa,CO2流量为20 kg/h,脱水干燥5h。在该条件下,脱水干燥的竹木漆器,其含水率下降到了15%以下,漆皮完好如初,色泽鲜亮,样品形状完好、无收缩开裂损坏等现象,符合文物脱水保存的要求。     

Preparative-scale supercritical fluid extraction/supercritical fluid chromatography of corn bran

A preparative-scale supercritical fluid extraction/supercritical fluid chromatography (SFE/SFC) procedure has been developed for the removal of oil from corn bran to obtain fractions enriched with free sterols and ferulate-phytosterol esters (FPE). Operational parameters from an analytical-scale supercritical fluid fractionation technique were translated to and optimized on a home-built, preparatory-scale SFE/SFC apparatus. SFE was performed at 34.5 MPa and 40°C using supercritical carbon dioxide. These conditions did not result in exhaustive extraction of the corn bran, but yielded about 96% of the available oil. SFC was conducted in three steps, followed by reconditioning of the sorbent bed. Preparative-scale SFE/SFC of corn bran produced a fraction enriched greater than fourfold in free sterols and 10-fold in FPE, suggesting that such a scheme could be used industrially to produce a functional food ingredient.     

Characterization of supercritical fluid extracts from raw wool by TLC-FID and GC-MS

Extraction selectivity of whole wool wax from raw wool by using ethanol-modified carbon dioxide at constant pressure (100 bar) and temperature (60°C) was studied. A kinetic study was carried out to optimize the percentage of ethanol and the extraction time. The modified carbon dioxide was decompressed in ethanol as a collection solvent, leading to the formation of two different fractions as a function of their solubility. Qualitative and quantitative analyses of the lipid classes present in the collected fractions were performed by TLC coupled to an automated FID system (TLC-FID). Moreover, a detailed structural comparison was carried out between the aliphatic high-molecular-mass esters and the steryl ester patterns by means of subambient pressure GC-MS in both the EI and the ammonia positive Cl modes. Considerable differences in the lipid composition of the two wool wax fractions collected were observed by TLC-FID and GC-MS.