Enzymatic biodiesel production: Technical and economical considerations

It is well documented in the literature that enzymatic processing of oils and fats for biodiesel is technically feasible. However, with very few exceptions, enzyme technology is not currently used in commercial‐scale biodiesel production. This is mainly due to non‐optimized process design and a lack of available cost‐effective enzymes. The technology to re‐use enzymes has typically proven insufficient for the processes to be competitive. However, literature data documenting the productivity of enzymatic biodiesel together with the development of new immobilization technology indicates that enzyme catalysts can become cost effective compared to chemical processing. This work reviews the enzymatic processing of oils and fats into biodiesel with focus on process design and economy.     

Characterization of Polymer‐Coated RDX and HMX Particles

Fourier transform‐infrared spectroscopy (FT‐IR) in transmission and photoacoustic detection (PAS) techniques have been used for the characterization of polymeric coating of cyclotrimethylenetrinitramine (RDX) using a fluoroelastomer (Viton^®). Although the bands of the polymer were indicated by two different techniques, the transmission (casting film) showed better evidence of absorption of fluoroelastomer for the polymer coating of the energetic material. Also attenuated total reflectance (ATR), another FT‐IR technique, has been used to analyze a cyclotetramethylenetetramine (HMX)/Viton system for the characterization of Viton bands and it showed excellent results without sample preparation.     

A New Method of Dealcoholization of Crude Biodiesel Fuel

In the production of biodiesel fuel from natural oils and fats via transesterification with a surplus of low molecular alcohols biodiesel and glycerol phases are obtained with alcohol residues. The utilization of the dealcoholized glycerol phase for dealcoholization of crude biodiesel phase is discussed. Theoretical relations for the calculation of the optimum conditions of this operation are derived and their validity is experimentally tested on the reaction between rapeseed oil and methanol catalyzed by KOH.     

Versuchsplanerische Untersuchung der Umesterung von Sojaöl mit Ethanol im Mikroreaktor

Base‐catalyzed transesterification of fats and oils with primary alcohols in discontinuous operation is an established batch process for the biodiesel production. However, the application of microreaction technology and continuous flow process lead to an increase of process intensification. The ethanol/soy bean oil ratio at low flow rates as well as the reactor geometry have the most evident effects on the fatty acid ethyl ester yield of KOH‐catalyzed ethanolysis of soy bean oil in microreactors. The influence of the catalyst concentration is of a lower importance.     

生物柴油的制备及发展趋势

生物柴油是一种对环境友好可再生燃料,对解决日益枯竭石油资源和由石化柴油燃烧而带来环境问题有重要意义。本文简要介绍了生物柴油的发展现状、定义、特点及其原料,主要论述了生物柴油的制备方法,并且指出了生物柴油的发展趋势。     

Differentiation of mixtures of monovarietal olive oils by mid‐infrared spectroscopy and chemometrics

Fourier transform infrared (FT‐IR) spectroscopy in combination with chemometric techniques has become a useful tool for authenticity determination of extra‐virgin olive oils. Spectroscopic analysis of monovarietal extra‐virgin olive oils obtained from three different olive cultivars (Erkence, Ayvalik and Nizip) and mixtures (Erkence‐Nizip and Ayvalik‐Nizip) of monovarietal olive oils was performed with an FT‐IR spectrometer equipped with a ZnSe attenuated total reflection sample accessory and a deuterated tri‐glycine sulfate detector. Using spectral data, principal component analysis successfully classified each cultivar and differentiated the mixtures from pure monovarietal oils. Quantification of two different monovarietal oil mixtures (2–20%) is achieved using partial least square (PLS) regression models. Correlation coefficients (R²) of the proposed PLS regression models are 0.94 and 0.96 for the Erkence‐Nizip and Ayvalik‐Nizip mixtures, respectively. Cross‐validation was applied to check the goodness of fit for the PLS regression models, and R² of the cross‐validation was determined as 0.84 and 0.91, respectively, for the two mixtures.     

Oxidation stability of biodiesel fuel as prepared by supercritical methanol

A non-catalytic supercritical methanol method is an attractive process to convert various oils/fats efficiently into biodiesel. To evaluate oxidation stability of biodiesel, biodiesel produced by alkali-catalyzed method was exposed to supercritical methanol at several temperatures for 30 min. As a result, it was found that the tocopherol in biodiesel is not stable at a temperature higher than 300 °C. After the supercritical methanol treatment, hydroperoxides were greatly reduced for biodiesel with initially high in peroxide value, while the tocopherol slightly decreased in its content. As a result, the biodiesel prepared by the supercritical methanol method was enhanced for oxidation stability when compared with that prepared by alkali-catalyzed method from waste oil. Therefore, supercritical methanol method is useful especially for oils/fats having higher peroxide values.     

中国油脂化学工业的进展与预测

叙述了中国油脂化学工业近20年来的发展，肥皂工业经过1989年消费高峰，肥皂产量迅速下降，目前正处在产品结构调整阶段，开始有了较好的效果，油化学品一脂肪酸，脂肪醇和脂肪胺都有较大的发展，但都存在产品供大于求的困难。对此，作了分析和预测，考虑到中国植物油资源基本是以C18脂肪酸为主，对发展油脂化学工业带来了局限性，应充分利用国内外两种油脂资源。     

Risk assessment for prion protein reduction under the conditions of the biodiesel production process

Due to the increased demand for biofuels, all different feedstocks from oils and fats have to be considered for biodiesel production. Animal fats have proved to be excellent sources for biodiesel due to their high cetane number and good stability. Large amounts of fat from so‐called high‐risk material, possibly contaminated with infectious prions, are available for biodiesel production. In this paper, the grade of destruction of prions during the biodiesel production process, including pre‐esterification with conc. sulfuric acid followed by KOH‐catalyzed transesterification, was studied. The starting material of the different production steps was spiked with purified and highly infectious prion rods, and the destruction of these prions was determined by gel electrophoresis (SDS‐PAGE) and Western blot. The pre‐esterification step led to a destruction factor of at least 100, the transesterification led to a factor of at least 250, and the distillation of the final biodiesel showed a destruction factor of at least 1000. During all experiments, no traces of prions could be detected after the different reaction steps. Based on these data, a complete and unequivocal risk assessment regarding the industrial process of biodiesel production was carried out, leading to a calculated overall risk of 5.8×10^?15 ID₅₀ units/person and year, which means that a hypothetical BSE contamination from biodiesel is more than 10⁹ times lower than the background risk.     

The application of biotechnological methods for the synthesis of biodiesel

Synthesis of biodiesel is performed mainly by chemical catalysis, but can also be performed by enzymatic or microbial methods, and these might play an important role in future substitution of petroleum‐based diesel. To discover sustainable, economically attractive biotechnological processes for biodiesel synthesis, close cooperation between different disciplines is needed. Currently, lipases are the enzymes of choice for the synthesis of fatty acid esters (FAE) from fats and oils, yielding biodiesel with the methyl esters (FAME) as the most important product. More recently, the direct production of FAE using engineered whole cell microorganism has also been described (MicroDiesel). Current enzymatic processes are still hampered by the high costs of the biocatalyst, but significant progress has recently been made leading to the first industrial enzymatic biodiesel production. Enzymatic biodiesel production is mostly attractive because of the starting materials (waste frying oils, oils with high water content, etc.), for which conventional chemical interesterification can hardly be applied.     

A review of conventional and renewable biodiesel production

The need for sustainable fuels has resulted in the production of renewables from a wide range of sources, in particular organic fats and oils. The use of biofuel is becoming more widespread as a result of environmental and economic considerations. Several efforts have been made to substitute fossil fuels with green fuels. Ester molecules extracted from processed animal fats and organic plant materials are considered alternatives for the use in modern engine technologies. Two different methods have been adopted for converting esters in vegetable oils/animal fats into compounds consistent with petroleum products, namely the transesterification and the hydro-processing of ester bonds for the production of biodiesel. This review paper primarily focuses on conventional and renewable biodiesel feedstocks, the catalyst used and reaction kinetics of the production process.     

废弃食用油脂运用活性凹凸棒土脱色的试验研究

因为废弃食用油脂直接采用超临界法制备生物柴油的外观品质很差,所以本文选用活性凹凸棒土对废弃食用油脂进行预处理脱色研究,对影响废弃食用油脂脱色率的因素进行了讨论。得出活性凹凸棒土对废弃食用油脂脱色的最佳条件:活性凹凸棒土质量分数15%,初始脱色温度60℃,终止脱色温度110℃,脱色时间20m in,凹凸棒土投放次数为1次,搅拌速度350 r/m in。     

Ester content evaluation in biodiesel from animal fats and lauric oils

A modified method for the determination of ester contents of biodiesel based on EN 14103 has been developed. The method includes natural contents of heptadecanoic acid ester, which are found in animal fats and interfere with the standard method, into the calculation of ester content values. As a result, biodiesel samples prepared from waste animal fats and oils showed an increase in ester content between 2 and 7 wt‐% compared to values measured according to EN 14103. Furthermore, modifications of the GC temperature program made it possible to include also short‐chain fatty acid esters C₈–C₁₂, which can be found in coconut and palm kernel oil, into the calculation. Measurements showed that the ester content of such biodiesel differs by more than 40 wt‐% compared to EN 14103 determinations. However, also the stability of the internal standard solution methyl heptadecanoate influences the values of ester content. It can be demonstrated that after a period of 7 days, an ester content decrease of about 2 wt‐% can be observed. Therefore, the use of almost freshly prepared standard solutions should be recommended.     

Comparison of fatty acid profiles and mid‐infrared spectral data for classification of olive oils

The composition of olive oils may vary depending on environmental and technological factors. Fatty acid profiles and Fourier‐transform infrared (FT‐IR) spectroscopy data in combination with chemometric methods were used to classify extra‐virgin olive oils according to geographical origin and harvest year. Oils were obtained from 30 different areas of northern and southern parts of the Aegean Region of Turkey for two consecutive harvest years. Fatty acid composition data analyzed with principal component analysis was more successful in distinguishing northern olive oil samples from southern samples compared to spectral data. Both methods have the ability to differentiate olive oil samples with respect to harvest year. Partial least squares (PLS) analysis was also applied to detect a correlation between fatty acid profile and spectral data. Correlation coefficients (R²) of a calibration set for stearic, oleic, linoleic, arachidic and linolenic acids were determined as 0.83, 0.97, 0.97, 0.83 and 0.69, respectively. Fatty acid profiles were very effective in classification of oils with respect to geographic origin and harvest year. On the other hand, FT‐IR spectra in combination with PLS could be a useful and rapid tool for the determination of some of the fatty acids of olive oils.     

Short‐chain fatty acids as marker for the degradation of frying fats and oils

The determination of fatty acid composition by gas chromatography as a routine task is established in most laboratories dealing with oils and fats. The scope of this method can be enlarged for a preliminary quality control of used frying fats and oils, which is commonly characterized by the determination of polar compounds and polymerized triacylglycerols. However, for screening purposes the determination of the short‐chain fatty acids C7:0 and C8:0 can give an early indication about the quality of used frying fats and oils.     

Biodiesel: Current Trends and Properties

Biodiesel, an alternative to petroleum-derived diesel fuel, is defined as the mono-alkyl esters of vegetable oils and animal fats. Several current issues affecting biodiesel that are briefly discussed include the role of new feedstocks in meeting increased demand for biodiesel and circumventing the food versus fuel issue, biodiesel production, as well as fuel properties and their improvement.     

Ultra high performance liquid chromatography–mass spectrometric analysis of oxidized free fatty acids and acylglycerols

A fast ultra high performance liquid chromatography (UHPLC)–electrospray ionization (ESI)–mass spectrometric (MS) method was developed for simultaneous analysis of free fatty acids (FFAs), monoacylglycerols (MAG), diacylglycerols (DAG), triacylglycerols (TAG), and their oxidized equivalents. Effect of elevated column temperature was studied in order to optimize the chromatography of closely eluting peaks and to reduce high back pressure formed in UHPLC. The elevated temperature enabled high flow rate, better mass transfer, and therefore more narrow peaks and better separation of the analytes. The new method was applied to the analysis of total lipid extracts of lipolysis samples prepared by an artificial digestion model in order to investigate oxidized lipids and changes in their profiles in the chyme. Over 150 compounds were identified from the extracts. The UHPLC–ESI–MS method was proved to be fast, highly selective, and sensitive. Compared to a previously used high performance LC–ESI–MS method, the new UHPLC–ESI–MS method was over five times faster and consumed one tenth of the solvents while producing comparable quantitative results. Practical applications: Edible oils and fats contain mainly TAGs, the lipolysis of which produces FFAs and MAGs with minor DAG components. These compounds are susceptible to oxidation in the stomach, and therefore the analysis of the oxidation products is important. Fast determination of FFAs and acylglycerols is also important in quality control of biodiesel. Our new method enables accurate and sensitive determination of different molecular species present in digested and processed samples with minimal sample preparation requirements. In this respect, the new method is applicable to large scale and fast screening of biological samples for lipidomic and metabolomic studies.     

Natural plant oils and fats as renewable resources: A sustainable option?

Whilst many opportunities for the utilisation of natural oils and fats have been identified in scientific and technical studies there has been little uptake by the marketplace. Recent policy decisions related to climate change have driven a new market development in biodiesel and this development has overshadowed almost all of the other potential market developments that could occur in this sector. A re‐establishment of balance is required. Further, there is a need to develop awareness and promote the uptake of the opportunities available; frequently there are non‐technical barriers to development.     

Evaluation of partially hydrogenated methyl esters of soybean oil as biodiesel

Biodiesel, an alternative fuel derived from vegetable oils or animal fats, continues to undergo rapid worldwide growth. Specifications mandating biodiesel quality, most notably in Europe (EN 14214) and the USA (ASTM D6751), have emerged that limit feedstock choice in the production of biodiesel fuel. For instance, EN 14214 contains a specification for iodine value (IV; 120 g I₂/100 g maximum) that eliminates soybean oil as a potential feedstock, as it generally has an IV >120. Therefore, partially hydrogenated soybean oil methyl esters (PHSME; IV = 116) were evaluated as biodiesel by measuring a number of fuel properties, such as oxidative stability, low‐temperature performance, lubricity, kinematic viscosity, and specific gravity. Compared to soybean oil methyl esters (SME), PHSME were found to have superior oxidative stability, similar specific gravity, but inferior low‐temperature performance, kinematic viscosity, and lubricity. The kinematic viscosity and lubricity of PHSME, however, were within the prescribed US and European limits. There is no universal value for low‐temperature performance in biodiesel specifications, but PHSME have superior cold flow behavior when compared to other alternative feedstock fuels, such as palm oil, tallow and grease methyl esters. The production of PHSME from refined soybean oil would increase biodiesel production costs by US$ 0.04/L (US$ 0.15/gal) in comparison to SME. In summary, PHSME are within both the European and American standards for all properties measured in this study and deserve consideration as a potential biodiesel fuel.     

Lipidomic analysis of fats and oils – a lot more than just omega‐3

Edible oils and fats are among the most abundant cooking ingredients in the world, and are an important part of a healthy balanced diet, especially if they are high in omega‐6 and omega‐3 polyunsaturated fatty acids. Rather than just the total fatty acid compositions, the analysis of individual lipid species within these oils and fats has become increasingly important. Within the past decade several mass spectrometric lipidomics methods have been adapted and applied to the analysis of edible oils and fats. These methodologies are vital for the analysis of a plethora of lipid species that will be important for numerous health and sustainability issues in the future.