Characteristics of structured lipid prepared by lipase-catalyzed acidolysis of roasted sesame oil and caprylic acid in a bench-scale continuous packed bed reactor

Structured lipid (SL) was prepared from roasted sesame oil and caprylic acid (CA) by Rhizomucor miehei lipase-catalyzed acidolysis in a bench-scale continuous packed bed reactor. Total incorporation and acyl migration of CA in the SL were 42.5 and 3.1 mol %, respectively, and the half-life of the lipase was 19.2 days. The SL displayed different physical and chemical properties, less saturated dark brown color, lower viscosity, lower melting and crystallization temperature ranges, higher melting and crystallization enthalpies, higher smoke point, higher saponification value, and lower iodine value, in comparison to those of unmodified sesame oil. The oxidative stability of purified SL was lower than that of sesame oil. There were no differences in the contents of unsaponifiables including tocopherols and phytosterols. However, total sesame lignans content was decreased in SL due to the loss of sesamol when compared to sesame oil. Most of the 70 volatiles present in roasted sesame oil were removed from SL during short-path distillation of SL. These results indicate that the characteristics of SL are different from those of original sesame oil in several aspects except for the contents of tocopherols and phytosterols.     

利用小型流化床的生物质热裂解影响因素分析

化石能源的储量减少与污染使人们必须寻找其他替代能源,其中生物质能是一个很好的替代品.该文以榆木木屑、红松木屑和秸秆为原料,在自制的小型流化床上开展了生物质热裂解生物油的实验研究.结果表明红松木屑的产油率最高,热裂解的温度对产油率的影响很大,500℃时生物油的产量最高,热裂解温度越高,裂解气体产量越高,气体热值也越高,而碳的产量越低.而且随着反应时间的变化,裂解气体成分也发生变化,在裂解10 min左右,裂解气体中可燃气体成分最高.     

Synthesis of structured triacylglycerols by lipase-catalyzed acidolysis in a packed bed bioreactor

Structured triacylglycerols (ST) from canola oil were produced by enzymatic acidolysis in a packed bed bioreactor. A commercially immobilized 1,3-specific lipase, Lipozyme IM, from Rhizomucormiehei, was the biocatalyst and caprylic acid the acyl donor. Parameters such as substrate flow rate, substrate molar ratio, reaction temperature, and substrate water content were examined. High-performance liquid chromatography was used to monitor the reaction and product yields. The study showed that all of the parameters had effects on the yields of the expected di-incorporated (dicaprylic) ST products. Flow rates below 1 mL/min led to reaction equilibrium, and lower flow rates did not raise the incorporation of caprylic acid and the product yield. Incorporation of caprylic acid and the targeted di-incorporated ST was increased by approximately 20% with temperature increase from 40 to 70 degrees C. Increasing the substrate molar ratio from 1:1 to 7:1 increased the incorporation of caprylic acid and the product yield slightly. Water content in the substrate also had a mild influence on the reaction. Water content at 0.08% added to the substrate gave the lowest incorporation and product yield. The use of solvent in the medium was also studied, and results demonstrated that it did not increase the reaction rate at 55 degrees C when 33% hexane (v/v) was added. The main fatty acids at the sn-2 position of the ST were C(18:1), 54. 7 mol %; C(18:2), 30.7 mol %; and C(18:3), 11.0 mol %.     

开孔支管旋转导向管喷动床干燥油菜籽试验

为了改善旋转导向管喷动床环隙区的干燥性能,提出了附带支管的旋转导向管喷动床的新设计方案,采用油菜籽为原料,研究此新型喷动床的干燥性能。分别以单位质量水的热耗值、油菜籽的最高温度和干燥过程中油菜籽在喷动床柱体中的平均温度为试验指标,对支管式旋转导向管喷动床按L16(45)正交试验设计方法进行了风温、风量、导喷距及支管孔开放率4因素4水平的正交试验,得到以单位质量水热耗值为指标的最优干燥工艺为：风温130.0℃、标态风量为 58.0 m3/h、导喷距75.0 mm、开孔支管的孔开放率67%,最优工艺下单位质量水分热耗值为2736.8 kJ/kg,比不带支管的旋转导向管喷动床的最优值3941.4 kJ/kg低,说明支管的引入能够降低干燥热耗,可考虑用于放大柱锥形喷动床。     

Hypolipidemic effect of oils with balanced amounts of fatty acids obtained by blending and interesterification of coconut oil with rice bran oil or sesame oil

Blended oils comprising coconut oil (CNO) and rice bran oil (RBO) or sesame oil (SESO) with saturated fatty acid/monounsaturated fatty acid/polyunsaturated fatty acid at a ratio of 1:1:1 and polyunsaturated/saturated ratio of 0.8-1 enriched with nutraceuticals were prepared. Blended oils (B) were subjected to interesterification reaction using sn-1,3 specific Lipase from Rhizomucor miehei. Fatty acid composition and nutraceutical contents of the blended oil were not affected by interesterification reaction. Male Wistar rats were fed with AIN-76 diet containing 10% fat from CNO, RBO, SESO, CNO+RBO blend (B), CNO+SESO(B), CNO+RBO interesterified (I), or CNO+SESO(I) for 60 days. Serum total cholesterol (TC), low-density lipoprotein cholesterol, and triacylglycerols (TAGs) were reduced by 23.8, 32.4, and 13.9%, respectively, in rats fed CNO+RBO(B) and by 20.5, 34.1, and 12.9%, respectively, in rats fed CNO+SESO(B) compared to rats given CNO. Rats fed interesterified oils showed a decrease in serum TC, low-density lipoprotein cholesterol (LDL-C), and TAGs in CNO+RBO(I) by 35, 49.1, and 23.2 and by 33.3, 47, and 19.8% in CNO+SESO(I), respectively, compared to rats given CNO. Compared to rats fed CNO+RBO blended oils, rats on CNO+RBO interesterified oil showed a further decrease of 14.6, 24.7, and 10% in TC, LDL-C, and TAG. Rats fed CNO+SESO interesterified oils showed a decrease in serum TC, LDL-C, and TAG by 16.2, 19.6, and 7.8%, respectively, compared to rats given blended oils of CNO+SESO (B). Liver lipid analysis also showed significant change in the TC and TAG concentration in rats fed blended and interesterified oils of CNO+RBO and CNO+SESO compared to the rats given CNO. The present study suggests that feeding fats containing blended oils with balanced fatty acids lowers serum and liver lipids. Interesterified oils prepared using Lipase have a further lowering effect on serum and liver lipids even though the fatty acid composition of blended and interesterified oils remained same. These studies indicated that the atherogenic potentials of a saturated fatty acid containing CNO can be significantly decreased by blending with an oil rich in unsaturated lipids in appropriate amounts and interesterification of blended oil.     

Characterization of stearidonic acid soybean oil enriched with palmitic acid produced by solvent-free enzymatic interesterification

Stearidonic acid soybean oil (SDASO) is a plant source of n-3 polyunsaturated fatty acids (n-3 PUFAs). Solvent-free enzymatic interesterification was used to produce structured lipids (SLs) in a 1 L stir-batch reactor with a 1:2 substrate mole ratio of SDASO to tripalmitin, at 65 °C for 18 h. Two SLs were synthesized using immobilized lipases, Novozym 435 and Lipozyme TL IM. Free fatty acids (FFAs) were removed by short-path distillation. SLs were characterized by analyzing FFA and FA (total and positional) contents, iodine and saponification values, melting and crystallization profiles, tocopherols, and oxidative stability. The SLs contained 8.15 and 8.38% total stearidonic acid and 60.84 and 60.63% palmitic acid at the sn-2 position for Novozym 435 SL and Lipozyme TL IM SL, respectively. The SLs were less oxidatively stable than SDASO due to a decrease in tocopherol content after purification of the SLs. The saponification values of the SLs were slightly higher than that of the SDASO. The melting profiles of the SLs were similar, but crystallization profiles differed. The triacylglycerol (TAG) molecular species of the SLs were similar to each other, with tripalmitin being the major TAG. SDASO's major TAG species comprised stearidonic and oleic acids or stearidonic, α-linolenic, and γ-linolenic acids.     

水酶法提取菜籽乳化油的工艺研究

为获得温和的制油工艺，该文采用了多种细胞壁多糖酶制剂对湿磨菜籽浆进行水相酶解法提油。同时对菜籽内源硫苷酶的湿热灭活条件及硫苷的湿热稳定性进行了研究，并优化了酶解的工艺条件。结果表明：沸水处理5 min可以有效钝化菜籽内源硫苷酶，此时硫苷的降解率为11.28％；果胶酶、纤维素酶和β-葡聚糖酶经复配(4∶1∶1)后处理菜籽比单一酶制剂的作用效果好，复合酶解最适工艺条件为：固液比1∶5，加酶量3％，酶解时间5 h，在此条件下乳化油得率为92.45％。     

Enrichment of anhydrous milk fat in polyunsaturated fatty acid residues from linseed and rapeseed oils through enzymatic interesterification

Lipozyme TL IM was used in a solvent-free batch and microaqueous system for enzymatic interesterification of anhydrous milkfat (AMF) with linseed oil (LO) in binary blends and with rapeseed oil (RO) in one ternary blend. The aim was to obtain and characterize physicochemically fats enriched with unsaturated C 18 fatty acids (oleic, linoleic, and, especially, linolenic acids) from natural vegetable oils. Binary blends of AMF/LO 100/0, 90/10, 80/20, 70/30, and 60/40 (w/w) were interesterified. The change in triacylglycerol (TAG) profiles showed that quasi-equilibrium conditions were reached after 4-6 h of reaction. Free fatty acid contents <1%. The decrease in solid fat content and in dropping point temperature obtained with increasing content of LO and interesterification resulted in good plastic properties for the products originating from the blends 70/30 and 60/40. This was confirmed by textural measurements. Melting profiles determined by differential scanning calorimetry showed complete disappearance of low-melting TAGs from LO and the formation of intermediary species with a lower melting temperature. Oxidative stability of the interesterified products was diminished with increasing LO content, resulting in low oxidation induction times. A ternary blend composed of AMF/RO/LO 70/20/10 gave satisfactory rheological and oxidative properties, fulfilling the requirements for a marketable spread and, moreover, offering increased potential health benefits due to the enriched content in polyunsaturated fatty acid residues.     

Chemical interesterification of blends of palm stearin, coconut oil, and canola oil: physicochemical properties

trans-Free interesterified fat was produced for possible usage as a margarine. Palm stearin, coconut oil, and canola oil were used as substrates for chemical interesterification. The main aim of the present study was to evaluate the physicochemical properties of blends of palm stearin, coconut oil, and canola oil submitted to chemical interesterification using sodium methoxide as the catalyst. The original and interesterified blends were examined for fatty acid composition, softening and melting points, solid fat content, and consistency. Chemical interesterification reduced softening and melting points, consistency, and solid fat content. The interesterified fats showed desirable physicochemical properties for possible use as a margarine. Therefore, our result suggested that the interesterified fat without trans-fatty acids could be used as an alternative to partially hydrogenated fat.     

Interesterification of olive oil with a fully hydrogenated fat in a batch reactor using step changes in temperature

Interesterification of a 60:40 (wt/wt) mixture of olive oil and fully hydrogenated canola oil was carried out in a batch reactor using a commercial immobilized lipase from Thermomyces lanuginose as a biocatalyst. The effects of a stepwise change of temperature on the degree of conversion, the solid fat content (SFC) of the products, and the residual activity of the enzyme were investigated. As a reference condition, an interesterification trial was conducted at a constant temperature of 70 degrees C for 48 h. For trials in which a temperature of 70 degrees C was used for the first 4 h of reaction and a temperature of 60 degrees C was employed for the following 44 h, there were no significant differences (p < 0.05) in the overall degree of conversion relative to the reference condition. Oils interesterified for only 1 or 2 h at 70 degrees C had melting points higher than 60 degrees C, whereas an oil produced by interesterification at 70 degrees C for only 4 h had a melting point of 58 degrees C. There was little difference (p < 0.05) between the SFC profiles of the interesterification products prepared by two different temperature protocols (70 degrees C for 24 h; 70 degrees C for 4 h followed by 60 degrees C for 20 h). Use of the protocol involving a step decrease in temperature significantly decreased catalyst deactivation effects, thereby increasing the residual activity of the immobilized lipase.     

油菜籽过热蒸汽流化床常压干燥过程的数学模拟

为提高过热蒸汽流化床干燥模型的模拟精度,该文基于过热蒸汽流化床干燥机理,结合“双流体”理论建立了描述过热蒸汽流化床干燥过程的非稳态轴对称二维数学模型。利用有限体积法求解模型,模拟研究了常压下油菜籽的过热蒸汽流化床干燥过程及其干燥动力学特性,模拟结果与试验数据相吻合。研究结果表明,该模型能够很好地描述常压下油菜籽的过热蒸汽流化床干燥过程和物料在干燥过程中的运动状态。     

Determination of multiresidues in rapeseed, rapeseed oil, and rapeseed meal by acetonitrile extraction, low-temperature cleanup, and detection by liquid chromatography with tandem mass spectrometry

A multiresidue method for determining pesticides in rapeseed, rapeseed oil, and rapeseed meal by use of liquid chromatography-tandem mass spectrometry is developed. Samples were extracted with acetonitrile or acidified acetonitrile and cleaned up by a 12 h freezing step. The recovery data were obtained by spiking blank samples at three concentration levels. The recoveries of 27 selected pesticides in rapeseed, rapeseed oil, and rapeseed meal were in the range of 70-118%, at the concentration level of 10 μg kg(-1), with intraday and interday precisions of lower than 22 and 27%, respectively. Linearity was studied between 2 and 500 μg L(-1) with determination coefficients (R(2)) of higher than 0.98 for all compounds in the three matrices. The limits of quantitation (LOQs) of pesticides in rapeseed, rapeseed oil, and rapeseed meal ranged from 0.3 to 18 μg kg(-1). The n-octanol-water partition coefficient showed more influence than water solubility in extracting pesticides by acetonitrile from matrices of high fat content. This method was successfully applied for routine analysis in commercial products.     

利用菜籽油酶法生产生物柴油的初步研究

生物柴油作为可再生能源，对环境友好，引起了世界范围内的广泛关注。该文利用固定化脂肪酶－Novo435，在无有机溶剂存在的情况下，催化菜籽油与甲醇酯交换反应制取生物柴油，对影响酯交换反应过程的因素：甲醇与油脂的摩尔比、反应温度、反应时间、脂肪酶用量、转速、水分等进行深入研究，得到了菜籽油间歇酯交换反应的适宜工艺条件：转速200 r/min、醇油摩尔比1.5∶1、反应温度50℃、酶用量10%(与油脂的质量比)、反应10 h后菜籽油的酯交换率达到47％。水分的存在不利于固定化酶在无有机溶剂系统下催化菜籽油的酯交换反应，使酯交换率降低到30％。反应所需理论甲醇量分两次加入，反应26 h后，油脂的酯交换率达到80％。     

叔丁醇体系脂肪酶催化菜籽油制备生物柴油

为了在生物柴油制备中改善酶的催化环境,该文通过对脂肪酶LVK催化菜籽油乙醇解反应几个主要影响因素的研究,得出其最佳反应条件为：醇油摩尔比5∶1,催化剂用量10%,叔丁醇用量10%,反应温度40℃,反应时间为30 h,转酯率达到94.7%。研究表明10%的叔丁醇体系能完全解除乙醇对脂肪酶LVK的催化抑制作用;还消解除副产物甘油对脂肪酶LVK的失活。     

菜籽油生物柴油的生产方法研究进展

该文阐述了菜籽油用于生物柴油生产的优势及菜籽油生物柴油的环境友好性,认为该产业很有发展前途,并概述了国内外利用化学法、脂肪酶法和超临界流体法制备菜籽油生物柴油的研究进展,并评价了各种制备方法的优劣性.发现化学法是比较成熟的工业化方法,具有反应快、成本低的特点,但污染大;酶法反应温和,但成本高、反应缓慢;超临界流体法不需使用催化剂,但要在高温高压下反应;最后提出了影响菜籽油生物柴油产业化发展的因素及对策.     

Apple juice clarification by immobilized pectolytic enzymes in packed or fluidized bed reactors

The catalytic behavior of a mixture of pectic enzymes, covalently immobilized on different supports (glass microspheres, nylon 6/6 pellets, and PAN beads), was analyzed with a pectin aqueous solution that simulates apple juice. The following parameters were investigated: the rate constant at which pectin hydrolysis is conducted, the time (tau(50)) in which the reduction of 50% of the initial viscosity is reached, and the time (tau(comp,dep)) required to obtain complete depectinization. The best catalytic system was proven to be PAN beads, and their pH and temperature behavior were determined. The yields of two bed reactors, packed or fluidized, using the catalytic PAN beads, were compared to the circulation flow rate of real apple juice. The experimental conditions were as follows: pH 4.0, T = 50 degrees C, and beads volume = 20 cm(3). The initial pectin concentration was the one that was present in our apple juice sample. No differences were observed at low circulation rates, while at higher recirculation rates, the time required to obtain complete pectin hydrolysis into the fluidized reactor was found to be 0.25 times smaller than in the packed bed reactor: 131 min for the packed reactors and 41 min for the fluidized reactors.     

Hydrogenation and interesterification effects on the oxidative stability and melting point of soybean oil

Soybean oil with an iodine value of 136 was hydrogenated to have iodine values of 126 and 117. The soybean oils with iodine values of 136, 126, and 117 were randomly interesterified using sodium methoxide. The oxidative stabilities of the hydrogenated and/or interesterified soybean oils were evaluated by measuring the headspace oxygen content by gas chromatography, and the induction time was measured using Rancimat. The melting points of the oils were evaluated by differential scanning calorimetry. Duncan's multiple range test of the headspace oxygen and induction time showed that hydrogenation increased the headspace oxygen content and induction time at alpha = 0.05. Interesterification decreased the headspace oxygen and the induction time for the soybean oils with iodine values of 136, 126, and 117 at alpha = 0.05. Hydrogenation increased the melting points as the iodine value decreased from 136 and 126 to 117 at alpha = 0.05. The random interesterification increased the melting points of soybean oils with iodine values of 136, 126, and 117 at alpha = 0.05. The combined effects of hydrogenation and interesterification increased the oxidative stability of soybean oil at alpha = 0.05 and the melting point at alpha = 0.01. The optimum combination of hydrogenation and random interesterification can improve the oxidative stability and increase the melting point to expand the application of soybean oil in foods.     

固体碳源填充床反应器脱除污水硝态氮效能的预测模型

为了预测固相反硝化反应器出水的硝酸盐浓度,优化工艺参数,以聚羟基丁酸戊酸共聚酯[Poly(3-Hydroxybutyrate-co-3-Hydroxyvalerate),PHBV]作为反应器的碳源和生物膜载体,对受硝酸盐污染的水进行生物反硝化脱氮。采用Box-Behnken试验设计,利用响应曲面法研究了反应器出水硝态氮浓度与进水硝态氮浓度、水力停留时间(hydraulic retention time,HRT)和温度之间的关系,建立了以出水硝态氮浓度为响应值的二次多项式回归模型。该数学模型可以定量描述进水硝态氮浓度、HRT和温度对出水硝态氮浓度的影响,模型预测值与试验值能吻合较好。方差分析结果表明,进水硝态氮浓度、温度和HRT及其交互作用对响应值均具有显著性影响(P<0.05)。     

近红外光谱分析法测定菜籽油中芥酸的含量

采用多通道PDA型近红外光谱仪,应用偏最小二乘法建立了菜籽油中芥酸含量与近红外透射光谱的校正模型,讨论多项式求导及平滑的窗口宽度和相关系数法筛选有效波长对校正模型的影响,并对10个预测集样品利用预测相关系数R_p和预测均方根误差RMSEP指标进行了预测精度分析,结果发现：在使用全谱数据进行偏最小二乘回归建模时,一阶7点求导及平滑的预处理方法结果最佳,此时建模效果为：R_p=0.739,RMSEP=1.659;在此基础上通过相关系数法筛选波长后的建模效果为：R_p=0.958,RMSEP=0.963。后者R_p提高29%,RMSEP减少42%。由此可得出多项式求导及平滑法和相关系数法相结合对校正模型稳健性,预测精度都有较大提高的结论。研究证明：多通道近红外光谱仪快速测测菜籽油中芥酸含量的方法是可行的。     

固定化细胞磁稳定流化床反应器制备生物柴油

为了探索生物酶法制备生物柴油新工艺,克服现有工艺的不足,采用超顺磁性全细胞催化剂在自制的磁稳定流化床中对废油脂连续生产生物柴油进行了试验研究。考察了改变磁场强度、进料醇油摩尔比、催化剂用量及流量等因素对连续酯交换反应的影响,进而得到单级磁流化床酯交换反应的最佳工艺条件：磁稳态操作,醇油摩尔比为1∶1,催化剂用量为原料油质量的12%,进料流量为42.6?mL/min。四级磁流化床连续系统最终转酯化率达到85%以上,连续反应200 h后四级出口的甲酯产率仍在80%以上。这说明全细胞催化剂在磁稳定流化床中活性较高,使用寿命较长,该系统具有良好的操作稳定性。