酶催化酯交换制备零反式脂肪酸食品专用油脂基料的性质研究

研究了以大豆油和极度氢化棕榈油为原料,采用脂肪酶Lipozyme TLIM催化酯交换反应制备的零反式脂肪酸食品专用油脂基料的性质。酶法酯交换反应条件为反应温度60℃、反应时间3 h、酶添加量4%(占油脂总质量)、大豆油与极度氢化棕榈油质量比4∶3。对比了酯交换反应前后混合油脂的热性质、固体脂肪含量、晶体形态和微观形态。结果表明:酶法酯交换反应后,产物熔融、结晶温度均降低;酯交换产物以β'晶型为主,晶体颗粒均匀、较小;当温度高于25℃后固体脂肪含量减小,产物在高于45℃时可全部融化。因此,酯交换油脂适用于制备烘焙型食品专用油脂基料。     

利用酯交换法制备零反式脂肪酸人造奶油基料油的研究

极度氢化大豆油为饱和甘三酯,几乎没有双键,故不存在反式酸,将大豆油与极度氢化大豆油按不同比例混合进行酯交换反应可以得到不同固体特征的油脂。利用酯交换油脂代替氢化油做基料,降低反式酸,开发健康营养型的人造奶油,对酯交换油脂的固体含量（SFC）、熔点以及融化和结晶特性进行了分析,为今后的新产品研究和开发提供参考。     

超临界CO_2条件下大豆油极度氢化的研究

以机榨大豆油为原料,在超临界CO_2体系中,选取Pd/C作为催化剂催化极度氢化反应,通过单因素试验,确定催化剂添加量、氢气压力、反应时间、反应温度及搅拌速度的最适量。在最优条件下制备出极度氢化大豆油的碘值为2.6 gI_2/100 g,反式脂肪酸含量为0.23%(可看作零反式脂肪酸含量),VE含量186.7 mg/kg。与常规极度氢化反应相比,反应温度降低了70℃,反应时间缩短了60 min,提高了极度氢化油的质量。Pd/C催化剂可回收重复使用6次,降低了生产成本。     

食用级大豆油极度氢化工艺探索

研究了大豆油极度氢化的速率和氢化工艺参数之间的关素,讨论了氢气压力、反应温度、催化剂浓度对大豆油极度氢化速度和选择性的影响。并得出结论:大豆油在较高的氢气压力、适中的反应温度和适量的催化剂浓度的条件下极度氢化可以得到较满意的加氢速度及较理想的产品质量;并通过研究证实,用快速熔点测定法判断极度氢化反应终点,简便易行且比较可靠,对油脂极度氢化工业生产具有指导意义。     

蒙脱土负载KF和SrO催化制备生物柴油的研究

以蒙脱土(MMT)、KF和Sr O为原料,采用浸渍法制备了负载型固体碱催化剂(KSr/MMT),并研究了KSr/MMT催化大豆油和甲醇反应制备生物柴油的性能。利用X射线衍射(XRD)、扫描电子显微镜(SEM)、二氧化碳程序升温脱附(CO2-TPD)对催化剂进行了结构表征,探讨了催化剂结构与性能之间的关系,考察了催化剂制备因素和反应条件对酯交换反应的影响。结果表明:在催化剂KSr/MMT中,Sr F2为主要的活性组分;在常压下,醇油摩尔比9∶1、KF负载量为25%的KSr/MMT用量3%、反应温度65℃和反应时间1 h催化大豆油和甲醇酯交换反应的产率高达99%。同时对KSr/MMT催化酯交换反应的动力学进行研究。     

鸭蛋壳制备的CaO固体碱催化大豆油制备生物柴油

将700~1000℃焙烧鸭蛋壳4h制备的氧化钙(CaO)固体碱催化剂用于大豆油与甲醇酯交换反应制备生物柴油,用XRD和N2-吸附对其进行了表征,研究了焙烧温度对催化剂结构及催化性能的影响,考察了反应温度、甲醇与大豆油摩尔比、催化剂用量和反应时间对生物柴油收率的影响。结果表明:以900℃焙烧鸭蛋壳制备的CaO固体碱为催化剂,在反应温度90℃、甲醇与大豆油摩尔比9∶1、催化剂用量3.0%(占大豆油质量)、正庚烷用量30.0%(占大豆油质量)和反应时间4h的条件下,生物柴油的收率可达99.1%。催化剂重复使用12次后,生物柴油的收率仍大于97%。说明CaO固体碱催化剂在大豆油与甲醇酯交换反应中具有良好的催化活性和重复使用性。     

脂酶催化下大豆粉末磷脂与全氢化大豆油酯交换反应的研究

本文利用脂酶的特异性催化作用,研究了正己烷体系中,大豆粉末磷脂与全氢化大豆油的酯交换反应。利用碘值和产率为指标,考察了酶的种类及用量、底物摩尔比、温度、时间等因素对酯交换反应的影响,通过单因素和正交试验优化了大豆粉末磷脂与全氢化大豆油酯交换反应条件。发现在25%磷脂酶A1(以磷脂质量为基准)催化下,摩尔比4:1的全氢化大豆油和大豆粉末磷脂的正己烷溶液(磷脂浓度为0.20 g/mL),在50 ℃下反应24 h,得到产率为72.9%的改性磷脂。与原料磷脂相比,改性磷脂的碘值由89 g /100 g降至52 g /100 g,脂肪酸组成变化较大,硬脂酸含量约为原料磷脂的9倍,不饱和脂肪酸亚麻酸和亚油酸含量降低了约一半,实现了大豆粉末磷脂的结构修饰。     

废工业棕榈油制备生物柴油的研究

利用固体酸作催化剂对酸值较高的废棕榈油进行预酯化,采用正交试验优化预酯化的工艺条件,最佳工艺条件是:反应温度为70 ℃,反应时间为4.0 h,固体酸催化剂的用量为3.0%,预处理后废棕榈油的酸值为2.18 mg KOH/g.研究了预酯化后的废棕榈油与甲醇进行的酯交换反应,得到最优工艺条件是:反应温度为65 ℃,反应时间为1.0 h,催化剂KOH的用量为1.0%,酯交换反应的转化率为96.85%,生物柴油总得率为93.2%.以废棕榈油为原料制备的生物柴油,除倾点较高外,其主要性能均符合柴油标准.     

非水相酶促酯交换法合成抗坏血酸脂肪酸酯

研究了一种L-抗坏血酸脂肪酸酯（AFAE）合成新途径。实验结果表明，氢化棕榈油、大豆油和海狗油等食用油脂作为脂肪酸基团供体，在固定化脂肪酶的催化下，在有机溶荆中与L-抗坏血酸直接进行酯交换反应形成L-抗坏血酸脂肪酸酯。对反应介质体系的筛选发现，在叔戊醇中用Novozym435催化此反应所得的产物浓度最高。对影响合成抗坏血酸脂肪酸酯的因素进行了探讨，确定了最适反应条件：初始油脂底物浓度为200-600mmol／L，温度为55℃，反应时间为9h。此条件下产物质量浓度可达43．51g／L。     

SnO2-Al2O3固体酸催化大豆油酯交换制备生物柴油

采用共沉淀法制备SnO2-Al2O3复合固体酸催化剂,用于催化大豆油甲醇解反应,考察催化剂制备条件和酯交换反应条件对大豆油转化率影响。研究结果表明,催化剂最佳制备条件为Sn／A1摩尔比3：1,煅烧温度为923K;催化大豆油酯交换反应醇油摩尔比30：1,催化剂用量3wt．％,反应时间5h,反应温度200℃,此时大豆油转化率最高,为75．05％。当向酯交换反应体系加入一定量游离脂肪酸或水分时,SnO2-Al2O3催化剂催化活性几乎不受影响,且还能同时催化酯化反应;结果还表明,固体酸SnO2-Al2O3具有很好稳定性,可多次重复利用。     

Thermal and crystal characteristics of enzymatically interesterified fats of fatty acid-balanced oil and fully hydrogenated soybean oil in supercritical CO2 system

Blends of fatty acid-balanced oil that was prepared by the aqueous enzymatic extraction, and with fully hydrogenated soybean oil in different weight ratios from 30:70 to 80:20 (wt%) were interesterified using Lipozyme RM IM in a supercritical CO₂ system. The optimal immobilized enzyme dosage, pressure, substrate ratio, temperature, and time were 6% (w/w) of initial substrates, 8 MPa, blend ratio with 60:40 (wt%) of fatty acid-balanced oil and fully hydrogenated soybean oil, a temperature of 70°C, and reaction time of 2 h, respectively. It was observed that at the optimal conditions, under supercritical CO₂ conditions, the reaction time of the interesterification was shorter than that of conventional enzymatic interesterification. The slip melting point, solid fat content, fatty acid composition, differential scanning calorimetry, polymorphic form and crystal morphology of the enzymatically interesterified fats were evaluated. The results indicated that the interesterified fats showed desirable physical properties with lower slip melting point and solid fat content, suitable crystal form (β′ polymorph), and without trans-fatty acid for possible use as a shortening and margarine stock.     

6种食品专用油脂的风味特征研究

旨在为食品专用油脂的风味提升提供参考,采用顶空固相微萃取-气相色谱-质谱联用(HS-SPME-GC-MS)技术和感官评定分析黄油、椰子油、全氢化棕榈仁油、全氢化棕榈仁油硬脂、部分氢化大豆油和全氢化大豆油6种代表性食品专用油脂的挥发性成分和感官特征,并结合相对气味活度值(ROAV)及其聚类分析确定关键风味化合物。结果显示：椰子油的挥发性成分最为丰富,共鉴定出13个关键风味化合物,主要为内酯类、醛类化合物,椰子香和奶油香风味浓郁;黄油共鉴定出8个关键风味化合物,主要为内酯类、酮类和醛类化合物,具有果香、奶油香和青香;部分氢化大豆油共鉴定出6个关键风味化合物,主要为醛类和酮类化合物,主要呈果香、蜜蜡香、脂肪气味和奶油香;全氢化棕榈仁油、全氢化大豆油和全氢化棕榈仁油硬脂检出的关键风味化合物种类较少,分别为5个、2个和4个,主要为醛类和甲酯类/酸类化合物,主要呈果香风味和脂肪气味;感官评价结果和关键风味化合物分析结果存在一定联系。综上,6种食品专用油脂中,黄油、椰子油和部分氢化大豆油风味化合物较为丰富,具有突出的感官特征。     

An investigation on the physicochemical characterization of interesterified blends of fully hydrogenated palm olein and soybean oil

In this study, the effect of interesterification (using sodium methoxide) on physicochemical characteristics of fully hydrogenated palm olein (FHPO)/soybean oil blends (10 ratios) was investigated. Interesterification changed free fatty acid content, decreased oil stability index, solid fat content (SFC) and slip melting point (SMP), and does not affected the peroxide value. With the increase of FHPO ratio, oil stability index, SFC and SMP increased in both the interesterified and non-interesterified blends. Fats with higher FHPO ratio had narrower plastic range, as well. Compared to the initial blends, interesterified fats had wider plastic ranges at lower temperatures. Both the non-interesterified and interesterified blends showed monotectic behavior. The Gompertz function could describe SFC curve (as a function of temperature, saturated fatty acid (SFA) content or both) and SMP (as a function of SFA) of the interesterified fats with high R² and low mean absolute error.     

Pd/碳纳米管催化转移氢化大豆油工艺优化及动力学分析

为降低油脂氢化过程中反式脂肪酸的含量,本实验以自制的Pd/碳纳米管（Pd/carbon nanotubes,Pd/CNTs）为催化剂,在催化转移氢化体系中氢化大豆油,通过响应面试验以大豆油碘值为响应值摸索最优工艺条件,同时对催化转移氢化大豆油进行动力学分析。结果表明：最佳工艺条件为氢化温度84 ℃、催化剂添加量0.20%（以体系质量计）、甲酸铵供体浓度0.33 mol/50 mL、氢化时间90 min,产品的三烯酸、二烯酸和单烯酸反应速率常数分别为4.9×10－2、8.7×10－3和8.31×10－4,氢化亚麻酸和亚油酸的选择性高达5.63和10.47,氢化后大豆油碘值为95.3 g/100 g,反式脂肪酸相对含量仅为10.2%。采用催化转移氢化的方式进行油脂氢化,对制备低反式氢化油脂具有一定的研究意义和应用前景,也可为油脂氢化工业的发展提供一定的理论依据。     

Lipase-catalyzed interesterification in packed bed reactor using 2 different temperatures

Lipase-catalyzed interesterification of high oleic sunflower oil and fully hydrogenated soybean oil (70 : 30, wt/ wt) was carried out in a packed bed reactor using an immobilized lipase from Thermomyces lanuginosus (Lipozyme TL IM) and the effect of a stepwise temperature protocol involving the 2 different temperatures, 60 and 70 °C, was investigated. The melting point of a fat that was incubated at 70 °C for 9 min was 57 °C, which suggested that it should be to employ a lower reaction temperature of 60 °C, after the first 9 min of the reaction. There were no significant differences (P < 0.05) in the conversion degree, triacylglycerol profile, and solid fat content between a constant temperature protocol (70 °C) and a stepwise temperature protocol (a combination of 70 and 60 °C). After 50 cycles, the overall residual activities of enzymes employed in stepwise temperature protocol were significantly (P < 0.05) higher than those of enzymes employed in constant temperature protocol.     

Effects of chemical interesterification on solid fat content and slip melting point of fat/oil blends

Fat/oil blends, formulated by mixing fully hydrogenated palm oil stearin or palm oil stearin with vegetable oils (canola oil and cottonseed oil) in different ratios from 30:70 to 70:30 (w/w %), were subjected to chemical interesterification reactions on a laboratory scale. Fatty acid (FA) composition, iodine value, slip melting point (SMP) and solid fat content (SFC) of the starting blends were analysed and compared with those of the interesterified blends. SMPs of interesterified blends were decreased compared to starting blends because of extensive rearrangement of FAs among triacylglycerols. These changes in SMP were reflected in the SFCs of the blends after the interesterification. SFCs of the interesterified blends also decreased with respect to the starting blends, and the interesterified products were softer than starting blends. These interesterified blends can be used as an alternative to partial hydrogenation to produce a plastic fat phase that is suitable for the manufacture of margarines, shortenings and confectionary fats.     

酯交换技术及其在油脂工业中的应用

酯交换是目前改善油脂物理性质较有效的一种油脂改性技术 ,主要分两种 :化学酯交换和脂肪酶催化酯交换。化学酯交换的催化机制有两种 ,即羰基加合机制和Claisen浓缩机制 ,而脂肪酶催化的酯交换机制类似于化学催化 ,它的催化位点由Asp/Glu His Ser氨基残基组成。还概述了酯交换在油脂工业中的应用 ,包括在猪油、大豆油以及棕榈油、乳脂、可可代用脂、乳幼儿用脂质、DHA以及EPA等中的应用     

零反式脂肪酸涂抹脂基料油酶法酯交换制备研究

利用固定化脂肪酶催化棕榈油硬脂和葵花籽油进行酯交换反应,制备零反式脂肪酸涂抹脂基料油。考察了不同搅拌速度、反应温度、酶加量和反应时间对酯交换反应的影响,并对反应前后油脂的熔点、晶型和结晶速率等结晶行为进行了分析和比较。结果表明:搅拌速度200 r/min,酶加量6%,在70℃下反应3 h为最优的酯交换条件。酯交换产物的熔点大幅下降,晶型主要以β’晶型为主,结晶速率变慢。     

SEMI-SOLID FAT BY INTERESTERIFICATION OF RED PALM OIL WITH OTHER VEGETABLE OILS

Interesterification of appropriate blends of vegetable oils offers an alternative method for obtaining semi-solid fats without hydrogenation. Random interesterification was carried out on blends of different oils, namely palm oil and sunflower oil (8:2, 7:3 and 6:4 w/w), palm oil and rice bran oil (8:2 and 7:3 w/w), palm oil and coconut oil (9:1 and 6:4 w/w), as well as palm oil and soybean oil (7:3 w/w), in the presence of sodium methoxide as a catalyst (0.2% w/v). The melting characteristic of the interesterified fat obtained from a blend of refined red palm oil and sunflower oil blend, in the ratio of 4:1 (w/w; slip melting point 41C) indicated that this combination could be an ideal margarine fat base.     

Lipase-catalyzed interesterification of high oleic sunflower oil and fully hydrogenated soybean oil comparison of batch and continuous reactor for production of zero trans shortening fats

Lipase-catalyzed interesterification of high oleic sunflower oil (HO) and fully hydrogenated soybean oil (FHSBO) at different weight ratios (55:45, 60:40, 65:35 and 70:30, HO:FHSBO) was carried out in both a batch-type reactor (BA) and a packed-bed reactor (PBR) to produce zero trans shortening. Interesterified products in both PBR and BA consisted of 34-46 g/100 g saturated fatty acids (SFA) (mainly stearic acid) and 54-66 g/100 g unsaturated fatty acid (USFA) (mainly oleic acid). After interesterification the physical characteristics such as melting point and solid fat content (SFC) were changed in each product. The differential scanning calorimetry (DSC) result showed that SFC content in PBR was higher than that in BA at each measured temperature. Decrease in tocopherols was also observed, however, the PBR product contained much higher amounts of tocopherols than BA product.