利用酯交换法改进棕榈油硬脂的加工性能

将棕榈油硬脂(ST)与大豆油(SBO)按不同比例混合再进行酯交换反应可以得到不同固脂特征的油脂。实验发现,其中的酯交换油脂IE(70%ST 30%SBO)最适合于加工成通用型起酥油。对这种酯交换油脂的打发性、软硬度及氧化稳定性进行了分析,并与目前市场上常见的全棕榈油基起酥油进行了比较,发现酯交换油脂的柔软度和打发性能均优于后者,但其氧化稳定性不及全棕榈油基起酥油。     

棕榈油硬脂和大豆油酶法酯交换的研究

进行了固定化脂肪酶Lipozyme TL IM催化棕榈油硬脂和大豆油酶法酯交换的研究,考察了酶法酯交换分批操作的反应动力学曲线,发现5%的加酶量、70℃下反应,反应3 h内达到平衡,反应温度在70~90℃对反应速度无明显影响。采用填充床式反应器进行连续反应,结果表明通过装有10 g脂肪酶柱子的最佳流速为30 g/h。对化学酯交换和酶法酯交换产品性质的比较发现,二者SFC无明显差异。采用填充床式反应器对40∶60和30∶70的棕榈油硬脂和大豆油的混合物进行酶法酯交换反应,测定了反应产物的SFC曲线,为将来的应用开发提供参考数据。     

Production of trans‐free margarine stock by enzymatic interesterification of rice bran oil,palm stearin and coconut oil

BACKGROUND: Trans‐free interesterified fat was produced for possible usage as a spreadable margarine stock. Rice bran oil, palm stearin and coconut oil were used as substrates for lipase‐catalyzed reaction. RESULTS: After interesterification, 137–150 g kg^?1 medium‐chain fatty acid was incorporated into the triacylglycerol (TAG) of the interesterified fats. Solid fat contents at 25 °C were 15.5–34.2%, and slip melting point ranged from 27.5 to 34.3 °C. POP and PPP (β‐tending TAG) in palm stearin decreased after interesterification. X‐ray diffraction analysis demonstrated that the interesterified fats contained mostly β′ polymorphic forms, which is a desirable property for margarines. CONCLUSIONS: The interesterified fats showed desirable physical properties and suitable crystal form (β′ polymorph) for possible use as a spreadable margarine stock. Therefore, our result suggested that the interesterified fat without trans fatty acid could be used as an alternative to partially hydrogenated fat. Copyright © 2010 Society of Chemical Industry     

棉籽油硬脂和全氢化棉籽油硬脂的组成、热性质和微观结构分析

为扩大棉籽油用途,提高其附加值,采用气相色谱、高效液相色谱、低场脉冲核磁共振分析仪、差示扫描量热仪、X-射线衍射仪和偏光显微镜分析了棉籽油改性后的产物棉籽油硬脂(COS)和全氢化棉籽油硬脂(FHCOS)的脂肪酸组成、甘三酯组成、SFC含量、热性质和微观结构。结果表明：COS主要由不饱和脂肪酸和非三饱和的甘三酯组成,FHCOS几乎全部由饱和脂肪酸和三饱和甘三酯组成;随温度升高,COS的SFC不断降低,FHCOS的SFC在温度高于35℃时开始降低,相同温度下FHCOS的固体脂肪含量(SFC)均高于COS的,COS在结晶和熔化过程中均有2个峰,FHCOS有1个峰,FHCOS的熔化和结晶温度均高于COS的;COS在15℃时无明确的晶型及稳定的结构,FHCOS为二倍链长堆积的β′晶型,结晶体为针状或棒状,结晶聚集体为类似玫瑰花状。因此,以COS和FHCOS代替棕榈油作为生产起酥油、人造奶油、黄油等的基料油具有一定的开发和应用前景。     

Kinetic analysis of isothermal crystallization in hydrogenated palm kernel stearin with emulsifier mixtures

The kinetics of isothermal crystallization of hydrogenated palm kernel stearin (HPKS) with emulsifiers was evaluated by applying the Avrami equation. Effects of five commercial emulsifiers (lecithin, monoglyceride, polyglycerol polyricinoleate, Span 60, and Tween 60) on crystallization behaviors were tested at four different isothermal temperatures (15, 20, 25, and 30 °C). It is shown that, as temperature increases, induction time for HPKS samples generally increased especially from 25 to 30 °C. Meanwhile, different nucleation mechanisms were observed according to Avrami exponent (n) values. The addition of emulsifiers generally accelerated crystallization rate without changing the growth mechanism (plate-like growth) under 25 °C. However, when the temperature increased to 30 °C, n ranged from 1.0 to 5.1, which indicated different nucleation mechanisms induced by different emulsifiers. Avrami constant (k) (indicating the crystallization rate) decreased as the temperature increased except for samples with Span 60. At higher temperatures, values of t_1/2 were significantly higher which reflects the decrease in k at higher temperatures. Crystal microstructures at 30 °C were obtained by using polarized light microscope. Lecithin and Span 60 samples showed large and dense crystals compared with the control sample. Tween 60 sample showed very small crystals which aggregated in a line trend. However, small differences were observed in fractal dimension results except for Tween 60 sample.     

Zero trans shortening using rice bran oil, palm oil and palm stearin through interesterification at pilot scale

Fat blends, formulated by mixing refined, bleached and deodorised (RBD) palm oil (PO) or RBD palm stearin (PS) with RBD rice bran oil (RBO) in various ratios were subjected to chemical interesterification (CIE) at pilot scale using sodium methoxide (NaOMe) as catalyst. The resultant interesterified fat was processed through a margarine crystalliser under optimised conditions. The blends before and after CIE were investigated for triacylglycerol (TAG) composition, solid fat content (SFC) and melting characteristics, polymorphic form, fatty acid composition (FAC), bioactive (tocols, sterols, oryzanol) constituents and trans fatty acids (TFA). CIE was found to be very effective in terms of rearrangement of fatty acids (FAs) among TAGs and consequent changes in the physical characteristics. The SFC of the interesterified PS/RBO blends decreased significantly ( P  ≤ 0.05) when compared with those of PO/RBO blends. The interesterified binary blends with 50–60% PS and 40–50% RBO, and 70–80% PO and 20–30% RBO had SFC curves in the range of all-purpose type shortenings. CIE facilitated the formation of β' polymorphic forms. FAC of shortenings prepared using the optimised blends contained 15–20% C_18:2 polyunsaturated fatty acid (PUFA) and no TFA. Total tocol, sterol and oryzanol content of zero trans shortenings were 650–1145, 408–17 583 and 1309–14 430 ppm. CIE using NaOMe did not affect the bioactive constituents significantly ( P  ≤ 0.05).     

蔗糖形态对氢化棕榈仁油/可可脂混合体系结晶性质的影响

以氢化棕榈仁油/可可脂(质量比9∶1)混合体系为基料油,采用差示扫描量热仪(DSC)考察不同形态蔗糖(结晶糖、糖粉)和卵磷脂对熔化结晶性质的影响。结果表明:未添加卵磷脂时,蔗糖形态对基料油的熔化结晶性质影响不大;添加卵磷脂后,蔗糖颗粒越细,熔化和结晶温度越高;两种形态的蔗糖体系,添加卵磷脂均使结晶温度显著降低。     

猪油与棕榈硬脂酶法酯交换制备零反式脂肪酸起酥油的研究

研究了固定化脂肪酶Lipozyme RM IM催化猪油和棕榈硬脂酯交换制备起酥油的工艺,考察了反应温度、酶添加量、反应时间对酯交换反应的影响.并以反应后体系在20℃下的固体脂肪含量(SFC)为指标,确定了理想的工艺条件:反应温度60℃,酶添加量8％,反应时间1h.利用等温曲线和X-射线衍射技术研究了混合体系酯交换前后的相容性和晶体形态,结果表明:经酯交换后,混合体系的相容性得到显著改善,晶型由β型转变为β’型,适宜用作焙烤起酥油.     

米糠固脂与棕榈硬脂混合应用于起酥油的研究

米糠固脂是米糠油冬化或分提获得的副产物。以3种具有不同固体脂肪含量(SFC)曲线的米糠固脂(RBS1、RBS2及RBS3)、棕榈硬脂(PS)为原料,按照米糠固脂与棕榈硬脂质量比40∶60进行二元混合制备起酥油,并以市售起酥油为参考,对混合体系的SFC、晶型、脂肪酸组成、微量营养素含量进行了分析。结果表明:由不同米糠固脂组成的二元混合体系差异不大,且与市售起酥油具有相似的SFC曲线;其棕榈酸、亚油酸含量较市售起酥油高,硬脂酸含量较市售起酥油低;体系表现为β'晶型;此外,二元混合体系中含有丰富的谷维素、植物甾醇,可丰富起酥油的营养特性。     

氢化棕榈硬脂结晶特性及其对蜡烛外观的影响

为解决分提棕榈硬脂用作蜡材时渗油的问题,对其进行了不同程度的氢化。利用差示扫描量热仪、脉冲核磁共振仪、偏振光显微镜和X-射线衍射仪等手段对其结晶行为进行研究,并比较了氢化前后化学组成的变化。结果表明:棕榈硬脂氢化的第一个阶段,部分油酸和亚油酸迅速转变为反式油酸,它促进了α型晶体的形成及其向β'型的转变,虽然45℃以下时固体脂肪含量高于原料油,但其熔点却降低;氢化的第二个阶段,大量油酸和反式油酸转变为硬脂酸,高熔点组分增加,虽然晶型仍处于β'型,但此时熔点及各温度下的固体脂肪含量均高于原料油。氢化15 min后低熔点峰基本消失,蜡烛渗油现象也消失;继续氢化至20 min后样品结晶峰狭窄、尖锐,蜡烛容易断裂。因此,适度氢化样品(氢化15~20 min)较适合用作蜡材。     

Production of lipase‐catalyzed solid fat from mustard oil and palm stearin with linoleic acid by response surface methodology

BACKGROUND: Solid fat was produced from mustard oil and palm stearin through lipase‐catalyzed reaction, in which linoleic acid was intentionally incorporated. For optimizing the reaction condition of melting point and ω6/ω3 fatty acids, response surface methodology (RSM) was employed with three reaction variables such as substrate mole ratio of mustard oil (MO) to palm stearin (PS) (X₁), reaction temperature (X₂) and reaction time (X₃). RESULTS: The predictive model for melting point of solid fat was adequate and reproducible due to no significant lack of fit (P = 0.0764), P‐value (0.0037) of the model, and satisfactory level of coefficient of determination (R² = 0.92). For the ω6/ω3 ratio model, R² and P‐value were 0.89 and 0.0132, respectively, but lack of fit was significant (P = 0.0389). The melting point of the produced solid fat was affected by substrate mole ratio, whereas reaction temperature and time had no significant effect. The ω6/ω3 ratio of solid fat was influenced by substrate mole ratio and reaction temperature but not by reaction time. Based on ridge analysis, lower ω6/ω3 ratio was predicted by decreasing substrate mole ratio and reaction time, and by increasing reaction temperature. CONCLUSIONS: For producing solid fat with a specific melting point of 34.57 °C, a combination of 1:2 (X₁), 65.17 °C (X₂) and 21.46 h (X₃) was optimized, and the optimization was confirmed under the same reaction conditions. The solid fat contained palmitic (37.8%), linoleic (24.8%), oleic (21.3%), and erucic acid (9.7%), and its solid fat content was 30.3% and 10.3% at 20 and 30 °C, respectively. Copyright © 2009 Society of Chemical Industry     

棕榈仁油干法分提工艺实践

为开发代可可脂系列产品,介绍了采用油盘冷房结晶-高压膜压滤机过滤的精炼棕榈仁油干法分提生产棕榈仁硬脂工艺。对该工艺操作控制要点进行了说明,并对生产中的一些问题进行了讨论,将该工艺制备的棕榈仁硬脂及其氢化硬脂与天然可可脂和商业氢化棕榈仁硬脂代可可脂产品质量进行了对比。原料油主要质量指标为酸值(KOH)≤0.3 mg/g、碘值(I)16～19 g/100 g、熔点25～28℃和固体脂肪含量(25℃)≥18%。适合的工艺条件为预冷温度29～30℃,预冷时间3 h,冷房温度17～19℃,冷房结晶时间6～8 h,油结晶温度25～27℃,过滤压力0～0.3 MPa、挤压压力1.6～1.8 MPa。产品主要质量指标为酸值(KOH)≤0.3 mg/g、碘值(I)5.6～7.5 g/100 g、熔点30～34℃、固体脂肪含量(30℃) 34%～44%。采用该工艺所得棕榈仁硬脂的熔点和固体脂肪含量与天然可可脂相当,氢化后产品在25～30℃的固体脂肪含量高于商业氢化棕榈仁硬脂代可可脂。     

棕榈硬脂大豆油相容性分析及调和性研究

以棕榈硬脂和大豆油为研究对象,采用ΔSFC分析两者的相容性,利用单因素实验和正交实验优化调和技术参数。结果表明,在考察的温度范围内棕榈硬脂和大豆油存在共晶现象,相容性较差,而使用卵磷脂、斯潘60和分子蒸馏单甘酯作为调和剂,能达到稳定的调和效果。调和剂的种类和添加量对调和油样的稳定性有显著影响,调和剂之间存有交互作用。在斯潘60添加量0.6g/kg、调和温度60℃、时间20min条件下,按照棕榈硬脂和大豆油1∶9的比例制备的调和油,常温存储稳定性较好,离心分离率为1.3%,氧化稳定性优于大豆油。      

Enzymatic interesterification of palm and coconut stearin blends

Hard fractions of palm oil and coconut oil, blended in the ratios of 90:10, 85:15, 80:20 and 75:25, were interesterified for 8 h using Lipozyme TL IM. Major fatty acids in the blends were palmitic acid (41.7–48.4%) and oleic acid (26.2–30.8%). Medium‐chain fatty acids accounted for 4.5–13.1% of the blends. After interesterification (IE), slip melting point was found to decrease from 44.8–46.8 °C to 28.5–34.0 °C owing to reduction in solids content at all temperatures. At 37.5 °C, the blends containing 25% coconut stearins had 17.4–19% solids, which reduced to 0.4–1.5% on IE, and the slip melting point (28.6 and 28.8 °C) indicated their suitability as margarine base. The reduction in solid fat index of the interesterified fats is attributed to the decrease in high‐melting triacylglycerols in palm oil (GS₃ and GS₂U type) and increase in triolein (GU₃) content from 1 to 9.2%. Retention of tocopherols and β‐carotene during IE was 76 and 60.1%, respectively, in 75:25 palm stearin and coconut stearin blend.     

棕榈油硬脂和棕榈油中间分提物性能及相容性研究

为改善油脂可塑性和口溶性,及为开发以棕榈油产品为主要原料专用油脂产品提供理论依据,研究棕榈油硬脂(PSt)、棕榈油中间分提物(PMF)两者间相容性。测定二元混合体系固体脂肪含量(SFC)值,并通过计算其理论值与实测值之间差值△SFC,结合T–△SFC曲线、二元等温曲线等直观分析,结果表明:PSt与PMF混合物在25℃、PSt含量为30%～50%时,二者间偏晶现象严重;而在35℃～50℃时,二者间共晶现象较为严重;在0℃～10℃和30℃～35℃范围内,二者间具有较好相容性。     

不同熔点棕榈油脂肪酸组成和SFC测定分析

分析七种不同棕榈油脂肪酸组成及在0℃~25℃(5℃间隔)温度下固体脂肪含量(SFC)及其变化规律。结果表明:随熔点降低,棕榈酸含量有逐渐降低趋势,而油酸和亚油酸含量则逐渐上升;饱和脂肪酸含量逐渐减少,而不饱和脂肪酸含量则逐渐升高;低熔点棕榈油营养价值要比高熔点棕榈油高;在不同温度段,SFC值增加幅度有所不同。该试验为棕榈油进一步深加工研究提供参考数据。     

核桃油与棕榈硬脂复配体系在涂抹脂基料油中的应用

对棕榈硬脂与核桃油复配体系的相容性及结晶性质变化进行探究,考察复配体系在涂抹脂基料油中的应用。结果表明,当核桃油含量达到20%以上时,复配体系的固体脂肪含量(Solid Fat Content,SFC)变化趋势符合涂抹脂的最佳SFC曲线特征,适合用作涂抹脂基料油;在温度高于33.3℃时,核桃油与棕榈硬脂在复配比例(1∶9、2∶8、3∶7、4∶6)下可以完全相容;在核桃油比例达到3∶7以上时,复配体系的屈服值符合涂抹脂的最佳屈服值范围;在温度低于30℃时,棕榈硬脂及复配体系具有较强的晶体网络结构,能在运输和贮藏过程中维持稳定的形态,在接近体温时也能快速熔化,产生涂抹脂类似的口感,复配体系中晶体以β′晶型为主。该结果为棕榈硬脂及核桃油复配体系在涂抹脂中的应用奠定基础。     

搅打稀奶油的乳液特征和打发性能研究

为了对搅打稀奶油的科学应用提供参考,以19款市售代表性搅打稀奶油（常温型、冷藏型和冷冻型产品）为研究对象,通过分析乳液的离心乳析率、黏度、粒径和微观结构研究其乳液的质量,通过分析打发时间、起泡率、泄漏率和裱花性能研究其打发性能。结果显示：常温型产品的离心乳析率为22.17%～32.68%,显著高于冷藏型产品的离心乳析率(1.36%～13.09%)和冷冻型产品的离心乳析率(2.97%～12.87%);常温型和冷藏型产品的黏度、粒径分布特征接近,呈流动性较好且脂肪球分布较均匀的乳液,而冷冻型产品相对黏稠且乳液中无明显脂肪球结构;常温型产品和冷藏型产品的打发时间在13244～291.28 s之间（只有1款冷藏型产品打发时间为79.49 s）,起泡率在111.49%～202.50%之间（只有2款冷藏型产品起泡率分别为92.30%、328.25%）,部分有泡沫泄漏,裱花维持能力较弱;而冷冻型产品打发时间为89.91～158.52 s,起泡率在240.39%～27815%,无泡沫泄漏,裱花维持能力强。综合而言,常温型搅打稀奶油的乳液相对不稳定,打发性能与冷藏型搅打稀奶油接近,而冷冻型搅打稀奶油的打发性能最强。     

Characterisation of zero‐trans margarine fats produced from camellia seed oil,palm stearin and coconut oil using enzymatic interesterification strategy

Zero‐trans interesterified fats were produced from camellia seed oil (CSO), palm stearin (PS) and coconut oil (CO) with three weight ratios (CSO/PS/CO, 50:50:10, 40:60:10 and 30:70:10) using Lipozyme TL IM. Results showed that the interesterified products contained palmitic acid (34.28–42.96%), stearic acid (3.96–4.72%), oleic acid (38.73–47.95%), linoleic acid (5.92–6.36%) and total medium‐chain fatty acids (MCFA)s (∑MCFAs, 5.03–5.50%). Compared with physical blends, triacylglycerols of OOO and PPP were decreased and formed new peaks of equivalent carbon number (ECN) 44 in the interesterified products. The product CPC3′ showed a slip melting point of 36.8 °C and a wide plastic range of solid fat content (SFC) (45.8–0.4%) at 20–40 °C. Also, the major β′ form was determined. These data indicated that the zero‐trans interesterified fats would have a potential functionality for margarine fats. Subsequently, the antioxidative stabilities of interesterified products with the addition of α‐tocopherol (α‐TOH) and ascorbyl palmitate (AP) were investigated. The results indicated that AP had a dose‐dependent effect at concentrations of 100, 200 and 400 ppm.