牛油基起酥油品质缺陷及其改善的研究
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摘要
牛油基起酥油由于留香持久、风味厚实而广泛应用于焙烤工业,但在储运过程中,由于温度波动及自身结晶特性有产生砂粒的危险,容易引起产品品质改变。因此,本文从对比劣质牛油基起酥油中砂粒部分和无砂部分差异出发,在研究起砂机理的基础上对配方进行改善,解决牛油基起酥油起砂现象。
本文以砂粒部分与无砂部分为对象分别对比了两者熔点、脂肪酸、甘三酯组成,晶型、DSC曲线和晶体形态差异,结果表明对称型单不饱和甘三酯POP、POS、SOS在砂粒中含量明显偏高,而多不饱和型甘三酯PLO、POO、SOO/SSL等更多的聚集在无砂部分;X-衍射(XRD)结果表明,砂粒部分已经出现明显的β结晶;DSC融化曲线表明,砂粒部分存在多种复杂的晶型;偏光显微镜观察砂粒部分的晶体形态也较为粗大。据实验结果可推断:当温度升高时,低熔点甘三酯可能熔化,而对称型甘三酯(POP、POS、SOS)仍以结晶形式存在并且有移动空间,聚集形成晶核。波动的温度使聚集的对称型甘三酯转化为大的、片状β型晶体,晶体进一步聚集形成更大的晶束,最终形成了肉眼可见的砂粒。从本质上看劣质牛油基起酥油起砂的关键因素是对称型单不饱和甘三酯的迁移聚集。
在此基础上分别采用酯交换及调和两种油脂改性方法对基料油进行筛选以改善牛油基起酥油的起砂问题。牛油/低芥酸菜籽油酯交换结果表明,当菜籽油与牛油质量比为20:80,催化剂(甲醇钠)用量0.6%,在60℃下反应90min后,对称型单不饱和甘三酯含量下降比例最大,产物在温度波动下能稳定在β′晶型,晶体形态更为细腻,SFC曲线满足烘焙起酥油的固脂塑性要求,可作为起酥油的基料油。相容性研究表明,牛油-棕榈油系列及牛油-低芥酸菜籽油所组成的二元体系相容性较好,而牛油-棕榈仁油通常呈显著的共晶作用。在所有三元体系中,以牛油为主的混合物整体相容性较好,且牛油的增加能弥补单一油品塑性不足,调节混合物有合适于起酥油的塑性。在相容性研究基础上通过合适的SFC及晶型筛选确定用于牛油基起酥油最合适的油相配方为:牛油-菜籽油-棕榈油(0.8:0.1:0.1)。
最后,进行牛油基起酥油配方的设计和应用。以酪化性及吸水性为指标分别对蒸馏单甘酯、斯潘60和大豆卵磷脂进行了筛选,确定了复配乳化剂,最终确定起酥油的配方:(1)牛油-菜籽油-棕榈油质量比为80:10:10混合,复配乳化剂添加量为1%,其中分子蒸馏单甘酯、斯潘60和卵磷脂质量比为0.8:0.1:0.1;(2)牛油-菜籽油质量比为80:20混合,甲醇钠用量0.6%,反应温度60℃,反应90min后的酯交换油,复配乳化剂添加量为1%,其中分子蒸馏单甘酯、大豆卵磷脂和斯潘60质量比为0.1:0.45:0.45。按照配方制备起酥油小试样品,所得产品在冬季温度条件(5～15℃)下存放两个半月,未发现起砂颗粒。烘焙产品感官评价表明,自制起酥油符合烘焙油脂的要求。
Traditionally edible beef tallow is widely used in the baking industry because of enhanced aroma and flavor of food products. However, beef tallow-based shortening is easy to undergo sandiness or graininess which leads to bad physical properties when temperature fluctuates during handling, storage and transportation. This paper is aimed to compared and discuss the essential reasons of the graininess crystals in beef tallow shortening and solve the graininess by modificated formulation.
Firstly, the difference of slip melting, fatty acids , triacylglycerols (TAGs) ,polymorphism, DSC melting curves and morphology of the grainy crystals and surrounding materials in the bad beef tallow-based shortening were studied. TAGs results showed that the contents of polyunsaturated TAGs (POL, POO and SOO /SSL) of grainy crystals decreased markedly compared with their surrounding materials while the contents of symmetrical monounsaturated TAGs (POP, POS and SOS) rose in the graininess. The results of X-ray diffraction (XRD) showed that there were someβform grainy crystals exceptβ′form. The melting curves of grainy (DSC) certified the existence of complex polymorphism. The morphology of grainy crystals is coarser than that of surrounding materials. It can be confirmed that low melting point TAGs will melt with rising temperature, which would provide enough spaces for the symmetrical monounsaturated TAGs to move and form the crystal nuclei. Symmetrical TAGs(POP、POS、SOS)agglomerates and form the bigger and sheetβpolymorph.The crystal agglomerates form the bigger crystal clusters and result in the graininess crystal in shortening. These results showed that monounsaturated TAGs were the key factor for the formation of granular crystals in shortening.
Interesterification and blending were used to modify natural oil to obtain the desired tallow-based shortening. Beef tallow (BT) and low erucic acid rapeseed oil (LERSO) at different rate by chemical interesterification was studied to solve the graininess in beef tallow shortening. The results of interesterification showed that the amount of high melting point TAGs (POP、POS、SOS) of the blends of BT and LERSO(80:20 w/w) reduced greatest in following reaction conditions: the addition of methanol sodium was 0.6%(w/w) for 90mins at reaction temperature 60℃.The chemical interesterification products have the stableβ′form and the morphology of crystals appeared less densely packed. The SFC profile of chemical interesterification products was satisfied for the solid shortening stock. The binary and ternary phase behaviors of mixtures of BT with palm kernel oil (PKO), hydrogenated palm oil (HPO), palm oil (PO), palm olein (POo) and LERSO were studied using isosolid diagrams respectively. Both BT/palm oil-based fat and BT/LERSO binaries displayed good compatibility while addition of PKO would increase eutectic behavior whatever in binaries or ternaries. It was found that when the content of BT was predominant, ternary mixtures have good compatibility. The addition of BT would make up the defects of single base oil and improve the plastic property of shortening. The appropriate formulation of BT-based shortening based on the studies of ternary phase behaviors and polymorphism was following: the blends of BT and LERSO and PO as 0.8:0.1:0.1.
Distill monostearate, Span 60 and lecithin was optimized as single and compound emulsifiers respectively. The formulation of base oil and emulsifiers were optimized as follows: (1) the blends of BT and LERSO(80:20 w/w) by chemical interesterification at the following conditions: reaction temperature at 60℃, methanol sodium 0.6%(w/w) for 90min, the ratio of distill monostearate, Span 60 and lecithin was 0.1:0.45:0.45 and the total addition was 1%; (2) the ratio of BT, LERSO and PO was 0.8:0.1:0.1 and mixed distill monostearate, Span 60 and lecithin was 0.8:0.1:0.1, the addition was 1%. Shortening according to this formulation prepared in the laboratory was saved in winter ( temperature range 5～15℃) for two and half months and there was no visible grainy crystals existing in the product. Baking products has the similar sense evaluation using the prepared shortening product compared with commercial shortening obtained from market in baking.
本文以砂粒部分与无砂部分为对象分别对比了两者熔点、脂肪酸、甘三酯组成,晶型、DSC曲线和晶体形态差异,结果表明对称型单不饱和甘三酯POP、POS、SOS在砂粒中含量明显偏高,而多不饱和型甘三酯PLO、POO、SOO/SSL等更多的聚集在无砂部分;X-衍射(XRD)结果表明,砂粒部分已经出现明显的β结晶;DSC融化曲线表明,砂粒部分存在多种复杂的晶型;偏光显微镜观察砂粒部分的晶体形态也较为粗大。据实验结果可推断:当温度升高时,低熔点甘三酯可能熔化,而对称型甘三酯(POP、POS、SOS)仍以结晶形式存在并且有移动空间,聚集形成晶核。波动的温度使聚集的对称型甘三酯转化为大的、片状β型晶体,晶体进一步聚集形成更大的晶束,最终形成了肉眼可见的砂粒。从本质上看劣质牛油基起酥油起砂的关键因素是对称型单不饱和甘三酯的迁移聚集。
在此基础上分别采用酯交换及调和两种油脂改性方法对基料油进行筛选以改善牛油基起酥油的起砂问题。牛油/低芥酸菜籽油酯交换结果表明,当菜籽油与牛油质量比为20:80,催化剂(甲醇钠)用量0.6%,在60℃下反应90min后,对称型单不饱和甘三酯含量下降比例最大,产物在温度波动下能稳定在β′晶型,晶体形态更为细腻,SFC曲线满足烘焙起酥油的固脂塑性要求,可作为起酥油的基料油。相容性研究表明,牛油-棕榈油系列及牛油-低芥酸菜籽油所组成的二元体系相容性较好,而牛油-棕榈仁油通常呈显著的共晶作用。在所有三元体系中,以牛油为主的混合物整体相容性较好,且牛油的增加能弥补单一油品塑性不足,调节混合物有合适于起酥油的塑性。在相容性研究基础上通过合适的SFC及晶型筛选确定用于牛油基起酥油最合适的油相配方为:牛油-菜籽油-棕榈油(0.8:0.1:0.1)。
最后,进行牛油基起酥油配方的设计和应用。以酪化性及吸水性为指标分别对蒸馏单甘酯、斯潘60和大豆卵磷脂进行了筛选,确定了复配乳化剂,最终确定起酥油的配方:(1)牛油-菜籽油-棕榈油质量比为80:10:10混合,复配乳化剂添加量为1%,其中分子蒸馏单甘酯、斯潘60和卵磷脂质量比为0.8:0.1:0.1;(2)牛油-菜籽油质量比为80:20混合,甲醇钠用量0.6%,反应温度60℃,反应90min后的酯交换油,复配乳化剂添加量为1%,其中分子蒸馏单甘酯、大豆卵磷脂和斯潘60质量比为0.1:0.45:0.45。按照配方制备起酥油小试样品,所得产品在冬季温度条件(5～15℃)下存放两个半月,未发现起砂颗粒。烘焙产品感官评价表明,自制起酥油符合烘焙油脂的要求。
Traditionally edible beef tallow is widely used in the baking industry because of enhanced aroma and flavor of food products. However, beef tallow-based shortening is easy to undergo sandiness or graininess which leads to bad physical properties when temperature fluctuates during handling, storage and transportation. This paper is aimed to compared and discuss the essential reasons of the graininess crystals in beef tallow shortening and solve the graininess by modificated formulation.
Firstly, the difference of slip melting, fatty acids , triacylglycerols (TAGs) ,polymorphism, DSC melting curves and morphology of the grainy crystals and surrounding materials in the bad beef tallow-based shortening were studied. TAGs results showed that the contents of polyunsaturated TAGs (POL, POO and SOO /SSL) of grainy crystals decreased markedly compared with their surrounding materials while the contents of symmetrical monounsaturated TAGs (POP, POS and SOS) rose in the graininess. The results of X-ray diffraction (XRD) showed that there were someβform grainy crystals exceptβ′form. The melting curves of grainy (DSC) certified the existence of complex polymorphism. The morphology of grainy crystals is coarser than that of surrounding materials. It can be confirmed that low melting point TAGs will melt with rising temperature, which would provide enough spaces for the symmetrical monounsaturated TAGs to move and form the crystal nuclei. Symmetrical TAGs(POP、POS、SOS)agglomerates and form the bigger and sheetβpolymorph.The crystal agglomerates form the bigger crystal clusters and result in the graininess crystal in shortening. These results showed that monounsaturated TAGs were the key factor for the formation of granular crystals in shortening.
Interesterification and blending were used to modify natural oil to obtain the desired tallow-based shortening. Beef tallow (BT) and low erucic acid rapeseed oil (LERSO) at different rate by chemical interesterification was studied to solve the graininess in beef tallow shortening. The results of interesterification showed that the amount of high melting point TAGs (POP、POS、SOS) of the blends of BT and LERSO(80:20 w/w) reduced greatest in following reaction conditions: the addition of methanol sodium was 0.6%(w/w) for 90mins at reaction temperature 60℃.The chemical interesterification products have the stableβ′form and the morphology of crystals appeared less densely packed. The SFC profile of chemical interesterification products was satisfied for the solid shortening stock. The binary and ternary phase behaviors of mixtures of BT with palm kernel oil (PKO), hydrogenated palm oil (HPO), palm oil (PO), palm olein (POo) and LERSO were studied using isosolid diagrams respectively. Both BT/palm oil-based fat and BT/LERSO binaries displayed good compatibility while addition of PKO would increase eutectic behavior whatever in binaries or ternaries. It was found that when the content of BT was predominant, ternary mixtures have good compatibility. The addition of BT would make up the defects of single base oil and improve the plastic property of shortening. The appropriate formulation of BT-based shortening based on the studies of ternary phase behaviors and polymorphism was following: the blends of BT and LERSO and PO as 0.8:0.1:0.1.
Distill monostearate, Span 60 and lecithin was optimized as single and compound emulsifiers respectively. The formulation of base oil and emulsifiers were optimized as follows: (1) the blends of BT and LERSO(80:20 w/w) by chemical interesterification at the following conditions: reaction temperature at 60℃, methanol sodium 0.6%(w/w) for 90min, the ratio of distill monostearate, Span 60 and lecithin was 0.1:0.45:0.45 and the total addition was 1%; (2) the ratio of BT, LERSO and PO was 0.8:0.1:0.1 and mixed distill monostearate, Span 60 and lecithin was 0.8:0.1:0.1, the addition was 1%. Shortening according to this formulation prepared in the laboratory was saved in winter ( temperature range 5～15℃) for two and half months and there was no visible grainy crystals existing in the product. Baking products has the similar sense evaluation using the prepared shortening product compared with commercial shortening obtained from market in baking.
引文
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