乳化剂对棕榈油基人造奶油结晶行为的影响
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摘要
棕榈油基基料油由于高产、价廉以及优良的稳定性而广泛应用于人造奶油等专用油脂的基料油配方,但因其结晶缺陷而使人造奶油后变硬、棕榈油基巧克力起霜等问题困扰食品专用油脂加工产业。本文以棕榈油硬脂分提物(POS)、棕榈油中熔点产物(PMF)及棕榈仁油(PKO)为原料,对人造奶油的基料油配方及乳化剂对乳化体系结晶行为的影响进行研究,由此指导人造奶油基料油配方、乳化剂的选用及品质改良。
首先分析POS、PMF及PKO的基本理化性质及结晶性质,发现其既能作为结晶网络的骨架,又能迅速融化赋予产品良好的口感,因此适宜用作人造奶油的基料油。采用混料回归设计分析POS-PMF-PKO三元混合体系的相容性,并辅以偏光显微镜(PLM)技术和等固曲线,发现POS:PMF:PKO为0.45:0.45:0.1时相容性最好。
其次,选用分子蒸馏单甘酯(DMGS)、丙二醇酯(PGMS)、聚甘油酯(PGE)、单双混甘油酯(MONO-DIGS)、乳酸甘油酯(LACTEM)及蔗糖酯(SE)六种乳化剂,添加量为0.3%、0.5%和0.7%考察对乳化体系平均粒径和表面张力的影响。平均粒径的结果发现0.5%PGE体系的粒径最小,0.3%DMGS及各浓度下SE体系的粒径都较大。表面张力结果表明SE效果最好。对乳化体系的结晶形态、固体脂肪含量(SFC)、硬度及晶型等进行研究,发现PGE、SE体系在20℃的结晶尺寸细小,并伴有絮状结晶,其它体系多为枝状或粒状结晶;采用盒维数法分析PGMS、PGE体系的不规则碎片维数(Db)最大;硬度分析中PGE和SE体系的硬度最大;21.1℃时PGE、LACTEM及MONO-DIGS体系的SFC值相对较大;PGE体系主要为β晶型,PGMS体系中β′、β二者比例相当,LACTEM及MONO-DIGS体系只存在β′晶型,其余则以β′晶型为主。
采用Avrami及Gompertz模型对等温结晶动力学进行分析,发现Gompertz模型的拟合度较高。Avrami模型的结果表明,在25℃~30℃存在某个临界温度使得此温度左右两侧温度下晶体的成核和生长机制相异;PGE加速结晶生长,而DMGS抑制结晶生长。在Gompertz模型中,DMGS对晶核形成的抑制作用最强,PGE可促进晶核的形成及晶体的生长。通过Jeiorny方程描述饱和及不饱和组分的非等温结晶动力学,其对不饱和组分结晶曲线的拟合程度较高,且降温速率为1℃/min时,不饱和组分的n值最大,结晶机制最为复杂。
最后,分析复配乳化剂对体系结晶行为的影响。相比于单一乳化剂,整体而言复配乳化剂体系的SFC较高;复配使得体系的硬度降低,但程度存在差异;复配的各比例中未出现β晶型。等温结晶曲线经Gompertz模型拟合的结果表明DMGS:LACTEM2:8会加速晶体成核,PGE:SE5:5会加速晶体的生长。非等温结晶的结果表明饱和组分中PGE:SE2:8的结晶速率最快,不饱和组分中DMGS:LACTEM2:8的结晶速率最快。
Palm based oil is widely used in margarine and other specialty fats due to high-yield, low cost and excellent stability, but its crystal defects bring inconvenience for industry of specialty oil processing, such as post-harden of margarine, blooming of chocolate. This research used palm oil stearin POS, palm oil middle fraction PMF and palm kernel oil PKO to investigate based oil formulas and effects of emulsifiers on crystallization behavior in emulsified system, which guided the formula of margarine, the selection of emulsifiers and quality improvement.
Firstly, through the analysis of the basic physical and chemical properties and crystalline characters of POS, PMF and PKO, it found that can be as skeleton of crystalline network and rapidly melted to give the product a good taste, which were suitable for based oil of margarine. According to mixing regression design, PLM and iso-solid curves, it could be found that the best formula is POS:PMF:PKO 0.45:0.45:0.1.
Then,choosing DMGS,PGMS,PGE,MONO-DIGS,LACTEM and SE,and concentration are 0.3%, 0.5%, 0.7%, investigated average particle size and surface tension for emulsified system,it found that 0.5%PGE had minimum average particle size,0.3%DMGS and all concertration of SE had larger particle size.SE reduced surface tension greatly.From analysis of PLM,SFC,hardness and crystal morphology.It found that PGE and SE corresponded small crystalline size at 20℃,accompanied by flocculent crystalline,and others were dendrite or granular,but Db of PGE and PGMS were maximum.Adding MONO-DIGS,PGE,LACTEM, values of SFC at 21.1℃were relatively large.Adding PGE and SE had maximum values of hardness.Adding PGE correspondedβcrystal,PGE had near quantity ofβandβ'.When added LACTEM and MONO-DIGS, it appearedβ' crystal. The rest were dominated byβ'crystal.
Using Avrami and Gompertz model to analyze the isothermal crystallization kinetics. Gompertz model is more applicable for this system. In Avrami model, it was a critical temperature between 25℃and 30℃, leading to different nucleation and growth mechanism, PGE accelerated crystal growth, but DMGS inhibited crystalline growth. In Gompertz model, it found that PGE not only accelerated the crystal nucleation, but also accelerate the growth, DMGS and SE had strongest inhibitory effect on nucleation.Non-isothermal crystallization kinetics was described by Jeiorny equations, unsaturated components had a better fit, the values of n were lower than the isothermal crystallization, values of n higher for unsaturated components,delegating the most complex mechanism of crystallization.
Finally, effect of formulated emulsifiers on crystallization behavior was researched. Compared to single emulsifier, the SFC values were higher in whole.Hardness of those system was reduced,but had difference degree.It didn’t appearβin all formulations.Gompertz model showed that DGMS:LACTEM2:8 accelerated nucleation, PGE:SE5:5 accelerted crystal growth.The results of non-isothermal crystallization showed that in saturated component crystallization rate of PGE:SE2:8 was the fastest, in unsaturated component crystallization rate of DMGS: LACTEM2:8 was the fastest.
首先分析POS、PMF及PKO的基本理化性质及结晶性质,发现其既能作为结晶网络的骨架,又能迅速融化赋予产品良好的口感,因此适宜用作人造奶油的基料油。采用混料回归设计分析POS-PMF-PKO三元混合体系的相容性,并辅以偏光显微镜(PLM)技术和等固曲线,发现POS:PMF:PKO为0.45:0.45:0.1时相容性最好。
其次,选用分子蒸馏单甘酯(DMGS)、丙二醇酯(PGMS)、聚甘油酯(PGE)、单双混甘油酯(MONO-DIGS)、乳酸甘油酯(LACTEM)及蔗糖酯(SE)六种乳化剂,添加量为0.3%、0.5%和0.7%考察对乳化体系平均粒径和表面张力的影响。平均粒径的结果发现0.5%PGE体系的粒径最小,0.3%DMGS及各浓度下SE体系的粒径都较大。表面张力结果表明SE效果最好。对乳化体系的结晶形态、固体脂肪含量(SFC)、硬度及晶型等进行研究,发现PGE、SE体系在20℃的结晶尺寸细小,并伴有絮状结晶,其它体系多为枝状或粒状结晶;采用盒维数法分析PGMS、PGE体系的不规则碎片维数(Db)最大;硬度分析中PGE和SE体系的硬度最大;21.1℃时PGE、LACTEM及MONO-DIGS体系的SFC值相对较大;PGE体系主要为β晶型,PGMS体系中β′、β二者比例相当,LACTEM及MONO-DIGS体系只存在β′晶型,其余则以β′晶型为主。
采用Avrami及Gompertz模型对等温结晶动力学进行分析,发现Gompertz模型的拟合度较高。Avrami模型的结果表明,在25℃~30℃存在某个临界温度使得此温度左右两侧温度下晶体的成核和生长机制相异;PGE加速结晶生长,而DMGS抑制结晶生长。在Gompertz模型中,DMGS对晶核形成的抑制作用最强,PGE可促进晶核的形成及晶体的生长。通过Jeiorny方程描述饱和及不饱和组分的非等温结晶动力学,其对不饱和组分结晶曲线的拟合程度较高,且降温速率为1℃/min时,不饱和组分的n值最大,结晶机制最为复杂。
最后,分析复配乳化剂对体系结晶行为的影响。相比于单一乳化剂,整体而言复配乳化剂体系的SFC较高;复配使得体系的硬度降低,但程度存在差异;复配的各比例中未出现β晶型。等温结晶曲线经Gompertz模型拟合的结果表明DMGS:LACTEM2:8会加速晶体成核,PGE:SE5:5会加速晶体的生长。非等温结晶的结果表明饱和组分中PGE:SE2:8的结晶速率最快,不饱和组分中DMGS:LACTEM2:8的结晶速率最快。
Palm based oil is widely used in margarine and other specialty fats due to high-yield, low cost and excellent stability, but its crystal defects bring inconvenience for industry of specialty oil processing, such as post-harden of margarine, blooming of chocolate. This research used palm oil stearin POS, palm oil middle fraction PMF and palm kernel oil PKO to investigate based oil formulas and effects of emulsifiers on crystallization behavior in emulsified system, which guided the formula of margarine, the selection of emulsifiers and quality improvement.
Firstly, through the analysis of the basic physical and chemical properties and crystalline characters of POS, PMF and PKO, it found that can be as skeleton of crystalline network and rapidly melted to give the product a good taste, which were suitable for based oil of margarine. According to mixing regression design, PLM and iso-solid curves, it could be found that the best formula is POS:PMF:PKO 0.45:0.45:0.1.
Then,choosing DMGS,PGMS,PGE,MONO-DIGS,LACTEM and SE,and concentration are 0.3%, 0.5%, 0.7%, investigated average particle size and surface tension for emulsified system,it found that 0.5%PGE had minimum average particle size,0.3%DMGS and all concertration of SE had larger particle size.SE reduced surface tension greatly.From analysis of PLM,SFC,hardness and crystal morphology.It found that PGE and SE corresponded small crystalline size at 20℃,accompanied by flocculent crystalline,and others were dendrite or granular,but Db of PGE and PGMS were maximum.Adding MONO-DIGS,PGE,LACTEM, values of SFC at 21.1℃were relatively large.Adding PGE and SE had maximum values of hardness.Adding PGE correspondedβcrystal,PGE had near quantity ofβandβ'.When added LACTEM and MONO-DIGS, it appearedβ' crystal. The rest were dominated byβ'crystal.
Using Avrami and Gompertz model to analyze the isothermal crystallization kinetics. Gompertz model is more applicable for this system. In Avrami model, it was a critical temperature between 25℃and 30℃, leading to different nucleation and growth mechanism, PGE accelerated crystal growth, but DMGS inhibited crystalline growth. In Gompertz model, it found that PGE not only accelerated the crystal nucleation, but also accelerate the growth, DMGS and SE had strongest inhibitory effect on nucleation.Non-isothermal crystallization kinetics was described by Jeiorny equations, unsaturated components had a better fit, the values of n were lower than the isothermal crystallization, values of n higher for unsaturated components,delegating the most complex mechanism of crystallization.
Finally, effect of formulated emulsifiers on crystallization behavior was researched. Compared to single emulsifier, the SFC values were higher in whole.Hardness of those system was reduced,but had difference degree.It didn’t appearβin all formulations.Gompertz model showed that DGMS:LACTEM2:8 accelerated nucleation, PGE:SE5:5 accelerted crystal growth.The results of non-isothermal crystallization showed that in saturated component crystallization rate of PGE:SE2:8 was the fastest, in unsaturated component crystallization rate of DMGS: LACTEM2:8 was the fastest.
引文
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