白酒陈化机理的研究及应用
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摘要
白酒是我国传统的蒸馏酒,历史悠久,源远流长,以其独特的色、香、味在酒类产品中独树一帜。然而新酿造的白酒,入口暴辣、刺激性强,常需贮存一年或数年,甚至更长的时间,以消除新酒味、增加陈酒感,这一陈酿过程(也叫老熟或陈化)必然会积压大量资金、增加设备投资,加之每年近2%的酒损,给企业造成巨大的经济损失,成为各酒厂亟待解决的重大技术难题。为此,人们寻找各种人工催熟方法缩短白酒陈酿时间,然而由于对白酒陈化机理的认识还不够深入,现有人工催熟技术大都属于经验性质的,尚无一切实可行的方法。因而将白酒陈化机理的研究工作引向深处,对我国白酒催陈老熟技术的研究加以突破,这正是白酒行业中的重中之重。
本论文通过对白酒中氢键缔合行为的系统研究,结合不同酒龄汾酒0到30年自然贮存期内诸多变化行为的详尽分析,提出了白酒自然存放的陈化机制,并在此基础上模拟白酒自然老熟环境及过程,建立了一种缩短白酒陈酿时间的方法。具体内容如下：
一、白酒中氢键缔合行为的研究
以不同浓度的乙醇-水溶液为模型白酒,系统考察了酒度、贮存时间及汾酒中主要微量成分对模型白酒黏度和荧光光谱行为的影响；同时考察了汾酒的黏度及荧光光谱行为随酒度和贮存时间的变化规律。结果表明：白酒中总的氢键缔合强度及乙醇-水缔合强度与其中的微量成分有一定的关系,但决定总氢键缔合强度及乙醇-水缔合强度的主要影响因素是酒度而不是贮存时间,该结论为探明白酒的陈化机理提供了重要的理论和实验依据。
二、汾酒自然老熟行为的分析
系统考察了不同酒龄汾酒0到30年自然贮存过程中酒度、pH、电导率、黏度、荧光发射强度、香味成分及金属离子含量的转化行为,结果发现,贮存过程中,汾酒的酒度和pH逐渐降低,电导率不断升高,其黏度逐渐增大而荧光发射强度没有明显的变化趋势,金属离子含量逐年增加,香味成分变化规律多样。其中乙酸乙酯和乳酸乙酯的含量先增大后减小,乙酸的含量先减小后增大,醇类物质的含量变化不大,低沸点醛类物质的含量降低高沸点醛类物质的含量升高；这些结论为揭示白酒老熟机制提供了有益的数据参考。
三、白酒陈化机理探讨
在对汾酒自然老熟行为具体分析和白酒中氢键缔合行为系统研究的基础上,结合不同酒龄汾酒的三维荧光光谱,发现白酒的自然老熟机制不是“缔合说”、“酯化说”等任何一种或两种学说就可以阐明的,而是“低沸点物质挥发、溶解氧氧化、酯化水解平衡、分子间弱相互作用以及贮存容器表面活性中心的参与等综合作用”的结果,这一机制为研究人工催陈奠定了理论基础。
四、超重力旋转技术在白酒陈酿中的应用
基于白酒自然陈酿机理,模拟白酒自然存放的环境及过程,研制了一台多级雾化超重力旋转白酒陈酿装置,首次将超重力旋转技术应用于白酒陈酿。并考察了酒样流速、酒样温度及气体流速对酒样处理效果的影响,同时对处理前后及自然陈酿两年酒样的各指标进行了比较。结果表明：使用自制装置,在酒样流速80L/h、酒样温度45℃、气体流速15L/min的处理条件下,所得酒样各项指标均相当于自然陈酿两年以上的酒样,其色、香、味感观评价也优于自然贮存两年的白酒。该方法为白酒催陈提供了一种新途径,同时也拓宽了超重力旋转技术的应用范围。
Chinese distilled spirits play a superior role in alcoholic beverages, due to her ancient history and unique appearance, aroma and taste. However, fresh Chinese distilled spirits have a strong fresh spirit scent, and a pungent, bitter and puckery taste. Thereupon, it is necessary for freshly distilled spirits to store for1to several years or even decades, in order to decrease the fresh spirit scent and improve the aged taste. In this aging period, tremendous economy loss was resulted from the instrument investment,2%(V/V) spirit loss per year and massive storage of spirits. Thus obviously, for commercial profit, a variety of methods were used to accelerate the aging process as well as shorten the storage time. Nevertheless, most of existing technologies are in the empirical form due to general lacks of understanding on the maturation mechanism of Chinese distilled spirits. Hence, it is very important to deepen the maturation mechanism of Chinese distilled spirits for making some breakthrough in maturation technologies.
Associative behavior of hydrogen bonding and various physicochemical parameter changes of Fenjiu during its traditional aging course from0to30years were investigated systematically. Based on the results of these experiments, the traditional maturation mechanism of Chinese distilled spirits was put forward, and a novel alternative method, which imitated the traditional aging process, was developed.
The thesis includes four aspects as follows.
In the first section, effects of ethanol content, age time and trace components in Fenjiu on the viscosity and fluorescence spectrum of ethanol-water mixtures were thoroughly studied. At the same time, effects of ethanol content and age time on the viscosity and fluorescence spectrum of Fenjiu were also investigated. The results show that the strength of the ethanol-water hydrogen bonding as well as the total hydrogen bonding in aged Fenjiu were predominated by ethanol content but not aging time. And strengths of these two kinds of hydrogen bonding are also influenced by trace components in Fenjiu.
In the second part, changes of the content of ethanol, aroma and metal ions, and of the value of pH, electric conductivity, viscosity and fluorescence intensity, were systematically examined for Fenjiu during its30years traditional aging. The results show that with prolong of aging time, the ethanol content and pH decrease gradually, the values of electric conductivity, viscosity and metal content increase continuously, and the fluorescence intensity has no obvious trend. While the aromas contents showed diversity changes, in which the contents of ethyl acetate and lactate increase first and then decrease, contrarily to the decrease first and then increase of acetic acid, alcohols contents change slightly, and for aldehydes, the content of low-boiling ones decrease while that of high-boiling ones increase.
In the third section, the maturation mechanism of Chinese distilled spirits was studied based on hydrogen bonding behaviors, various physicochemical parameters changes and three-dimensional fluorescence spectra of Fenjiu during its traditional aging. It was found that the maturation of Chinese distilled spirits is affected by a variety of factors, including evaporative loss of low-boiling-point compounds, oxidation related to dissolved oxygen, equilibrium of esterification-hydrolysis, weak interactions between moleculars, and permeation of active metal ions from the surface of ceramic containers. The conclusion goes beyond each of exsisting theories, such as "association theory","esterification theory", etc.
In the fourth section, by imitating the traditional aging course of Fenjiu, the effect on its maturation of high-gravity field generated by a rotating packed bed (RPB) reactor was investigated. To determine the optimum condition, experiments were performed to examine the effects of spirit flow rate, spirit temperature and gas flow rate on the sensory score of treated spirits. Meanwhile, comparisons of each parameter were made between the treated and untreated samples. The optimum experimental condition was found to be at a spirit flow rate of80L/h, with a spirit temperature of45℃and gas flow rate of900L/h. Under this optimal condition, the treated spirit obtained a quality equivalent to that of a spirit conventionally aged for two years. Results show that the RPB treatment aged Fenjiu much faster than did conventional aging, with similar quality. Thus, RPB treatment is a potential alternative method for aging alcoholic beverages made from various materials.
本论文通过对白酒中氢键缔合行为的系统研究,结合不同酒龄汾酒0到30年自然贮存期内诸多变化行为的详尽分析,提出了白酒自然存放的陈化机制,并在此基础上模拟白酒自然老熟环境及过程,建立了一种缩短白酒陈酿时间的方法。具体内容如下：
一、白酒中氢键缔合行为的研究
以不同浓度的乙醇-水溶液为模型白酒,系统考察了酒度、贮存时间及汾酒中主要微量成分对模型白酒黏度和荧光光谱行为的影响；同时考察了汾酒的黏度及荧光光谱行为随酒度和贮存时间的变化规律。结果表明：白酒中总的氢键缔合强度及乙醇-水缔合强度与其中的微量成分有一定的关系,但决定总氢键缔合强度及乙醇-水缔合强度的主要影响因素是酒度而不是贮存时间,该结论为探明白酒的陈化机理提供了重要的理论和实验依据。
二、汾酒自然老熟行为的分析
系统考察了不同酒龄汾酒0到30年自然贮存过程中酒度、pH、电导率、黏度、荧光发射强度、香味成分及金属离子含量的转化行为,结果发现,贮存过程中,汾酒的酒度和pH逐渐降低,电导率不断升高,其黏度逐渐增大而荧光发射强度没有明显的变化趋势,金属离子含量逐年增加,香味成分变化规律多样。其中乙酸乙酯和乳酸乙酯的含量先增大后减小,乙酸的含量先减小后增大,醇类物质的含量变化不大,低沸点醛类物质的含量降低高沸点醛类物质的含量升高；这些结论为揭示白酒老熟机制提供了有益的数据参考。
三、白酒陈化机理探讨
在对汾酒自然老熟行为具体分析和白酒中氢键缔合行为系统研究的基础上,结合不同酒龄汾酒的三维荧光光谱,发现白酒的自然老熟机制不是“缔合说”、“酯化说”等任何一种或两种学说就可以阐明的,而是“低沸点物质挥发、溶解氧氧化、酯化水解平衡、分子间弱相互作用以及贮存容器表面活性中心的参与等综合作用”的结果,这一机制为研究人工催陈奠定了理论基础。
四、超重力旋转技术在白酒陈酿中的应用
基于白酒自然陈酿机理,模拟白酒自然存放的环境及过程,研制了一台多级雾化超重力旋转白酒陈酿装置,首次将超重力旋转技术应用于白酒陈酿。并考察了酒样流速、酒样温度及气体流速对酒样处理效果的影响,同时对处理前后及自然陈酿两年酒样的各指标进行了比较。结果表明：使用自制装置,在酒样流速80L/h、酒样温度45℃、气体流速15L/min的处理条件下,所得酒样各项指标均相当于自然陈酿两年以上的酒样,其色、香、味感观评价也优于自然贮存两年的白酒。该方法为白酒催陈提供了一种新途径,同时也拓宽了超重力旋转技术的应用范围。
Chinese distilled spirits play a superior role in alcoholic beverages, due to her ancient history and unique appearance, aroma and taste. However, fresh Chinese distilled spirits have a strong fresh spirit scent, and a pungent, bitter and puckery taste. Thereupon, it is necessary for freshly distilled spirits to store for1to several years or even decades, in order to decrease the fresh spirit scent and improve the aged taste. In this aging period, tremendous economy loss was resulted from the instrument investment,2%(V/V) spirit loss per year and massive storage of spirits. Thus obviously, for commercial profit, a variety of methods were used to accelerate the aging process as well as shorten the storage time. Nevertheless, most of existing technologies are in the empirical form due to general lacks of understanding on the maturation mechanism of Chinese distilled spirits. Hence, it is very important to deepen the maturation mechanism of Chinese distilled spirits for making some breakthrough in maturation technologies.
Associative behavior of hydrogen bonding and various physicochemical parameter changes of Fenjiu during its traditional aging course from0to30years were investigated systematically. Based on the results of these experiments, the traditional maturation mechanism of Chinese distilled spirits was put forward, and a novel alternative method, which imitated the traditional aging process, was developed.
The thesis includes four aspects as follows.
In the first section, effects of ethanol content, age time and trace components in Fenjiu on the viscosity and fluorescence spectrum of ethanol-water mixtures were thoroughly studied. At the same time, effects of ethanol content and age time on the viscosity and fluorescence spectrum of Fenjiu were also investigated. The results show that the strength of the ethanol-water hydrogen bonding as well as the total hydrogen bonding in aged Fenjiu were predominated by ethanol content but not aging time. And strengths of these two kinds of hydrogen bonding are also influenced by trace components in Fenjiu.
In the second part, changes of the content of ethanol, aroma and metal ions, and of the value of pH, electric conductivity, viscosity and fluorescence intensity, were systematically examined for Fenjiu during its30years traditional aging. The results show that with prolong of aging time, the ethanol content and pH decrease gradually, the values of electric conductivity, viscosity and metal content increase continuously, and the fluorescence intensity has no obvious trend. While the aromas contents showed diversity changes, in which the contents of ethyl acetate and lactate increase first and then decrease, contrarily to the decrease first and then increase of acetic acid, alcohols contents change slightly, and for aldehydes, the content of low-boiling ones decrease while that of high-boiling ones increase.
In the third section, the maturation mechanism of Chinese distilled spirits was studied based on hydrogen bonding behaviors, various physicochemical parameters changes and three-dimensional fluorescence spectra of Fenjiu during its traditional aging. It was found that the maturation of Chinese distilled spirits is affected by a variety of factors, including evaporative loss of low-boiling-point compounds, oxidation related to dissolved oxygen, equilibrium of esterification-hydrolysis, weak interactions between moleculars, and permeation of active metal ions from the surface of ceramic containers. The conclusion goes beyond each of exsisting theories, such as "association theory","esterification theory", etc.
In the fourth section, by imitating the traditional aging course of Fenjiu, the effect on its maturation of high-gravity field generated by a rotating packed bed (RPB) reactor was investigated. To determine the optimum condition, experiments were performed to examine the effects of spirit flow rate, spirit temperature and gas flow rate on the sensory score of treated spirits. Meanwhile, comparisons of each parameter were made between the treated and untreated samples. The optimum experimental condition was found to be at a spirit flow rate of80L/h, with a spirit temperature of45℃and gas flow rate of900L/h. Under this optimal condition, the treated spirit obtained a quality equivalent to that of a spirit conventionally aged for two years. Results show that the RPB treatment aged Fenjiu much faster than did conventional aging, with similar quality. Thus, RPB treatment is a potential alternative method for aging alcoholic beverages made from various materials.
引文
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