• 《浓香型枝江白酒香味成分的分析研究》
  • 作者:徐军著
  • 单位:华中农业大学
  • 论文名称 浓香型枝江白酒香味成分的分析研究
    作者 徐军著
    学科 食品科学. 食品品质控制
    学位授予单位 华中农业大学
    导师 刘晓宇指导
    出版年份 2019
    中文摘要 中国白酒历史悠久,深受国内外广大消费者喜爱。中国地域广阔,不同省份的酿酒工艺各有特点,使得中国白酒具有多种类型和风格。根据生产工艺、糖化发酵剂、贮存容器、发酵容器等不同将白酒香型分:浓香型、酱香型、清香型、米香型及其他香型等共10种。其中,浓香型白酒市场占有率最大,每年消费量到达70%左右。 浓香型枝江白酒产于我国长江中游,是浓香型白酒的新名酒品牌,是市场全国化的白酒产品。因此对枝江白酒香味成分进行分析研究,对掌握浓香型白酒呈香呈味物质,提闻白酒品质都具有重要意义。 本文以枝江浓香型白酒作为研究对象,对浓香型原酒香味成分及其分析技术进行了系统的研究。对浓香型枝江白酒中的香味成分进行了较全面的定性和定量分析,采用4种分析方法总结得出了浓香型白酒重要特征风味物质,掌握了原酒中31种重要香味成分在贮存过程中的变化规律。对枝江酒的特征风味进行提炼,由此建立了枝江白酒风味特征指纹图谱,提高和稳定产品质量。 主要研究内容和结果如下: 1、浓香型枝江白酒香味成分的定性研究 针对浓香型枝江白酒中香味成分的含量及性质特点,建立了系统的样品前处理技术及分析方法,包括酸碱性分离浓缩,根据极性分离浓缩,直接进样分析,一次性液液萃取浓缩等方法,精确地完成了对浓香型枝江白酒香味成分的分离浓缩,并采用GC-MS对各色谱峰进行了定性分析。在选取的浓香型枝江原酒样品中共检测出908种香味成分。其中182种酯类化合物,78种醇类化合物,59种芳香类化合物, 45种脂肪酸类,23种醛类化合物,29种缩醛类化合物,29种酮类化合物,11种萜烯类化合物,22种硫化物,23种呋喃类化合物,8种吡啶及吡咯类化合物,12种吡嗪类化合物,其他类化合物108种,279种有色谱峰,尚不能确定的未知化合物。 2、浓香型枝江白酒香味成分的定量研究 在对浓香型枝江白酒定性研究基础之上,针对香味成分在酒样中的含量范围应用不同分析方法对不同种类的化合物进行了定量分析。主要采用气相色谱(GC)毛细管直接进样定量分析色谱骨架成分;采用顶空固相微萃取及气质联用定量分析复杂微量风味成分;采用气质联用(GC-MS)定量分析含硫化合物;采用顶空固相微萃取和气质联用相结合分析含氮化合物;采用离子色谱分析法定量分析有机酸和多元醇。使用以上方法对浓香型枝江白酒样品进行了定量分析,结果定量香味成分156种。其中,能定量检出132种,大部分香味成分含量低于1㎎/L,另有24种未检出或风味含量低于检出限。对定量结果进行了分析统计,酯类含量最高约占香味成分总量的69.26%,其次是脂肪酸类,约占香味成分总量的14.42%,醇类化合物占总量的9.43%,羰基类化合物占总量的5.75%。其中己酸乙酯含量占总酯的41.96%,乳酸乙酯占总酯的28.27%,乙酸乙酯、己酸乙酯、乳酸乙酯、丁酸乙酯4种酯类总含量占总酯的93.82%。乙酸、己酸、乳酸、丁酸4种酸类约占总酸量的91.60%。 3、浓香型枝江白酒呈香化合物的研究 研究了酒样前处理技术,包括酸碱分离、稀释等方法,并采用GC-O对浓香型枝江白酒进行分析,嗅闻到风味活性成分94种。总结出了这些风味成分的呈香特征。计算了浓香型枝江白酒风味成分的OAV值,得出23种浓香型枝江白酒的重要香气成分。综合原酒直接进样分析、Osme分析法、AEDA分析法与OAV值分析方法等4种方法的结果,确定浓香型枝江白酒重要呈香物质为:己酸乙酯、辛酸乙酯、乙酯己酸、乙缩醛、乙酸、丁酸乙酯、丁酸、乳酸乙酯、2-乙基-6-甲基吡嗪、异戊醇、乙酸乙酯、戊酸乙酯、异戊酸乙酯、异戊酸、苯乙醛、2-甲基丁酸乙酯、正丙醇、己酸甲酯、异丁酸乙酯等共19种。结果发现辛酸乙酯OAV值仅次于己酸乙酯,这个结果对研究浓香型白酒重要呈香物质是一个重要发现和补充。 4、不同酒度浓香型枝江白酒贮存过程中香味成分变化的研究 按照生产中白酒馏出时间顺序,摘取了72.7%vol,65.3%vol,55.8%vol三个酒样。对酒样中的31种重要的香味成分,跟踪检测27个月。结果表明:摘酒度数愈高,其主要醛类、醇类、直链低级脂肪酸乙酯的含量就愈高,但其主要酸类物质含量反而愈低。总结为:“酒头”中醛类、醇类、直链低级脂肪酸乙酯含量高,“酒尾”中酸类物质含量高。不同酒度的酸、醛、醇和酯在贮存过程中各自的变化趋势大致是相同的,不会随摘酒度数变化而改变。整体来说低级脂肪酸乙酯在贮存期内含量是逐渐增加的,醇类物质含量绝大多数都呈上升趋势,大部分酸的含量在第24个月后呈上升趋势,特别是乳酸含量在检测期间含量上升了4倍。乳酸乙酯在贮存期内含量下降幅度较大,由此推断白酒在贮存过程中发生了水解和酯化反应。 5、浓香型枝江白酒“风味指纹图谱”的建立及应用 创新性的以嗔味觉在白酒中建立风味指纹图谱。以5种枝江白酒为研究对象,根据品酒师对酒样的品鉴和评分,确定了窖香、酯香、多粮香、醇甜味、回味、陈酒味、绵柔感、爽净感、丰满感、协调感等10项主要风味特征,以此为基础建立了风味指纹图谱,并开发设计出了特有的“风味特征分值判定评分表”和“产品相似性判定评分表”。通过建立的风味指纹图谱并结合酒样中主要常规成分理化指标的检测结果对白酒真伪鉴定和判定产品品质稳定性以及等级等方面进行了生产实践应用。对产品的风格特点的描述,产品缺陷的改进有一定的帮助作用。 关键词:浓香型白酒;香味成分;贮存变化;呈香化合物;指纹图谱
    英文摘要 Chinese baijiu has a long history and is very popular among consumers at home and abroad. China has a vast territory and various baijiu making techniques have its own characteristics, making baijiu of various types and styles. According to the production process, saccharification starter, storage container, and fermentation container, the liquor is divided into 10 kinds: strong aroma, sauce aroma, light aroma, rice aroma, and other flavors. Among them, the strong flavor baijiu market has the largest share, and the annual consumption reaches about 70%. Zhijiang baijiu is produced in the middle and lower reaches of the Changjiang River and is one of the typical representatives of strong aroma baijiu. Therefore, the analysis and research on the trace components of Zhijiang baijiu is a great significance for mastering the flavor of stong aroma baijiu and improving the quality. This paper takes Zhijiang strong aroma baijiu as the research object, and systematically studies the trace components and analytical techniques. A comprehensive qualitative and quantitative analysis was carried out on the trace components in Zhijiang baijiu. Four important methods were used to summarize the flavor characteristics of strong flavor liquor. The changes of 31 important trace components during storage were studied. The characteristic flavor of Zhijiang baijiu was refined, and the fingerprint characteristic of Zhijiang was established to improve and stabilize the product quality. The main research contents and results are as follows: 1.Qualitative study on the trace components of strong-aroma Zhijiang baijiu Aiming at the content and characteristics of trace components in Zhijiang baijiu, a systematic sample preparation technique and analysis method were established, including acid-alkaline separation and concentration, separation and concentration according to polarity, direct injection analysis, disposable liquid and liquid. The extraction and concentration methods were used to accurately separate and concentrate the trace components, and the chromatographic peaks were qualitatively analyzed by GC-MS. 908 trace components were detected from the selected strong-aroma Zhijiang baijiu samples. There are 23 aldehyde compounds, 29 acetal compounds, 29 ketone compounds, 78 alcohol compounds, 182 ester compounds, 45 fatty acids, 11 terpenoids, 22 sulfides, and aromatics. 59 kinds of compounds, 8 kinds of pyridine and azole compounds, 12 kinds of pyrazines, 23 kinds of furan compounds, 108 kinds of other compounds, and 279 kinds were unknown components (with chromatographic peaks but not currently determined). 2.Quantitative study on the trace components of strong-aroma Zhijiang baijiu Based on the qualitative research of Zhijiang baijiu, different analytical methods were applied to quantitatively analyze different kinds of compounds in the range of content of trace components. The chromatographic framework components were directly analyzed by gas chromatography (GC) capillary direct injection; the complex trace flavor components were quantitatively analyzed by headspace solid phase microextraction and GC/MS; and the sulfur compounds were quantitatively analyzed by GC-MS; The nitrogen-containing compounds were analyzed by headspace solid phase microextraction and gas chromatography-mass spectrometry; the organic acids and polyols were quantitatively analyzed by ion chromatography. Using the above quantitative analysis method, 156 kinds of trace components were quantified, among which 132 kinds of Zhijiang baijiu could be quantitatively detected, most of which were trace flavor components with content less than 1 ㎎/L, and about 24 undetected. Zhijiang baijiu has the highest ester content, accounting for 69.26%, fatty acids, accounting for 14.42%, alcohols accounting for 9.43%, and carbonyl compounds accounting for 5.75%. The ethyl hexanoate content in the baijiu is high, accounting for 41.96% of the total ester, followed by ethyl lactate, accounting for 28.27% of the total ester. Four ethyl esters (ethyl acetate, ethyl hexanoate, ethyl lactate, butyl) Ethyl acetate accounted for 93.82% of the total ester. Correspondingly, the sum of acetic acid, caproic acid, lactic acid and butyric acid accounts for about 91.60% of the total acid amount. 3.Study on the aroma compounds of strong-aroma Zhijiang baijiu The sample pretreatment technology was studied, including acid-base separation and dilution. 94 kinds of flavored active ingredients were smelled by GC-O. The OAV value of the flavor component was calculated, and 23 kinds of important aroma components were obtained. Based on the results of four methods, such as direct injection analysis, Osme analysis, AEDA analysis and OAV analysis, the important flavors of Zhijiang baijiu were determined to be ethyl hexanoate, ethyl octanoate and ethyl ester. Caproic acid, acetal, acetic acid, ethyl butyrate, butyric acid, ethyl lactate, 2-ethyl-6-methylpyrazine, isoamyl alcohol, ethyl acetate, ethyl valerate, isovalerate There are 19 kinds of esters, isovaleraldehyde, phenylacetaldehyde, ethyl 2-methylbutyrate, n-propanol, methyl hexanoate and ethyl isobutyrate. 4.Analysis of trace components changes during storage of different flavors of Zhijiang baijiu According to the time sequence of liquor distillation in production, 72.7% vol, 65.3% vol, and 55.8% vol were taken. The 31 important trace components were followed up for 27 months. The results showed that the higher the degree of alcohol extraction, the higher the content of main aldehydes, alcohols and linear lower fatty acid ethyl esters, but the lower the content of main acid substances. "Baijiu head" has a high content of aldehydes, alcohols, and linear low-grade fatty acid ethyl esters, and the content of acid substances in "baijiu tail" is high. The acid, aldehyde, alcohol and ester of different alcoholic beverages have the same change trend during storage, and will not change with the degree of picking. As a whole, the content of lower fatty acid ethyl esters gradually increased during storage, and the content of alcohols mostly increased. Most of the acid content increased after 24 months, especially the detection of lactic acid content. The content increased by 4 times during the period. 5.Establishment and application of "flavor fingerprint" on Zhijiang baijiu Taking 5 kinds of Zhijiang baijiu as research objects, according to the tasting and scoring of the samples by the sommelier, the musk, ester, multi-grain, sweet and mellow, aftertaste, wine taste, softness and refreshing were determined. Based on the 10 main flavor characteristics such as sense, fullness and coordination, the flavor fingerprints were established, and the unique "flavor feature score judgment score table" and "product consistency judgment score table" were developed. Combining the flavor fingerprint and the two scoring tables designed the application of baijiu authenticity identification and determination of product quality stability was applied. Key words: strong-aroma baijiu; trace components; storage change; fragrant compounds; fingerprint
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