For thousands of years, extracting natural fermented flavor substances from high-quality liquor resources has been a major problem that puzzles the world's distilled liquor enterprises. China liquor, brandy, whisky, gin, rum and vodka are called the six major distilled spirits in the world. However, because China Liquor is enriched by natural microorganisms and fermented naturally in solid state, it is different from other distilled liquors in that it is rich in aroma, taste and healthy active substances such as alcohol, aldehyde, acid and ester. These substances can be divided into three categories according to their contents, namely skeleton components, coordination components and composite components. Brandy, whisky, gin and rum are "pot distillation" and vodka is "tower distillation". China liquor (retort), like other distilled liquors in the world, uses the volatility difference between alcohol and water to extract volatile flavor components, but there are many skeleton components and some harmonious components extracted by this method, and a large number of complex components that can improve liquor grade and liquor taste are not fully extracted. In order to overcome this technical defect, well-known distilled liquor enterprises at home and abroad are seeking to break through the existing distillation methods. How to transform more aroma components, especially the complex components and healthy active components in high-quality brewing resources into wine has become a worldwide problem that puzzles distilled liquor enterprises.
To this end, solving this technical problem has become the dream of the world's brewing science and technology workers for thousands of years. Although they made great efforts to this end, most of them ended in failure. It is understood that supercritical fluid extraction (SFE) is a physical separation technology that has emerged internationally since 1970s. It mainly uses the special physical and chemical properties of supercritical carbon dioxide and other fluids to separate and extract some components from substances. Compared with the traditional separation and extraction technology, it is non-toxic, tasteless, non-corrosive, non-flammable, non-residue and non-environmental pollution, and it can completely retain the advantages of natural products and bioactive substances, which conforms to the taste pursuit of "returning to nature" today and is recognized as a perfect "green separation technology".
As one of the giants in China liquor industry, Shede Tuopai Company has long implemented the strategy of "independent innovation, surpassing quality", relying on independent innovation to boost enterprise development, seeking benefits from innovation and leaping over quality. Many technologies, such as "wheel-wheel double-wheel fermentation technology", "artificial pit mud culture method", "distilled liquor blending and flavoring technology" and "health wine with beneficial functional components", have won national invention patents, combined traditional brewing and fermentation technology with 18 modern fermentation technology, filled the international gap, and successfully created "elegant" Sheshe and Tuopai series wines, which were deeply loved by consumers. In 2006, Shede series wine won the first prize of scientific and technological progress in Sichuan Province. From 65438 to 0992, in view of the worldwide problem of "high yield but no harvest" of modern distillation technology, Tuopai scientific research team began to March into "extraction technology of flavor substances from natural fermentation of distilled liquor".
The whole research is extremely difficult. It is understood that although the principle of separation technology sounds simple, it is difficult to know what to do. Due to the low content of effective components, complex components and poor stability in high-quality brewing resources, especially the separation and extraction of aroma substances from solid and liquid, both research ideas and specific technical routes are in the stage of research and exploration from scratch, and its complexity is unimaginable to ordinary people. According to the introduction of the project team, the research of this project lasted more than 10 years, roughly experienced three "stages" and achieved four "breakthroughs", among which the efforts and hardships are self-evident. I. The first stage
Considering the difficulty of the project, the project team first adopted vacuum distillation and other methods, which failed thousands of times after tens of thousands of experiments. Finally, by adding ester extractor and other technical measures, the controlled distillation of solid liquor was realized, with the average total acid increased by 0.2 ~ 0.4g/L and ethyl caproate increased by 50mg/ 100ml, which greatly improved the yield of skeleton components in high-quality liquor resources and achieved the first major breakthrough. 1994 65438+ 10, "Controlled Distillation Technology of Solid Liquor" won the second prize of Sichuan Science and Technology Progress. However, because the above method still belongs to steam distillation, the recovery effect of some complex components and functional components with low volatility or strong polarity is not obvious due to the solubility. 1999, in view of the wide application of supercritical technology in pharmaceutical industry, Tuopai gave up the idea of extracting natural fermented flavor substances from distilled liquor by supercritical technology, and Li Jiamin, the chief engineer, went to the laboratory of Professor Liu Kuifang of Xinjiang University, where there were small-scale and pilot-scale experimental devices for supercritical extraction. 1In August, 1999, the project group "Supercritical carbon dioxide extraction of natural fermented flavor substances in distilled liquor" was established, and the second stage of painstaking research began from extraction to extraction.
Second, the second stage
This research work met with difficulties from the beginning. Supercritical carbon dioxide extraction is affected by many factors, such as temperature, pressure, shape and viscosity of raw materials, properties of extracted substances, etc. These factors are intricately intertwined, which makes the extraction process extremely complicated. Tuopai Brewing Industry Ecological Park, in particular, has a unique brewing microbial flora formed by water, soil, air (air, climate), micro (microorganisms) and biological communities. Coupled with the essence of six grains, the wine style and taste of each grain are different, including sorghum flavor, barley alcohol, wheat gluten, rice net, corn sweetness and glutinous rice elegance, all of which are fermented and transformed together. Therefore, in this case, the difficulty of finding the best process conditions can be imagined. From 1999 to 2003, the project team spent four years analyzing and comparing the material characteristics for thousands of times, and made more than 10,000 process combinations according to different process conditions. Finally, through technical demonstration, more than 1000 combinations were selected, and more than 3,000 process optimization tests were conducted. Finally, the combination of the best technological conditions and the product recovery rate and quality was found, and the first supercritical extraction process of distilled liquor in the world was successfully developed, which broke the limitation of distillation technology formed for thousands of years, and made the recovery rate of flavor substances in high-quality brewing resources increase by 15 ~ 25 percentage points compared with modern distillation technology, achieving the second major "breakthrough". However, the application shows that the extraction process is more effective than the controlled distillation technology of solid liquor, but the yield and quality are unstable, and the extraction rate is low, especially the extraction of complex components and functional components that are not volatile is insufficient, the daily processing capacity is low, the energy consumption is high, the cost is high, and the industrial application value is not great. So far, few enterprises at home and abroad have adopted it.
Third, the third stage
Therefore, the project team summed up the experience and lessons over the years and started two major breakthroughs in the third phase of research. In view of people's increasing concern about food safety, the project team put forward more advanced technical ideas: starting with technical routes, further improving product yield and reducing production costs; Use that good selectivity of supercritical CO2, changing proces conditions, and selectively separating flavor substances; According to the function of extracted components in wine and consumers' preferences, the extracted products were separated and extracted by physical methods such as membrane separation to remove useless components, so that flavor substances were highly enriched and the quality and safety of products were further improved. However, to support this idea, we must support leading extraction equipment. Due to the limitation of domestic technology, domestic equipment can not meet the requirements of this fine process at all, and international cooperation must be sought. Therefore, Shede Tuopai Company cooperated with many scientific research units engaged in the flavor research of distilled liquor at home and abroad and the world's advanced supercritical extraction company to obtain technical support for the project research. In 2004, the world's leading distilled liquor flavor extraction technology was successfully designed.
After determining the extraction process route, after nearly two years of hard exploration, the project team successively used uniform design method to screen and compare the process technical parameters, and used different volume test devices to do process optimization and regression application tests, which successively solved a series of technical problems such as raw material treatment, internal sediment cleaning, selective separation of flavor substances and further rectification, and achieved the third major breakthrough. In June, 2006, the world's first natural fermentation technology of distilled liquor was successfully born. 1 1 June, 2008, the extraction of flavor components from Shede Tuo brand liquor-making quality resources was protected by the national invention patent.
Fourth, the fourth stage
However, in the application of the results, the project team encountered bigger problems. Although the extracted products belong to the natural fermented substances produced in the brewing process, if added to the wine body, they still belong to the "homecoming family" who left home for thousands of years. Therefore, how to "reduce" these naturally fermented extracts into liquor, keep the liquor body naturally coordinated and the shelf life stable is a big problem faced by supercritical extraction technology in the application of distilled liquor flavor substances. In order to solve this problem, Shetuo brand researchers used full two-dimensional gas chromatography/time-of-flight mass spectrometry to analyze the extracted products in detail and accurately, and then added them to different wines, and organized dealers, 57 national judges (national tasters) and provincial judges (provincial tasters) to code for thousands of times. First, make a dark comment, then make a clear comment, then solicit opinions widely, and randomly invite workers, salespeople and visit dealers. The samples were mailed to the sales area, and the dealers organized "drunkards" to get drunk, and then functional and health experiments were carried out with mice. Finally, master the characteristics of flavor substances extracted from different high-quality brewing resources, and then add them to various wines according to the design requirements of different grades and styles. In 2007, after a year of mass production, we successfully passed the technical threshold of application, achieved the fourth major "breakthrough", and drew a perfect full stop for the project research. According to Mr. Zeng Zuxun, a famous wine-making expert, China liquor will produce some non-volatile or low-volatile flavor substances with complex structure during the fermentation process, which plays an important role in increasing the elegance, roundness, freshness, length and purity of liquor and improving the taste. In order to increase the content of these substances, major domestic enterprises have made "articles" on the fermentation technology of solid liquor, and improved the content of non-volatile or less volatile flavor substances through technological measures such as "high temperature koji making". However, at present, "retort distillation" is mostly used to extract flavor substances from distilled liquor in China, which can not extract volatile or less volatile flavor substances, resulting in "high yield and poor harvest" Therefore, the effect of "writing" on solid liquor fermentation process is not obvious. The birth of Shetuopai supercritical extraction technology can not only make up for the shortcomings of modern distillation technology and existing supercritical extraction technology of liquor, but also greatly improve the quality rate of liquor, and raise the level of solid liquor or solid-liquid combined liquor to 1 ~ 3, making liquor a truly ecological, healthy and pure natural drink.
The researchers conducted a full two-dimensional analysis of the flavor substances extracted from Shede Tuopai, and found that there were more than 2,000 effective components, including 22 functional components such as ligustrazine and ferulic acid. And the products and flavor substances extracted from some famous wineries in China were added to several wines of the same amount for dark evaluation. The statistical results show that the wine brewed with the flavor substances extracted from Shede Tuo brand has the best taste quality and the lowest hygienic index content. The wine body is "elegant and comfortable, naturally soft and round, delicate and full, sweet and refreshing, with a long aftertaste" and has a better taste.