Method for accelerating aging of white spirit through cooperation of mesoporous molecular sieve and microwaves
By using a synergistic catalysis method combining mesoporous molecular sieves and microwave fields, the problems of long natural aging cycles and flavor loss in baijiu have been solved, achieving efficient and safe baijiu production.
Patent Information
- Application Number
- CN202511282254.1
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-09-09
- Publication Date
- 2026-01-09
AI Technical Summary
Existing methods for baijiu (Chinese liquor) involve long natural aging cycles, poor catalytic effects of zeolite materials on macromolecular components, and microwave catalysis leading to the volatilization of low-boiling-point components. Traditional techniques also pose risks of flavor loss and safety hazards.
Mesoporous molecular sieves with pore sizes of 5-30 nanometers are used, combined with microwave field synergistic catalysis. The porous structure and acidic sites of the mesoporous molecular sieves accelerate the esterification reaction, and microwave energy is used to activate molecular collisions to form a semi-closed microcavity structure to reduce flavor loss.
It significantly improves the aging efficiency of baijiu, reduces flavor loss, maintains the safety and stability of the liquor, and achieves efficient and energy-saving baijiu production.
Smart Images
Figure FT_1 
Figure SMS_1
Abstract
Description
[0001] This invention relates to the field of baijiu aging technology, specifically to a novel aging-accelerating method that combines mesoporous molecular sieves and microwave fields to synergistically accelerate the aging reaction of baijiu. Background Technology
[0002] Baijiu, a traditional Chinese distilled spirit, owes its unique taste and flavor largely to its aging process. Aging is a complex physicochemical process, involving physical and chemical changes that occur during long-term storage. It requires extended natural aging in a specific environment to improve its flavor and taste. However, natural aging of baijiu relies on slow esterification and condensation reactions, typically requiring 3-5 years to complete flavor development. This process is characterized by its long cycle, high storage pressure, and susceptibility to environmental conditions. Therefore, developing a technology that can effectively accelerate baijiu aging while preserving its original flavor is of great significance to the baijiu industry.
[0003] Microwave aging technology is a physical aging method that accelerates the transformation of various components in the liquor by applying electromagnetic waves with frequencies between 300 MHz and 300 GHz, thus promoting faster aging and shortening storage time. Its main function is that microwave radiation can penetrate the liquor, allowing water molecules and other component molecules to absorb microwave energy, increasing their vibrational frequency and kinetic energy. This promotes intermolecular interactions and accelerates chemical reactions such as esterification and oxidation, allowing aroma compounds to be generated and accumulated more quickly, thereby improving the flavor and taste. Compared to other physical aging techniques for liquor, such as ultrasonic aging (which can easily produce non-traditional components) and radiation aging (which carries radiation risks), microwave aging offers both efficiency and safety. However, due to the thermal effect of microwaves, irradiation can raise the temperature of the liquor, and excessive irradiation can lead to the loss of low-boiling-point flavor compounds through volatilization.
[0004] To enhance the catalytic effect of baijiu (Chinese liquor), increasing the contact area and providing catalytic sites can promote the reaction. However, existing technologies have shortcomings. For example, zeolite materials, such as HZSM-5, are limited by their pore size (0.5-0.6 nm) and cannot effectively catalyze the synthesis of large molecules in baijiu, such as fatty acids (e.g., hexanoic acid, octanoic acid) and their esters (e.g., ethyl hexanoate, with a molecular size of 1.5 nm), which is detrimental to the enrichment of flavor components. The taste of baijiu is a complex sensory system formed by the synergistic effect of multiple components such as esters, alcohols, aldehydes, and phenols. Relying solely on low-molecular-weight esters (e.g., ethyl acetate) leads to a single flavor profile, lack of complexity, and absence of the roundness and rich aroma characteristic of aged baijiu. Furthermore, zeolite materials like HZSM-5 also suffer from the drawback of being prone to carbon buildup in their one-dimensional straight pores. Summary of the Invention
[0005] To address the technical problems of the long aging time of baijiu, the poor catalytic effect of zeolite materials on the macromolecular components of baijiu, and the volatilization of low-boiling-point components due to the thermal effect of microwave catalysis, this invention provides a technical solution that combines the synergistic catalytic effect of mesoporous molecular sieves and microwave fields to significantly improve aging efficiency and reduce flavor loss.
[0006] (I) Catalytic effect of mesoporous molecular sieves
[0007] (1) Pore size adaptation and mass transfer optimization: Mesoporous molecular sieves are materials with porous structures and pore sizes between 5 and 30 nanometers. This pore size range is much larger than that of traditional zeolite molecular sieves (pore size 0.3-1.0 nanometers). Considering the large molecular size of C6-C12 fatty acids (such as hexanoic acid and octanoic acid) and their esters in baijiu, mesoporous molecular sieves with pore sizes of 5-30 nm are used to overcome the mass transfer bottleneck of traditional zeolite molecular sieves (0.3-1.0 nm). It can allow macromolecules to diffuse freely, unlike traditional zeolite molecular sieves where the pore size is too small, which restricts the entry and diffusion of macromolecules, thus achieving free diffusion of macromolecules and efficient mass transfer.
[0008] (2) Acidic site catalysis: Acidic sites are introduced into the pores through surface sulfonation (-SO3H) or loading phosphotungstic acid (HPW), accelerating key reactions such as esterification and condensation, and promoting the formation of flavor compounds. Sulfonic acid groups (-SO3H) are very strong acidic groups that can provide a large number of protons (H⁺). These protons can activate alcohols and acids in the reactants, making them more likely to react. Phosphotungstic acid (HPW) is also a strong acid that can provide a large number of protons, which can also activate the reactants and accelerate the esterification reaction. In addition, sulfonic acid groups or phosphotungstic acid can be evenly distributed on the mesoporous molecular sieve, which means that each active site can effectively participate in the reaction without the situation of active sites being blocked or reactants being unable to reach them.
[0009] (3) Anti-carbon deposit and structural advantages: The three-dimensional interpenetrating pore structure of mesoporous molecular sieves delays carbon deposit formation and improves the lifespan compared with one-dimensional straight pore zeolite molecular sieves; the three-dimensional semi-enclosed structure can constrain the escape of volatile gases and reduce the loss of flavor components.
[0010] (4) Safety assurance: The pure silicon-based framework of mesoporous molecular sieves has no risk of metal leaching, avoiding the leaching hazards of traditional aluminosilicate zeolites and ensuring the safety of the wine.
[0011] (II) Synergistic enhancement effect of microwave and mesoporous molecular sieve porous microcavity effect
[0012] (1) Dielectric activation reaction: Microwaves enhance the energy of polar molecules such as ethanol and acetic acid, increase the collision frequency and the proportion of activated molecules, and accelerate the chemical reaction rate.
[0013] (2) Energy focusing mechanism: The reflection of microwaves on the mesoporous wall forms a local energy storage effect, which enables molecules in the microcavity to obtain higher motion speed and vibrational energy, significantly improving reaction efficiency.
[0014] (3) Microenvironment constraint effect: The porous microcavities of mesoporous molecular sieves have a semi-closed structure, which can provide dense contact space for reaction molecules, enhance the probability of intermolecular collisions, and shorten the reaction path.
[0015] (4) Anti-escape effect: The semi-closed structure of the porous microcavities of mesoporous molecular sieves helps to reduce the volatilization of low-boiling-point flavor components caused by microwave irradiation heat effect.
[0016] (III) Technical Solution of the Invention A schematic diagram of the baijiu aging device is shown in the attached diagram of the instruction manual. Figure 1 As shown.
[0017] Step 1: The wine is poured into and fully impregnates the multi-cavity mesoporous molecular sieve treatment container 1. This container 1 contains sulfonated mesoporous molecular sieve material with a pore size of 5-30 nm. The outer layer of the container 1 is made of a microwave-permeable material, such as polytetrafluoroethylene (PTFE). Furthermore, the container 1 is equipped with corresponding temperature control and airflow exchange devices to optimize the reaction environment to meet catalytic requirements.
[0018] Step 2: A microwave irradiation device 2 (including a magnetron, power regulator, and emission focusing port) is installed outside the multi-cavity mesoporous molecular sieve treatment container 1. This device supports multi-band microwave output at frequencies such as 2450MHz, 915MHz, or 433MHz, and can irradiate the wine in the container 1. Microwave parameters (such as irradiation energy density, irradiation time, and temperature control) can be set according to the characteristics of the wine (such as aroma and alcohol content) to achieve precise irradiation using the microwave irradiation device 2.
[0019] Step 3: The irradiated wine can be output to the storage tank through the configured pump and pipeline device 3 for cooling and depressurization. There is also a circulation pipeline and equipment to facilitate multiple treatments. After the treatment is completed, it is sent to the next process node. Attached Figure Description Figure 1 This is a schematic diagram of the structure of a mesoporous molecular sieve and a microwave-assisted aging device for baijiu (Chinese liquor) according to an embodiment of the present invention. Specific Implementation
[0020] Example 1: The microwave operating mode was dual-frequency (915MHz and 2450MHz) radiation. The microwave irradiation gradient power and irradiation time were controlled as follows: 3.0W / mL (10min) → 2.0W / mL (8min) → 2.5W / mL (15min). The temperature limit process was set at ≤±1℃ for each stage, with a peak temperature ≤45℃. The treatment was repeated 3 times (8h interval). Comparison of wine components before and after treatment: Wine sample Total acid (calculated as acetic acid) g / L Total esters (calculated as ethyl acetate) g / L Ethyl hexanoate g / L Unprocessed 1.64 2.64 0.04 deal with 2.30 3.06 0.10 Example 2: The microwave operating mode was 2450MHz alternating radiation. The microwave irradiation gradient power and irradiation time were controlled as follows: 3.5W / mL (10min) → 2.5W / mL (10min) → 2.5W / mL (10min). The temperature control process was set at a temperature difference of ≤±1℃ between each stage, with a peak temperature ≤50℃. The treatment was repeated 3 times (5h interval). Comparison of wine components before and after treatment: Wine sample Total acid (calculated as acetic acid) g / L Total esters (calculated as ethyl acetate) g / L Ethyl hexanoate g / L Unprocessed 1.64 2.64 0.04 deal with 2.11 2.94 0.12
[0021] Example 3: The microwave operating mode was 915MHz radiation. The microwave irradiation gradient power and irradiation time were controlled as follows: 3.0W / mL (10min) → 3.5W / mL (15min) → 2.0W / mL (10min). The temperature control process was set at a temperature difference of ≤±1℃ at each stage, with a peak temperature ≤50℃. The treatment was repeated 4 times (6h interval). Comparison of wine components before and after treatment: Wine sample Total acid (calculated as acetic acid) g / L Total esters (calculated as ethyl acetate) g / L Ethyl hexanoate g / L Unprocessed 1.64 2.64 0.04 deal with 2.23 2.98 0.09 According to GB / T 26760-2011 "Classification Table of Physicochemical Indicators for High-Proof Baijiu (Sauce-Flavored Type)" Using this technical solution can effectively improve the aging effect of baijiu.
[0022] The use of this technical solution to accelerate the aging of baijiu has the following beneficial effects:
[0023] (1) Improved aging efficiency. Due to the sulfonated mesoporous molecular sieve, the sulfonated group can be used for both catalysis and mass transfer of macromolecular components. Under the action of microwave irradiation energy, the aging efficiency of baijiu can be improved.
[0024] (2) Reduced loss of flavor quality. The semi-closed microcavity structure of the mesoporous molecular sieve material reduces the loss of low-boiling-point aromatic compounds, improves flavor retention, and increases the amount of esters generated by 30%.
[0025] (3) Safety and stability. Pure silicon-based molecular sieves with mesoporous molecular sieve materials have no risk of leaching, and the three-dimensional pore structure has anti-carbon deposit properties that extend the service life of equipment.
[0026] (4) Production flexibility. This technical solution supports multi-frequency microwave parameter adjustment and cyclic processing mode to adapt to different wine aging needs and realize customized production.
[0027] (5) Energy saving. The catalytic effect and microcavity structure of mesoporous molecular sieves can improve the energy efficiency of the aging process and save production energy consumption.
[0028] In summary, this technical solution addresses the bottlenecks of high energy consumption, long cycle, and flavor loss in traditional aging technologies by combining the three-in-one function of "mass transfer-catalysis-constraint" of mesoporous molecular sieves with the "energy focusing-molecular activation" effect of microwaves, thus providing the liquor industry with an efficient, energy-saving, and high-quality industrial solution.
[0029] Preparation method of sulfonated mesoporous molecular sieves
[0030] (1) The silicon source (tetraethyl orthosilicate), surfactant (polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer), sulfonic acid precursor (3-hydroxypropyltrimethoxysilane) and organic auxiliaries (hexadecyltrimethylammonium bromide) are dissolved in an acidic solvent to form a homogeneous mixed solution.
[0031] (2) Under hydrothermal conditions of 120-180℃ for 24-72 hours, 3-hydroxypropyltrimethoxysilane and tetraethyl orthosilicate jointly construct a mesoporous framework through hydrolysis-condensation reaction, while hexadecyltrimethylammonium bromide and surfactant synergistically regulate the pore structure.
[0032] (3) After the reaction is completed, the product is oxidized (e.g., H2O2 solution) to oxidize the mercapto group in 3-hydroxypropyltrimethoxysilane to a sulfonic acid group (-SO3H); then the template agent is removed by alkaline washing to obtain sulfonated mesoporous molecular sieve.
[0033] (4) The product is acid-treated (dilute hydrochloric acid) to remove unreacted byproducts, and the rigidity of the skeleton is further enhanced by calcination (300-500℃), and the specific surface area and pore size distribution are optimized.
Claims
1. A method for aging baijiu (Chinese liquor), characterized in that: Mesoporous molecular sieve materials with pore sizes of 5–30 nm and sulfonic acid groups introduced into the pore surface through chemical modification were used as catalysts and microwave irradiation was employed.
2. The method according to claim 1, characterized in that the process... include: The microwave operating mode is dual-frequency (915MHz and 2450MHz) radiation. The microwave irradiation gradient power and irradiation time are 3.0W / mL (10min) → 2.0W / mL (8min) → 2.5W / mL (15min). The temperature limit process is that the temperature difference of each stage is ≤±1℃, the peak temperature is ≤65℃, and the cycle treatment is 3 times (with an interval of 8h).
3. The method according to claim 1, characterized in that the process... include: The microwave operating mode is 2450MHz alternating radiation. The microwave irradiation gradient power and irradiation time are controlled as follows: 3.5W / mL (10min) → 2.5W / mL (10min) → 2.5W / mL (10min). The temperature limit process is that the temperature difference between each stage is ≤±1℃, the peak temperature is ≤50℃, and the cycle treatment is performed 3 times (with an interval of 5h).
4. The method according to claim 1, characterized in that the process... include: The microwave operating mode is 915MHz radiation. The microwave irradiation gradient power and irradiation time are controlled as follows: 3.0W / mL (10min) → 3.5W / mL (15min) → 2.0W / mL (10min). The temperature limit process is that the temperature difference at each stage is ≤±1℃, the peak temperature is ≤50℃, and the treatment is repeated 4 times (with an interval of 6h).
5. A liquor aging device, characterized by comprising the technical features described in claim 1.