Rare earth-doped graphene brewing composite materials, their preparation methods and applications

Abstract

This invention relates to rare-earth-doped graphene brewing composite materials, their preparation methods, and applications, belonging to the field of nanocomposite materials technology. The technical problem solved by this invention is to provide a rare-earth-doped graphene brewing composite material that can be used for water treatment, particularly for brewing water treatment. The chemical formula of the rare-earth-doped graphene brewing composite material of this invention is aLa₂O₃·bCeO₂·cAl₂O₃·4SiO₂·nH₂O·dC (n) The rare earth-doped graphene-based brewing composite material of this invention, wherein 0.070≤a≤0.090, 0.150≤b≤0.190, 0.18≤c≤0.24, 0.24≤d≤0.36, and 0.21≤e≤0.23, is used for pretreatment of brewing water, which can increase the yield of alcohol and greatly improve the quality of the alcohol.

Description

Technical Field

[0001] This invention relates to rare earth-doped graphene brewing composite materials, their preparation methods, and applications, belonging to the field of nanocomposite materials technology. Background Technology

[0002] Baijiu, one of the world's six most famous distilled spirits, has a history of thousands of years in my country, boasting advanced brewing and distillation techniques. With technological advancements and rising demands for baijiu quality, traditional styles and qualities are increasingly inadequate for modern consumers' expectations of drinking culture. Safety, hygiene, and nutritional value have become paramount. Therefore, it is crucial to address questions such as which substances can significantly and positively alter the content of esters, aldehydes, and alcohols produced during the brewing process, thereby optimizing the chemical composition of baijiu.

[0003] Traditional Chinese distilled spirits, even today, still employ a unique production method involving natural inoculation of various microorganisms for koji making, solid-state fermentation, barrel distillation, and open-air processing. This includes processes such as raw material selection, koji making, fermentation, distillation, aging, blending, and bottling. The equipment used remains primarily fermentation pits and earthenware jars, resulting in limited controllability. Significant differences in water, soil, and climate across regions lead to variations in the types and quantities of microorganisms, ultimately resulting in substantial differences in the amount of trace aroma compounds in the base spirit. In particular, traditional methods have proven extremely difficult to effectively address issues affecting spirit quality, such as methanol and the bitter, spicy, sour, and astringent tastes. Furthermore, variations in fermentation equipment, work teams, and the varying skill levels of different technicians contribute to the differences in the quantity and proportion of various trace aroma components in the base spirit, creating distinct characteristics.

[0004] Besides grains and yeast, high-quality water is essential for the fermentation of baijiu (Chinese liquor). Technological improvements in baijiu production involve several common water pollution control technologies, including biological-ecological restoration, microbial technology, and membrane separation technology. Two key issues need to be addressed: first, the quality of the water used for brewing, significantly reducing calcium and magnesium ions and heavy metals while maintaining essential trace elements to achieve hydrogen-rich water and enhance water quality; second, the removal of some heavy metals and chemicals from the grains and microbial agents during the process to eliminate the adverse effects of impurities on the liquor quality. These issues directly impact the quality of baijiu, resulting in problems such as loss of luster, turbidity, sedimentation, abnormal color, strong off-flavors, weak aromas, alcoholic tastes, raw material tastes, and other off-flavors, exhibiting an imbalance between aroma and taste (e.g., aroma overpowering taste, strong acidity and astringency, weak main aroma, low absolute content of main aroma components, and heavy off-flavors). To address these issues, a fundamental technical challenge is needed to balance the levels of total acids and esters with lower levels of methanol, isobutanol, n-propanol, acetaldehyde, and acetal. Summary of the Invention

[0005] The first technical problem solved by this invention is to provide a rare earth-doped graphene brewing composite material that can be used for water treatment, especially for brewing water treatment.

[0006] The chemical formula of the rare earth-doped graphene brewing composite material of the present invention is a La2O3·b CeO2·c Al2O3·4SiO2·nH2O·d C(n)·e C6H8O7, wherein 0.070≤a≤0.090, 0.150≤b≤0.190, 0.18≤c≤0.24, 0.24≤d≤0.36, and 0.21≤e≤0.23.

[0007] Preferably, 0.075≤a≤0.088, 0.160≤b≤0.180, 0.19≤c≤0.23, 0.25≤d≤0.34, and 0.21≤e≤0.23.

[0008] More preferably, 0.080≤a≤0.087, 0.164≤b≤0.172, 0.20≤c≤0.22, 0.29≤d≤0.33, and 0.21≤e≤0.23.

[0009] The optimal values ​​are a = 0.086, b = 0.170, c = 0.213, d = 0.32, and e = 0.23.

[0010] The second technical problem to be solved by the present invention is to provide a method for preparing the above-mentioned rare earth-doped graphene brewing composite material, the method comprising the following steps:

[0011] a. Prepare the oxides, hydroxides or salts of La and Ce according to the calculated amount, add nitric acid with a mass concentration of 60-70%, and stir thoroughly to completely dissolve the materials;

[0012] b. Heat to 90-100℃, add activated clay while stirring, and react for 40-50 minutes;

[0013] c. After reaction b is complete, the temperature is lowered to 60℃, and the corresponding weight of graphene is added while stirring. The temperature is then raised to 80-85℃ and the reaction is carried out for 30 minutes.

[0014] d. After the reaction is complete, the solution is heated to 110°C, concentrated, crystallized, dried, and ground until the product passes through 60 mesh to obtain composite material I;

[0015] e. First, crush composite material I and then put it into a mixer. While stirring, add citric acid and then grind it to obtain rare earth-doped graphene brewing composite material.

[0016] In order to improve the purity of the La and Ce compounds and thus improve the effect of the rare earth-doped graphene brewing composite material of the present invention, the oxides, hydroxides or salts of La and Ce in step a above are preferably dissolved in hydrochloric acid or nitric acid first, then converted with sodium hydroxide to obtain an alkali cake, and then reacted with nitric acid.

[0017] Furthermore, the purity of the above-mentioned activated clay is preferably ≥99.0%, the purity of graphene is preferably ≥99.9%, and the purity of citric acid is preferably ≥99.0%.

[0018] The third technical problem to be solved by the present invention is to provide a method for treating water used in brewing.

[0019] a. Obtain water for brewing;

[0020] b. Add the rare earth-doped graphene brewing composite material to the water to be treated at a dosage of 90-110 grams per cubic meter of water, stir evenly, and let stand.

[0021] c. Take the supernatant after step b has been allowed to stand, filter it, and then distill the filtrate three times. The distilled liquid is then distilled again at a temperature of 99°C to obtain the treated brewing water.

[0022] This invention relates to a rare earth-doped graphene brewing composite material that can be used for pretreatment of brewing water, thereby increasing the yield and significantly improving the quality of the liquor. The content of substances such as methanol, formaldehyde, fusel oil, lead, hydrogen cyanide, and aflatoxin not only fully meets national standards, but also comprehensively increases beneficial substances while significantly reducing harmful substances. For example, the content of methanol and toxic heavy metals is more than 10 times lower than the national standard. Comparative analysis of total acid, total ester, aldehydes, and alcohols that affect the quality of liquor shows a significant effect in eliminating harmful substances. Detailed Implementation

[0023] The embodiments of the present invention will be described in detail below with reference to specific examples. However, those skilled in the art will understand that the following embodiments are for illustrative purposes only and should not be considered as limiting the scope of the invention. Unless otherwise specified in the embodiments, conventional conditions apply.

[0024] Example 1

[0025] This invention relates to a rare-earth-doped graphene-based brewing composite material with the chemical formula aLa₂O₃·bCeO₂·cAl₂O₃·4SiO₂·nH₂O·dC(n)·eC₆H₈O₇, wherein...

[0026] a=0.083, b=0.168, c=0.21, d=0.29, e=0.23.

[0027] The preparation method is as follows:

[0028] a. According to the above ratio, add the measured La and Ce hydroxides to the reactor, and then mix at a ratio of 1 ton: 5 m³. 3 The solid-liquid ratio was adjusted by adding 33% hydrochloric acid, heating the reactor to 100°C and stirring for 45 minutes, and then filtering through a plate and frame filter to further remove impurities, resulting in a solution containing La and Ce.

[0029] b. Pump the filtered solution into the next stage reactor at a rate of 0.9 tons / 5m³. 3 Sodium hydroxide was added in a measured amount for conversion. The resulting alkali cake was repeatedly washed with water. When the pH of the washing solution reached 8.5, the alkali cake was converted to nitric acid at a weight ratio of 1 ton: 2.2 m³. 3 The liquid was acid-dissolved by adding 65wt% nitric acid. In the double salt stage, the modified liquid was treated with 100nm ultrafiltration porous membrane technology. Using pressure as the driving force, the core material was made to reach 50-100nm. The liquid was pumped into the next stage reactor and heated to 105℃. 99% pure activated clay was added while stirring and reacted for 45 minutes. Then graphene was added and stirred for 30 minutes.

[0030] c. Pump the mixture obtained in b into a special concentration and crystallization reactor equipped with a high-pressure jet pump, heat it to 115°C, and obtain the primary product through concentration and crystallization.

[0031] d. After crystallization, the product is first ground using a Raymond mill. The ground gray-white powdery semi-finished product is then transferred into a mixer and citric acid is added while stirring. After stirring for 30 minutes, the mixture is fed into an ultra-fine pulverizer. After ultra-fine pulverization, the rare earth-doped graphene brewing composite material of this invention is obtained.

[0032] Take brewing water; add rare earth-doped graphene brewing composite material to the water to be treated at a dosage of 95 grams per cubic meter of water, stir evenly, and let stand for 24 hours; take the supernatant after standing, filter, and the filtrate undergoes three-stage distillation. The distilled liquid is then distilled again at a temperature of 99°C to obtain the treated brewing water.

[0033] Example 2

[0034] The raw material ratios are shown in Table 1, and the preparation method is the same as in Example 1. The prepared sample was used for water treatment in brewing, and the results are shown in Table 1. Before treatment, the Ca(HCO3)2 content was 55 mg / L, Mg(HCO3)2 was 13.5 mg / L, As was 0.013 mg / L, and Hg was 0.004 mg / L.

[0035] Table 1

[0036]

[0037] Example 3

[0038] The raw material ratios are shown in Table 2, and the preparation method is the same as in Example 1. The prepared sample was used for water treatment in brewing, and the treated water was used for brewing. Untreated ordinary brewing water was used as a blank control. Except for the brewing water, the same brewing raw materials and processes were used. The results are shown in Table 2.

[0039] Table 2

[0040]

[0041] Table 2 shows the effects of different ratios on ethanol, methanol, ethyl acetate, and lead. It has a significant effect on increasing the content of ethanol and ethyl acetate, and a significant effect on removing toxic and harmful substances such as methanol and heavy metals.

[0042] This specific embodiment is merely an explanation of the present invention and is not intended to limit the present invention. After reading the specification of the present invention, those skilled in the art may make some modifications or improvements based on the present invention, but as long as they are within the scope of the claims of the present invention, they are protected by patent law.

Claims

1. A method for treating water used in brewing, characterized in that... Includes the following steps: 1) Take water for brewing; 2) Add the rare earth-doped graphene brewing composite material to the water to be treated at a dosage of 90-110 g / m³, stir evenly, and let stand. The chemical formula of the rare earth-doped graphene brewing composite material is aLa₂O₃·bCeO₂·cAl₂O₃·4SiO₂·nH₂O·dC. (n) ·e C6H8O7, where 0.070≤a≤0.090, 0.150≤b≤0.190, 0.18≤c≤0.24, 0.24≤d≤0.36, 0.21≤e≤0.23; 3) Take the supernatant after step 2) and let it stand. Filter it. The filtrate is then distilled three times. The distilled liquid is then distilled again at 99°C to obtain the treated brewing water.

2. The method for treating brewing water according to claim 1, characterized in that: 0.075≤a≤0.088, 0.160≤b≤0.180, 0.19≤c≤0.23, 0.25≤d≤0.34, 0.21≤e≤0.

23.

3. The method for treating brewing water according to claim 1, characterized in that: 0.080≤a≤0.087, 0.164≤b≤0.172, 0.20≤c≤0.22, 0.29≤d≤0.33, 0.21≤e≤0.

23.

4. The method for treating brewing water according to claim 1, characterized in that: a=0.086, b=0.170, c=0.213, d=0.32, e=0.

23.

5. The method for treating brewing water according to any one of claims 1-4, characterized in that, The preparation of rare earth-doped graphene brewing composite materials includes the following steps: A. Prepare the oxides, hydroxides or salts of La and Ce according to the calculated amount, add nitric acid with a mass concentration of 60-70%, and stir thoroughly to completely dissolve the materials; B. Heat to 90-100℃, add activated clay while stirring, and react for 40-50 minutes. C. After reaction B is complete, the temperature is lowered to 60°C, and the corresponding weight of graphene is added while stirring. The temperature is then raised to 80-85°C and the reaction is carried out for 30 minutes. D. After the reaction is complete, the solution is heated to 110℃ and concentrated, then crystallized, dried, and ground until the product passes through 60 mesh to obtain composite material I; E. Place composite material I into a mixer, add citric acid while stirring, and then grind to obtain rare earth-doped graphene brewing composite material.

6. The method for treating brewing water according to claim 5, characterized in that: In step A, the oxides, hydroxides, or salts of La and Ce are dissolved in hydrochloric acid or nitric acid, then converted with sodium hydroxide to obtain a alkali cake, which is then reacted with nitric acid.

7. The method for treating brewing water according to claim 5, characterized in that: The purity of activated clay is ≥99.0%, the purity of graphene is ≥99.9%, and the purity of citric acid is ≥99.0%.

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