阅读说明：本技术 一种富硒陶瓷酒瓶及其制备方法 (Selenium-rich ceramic wine bottle and preparation method thereof ) 是由 郭占峰 王浩 韩冰 于 2020-12-28 设计创作，主要内容包括：本发明涉及陶瓷制品技术领域,具体涉及一种富硒陶瓷酒瓶及其制备方法,该陶瓷酒瓶包括坯体,所述坯体由质量百分比为8～15％陶土、50～70％煤矸石和20～42％乌兰茶晶石组成,所述乌兰茶晶石中含有营养元素Se 1.5～5mg/kg。由于乌兰茶晶石中含有硒元素,由其制成的陶瓷酒瓶即富含硒元素,且具有硒溶出的功能,能够提供硒元素至储存于其中的白酒中,人们喝酒的同时能够摄入硒元素,保证人体健康。(The invention relates to the technical field of ceramic products, in particular to a selenium-rich ceramic wine bottle and a preparation method thereof, wherein the ceramic wine bottle comprises a blank body, wherein the blank body comprises 8-15% of argil, 50-70% of coal gangue and 20-42% of wulan tea crystal stone in percentage by mass, and the wulan tea crystal stone contains 1.5-5 mg/kg of nutrient element Se. Because the Wulan tea crystalloid contains selenium, the ceramic wine bottle made of the Wulan tea crystalloid is rich in the selenium, has the function of dissolving out the selenium, can provide the selenium into the white spirit stored in the wine bottle, and can absorb the selenium when people drink the wine, thereby ensuring the health of human bodies.)

1. The selenium-rich ceramic wine bottle comprises a blank body and is characterized in that: the green body consists of 8-15% of argil, 50-70% of coal gangue and 20-42% of wulan tea crystal stone in percentage by mass, wherein the wulan tea crystal stone contains 1.5-5 mg/kg of nutrient elements Se1.5-5 mg/kg.

2. The selenium-enriched ceramic wine bottle of claim 1, which is characterized in that: the nutrient elements in the oolong tea spar also comprise N250-400 Mg/kg, P250-350 Mg/kg, K35000-40000 Mg/kg, Ca 65000-70000 Mg/kg, Mg 1000-1300 Mg/kg, S120-150 Mg/kg, Cu 80-100 Mg/kg, Fe 15000-20000 Mg/kg, Mn 220-300 Mg/kg, Zn 50-100 Mg/kg, B6-12 Mg/kg and Mo 2-6 Mg/kg;

the glauconite contains conventional compound Al₂O₃ 13～15％、SiO₂ 70～74％、Fe₂O₃ 2～3.5％、CaO 1.2～1.6％、MgO 0.1～0.2％、K₂O 5.2～6％、Na₂O 3.5～4％、TiO₂0.2-0.4%, and the ignition loss is 0.7-1.2%;

the oolong tea spar contains rare earth compound La₂O₃ 80～200mg/kg、CeO₂ 200～300mg/kg、Pr₈O₁₁20～50mg/kg、Nd₂O₃ 60～100mg/kg、Sm₂O₃ 8～20mg/kg、Eu₂O₃ 0.5～1.5mg/kg、Gd₂O₃8～20mg/kg、Tb₄O₇ 1～3mg/kg、Dy₂O₃ 4～8mg/kg、Ho₂O₃ 0.6～2mg/kg、Er₂O₃ 2～6mg/kg、Tm₂O₃0.2～1mg/kg、Yb₂O₃ 2～5mg/kg、Lu₂O₃ 1～2mg/kg、Y₂O₃ 20～40mg/kg、Rb₂O 200～300mg/kg、Sc₂O₃ 0.5～2mg/kg；

The total content of iron and titanium in the wulan tea-colored crystal stone is less than or equal to 3 percent.

3. The selenium-enriched ceramic wine bottle of claim 1, which is characterized in that: the wulan tea crystal stone is prepared by gathering, homogenizing, stirring, settling and vacuum filtering and dehydrating powdery materials which are crushed, dedusted and collected in the production and purification process of pegmatite granite waste materials or superfine overflow materials which are hydraulically overflow-gathered.

4. The selenium-enriched ceramic wine bottle of claim 3, wherein: the giant granite waste material is derived from granite porphyry deposit in inner Mongolia, and contains a conventional compound Al₂O₃ 12～15％、SiO₂70～76％、Fe₂O₃ 1～2％、CaO 0.8～1.2％、MgO 0.1～0.3％、K₂O 5.3～6％、Na₂O 3.2～4％、TiO₂0.1 to 0.25% and a burning vector of 0.2～0.5％；

1000-1200 Mg/kg of nutrient elements N, 150-250 Mg/kg of P, 42000-50000 Mg/kg of K, 5800-6500 Mg/kg of Ca, 800-900 Mg/kg of Mg, 70-100 Mg/kg of S, Cu: 2-8 mg/kg, Fe 12000-15000 mg/kg, Mn 150-250 mg/kg, Zn 40-60 mg/kg, B6-12 mg/kg, Mo 3.0-6 mg/kg, Se 3.0-5 mg/kg;

rare earth compound La₂O₃ 50～100mg/kg、CeO₂ 100～200mg/kg、Pr₈O₁₁ 10～25mg/kg、Nd₂O₃40～60mg/kg、Sm₂O₃ 5～12mg/kg、Eu₂O₃ 0.5～2mg/kg、Gd₂O₃ 6～20mg/kg、Tb₄O₇ 0.5～2mg/kg、Dy₂O₃ 4～10mg/kg、Ho₂O₃ 0.8～3mg/kg、Er₂O₃ 2～6mg/kg、Tm₂O₃ 0.2～1mg/kg、Yb₂O₃ 2～6mg/kg、Lu₂O₃ 0.5～3mg/kg、Y₂O₃ 20～40mg/kg、Rb₂O 250～400mg/kg、Sc₂O₃ 1.5～5mg/kg。

5. The selenium-enriched ceramic wine bottle of claim 1, which is characterized in that: the chemical component of the coal gangue is Al₂O₃ 35～40％，SiO₂ 40～50％、Fe₂O₃ 0.1～2％、CaO 0.1～0.2％、MgO 0.1～0.2％、K₂O 0.1～0.2％、Na₂O 0.1～0.2％、TiO₂0.3 to 0.4%, and a burning vector of 12 to 18%.

6. The selenium-enriched ceramic wine bottle of claim 1, which is characterized in that: the argil is kaolin or purple clay, and the chemical component of the kaolin is Al₂O₃ 12～15％、SiO₂ 60～70％、Fe₂O₃ 0.5～1％、CaO 2～6％、MgO 2～4％、K₂O 0.5～1％、Na₂O 0.5～1％、TiO₂0.05 to 0.1% and a burning vector of 8 to 10%.

7. The method for preparing the selenium-enriched ceramic wine bottle as claimed in any one of claims 1 to 6, which comprises the following steps performed in sequence:

a grinding step, which is used for respectively grinding the wulan tea spar, the coal gangue and the argil until the fineness is less than 80 meshes;

an iron removal step, which is used for mixing the wulan tea spar, the coal gangue and the argil according to the formula amount and then carrying out iron removal treatment to obtain a mixed blank;

a ball milling step, namely grinding and homogenizing the mixed blank after iron removal by a wet overflow ceramic ball mill to obtain blank slurry;

and a blank making step, namely dehydrating and vacuum filtering the blank slurry, performing vacuum pugging for multiple times, ageing for 6-8 days, and then making and firing to obtain the ceramic wine bottle.

8. The method for preparing the selenium-rich ceramic wine bottle as claimed in claim 7, wherein the method comprises the following steps: in the ball milling step, the milling time is 18-22 hours, the fineness of the blank slurry is less than 400 meshes, and the screen residue is less than 0.2%.

9. The method for preparing the selenium-rich ceramic wine bottle as claimed in claim 7, wherein the method comprises the following steps: in the blank making step, the firing temperature is 1180-1220 ℃, and the firing time is 8-10 hours.

10. The method for preparing the selenium-rich ceramic wine bottle as claimed in claim 7, wherein the method comprises the following steps: in the grinding step, the fineness of the oolong tea spar powder is 40-80 meshes.

Technical Field

The invention relates to the technical field of ceramic products, in particular to a selenium-rich ceramic wine bottle and a preparation method thereof.

Background

The traditional wine bottle generally takes glass as a raw material and has the defects of high firing temperature and high energy consumption, so that the wine is usually packaged by adopting a ceramic wine bottle at present. On one hand, the light-tight characteristic of the ceramic wine bottle can prevent the white spirit from generating chemical reaction due to illumination, and the quality of the white spirit is ensured; on the other hand, the ceramic wine bottle has slower heat conduction than the glass wine bottle, can ensure the wine temperature and avoid the white wine from deteriorating in low-temperature or high-temperature environment. However, the ceramic wine bottle has the defects of long firing period (more than 12 h), high firing temperature (more than 1280 ℃) and high energy consumption, and is not beneficial to the production of the ceramic wine bottle and the development of the industry.

Medical research shows that selenium element is one of essential trace elements for human body, has multiple functions of resisting cancer, resisting aging and oxidation, enhancing human immunity, regulating the absorption and utilization of vitamins, regulating the synthesis of protein, enhancing the fertility function and the like, and is also an important component of muscle function. However, selenium cannot be synthesized in human body, and is required to be taken in by the outside, and insufficient selenium intake can cause diseases such as liver cancer, lung cancer, gastric cancer, esophageal cancer, bladder cancer, hepatitis, eye diseases, cardiovascular and cerebrovascular diseases, osteoarthritis and the like.

Chinese patent No. 97101549.X describes a production process of selenium-enriched beer, which is characterized by adding a step of adding sodium selenite into the original production process, specifically, when yeast paste is added before main fermentation, sodium selenite with required weight is prepared into aqueous solution with concentration range of 0.2-0.5%, and the aqueous solution is added into a yeast paste bin and pumped into a main fermentation tank along with the yeast paste, and the selenium-enriched beer is brewed under the action of biological enhancement of yeast. The weight (g) of sodium selenite added is determined by the following formula: g, K, A and B are determined by calculation, wherein A is the selenium content concentration (microgram/kilogram) in the beer; b is the total weight (ton) of beer to be produced and K is a coefficient of 9.847.

However, the production process of the selenium-enriched beer in the patent has many disadvantages: (1) sodium selenite is added before fermentation, and great loss is caused along with the precipitation of the selenium-enriched yeast; (2) the amount of sodium selenite entering the finished beer during the fermentation process is not easy to control, the addition amount is difficult to be accurate, and if the addition amount is too high, the selenium content in the beer is possibly overproof and the health of human bodies is damaged; (3) selenium affects the fermentation process of beer and tastes bad.

Disclosure of Invention

One of the objectives of the present invention is to provide a selenium-rich ceramic wine bottle, which is rich in selenium, has a function of dissolving out selenium, and can provide selenium to the spirit stored therein, so that people can drink the spirit while taking the spirit and intake a proper amount of selenium, thereby ensuring human health.

The second purpose of the invention is to provide a preparation method of the selenium-rich ceramic wine bottle aiming at the defects of the prior art, which has the advantages of simple process, low energy consumption and low cost and is suitable for large-scale production.

In order to achieve one of the purposes, the invention adopts the following technical scheme:

the selenium-rich ceramic wine bottle comprises a blank body, wherein the blank body comprises, by mass, 8-15% of pottery clay, 50-70% of coal gangue and 20-42% of wulan tea boulder, and the wulan tea boulder contains 250-400 Mg/kg of nutrient elements N, 250-350 Mg/kg of P, 35000-40000 Mg/kg of K, 65000-70000 Mg/kg of Ca, 1000-1300 Mg/kg of Mg, 120-150 Mg/kg of S, 80-100 Mg/kg of Cu, 15000-20000 Mg/kg of Fe, 220-300 Mg/kg of Mn, 50-100 Mg/kg of Zn, 6-12 Mg/kg of B, 2-6 Mg/kg of Mo and 1.5-5 Mg/kg of Se.

In the technical scheme, the wulan tea spar contains a conventional compound Al₂O₃ 13～15％、SiO₂ 70～74％、Fe₂O₃ 2～3.5％、CaO 1.2～1.6％、MgO 0.1～0.2％、K₂O 5.2～6％、Na₂O 3.5～4％、TiO₂0.2-0.4%, and the ignition loss is 0.7-1.2%;

the oolong tea spar contains rare earth compound La₂O₃ 80～200mg/kg、CeO₂ 200～300mg/kg、Pr₈O₁₁ 20～50mg/kg、Nd₂O₃ 60～100mg/kg、Sm₂O₃ 8～20mg/kg、Eu₂O₃ 0.5～1.5mg/kg、Gd₂O₃8～20mg/kg、Tb₄O₇ 1～3mg/kg、Dy₂O₃ 4～8mg/kg、Ho₂O₃ 0.6～2mg/kg、Er₂O₃ 2～6mg/kg、Tm₂O₃ 0.2～1mg/kg、Yb₂O₃ 2～5mg/kg、Lu₂O₃ 1～2mg/kg、Y₂O₃ 20～40mg/kg、Rb₂O 200～300mg/kg、Sc₂O₃ 0.5～2mg/kg；

The total content of iron and titanium in the wulan tea-colored crystal stone is less than or equal to 3 percent.

In the technical scheme, the wulan tea crystalloid is prepared by enriching, homogenizing, stirring and settling a powdery material which is crushed, dedusted and collected in the production and purification process of pegmatite granite waste or an ultrafine overflow material which is hydraulically overflow-enriched by using a concentration device, and then carrying out vacuum filtration and dehydration.

In the above technical scheme, the giant granite waste material is derived from granite porphyry deposit in inner Mongolia, and the giant granite waste material contains a conventional compound Al₂O₃ 12～15％、SiO₂ 70～76％、Fe₂O₃ 1～2％、CaO 0.8～1.2％、MgO 0.1～0.3％、K₂O 5.3～6％、Na₂O 3.2～4％、TiO₂0.1-0.25%, and the burning vector is 0.2-0.5%;

1000-1200 Mg/kg of nutrient elements N, 150-250 Mg/kg of P, 42000-50000 Mg/kg of K, 5800-6500 Mg/kg of Ca, 800-900 Mg/kg of Mg, 70-100 Mg/kg of S, Cu: 2-8 mg/kg, Fe 12000-15000 mg/kg, Mn 150-250 mg/kg, Zn 40-60 mg/kg, B6-12 mg/kg, Mo 3.0-6 mg/kg, Se 3.0-5 mg/kg;

rare earth compound La₂O₃ 50～100mg/kg、CeO₂ 100～200mg/kg、Pr₈O₁₁ 10～25mg/kg、Nd₂O₃40～60mg/kg、Sm₂O₃ 5～12mg/kg、Eu₂O₃ 0.5～2mg/kg、Gd₂O₃ 6～20mg/kg、Tb₄O₇ 0.5～2mg/kg、Dy₂O₃ 4～10mg/kg、Ho₂O₃ 0.8～3mg/kg、Er₂O₃ 2～6mg/kg、Tm₂O₃ 0.2～1mg/kg、Yb₂O₃ 2～6mg/kg、Lu₂O₃ 0.5～3mg/kg、Y₂O₃ 20～40mg/kg、Rb₂O 250～400mg/kg、Sc₂O₃ 1.5～5mg/kg。

In the technical scheme, the chemical component of the coal gangue is Al₂O₃ 35～40％，SiO₂ 40～50％、Fe₂O₃0.1～2％、CaO 0.1～0.2％、MgO 0.1～0.2％、K₂O 0.1～0.2％、Na₂O 0.1～0.2％、TiO₂0.3 to 0.4%, and a burning vector of 12 to 18%.

As described aboveIn the technical scheme, the argil is kaolin or purple clay, and the chemical component of the kaolin is Al₂O₃ 12～15％、SiO₂ 60～70％、Fe₂O₃ 0.5～1％、CaO 2～6％、MgO 2～4％、K₂O 0.5～1％、Na₂O 0.5～1％、TiO₂0.05 to 0.1% and a burning vector of 8 to 10%.

In order to achieve the second purpose, the invention adopts the following technical scheme:

the preparation method of the selenium-rich ceramic wine bottle comprises the following steps of sequentially executing:

a grinding step, which is used for respectively grinding the wulan tea spar, the coal gangue and the argil until the fineness is less than 80 meshes;

an iron removal step, which is used for mixing the wulan tea spar, the coal gangue and the argil according to the formula amount and then carrying out iron removal treatment to obtain a mixed blank;

a ball milling step, namely grinding and homogenizing the mixed blank after iron removal by a wet overflow ceramic ball mill to obtain blank slurry;

and a blank making step, namely dehydrating and vacuum filtering the blank slurry, performing vacuum pugging for multiple times, ageing for 6-8 days, and then making and firing to obtain the ceramic wine bottle.

In the technical scheme, in the ball milling step, the milling time is 18-22 hours, the fineness of the blank slurry is less than 400 meshes, and the screen residue is less than 0.2%.

In the technical scheme, in the blank making step, the firing temperature is 1180-1220 ℃, and the firing time is 8-10 hours.

Preferably, in the grinding step, the fineness of the oolong tea spar powder is 40-80 meshes.

The invention has the beneficial effects that:

(1) because the wulan tea stones contain selenium, the ceramic wine bottle made of the wulan tea stones is rich in selenium, after the ceramic wine bottle is used for containing white wine, the white wine contains a small amount of yeast, and the yeast can promote the selenium in the wulan tea stones to be dissolved out without damaging the ceramic wine bottle, so that the selenium is provided to the white wine stored in the ceramic wine bottle; and because the content of the yeast is very small, the amount of dissolved selenium is relatively small, so that when people drink the liquor, the amount of the selenium taken by the human body is small, the small amount of selenium is combined with the selenium in the food to provide the selenium necessary for the human body together, and the phenomenon of selenium poisoning of the human body caused by the excessive amount of the selenium in the white liquor can be avoided;

(2) the Wulan tea spar has the advantages of antibiosis, bacteriostasis and high strength, the coal gangue has higher hardness, and the addition of the Wulan tea spar and the coal gangue can endow the selenium-enriched ceramic wine bottle with higher hardness and fracture toughness, and simultaneously, the ceramic wine bottle has an antibacterial effect.

(3) The preparation method of the selenium-rich ceramic wine bottle adopts medium-temperature firing, effectively reduces the firing temperature and shortens the firing period, has the advantages of simple process, low energy consumption and low cost, and is suitable for large-scale production.

Detailed Description

In order to make the technical problems, technical solutions and advantageous effects solved by the present invention more apparent, the present invention is further described in detail below with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.

Example 1

A selenium-rich ceramic wine bottle comprises a blank body, wherein the blank body consists of 12% of kaolin, 60% of coal gangue and 28% of oolong tea spar in percentage by mass, and the oolong tea spar contains 250-400 Mg/kg of nutrient elements N, 250-350 Mg/kg of P, 35000-40000 Mg/kg of K, 65000-70000 Mg/kg of Ca, 1000-1300 Mg/kg of Mg, 120-150 Mg/kg of S, 80-100 Mg/kg of Cu, 15000-20000 Mg/kg of Fe, 220-300 Mg/kg of Mn, 50-100 Mg/kg of Zn, 6-12 Mg/kg of B, 2-6 Mg/kg of Mo and 1.5-5 Mg/kg of Se;

conventional compound Al₂O₃ 13～15％、SiO₂ 70～74％、Fe₂O₃ 2～3.5％、CaO 1.2～1.6％、MgO 0.1～0.2％、K₂O 5.2～6％、Na₂O 3.5～4％、TiO₂0.2-0.4%, and 0.9% loss on ignition;

rare earth compound La₂O₃ 80～200mg/kg、CeO₂ 200～300mg/kg、Pr₈O₁₁ 20～50mg/kg、Nd₂O₃60～100mg/kg、Sm₂O₃ 8～20mg/kg、Eu₂O₃ 0.5～1.5mg/kg、Gd₂O₃ 8～20mg/kg、Tb₄O₇ 1～3mg/kg、Dy₂O₃ 4～8mg/kg、Ho₂O₃ 0.6～2mg/kg、Er₂O₃ 2～6mg/kg、Tm₂O₃ 0.2～1mg/kg、Yb₂O₃ 2～5mg/kg、Lu₂O₃ 1～2mg/kg、Y₂O₃ 20～40mg/kg、Rb₂O 200～300mg/kg、Sc₂O₃ 0.5～2mg/kg；

The total content of iron and titanium in the wulan tea crystal stone is less than or equal to 3 percent, and the phenomenon that the dielectric property and whiteness of the ceramic wine bottle are affected or black spots are generated in the ceramic wine bottle due to overhigh content of iron and titanium is avoided.

In the embodiment, the wulan tea crystalloid is prepared by concentrating, homogenizing, stirring and settling a powdery material which is crushed, dedusted and collected in the production and purification process of pegmatite granite waste or an ultrafine overflow material which is hydraulically overflow-enriched and then carrying out vacuum filtration and dehydration;

the giant granite waste material is derived from granite porphyry deposit in inner Mongolia, and contains conventional compound Al₂O₃ 12～15％、SiO₂ 70～76％、Fe₂O₃ 1～2％、CaO 0.8～1.2％、MgO 0.1～0.3％、K₂O 5.3～6％、Na₂O 3.2～4％、TiO₂0.1-0.25% and a burning vector of 0.3%;

1000-1200 Mg/kg of nutrient elements N, 150-250 Mg/kg of P, 42000-50000 Mg/kg of K, 5800-6500 Mg/kg of Ca, 800-900 Mg/kg of Mg, 70-100 Mg/kg of S, Cu: 2-8 mg/kg, Fe 12000-15000 mg/kg, Mn 150-250 mg/kg, Zn 40-60 mg/kg, B6-12 mg/kg, Mo 3.0-6 mg/kg, Se 3.0-5 mg/kg;

rare earth compound La₂O₃ 50～100mg/kg、CeO₂ 100～200mg/kg、Pr₈O₁₁ 10～25mg/kg、Nd₂O₃40～60mg/kg、Sm₂O₃ 5～12mg/kg、Eu₂O₃ 0.5～2mg/kg、Gd₂O₃ 6～20mg/kg、Tb₄O₇ 0.5～2mg/kg、Dy₂O₃ 4～10mg/kg、Ho₂O₃ 0.8～3mg/kg、Er₂O₃ 2～6mg/kg、Tm₂O₃ 0.2～1mg/kg、Yb₂O₃ 2～6mg/kg、Lu₂O₃ 0.5～3mg/kg、Y₂O₃ 20～40mg/kg、Rb₂O 250～400mg/kg、Sc₂O₃ 1.5～5mg/kg。

In this embodiment, the coal gangue has a chemical component of Al₂O₃ 35～40％，SiO₂ 40～50％、Fe₂O₃ 0.1～2％、CaO 0.1～0.2％、MgO 0.1～0.2％、K₂O 0.1～0.2％、Na₂O 0.1～0.2％、TiO₂0.3-0.4%, and a burning vector is 15%.

In this example, the chemical component of kaolin is Al₂O₃ 12～15％、SiO₂ 60～70％、Fe₂O₃ 0.5～1％、CaO 2～6％、MgO 2～4％、K₂O 0.5～1％、Na₂O 0.5～1％、TiO₂0.05-0.1% and 9% of burning vector.

The preparation method of the selenium-rich ceramic wine bottle comprises the following steps of sequentially executing:

a grinding step, which is used for respectively grinding the wulan tea spar, the coal gangue and the argil until the fineness is less than 80 meshes;

an iron removal step, which is used for mixing the wulan tea spar, the coal gangue and the argil according to the formula amount and then carrying out iron removal treatment to obtain a mixed blank;

a ball milling step, namely grinding and homogenizing the mixed blank subjected to iron removal by a wet overflow ceramic ball mill for 20 hours, wherein the fineness of the blank slurry is less than 400 meshes, and the screen allowance is less than 0.2%, so as to obtain blank slurry;

and a blank making step, namely dehydrating and vacuum filtering the blank slurry, carrying out vacuum pugging for multiple times, ageing for 7 days, and then making and firing the blank at the firing temperature of 1200 ℃ for 9 hours to obtain the ceramic wine bottle.

In this example, the fineness of the wulan tea spar powder was 40 mesh.

Through detection, the hardness of the selenium-rich ceramic wine bottle is HRA 98, and the fracture toughness is 15 MPa.m^1/2The antibacterial rate is 99.5%.

Example 2

A selenium-rich ceramic wine bottle comprises a blank body, wherein the blank body consists of 12% of purple sand mud, 60% of coal gangue and 28% of oolong tea spar in percentage by mass, and the oolong tea spar contains 250-400 Mg/kg of nutrient elements N, 250-350 Mg/kg of nutrient elements P, 35000-40000 Mg/kg of nutrient elements K, 65000-70000 Mg/kg of nutrient elements Ca, 1000-1300 Mg/kg of nutrient elements Mg, 120-150 Mg/kg of nutrient elements S, 80-100 Mg/kg of nutrient elements Cu, 15000-20000 Mg/kg of nutrient elements Fe, 220-300 Mg/kg of nutrient elements Mn, 50-100 Mg/kg of nutrient elements Zn, 6-12 Mg/kg of nutrient elements B, 2-6 Mg/kg of Mo and 1.5-5 Mg/kg of Se;

conventional compound Al₂O₃ 13～15％、SiO₂ 70～74％、Fe₂O₃ 2～3.5％、CaO 1.2～1.6％、MgO 0.1～0.2％、K₂O 5.2～6％、Na₂O 3.5～4％、TiO₂0.2-0.4%, and 0.9% loss on ignition;

rare earth compound La₂O₃ 80～200mg/kg、CeO₂ 200～300mg/kg、Pr₈O₁₁ 20～50mg/kg、Nd₂O₃60～100mg/kg、Sm₂O₃ 8～20mg/kg、Eu₂O₃ 0.5～1.5mg/kg、Gd₂O₃ 8～20mg/kg、Tb₄O₇ 1～3mg/kg、Dy₂O₃ 4～8mg/kg、Ho₂O₃ 0.6～2mg/kg、Er₂O₃ 2～6mg/kg、Tm₂O₃ 0.2～1mg/kg、Yb₂O₃ 2～5mg/kg、Lu₂O₃ 1～2mg/kg、Y₂O₃ 20～40mg/kg、Rb₂O 200～300mg/kg、Sc₂O₃ 0.5～2mg/kg；

The total content of iron and titanium in the wulan tea crystal stone is less than or equal to 3 percent, and the phenomenon that the dielectric property and whiteness of the ceramic wine bottle are affected or black spots are generated in the ceramic wine bottle due to overhigh content of iron and titanium is avoided.

In the embodiment, the wulan tea crystalloid is prepared by concentrating, homogenizing, stirring and settling a powdery material which is crushed, dedusted and collected in the production and purification process of pegmatite granite waste or an ultrafine overflow material which is hydraulically overflow-enriched and then carrying out vacuum filtration and dehydration;

the giant granite waste material is derived from granite porphyry deposit in inner Mongolia, and contains conventional compound Al₂O₃ 12～15％、SiO₂ 70～76％、Fe₂O₃ 1～2％、CaO 0.8～1.2％、MgO 0.1～0.3％、K₂O 5.3～6％、Na₂O 3.2～4％、TiO₂0.1-0.25% and a burning vector of 0.3%;

1000-1200 Mg/kg of nutrient elements N, 150-250 Mg/kg of P, 42000-50000 Mg/kg of K, 5800-6500 Mg/kg of Ca, 800-900 Mg/kg of Mg, 70-100 Mg/kg of S, Cu: 2-8 mg/kg, Fe 12000-15000 mg/kg, Mn 150-250 mg/kg, Zn 40-60 mg/kg, B6-12 mg/kg, Mo 3.0-6 mg/kg, Se 3.0-5 mg/kg;

rare earth compound La₂O₃ 50～100mg/kg、CeO₂ 100～200mg/kg、Pr₈O₁₁ 10～25mg/kg、Nd₂O₃40～60mg/kg、Sm₂O₃ 5～12mg/kg、Eu₂O₃ 0.5～2mg/kg、Gd₂O₃ 6～20mg/kg、Tb₄O₇ 0.5～2mg/kg、Dy₂O₃ 4～10mg/kg、Ho₂O₃ 0.8～3mg/kg、Er₂O₃ 2～6mg/kg、Tm₂O₃ 0.2～1mg/kg、Yb₂O₃ 2～6mg/kg、Lu₂O₃ 0.5～3mg/kg、Y₂O₃ 20～40mg/kg、Rb₂O 250～400mg/kg、Sc₂O₃ 1.5～5mg/kg。

In this embodiment, the coal gangue has a chemical component of Al₂O₃ 35～40％，SiO₂ 40～50％、Fe₂O₃ 0.1～2％、CaO 0.1～0.2％、MgO 0.1～0.2％、K₂O 0.1～0.2％、Na₂O 0.1～0.2％、TiO₂0.3-0.4%, and a burning vector is 15%.

The preparation method of the selenium-rich ceramic wine bottle comprises the following steps of sequentially executing:

a grinding step, which is used for respectively grinding the wulan tea spar, the coal gangue and the argil until the fineness is less than 80 meshes;

an iron removal step, which is used for mixing the wulan tea spar, the coal gangue and the argil according to the formula amount and then carrying out iron removal treatment to obtain a mixed blank;

a ball milling step, namely grinding and homogenizing the mixed blank subjected to iron removal by a wet overflow ceramic ball mill for 20 hours, wherein the fineness of the blank slurry is less than 400 meshes, and the screen allowance is less than 0.2%, so as to obtain blank slurry;

and a blank making step, namely dehydrating and vacuum filtering the blank slurry, carrying out vacuum pugging for multiple times, ageing for 7 days, and then making and firing the blank at the firing temperature of 1200 ℃ for 9 hours to obtain the ceramic wine bottle.

In this example, the fineness of the wulan tea spar powder was 40 mesh.

Through detection, the hardness of the selenium-rich ceramic wine bottle in the embodiment is HRA 99, and the fracture toughness is 18 MPa.m^1/2The antibacterial rate is 99.8%.

Example 3

A selenium-rich ceramic wine bottle comprises a blank body, wherein the blank body consists of 8% of kaolin, 50% of coal gangue and 42% of oolong tea boulder in percentage by mass, and the oolong tea boulder contains 250-400 Mg/kg of nutrient elements N, 250-350 Mg/kg of P, 35000-40000 Mg/kg of K, 65000-70000 Mg/kg of Ca, 1000-1300 Mg/kg of Mg, 120-150 Mg/kg of S, 80-100 Mg/kg of Cu, 15000-20000 Mg/kg of Fe, 220-300 Mg/kg of Mn, 50-100 Mg/kg of Zn, 6-12 Mg/kg of B, 2-6 Mg/kg of Mo and 1.5-5 Mg/kg of Se;

conventional compound Al₂O₃ 13～15％、SiO₂ 70～74％、Fe₂O₃ 2～3.5％、CaO 1.2～1.6％、MgO 0.1～0.2％、K₂O 5.2～6％、Na₂O 3.5～4％、TiO₂0.2-0.4%, and 0.8% loss on ignition;

rare earth compound La₂O₃ 80～200mg/kg、CeO₂ 200～300mg/kg、Pr₈O₁₁ 20～50mg/kg、Nd₂O₃60～100mg/kg、Sm₂O₃ 8～20mg/kg、Eu₂O₃ 0.5～1.5mg/kg、Gd₂O₃ 8～20mg/kg、Tb₄O₇ 1～3mg/kg、Dy₂O₃ 4～8mg/kg、Ho₂O₃ 0.6～2mg/kg、Er₂O₃ 2～6mg/kg、Tm₂O₃ 0.2～1mg/kg、Yb₂O₃ 2～5mg/kg、Lu₂O₃ 1～2mg/kg、Y₂O₃ 20～40mg/kg、Rb₂O 200～300mg/kg、Sc₂O₃ 0.5～2mg/kg；

The total content of iron and titanium in the wulan tea crystal stone is less than or equal to 3 percent, and the phenomenon that the dielectric property and whiteness of the ceramic wine bottle are affected or black spots are generated in the ceramic wine bottle due to overhigh content of iron and titanium is avoided.

In the embodiment, the wulan tea crystalloid is prepared by concentrating, homogenizing, stirring and settling a powdery material which is crushed, dedusted and collected in the production and purification process of pegmatite granite waste or an ultrafine overflow material which is hydraulically overflow-enriched and then carrying out vacuum filtration and dehydration;

the giant granite waste material is derived from granite porphyry deposit in inner Mongolia, and contains conventional compound Al₂O₃ 12～15％、SiO₂ 70～76％、Fe₂O₃ 1～2％、CaO 0.8～1.2％、MgO 0.1～0.3％、K₂O 5.3～6％、Na₂O 3.2～4％、TiO₂0.1-0.25% and a burning vector of 0.4%;

1000-1200 Mg/kg of nutrient elements N, 150-250 Mg/kg of P, 42000-50000 Mg/kg of K, 5800-6500 Mg/kg of Ca, 800-900 Mg/kg of Mg, 70-100 Mg/kg of S, Cu: 2-8 mg/kg, Fe 12000-15000 mg/kg, Mn 150-250 mg/kg, Zn 40-60 mg/kg, B6-12 mg/kg, Mo 3.0-6 mg/kg, Se 3.0-5 mg/kg;

rare earth compound La₂O₃ 50～100mg/kg、CeO₂ 100～200mg/kg、Pr₈O₁₁ 10～25mg/kg、Nd₂O₃40～60mg/kg、Sm₂O₃ 5～12mg/kg、Eu₂O₃ 0.5～2mg/kg、Gd₂O₃ 6～20mg/kg、Tb₄O₇ 0.5～2mg/kg、Dy₂O₃ 4～10mg/kg、Ho₂O₃ 0.8～3mg/kg、Er₂O₃ 2～6mg/kg、Tm₂O₃ 0.2～1mg/kg、Yb₂O₃ 2～6mg/kg、Lu₂O₃ 0.5～3mg/kg、Y₂O₃ 20～40mg/kg、Rb₂O 250～400mg/kg、Sc₂O₃ 1.5～5mg/kg。

In this embodiment, the coal gangue has a chemical component of Al₂O₃ 35～40％，SiO₂ 40～50％、Fe₂O₃ 0.1～2％、CaO 0.1～0.2％、MgO 0.1～0.2％、K₂O 0.1～0.2％、Na₂O 0.1～0.2％、TiO₂0.3-0.4%, and a burning vector is 12%.

In this example, the chemical component of kaolin is Al₂O₃ 12～15％、SiO₂ 60～70％、Fe₂O₃ 0.5～1％、CaO 2～6％、MgO 2～4％、K₂O 0.5～1％、Na₂O 0.5～1％、TiO₂0.05-0.1% and 8% of burning vector.

The preparation method of the selenium-rich ceramic wine bottle comprises the following steps of sequentially executing:

a grinding step, which is used for respectively grinding the wulan tea spar, the coal gangue and the argil until the fineness is less than 80 meshes;

an iron removal step, which is used for mixing the wulan tea spar, the coal gangue and the argil according to the formula amount and then carrying out iron removal treatment to obtain a mixed blank;

a ball milling step, namely grinding and homogenizing the mixed blank subjected to iron removal by a wet overflow ceramic ball mill for 22 hours, wherein the fineness of the blank slurry is less than 400 meshes, and the screen allowance is less than 0.2%, so as to obtain blank slurry;

and a blank making step, namely dehydrating and vacuum filtering the blank slurry, carrying out vacuum pugging for multiple times, ageing for 8 days, and then making and firing the blank at the temperature of 1220 ℃ for 8 hours to obtain the ceramic wine bottle.

In this example, the fineness of the wulan tea spar powder was 60 mesh.

Through detection, the hardness of the selenium-enriched ceramic wine bottle in the embodiment is HRA 96, and the fracture toughness is 16 MPa.m^1/2The antibacterial rate is 99.3%.

Example 4

A selenium-rich ceramic wine bottle comprises a blank body, wherein the blank body comprises, by mass, 10% of kaolin, 70% of coal gangue and 20% of oolong tea spar, and the oolong tea spar contains 250-400 Mg/kg of nutrient elements N, 250-350 Mg/kg of P, 35000-40000 Mg/kg of K, 65000-70000 Mg/kg of Ca, 1000-1300 Mg/kg of Mg, 120-150 Mg/kg of S, 80-100 Mg/kg of Cu, 15000-20000 Mg/kg of Fe, 220-300 Mg/kg of Mn, 50-100 Mg/kg of Zn, 6-12 Mg/kg of B, 2-6 Mg/kg of Mo and 1.5-5 Mg/kg of Se;

conventional compound Al₂O₃ 13～15％、SiO₂ 70～74％、Fe₂O₃ 2～3.5％、CaO 1.2～1.6％、MgO 0.1～0.2％、K₂O 5.2～6％、Na₂O 3.5～4％、TiO₂0.2-0.4%, and the ignition loss is 1%;

rare earth compound La₂O₃ 80～200mg/kg、CeO₂ 200～300mg/kg、Pr₈O₁₁ 20～50mg/kg、Nd₂O₃60～100mg/kg、Sm₂O₃ 8～20mg/kg、Eu₂O₃ 0.5～1.5mg/kg、Gd₂O₃ 8～20mg/kg、Tb₄O₇ 1～3mg/kg、Dy₂O₃ 4～8mg/kg、Ho₂O₃ 0.6～2mg/kg、Er₂O₃ 2～6mg/kg、Tm₂O₃ 0.2～1mg/kg、Yb₂O₃ 2～5mg/kg、Lu₂O₃ 1～2mg/kg、Y₂O₃ 20～40mg/kg、Rb₂O 200～300mg/kg、Sc₂O₃ 0.5～2mg/kg；

The total content of iron and titanium in the wulan tea crystal stone is less than or equal to 3 percent, and the phenomenon that the dielectric property and whiteness of the ceramic wine bottle are affected or black spots are generated in the ceramic wine bottle due to overhigh content of iron and titanium is avoided.

In the embodiment, the wulan tea crystalloid is prepared by concentrating, homogenizing, stirring and settling a powdery material which is crushed, dedusted and collected in the production and purification process of pegmatite granite waste or an ultrafine overflow material which is hydraulically overflow-enriched and then carrying out vacuum filtration and dehydration;

the giant granite waste material is derived from granite porphyry deposit in inner Mongolia, and contains conventional compound Al₂O₃ 12～15％、SiO₂ 70～76％、Fe₂O₃ 1～2％、CaO 0.8～1.2％、MgO 0.1～0.3％、K₂O 5.3～6％、Na₂O 3.2～4％、TiO₂0.1-0.25% and a burning vector of 0.4%;

1000-1200 Mg/kg of nutrient elements N, 150-250 Mg/kg of P, 42000-50000 Mg/kg of K, 5800-6500 Mg/kg of Ca, 800-900 Mg/kg of Mg, 70-100 Mg/kg of S, Cu: 2-8 mg/kg, Fe 12000-15000 mg/kg, Mn 150-250 mg/kg, Zn 40-60 mg/kg, B6-12 mg/kg, Mo 3.0-6 mg/kg, Se 3.0-5 mg/kg;

rare earth compound La₂O₃ 50～100mg/kg、CeO₂ 100～200mg/kg、Pr₈O₁₁ 10～25mg/kg、Nd₂O₃40～60mg/kg、Sm₂O₃ 5～12mg/kg、Eu₂O₃ 0.5～2mg/kg、Gd₂O₃ 6～20mg/kg、Tb₄O₇ 0.5～2mg/kg、Dy₂O₃ 4～10mg/kg、Ho₂O₃ 0.8～3mg/kg、Er₂O₃ 2～6mg/kg、Tm₂O₃ 0.2～1mg/kg、Yb₂O₃ 2～6mg/kg、Lu₂O₃ 0.5～3mg/kg、Y₂O₃ 20～40mg/kg、Rb₂O 250～400mg/kg、Sc₂O₃ 1.5～5mg/kg。

In this embodiment, the coal gangue has a chemical component of Al₂O₃ 35～40％，SiO₂ 40～50％、Fe₂O₃ 0.1～2％、CaO 0.1～0.2％、MgO 0.1～0.2％、K₂O 0.1～0.2％、Na₂O 0.1～0.2％、TiO₂0.3-0.4%, and a burning vector is 14%.

In this example, the chemical component of kaolin is Al₂O₃ 12～15％、SiO₂ 60～70％、Fe₂O₃ 0.5～1％、CaO 2～6％、MgO 2～4％、K₂O 0.5～1％、Na₂O 0.5～1％、TiO₂0.05-0.1% and a burning vector of 10%.

The preparation method of the selenium-rich ceramic wine bottle comprises the following steps of sequentially executing:

a grinding step, which is used for respectively grinding the wulan tea spar, the coal gangue and the argil until the fineness is less than 80 meshes;

an iron removal step, which is used for mixing the wulan tea spar, the coal gangue and the argil according to the formula amount and then carrying out iron removal treatment to obtain a mixed blank;

a ball milling step, namely grinding and homogenizing the mixed blank subjected to iron removal by a wet overflow ceramic ball mill for 18 hours, wherein the fineness of the blank slurry is less than 400 meshes, and the screen allowance is less than 0.2%, so as to obtain blank slurry;

and a blank making step, namely dehydrating and vacuum filtering the blank slurry, carrying out vacuum pugging for multiple times, ageing for 6 days, and then making and firing the blank at 1180 ℃ for 10 hours to obtain the ceramic wine bottle.

In this example, the fineness of the wulan tea spar powder was 80 mesh.

Through detection, the hardness of the selenium-rich ceramic wine bottle in the embodiment is HRA 97, and the fracture toughness is 17 MPa.m^1/2The antibacterial rate is 99.6%.

Comparative example 1

The ceramic wine bottle blank raw material does not contain wulan tea stone, and other implementation conditions are the same as those in example 1.

Comparative example 2

The ceramic wine bottle blank raw material does not contain wulan tea stone, and other implementation conditions are the same as those in the example 2.

Comparative example 3

The fineness of the wulan tea crystal stone powder as the raw material of the ceramic wine bottle blank is 20 meshes, and other implementation conditions are the same as those in the example 1.

Comparative example 4

The fineness of the wulan tea crystal stone powder as the raw material of the ceramic wine bottle blank is 100 meshes, and other implementation conditions are the same as those in the example 1.

Crushing and grinding the fired ceramic wine bottle blanks of examples 1-4 and comparative examples 1-4 to a fineness of less than 200 meshes, and detecting the selenium content by Beijing Zhongke's chromatography chemical technology research institute, see Table 1; after storing the fired ceramic wine bottle blanks of examples 1-4 and comparative examples 1-2 for 7 days, the selenium content in the wine was determined by the research institute of the light-out chemical technology of Beijing Zhongke, see Table 1.

TABLE 1

Sample (I)	Winebottle powder selenium content (mg/kg)	Selenium content of Chinese liquor (mg/kg)
			Example 1	3.5	0.043
Example 2	3.3	0.04
			Example 3	4.9	0.064
Example 4	2.1	0.024
			Comparative example 1	0.8	0.002
Comparative example 2	0.9	0.001
			Comparative example 3	3.4	0.01
Comparative example 4	3.3	1.2

As shown in table 1, the results of the selenium content test of the wine bottles of examples 1 and 2 are equivalent, and the results of the selenium content test of the white spirit are equivalent, and the difference between the examples 1 and 2 is that kaolin or purple clay is selected as the pottery clay, and as can be seen from the results of the test of table 1, the selection of the pottery clay has little influence on the selenium content of the ceramic wine bottles and the selenium dissolving capacity of the wine bottles; the selenium content of the wine bottle and the selenium content of the white spirit in the embodiments 1, 3 and 4 are in a linear relation with the content of the wulan tea spar in the embodiments, and it can be shown that when the fineness of the wulan tea spar powder is between 40 and 80 meshes, the content of selenium in the wine bottle is increased along with the increase of the content of wulan tea spar, and further the content of selenium in the white spirit is increased, and the selenium dissolving capacity of the wine bottle is irrelevant to the content of the wulan tea spar because of the linear relation; comparing example 1 with comparative example 1 and comparing example 2 with comparative example 2, it can be known that the common wine bottle without wulan tea crystalloid has extremely low selenium content, and the white wine basically does not contain selenium element, and can not provide the selenium element required by human body; as can be seen from the comparison between the example 1 and the comparative example 3, the fineness of the wulan tea crystal powder is too low, the wulan tea crystal powder is wrapped by the coal gangue and the kaolin, and the selenium dissolving capacity of the white spirit is reduced, so that the content of selenium in the white spirit is lower; and the comparison of the strength 1 and the comparative example 4 shows that the Wulan tea crystal stone powder has too high fineness and is displayed on the surface of a ceramic wine bottle in a large amount, selenium is easily dissolved in the white wine, so that the selenium content in the white wine is too high, and people are easily subjected to selenium poisoning caused by excessive intake of the selenium when drinking the white wine.

Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the protection scope of the present invention, although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.