Preparation method of glaze with catalysis promoting function

Abstract

The invention discloses a preparation method of glaze with a catalysis promoting function. The glaze is prepared from talc, calcite, rare earth raw ore, Guizhou soil, Longyan kaolin, zirconium silicate, zinc oxide, cobalt chloride and calcium chloride. The conventional process method for preparing the glaze with the catalytic function mostly adopts a process method for synthesizing powder with the catalytic function at high temperature in advance and then preparing the glaze. According to the invention, a conventional glaze preparation process is innovatively adopted, rare earth raw ore is introduced, and glaze is utilized to realize in-situ synthesis in a firing process, so that a fired glaze layer has an obvious alcoholization promoting effect, and a blank glaze is good in combination, free of cracks after being dried, capable of preventing wine leakage and excellent in adhesiveness. Compared with the conventional preparation of the glaze with the catalytic function, the preparation process provided by the invention has remarkable innovativeness.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of ceramic wine bottle glaze, in particular to a glaze preparation method with catalytic promotion function. BACKGROUND

[0002] Ceramic wine bottles have unique advantages. On the one hand, the light-proof property of ceramic wine bottles can avoid chemical reactions of white wine caused by light, thereby ensuring the quality of white wine. On the other hand, ceramic wine bottles have slower heat conduction than glass wine bottles, which can ensure the wine temperature and avoid the deterioration of white wine in low or high temperature environment. In addition, ceramic wine bottles also have the characteristics of catalytic aging and appearance decoration diversity, which are not only used as wine containers, but also as decorations. Currently, ceramic wine bottles on the market include inner glaze and unglazed. The unglazed is not treated with inner wall coating and is directly fired, so that the wine and the wall directly contact. The inner glaze is coated with a layer of glaze on the inner wall of the wine jar, and then fired at high temperature to form a layer of acid and alkali resistant silicate melt, which plays a protective role for the inner wall and prevents wine leakage. The inner glaze treatment can ensure the smooth, sterile, corrosion-resistant and easy-to-clean surface of the inner wall of the wine jar, maintain the freshness and taste of the wine, and prevent wine leakage and oxidation. In addition, generally, ester substances are the main body of aroma, and are the most numerous and influential aroma substances in white wine. Most ester compounds are relatively volatile and have strong odor, and have fruit odor or unique aromatic odor, so they have strong odor characteristics. Different esters with different proportions will have different flavor characteristics, which greatly affect the flavor of white wine. The ester content of high-quality white wine is relatively high, with an average of 0.2%-0.6%. The ester content of ordinary solid-state white wine is twice that of liquid-state white wine, and the ester content of high-quality white wine is twice that of ordinary solid-state white wine, so the aroma of high-quality white wine is rich. Among the ester substances, ethyl acetate, ethyl hexanoate, ethyl lactate and ethyl butyrate account for more than 90% of the total ester content of white wine, and are the four major esters that form the flavor of white wine. However, the above ordinary glaze cannot increase the index of ethyl acetate in the wine in the later stage, and the glaze preparation process that can improve the taste of the wine at present is to first synthesize functional powder with catalytic promotion alcoholization effect at high temperature, and then mix the ground functional powder with glaze raw materials in a certain proportion. This process has the disadvantages of multiple processes, high energy consumption, high cost, etc. In addition, the extra introduction of quartz content in the ingredients has a great influence on the body of the glaze, and the quartz ratio needs to be accurately adjusted, otherwise it is easy to cause the wine bottle to seep in the later stage.

[0003] In order to solve the above defects, we propose a glaze preparation method with catalytic promotion function. SUMMARY

[0004] The technical problem solved by the present application is to provide a preparation method of functional glaze with catalytic promotion function.

[0005] To achieve the above object, the present application provides the following technical scheme: a preparation method of functional glaze with catalytic promotion function, raw materials of which include talc, calcite, rare earth ore, Guizhou soil, Longyan kaolin, zirconium silicate, zinc oxide, cobalt chloride and calcium chloride, and the preparation method is one-time synthesis, specifically including the following steps: S1, a tackifier and deionized water are weighed according to the weight fraction, fully mixed and uniformly obtained as a dispersion liquid; S2, talc, calcite, rare earth ore, Guizhou soil, Longyan kaolin, zirconium silicate, zinc oxide, cobalt chloride and calcium chloride are weighed according to the fraction ratio; S3, the dispersion liquid in step S1 and the raw materials in step S2 are mixed together and ball-milled to obtain functional inner glaze; S4, the functional inner glaze is applied to the inner surface of a ceramic wine bottle body, and after cooling and drying, the functional inner glaze is baked in a high-temperature furnace to form a ceramic wine bottle inner glaze.

[0006] Further, the talc, calcite, rare earth ore, Guizhou soil, Longyan kaolin, zirconium silicate, zinc oxide, cobalt chloride and calcium chloride each account for 16.49-17.39%, 11.34-12.42%, 53.17-55.87%, 1.09-1.99%, 4.97-6.52%, 5.47-6.08%, 3.38-4.47%, 0.007-0.01% and 0.08-0.10%, respectively.

[0007] Further, the talc, calcite, rare earth ore, Guizhou soil, Longyan kaolin, zirconium silicate, zinc oxide, cobalt chloride and calcium chloride each account for 17.39%, 12.42%, 53.17%, 1.99%, 4.97%, 5.47%, 4.47%, 0.01% and 0.10%, respectively.

[0008] Further, the rare earth ore includes La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y and Sc.

[0009] Further, the mass ratio of La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y is: 21.53mg / Kg, 69.23mg / Kg, 24.75mg / Kg, 78.36mg / Kg, 3.42mg / Kg, 0.56mg / Kg, 11.44mg / Kg, 1.56mg / Kg, 7.96mg / Kg, 1.58mg / Kg, 3.73mg / Kg, 0.53mg / Kg, 3.70mg / Kg, 0.73mg / Kg, 34.42mg / Kg.

[0010] Further, the mass ratio of Sc is less than 0.1mg / Kg.

[0011] Further, the inner glaze slurry obtained in the step S3 needs to be detected to detect the fineness, concentration, Baumé degree and specific gravity of the inner glaze slurry.

[0012] Further, the process of the calcination treatment is: first, the temperature is raised to 780-800 DEG C at a rate of 1-2 DEG C / min, then the temperature is raised to 920-950 DEG C at a rate of 0.5-1 DEG C / min, the temperature is kept for 20-30 min, then the temperature is raised to 1230-1250 DEG C at a rate of 0.5-1 DEG C / min, and then the furnace is cooled to room temperature.

[0013] Compared with the prior art, the beneficial effects of the present application are: the conventional preparation process of the glaze with catalytic function is to pre-synthesize the powder with catalytic function at high temperature, and then introduce the powder with catalytic function into the conventional glaze preparation with ceramic raw materials. The present application innovatively uses the conventional glaze preparation process, introduces rare earth ore, and realizes in-situ synthesis by using the glaze during the firing process, so that the fired glaze layer has obvious alcoholization promoting effect, good body-glaze combination, no crack after drying, prevents wine leakage, and excellent adhesion. The preparation process in the present application has significant innovation compared with the conventional preparation of catalytic functional glaze.

[0014] In the present application, rare earth ore is used to promote the esterification reaction of alcohol by far infrared, generate ethyl acetate, change the ethyl acetate index in the wine, promote the alcoholization effect of the wine in the bottle, and improve the taste of the wine. In addition, the proportion of rare earth ore is accurately controlled, which can promote the alcoholization of the wine and ensure the quality of the inner glaze. And the material prepared by the process of the application is also different from the existing material in catalytic efficiency, compared with the efficiency of the ceramic wine bottle body with catalytic effect, the glaze with catalytic function on the surface layer of the body in the application is more efficient in catalytic efficiency. In addition, the process does not need to synthesize powder with catalytic function in advance at high temperature, or add expensive rare earth metal oxide powder, but directly introduces rare earth ore, and the price of rare earth ore is low, which greatly improves the production efficiency and saves the production cost. BRIEF DESCRIPTION OF DRAWINGS

[0015] Figure 1 The composition detection report of the rare earth ore in the application; Figure 2 The influence detection report of the functional inner glaze on wine in the application; Figure 3 The effect picture after the functional inner glaze is fired in the application; Figure 4 The effect picture after the functional inner glaze is fired in the application under the condition of high proportion of rare earth ore; Figure 5 The influence detection report of the ordinary inner glaze on wine in the market; Figure 6 The process comparison chart of the preparation method of the ordinary functional inner glaze and the preparation method of the application; Figure 7 The preparation cost comparison chart of the ordinary functional inner glaze and the application. DETAILED DESCRIPTION

[0016] The technical solutions in the embodiments of the application will be clearly and completely described below with reference to the drawings in the embodiments of the application. Obviously, the described embodiments are only a part of the embodiments of the application, rather than all the embodiments of the application. Based on the embodiments in the application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the application.

[0017] The application provides a technical solution: A preparation method of glaze with catalytic function, comprising talc, calcite, rare earth ore, Guizhou soil, Longyan kaolin, zirconium silicate, zinc oxide, cobalt chloride and calcium chloride. EMBODIMENT

[0018] The proportions of talc, calcite, rare earth ore, Guizhou soil, Longyan kaolin, zirconium silicate, zinc oxide, cobalt chloride and calcium chloride are 17.39%, 12.42%, 53.17%, 1.99%, 4.97%, 5.47%, 4.47%, 0.01% and 0.10% respectively.

[0019] The rare earth ore includes La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y and Sc.

[0020] The mass ratio of La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and Y is 21.53 mg / Kg, 69.23 mg / Kg, 24.75 mg / Kg, 78.36 mg / Kg, 3.42 mg / Kg, 0.56 mg / Kg, 11.44 mg / Kg, 1.56 mg / Kg, 7.96 mg / Kg, 1.58 mg / Kg, 3.73 mg / Kg, 0.53 mg / Kg, 3.70 mg / Kg, 0.73 mg / Kg and 34.42 mg / Kg, and the mass ratio of Sc is less than 0.1 mg / Kg.

[0021] The calcium chloride also has the function of adjusting the suspension of glaze.

[0022] The rare earth ore promotes the esterification reaction of the wine through far infrared rays to generate ethyl acetate (generally, ester substances are the main body of aroma, are the most numerous and the most influential aroma substances in liquor, most of the ester compounds are relatively volatile and have strong odor, have fruit odor or unique aromatic odor, and therefore have strong odor characteristics, different esters and different proportions will have different flavor characteristics, and have a great influence on the flavor of liquor, the ester content of high-quality liquor is generally high, and is 0.2%-0.6% on average. The ester content of ordinary solid-state method liquor is twice that of liquid-state method liquor, and the ester content of high-quality liquor is twice that of ordinary solid-state method liquor, so the aroma of high-quality liquor is rich. Among the ester substances, ethyl acetate, hexanoic acid ethyl ester, lactic acid ethyl ester and butyric acid ethyl ester account for more than 90% of the total ester content of liquor, and are the four main esters forming the flavor of liquor. In the present case, the rare earth ore can change the index of ethyl acetate in the liquor, and ethyl acetate is the effect of alcoholizing the liquor, and the liquor can be mineralized at the same time, so that the liquor contains a variety of trace elements beneficial to the human body; the dissolved oxygen is increased, and harmful impurities are reduced; the liquor is mellow and refreshing, the aroma is harmonious, and the effect is obvious.

[0023] In the above, the principle of changing ethyl acetate is: 1. The rare earth ore is added to the inner glaze, and the composition of the rare earth ore is disclosed in the specification. The rare earth ore mineralizes the inner glaze, and the mineralized material can emit far infrared rays. Since far infrared rays can penetrate deep into the interior of a substance, they can affect molecular motion and accelerate esterification, thereby indirectly affecting the generation of ethyl acetate. 2. In addition, the rare earth ore contains cerium oxide, which has far infrared effects. Far infrared catalyzes the conversion of ethanol in the liquor to ethyl acetate. The far infrared performance and physical properties of cerium oxide in ceramics can be seen in: 2.1, the 45th volume of the journal of silicate, No. 9, "Effect of rare earth cerium doping on far infrared performance and physical properties of blast furnace slag ceramics"; 2.2, the thesis of Hebei University of Technology, "Study on the effect of far infrared functional rare earth primary mineral composite material on liquefied petroleum gas combustion".

[0024] At the same time, the promoting effect of far infrared on wine can be referred to Chinese patent: patent number CN201610919831.8, patent name: a ceramic ware inner coating material with far infrared strengthening function and its preparation method and application, which discloses that the far infrared emission rate of ceramic ware products is 0.86-0.91 in the wavelength range of 8-14 μm; after sealing for 1 month, the taste of ordinary white wine in the ceramic ware is more mellow, delicate and less spicy, and the chemical composition of the wine has changed significantly, among which the content of alcohol is reduced by more than 3.0%, the content of alkane, acid and ketone is reduced by more than 0.9%, 0.2% and 0.4% respectively, and the content of ester and olefin is increased by more than 4.0% and 0.5% respectively; the function index of slightly alkaline water: after boiling, 20 ml of ordinary bottled and barrelled drinking water (including pure water, mineral water and mountain spring water) is poured into the ceramic ware, and after 30 min storage, the pH value rises by 0.6-0.8, for details, see the above-mentioned reference patent file.

[0025] First, the rare earth primary ore is detected, and the detection result is shown in Figure 1 . Example 1

[0026] Then, 17.39 g of talc, 12.42 g of calcite, 53.17 g of rare earth primary ore, 1.99 g of Guizhou soil, 4.97 g of Longyan kaolin, 5.47 g of zirconium silicate, 4.47 g of zinc oxide, 0.01 g of cobalt chloride and 0.10 g of calcium chloride are weighed, and then a tackifier and deionized water are added for ball milling and mixing to obtain a slurry.

[0027] The inner glaze slurry is applied on the inner surface of the ceramic wine bottle body, and then is baked in a high temperature furnace for treatment, that is, the ceramic wine bottle inner glaze is formed, and the baking process is as follows: first, the temperature is raised to 780-800℃ at a rate of 1-2℃ / min, then the temperature is raised to 920-950℃ at a rate of 0.5-1℃ / min, the temperature is kept for 20-30 min, then the temperature is raised to 1230-1250℃ at a rate of 0.5-1℃ / min, and then the furnace is cooled to room temperature.

[0028] Take the functional inner glaze prepared above to check the firing effect and test its effect on wine, as shown in Figures 2-3 . Example 2

[0029] The firing process is the same as that of Example 1, and the proportion of rare earth ore is reduced this time, and the proportion of rare earth ore is less than 50%.

[0030] The results show that when the proportion of rare earth ore is less than 50%, the alcoholization effect of the wine liquid is not obvious, and the taste of the wine does not change. Example 3

[0031] As shown in Figure 4 , the firing process is the same as that of Example 1, and the proportion of rare earth ore is increased this time, and the proportion of rare earth ore is greater than 65%.

[0032] The results show that when the proportion of rare earth ore is greater than 65%, the glaze firing effect is not up to standard, and the glaze surface is not smooth and has a matte feel.

[0033] Among them, zirconium silicate has a whitening effect on glaze, enhances the stability of glaze, improves the hardness of glaze, improves the fluidity of glaze, and improves the oxidation resistance of glaze; and zinc oxide can assist in melting during glaze preparation, reduce the melting point, improve the physical properties of the glaze surface, and improve the color development and color adjustment ability, when applied to the inside of the wine bottle, it has a milky effect, forms a crystalline glaze, and reduces the water absorption rate; Cobalt chloride, as a colorant, makes the glaze surface show different colors, and can also increase the hardness and wear resistance of the glaze, and enhance the durability of the inside of the wine bottle; Calcium chloride can adjust the concentration of the glaze, promote the melting of the glaze, and improve the quality of the glaze surface.

[0034] Comparative Example 1 The ordinary wine bottle inner glaze on the market was used for experiments, as shown in Figure 5 , the ordinary inner glaze has no promoting effect on the wine liquid.

[0035] Comparative Example 2 The ceramic wine bottle inner glaze on the market with promoting effect on the wine liquid can promote the wine liquid, but the inner glaze is endowed with silica by quartz stone, and the introduction of silica by quartz method will cause the difference in the thermal expansion coefficient of the body and glaze, which will cause the glaze surface to crack easily. The embodiment 1 adjusts the silica-aluminum ratio of the glaze by a non-quartz method to introduce silica, avoiding the problem of large difference in the thermal expansion coefficient of the body and glaze caused by the introduction of silica by quartz method.

[0036] Table 1 Index data related to the taste of wine of Example 1 and Comparative Example 1 Total acid g / L Total ester g / L Hexanoic acid hexyl ester g / L Methanol g / L Oxide g / L Example 1 2.81 3.95 0.02 0.194 0.23 Comparative Example 1 2.81 3.91 0.02 0.172 0.20 Although embodiments of the present application have been shown and described, it is to be understood that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the present application, the scope of which is defined by the appended claims and their equivalents.

Claims

1. A method for preparing a glaze with catalytic promotion function, characterized in that: Its raw materials include talc, calcite, rare earth ore, Guizhou clay, Longyan kaolin, zirconium silicate, zinc oxide, cobalt chloride, and calcium chloride. The preparation method is a one-time synthesis, specifically including the following steps: S1. Weigh the thickener and deionized water according to the weight proportions, mix them thoroughly to obtain a dispersion; S2. Weigh out the following ingredients according to the specified proportions: talc, calcite, rare earth ore, Guizhou clay, Longyan kaolin, zirconium silicate, zinc oxide, cobalt chloride, and calcium chloride. S3. Mix the dispersion from step S1 and the raw materials from step S2 together, and then ball mill them to obtain the functional inner glaze. S4. Apply the functional inner glaze to the inner surface of the ceramic wine bottle blank, cool and dry it, and then fire it in a high-temperature furnace to form the inner glaze of the ceramic wine bottle.

2. The method for preparing a glaze with catalytic promotion function according to claim 1, characterized in that: The proportions of talc, calcite, rare earth ore, Guizhou clay, Longyan kaolin, zirconium silicate, zinc oxide, cobalt chloride, and calcium chloride are as follows: 16.49-17.39%, 11.34-12.42%, 53.17-55.87%, 1.09-1.99%, 4.97-6.52%, 5.47-6.08%, 3.38-4.47%, 0.007-0.01%, and 0.08-0.10%.

3. The method for preparing a glaze with catalytic promotion function according to claim 2, characterized in that: The proportions of talc, calcite, rare earth ore, Guizhou clay, Longyan kaolin, zirconium silicate, zinc oxide, cobalt chloride, and calcium chloride are 17.39%, 12.42%, 53.17%, 1.99%, 4.97%, 5.47%, 4.47%, 0.01%, and 0.10%, respectively.

4. The method for preparing a glaze with catalytic promotion function according to any one of claims 1-3, characterized in that: The rare earth ore includes La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y, and Sc.

5. The method for preparing a glaze with catalytic promotion function according to claim 4, characterized in that: The mass ratios of La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and Y are: 21.53 mg / Kg, 69.23 mg / Kg, 24.75 mg / Kg, 78.36 mg / Kg, 3.42 mg / Kg, 0.56 mg / Kg, 11.44 mg / Kg, 1.56 mg / Kg, 7.96 mg / Kg, 1.58 mg / Kg, 3.73 mg / Kg, 0.53 mg / Kg, 3.70 mg / Kg, 0.73 mg / Kg, and 34.42 mg / Kg.

6. The method for preparing a glaze with catalytic promotion function according to claim 4, characterized in that: The mass ratio of Sc is less than 0.1 mg / Kg.

7. The method for preparing a glaze with catalytic promotion function according to claim 1, characterized in that: The inner glaze slurry obtained in step S3 needs to be tested to determine its fineness, concentration, Baumé degree, and specific gravity.

8. The method for preparing a glaze with catalytic promotion function according to claim 1, characterized in that: The roasting process is as follows: first, the temperature is raised to 780-800℃ at a rate of 1-2℃ / min, then raised to 920-950℃ at a rate of 0.5-1℃ / min, held for 20-30 minutes, and then raised to 1230-1250℃ at a rate of 0.5-1℃ / min before being cooled down to room temperature in the furnace.

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