A water-purifying cerium-containing modified rare earth water-retaining glaze and preparation method thereof

Abstract

The present invention provides a water-purifying cerium-modified rare earth water-retaining glaze and a preparation method thereof. The glaze is made of the following raw materials in parts by weight: 20-25 parts of quartz, 20-25 parts of mica, 20-25 parts of dolomite, 2-250 parts of kaolin, 10-15 parts of talc, 8-10 parts of barium carbonate, 5-10 parts of rare earth water-retaining glaze additives, and 80-100 parts of deionized water. The water-purifying cerium-modified rare earth water-retaining glaze additive of the present invention is used to prepare a glaze, and the prepared glaze loads rare earth functional materials onto ceramics, and the formed ceramic products have a long-term water-retaining function; the contact between the glaze and drinking water can improve the water quality in the form of ion exchange, making the water biased to weak alkalinity, helping to remove residual chlorine and other harmful substances in the water, thereby improving the quality of drinking water, continuously improving the taste of water, making it sweeter and more delicious, helping to improve the quality of drinking water, and meeting the human body's demand for high-quality drinking water.

Description

Technical Field

[0001] The invention belongs to the field of ceramics, and in particular relates to a water-purifying cerium-containing modified rare earth water-retaining glaze and a preparation method thereof. Background Art

[0002] Rare earth elements have catalytic properties, which can reduce the surface tension of water and make it easier for water molecules to be divided into smaller groups. Such divided water clusters are easier to be absorbed by the human body, and their solubility and permeability are also improved. On the other hand, under the catalytic effect of rare earth glazes, the solubility of oxygen in water increases. The increased dissolved oxygen can promote the absorption of oxygen by human cells, enhance cell vitality, and play an important role in improving immunity and promoting blood circulation. At the same time, rare earth glazes can not only activate water quality, but also have the ability to adsorb and decompose harmful substances in water (such as heavy metals, residual chlorine, organic pollutants, etc.). This effect is mainly attributed to the chemical activity of rare earth elements, which can react with a variety of soluble harmful substances in water and convert them into harmless or low-toxic forms, thereby ensuring the safety and purity of water quality.

[0003] The preparation of glazes involves complex chemical and physical processes. The selection of raw materials, the accuracy of the ratio, and the strict control of temperature during the firing process are all key factors in determining the quality of the final product. With the advancement of science and technology, the modern ceramic industry has been able to use advanced equipment and technology to optimize these processes and improve the consistency and quality of products. Green and healthy is an important direction in the development of glaze technology in recent years. Traditional ceramic glazes may produce harmful substances during the production process, posing a threat to the environment and human health. Therefore, the development of green glazes with self-purification effects has become a new trend in the industry. This type of glaze not only meets environmental protection requirements, but also ensures people's safety in use. Summary of the invention

[0004] In view of this, the present invention aims to overcome the defects in the prior art and proposes a water-purifying cerium-modified rare earth water-retaining glaze additive and a preparation method thereof.

[0005] To achieve the above object, the technical solution of the present invention is achieved as follows:

[0006] A water-purifying cerium-modified rare earth water-retaining glaze, the glaze is made of the following raw materials in parts by weight: 20-25 parts of quartz, 20-25 parts of mica, 20-25 parts of dolomite, 2-250 parts of kaolin, 10-15 parts of talc, 8-10 parts of barium carbonate, 5-10 parts of rare earth water-retaining glaze additives, and 80-100 parts of deionized water;

[0007] The rare earth water-retaining glaze additive is prepared by a method comprising the following steps: adding urea, cobalt nitrate, ferric nitrate and modified nano rare earth oxide into deionized water, stirring magnetically at room temperature, and then reacting under heating conditions, and drying and calcining after the reaction to obtain the purified water-containing cerium-modified rare earth water-retaining glaze additive.

[0008] Furthermore, the duration of the magnetic stirring step is 10-30 minutes; the temperature of the reaction step is 60-90°C and the duration is 4-7 hours; and the temperature of the calcination step is 500-1200°C.

[0009] Furthermore, the mass ratio of the urea, cobalt nitrate, iron nitrate, modified nano rare earth oxide and deionized water is 1:1-2:1-3:1-6:10-20.

[0010] Furthermore, the modified nano rare earth oxide is prepared by a method comprising the following steps:

[0011] (1) Dissolve NaOH in anhydrous ethanol to obtain a NaOH-ethanol solution;

[0012] (2) Change Ce(NO 3 ) 3 •6H 2 O is dissolved in anhydrous ethanol to obtain Ce(NO 3 ) 3 •6H 2 O-ethanol solution;

[0013] (3) Slowly pour the NaOH-ethanol solution into the Ce(NO 3 ) 3 •6H 2 O-ethanol solution, stirring continuously until yellow flocculent precipitate appears, then centrifuge to separate the precipitate;

[0014] (4) Al 2 O 3 The modified nano rare earth oxide is obtained by dissolving it in anhydrous ethanol, adding the precipitate thereto, reacting under high temperature conditions, cooling and washing to neutrality after the reaction is completed, and then drying and grinding.

[0015] Furthermore, the concentration of the NaOH-ethanol solution in step (1) is 1-1.2 mol / L; the Ce(NO 3 ) 3 •6H 2 The concentration of O-ethanol solution is 1-1.5 mol / L.

[0016] Further, the NaOH-ethanol solution in step (3) and the Ce(NO 3 ) 3 •6H 2 The volume of the O-ethanol solution is the same; the Al in step (4) 2 O 3 The solid-liquid ratio with anhydrous ethanol is 1g:8-10 mL.

[0017] Furthermore, the reaction step in step (4) is carried out at a temperature of 180-220° C. for 5-6 hours; and the drying step in step (4) is carried out at a temperature of 80-100° C. for 10-12 hours.

[0018] The preparation method of the cerium-modified rare earth water-retaining glaze for purified water comprises the following steps: ball milling the cerium-modified rare earth water-retaining glaze additive for purified water to obtain rare earth additive powder, and uniformly mixing the rare earth additive powder with quartz, mica, dolomite, kaolin, talc, barium carbonate and water to obtain the glaze.

[0019] Furthermore, the particle size of the rare earth additive powder is 500-1000 nm.

[0020] The modified nano rare earth oxide is first prepared by slowly adding Ce(NO 3 ) 3 •6H 2 O-ethanol solution, sodium hydroxide (NaOH) and cerium nitrate (Ce(NO 3 ) 3 •6H 2 O) undergoes a double decomposition reaction. Sodium hydroxide, as a strong base, provides OH⁻ ions, while cerium nitrate provides Ce 3+ When these two ions meet in solution, they quickly combine to form cerium hydroxide (Ce(OH) 3 ), precipitated in the form of yellow flocculent precipitate. During the process, the alkali solution drop rate was strictly controlled. The concentration of the reactants and the stirring speed would affect the generation rate and particle size of the precipitate. Then, the Ce(OH) 3 Precipitation and alumina (Al 2 O 3 ) are mixed and placed in a hydrothermal reactor for high temperature reaction. Under the conditions of 180°C and high pressure, cerium hydroxide and aluminum oxide react in a solid phase, Ce(OH) 3 First decompose into Ce 2 O 3 and H 2 O, then Ce 2 O 3 With Al2 O 3 CeAlO is formed by solid phase diffusion and recrystallization processes. 3 Crystal (ACO).

[0021] Compared with the prior art, the present invention has the following advantages:

[0022] The water-purifying cerium-containing modified rare earth water-retaining glaze additive of the present invention is prepared by using modified nano rare earth oxides, urea, cobalt nitrate, and ferric nitrate. This rare earth glaze additive can not only play a purification role, but also form an antibacterial protective layer on the ceramic surface, increase the hygienic and safe performance of the product, and effectively improve the quality of the glaze surface, making the product surface smoother and brighter, and reducing defects. This additive not only improves the quality and market competitiveness of ceramic products, but also has a wide range of application prospects in the production of high-performance ceramic products due to its environmental protection and cost-effectiveness advantages.

[0023] The water-purifying cerium-modified rare earth water-retaining glaze described in the present invention loads rare earth functional materials onto ceramics, and the formed ceramic products have a long-lasting water-retaining function; the contact between the glaze and drinking water can improve the water quality through ion exchange, making the water tend to be weakly alkaline, which helps to remove residual chlorine and other harmful substances in the water, thereby improving the quality of drinking water, continuously improving the taste of water, making it sweeter and more delicious, helping to improve the quality of drinking water, and meeting the human body's demand for high-quality drinking water. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 This is a particle size distribution diagram of Ce@CFO described in Example 1 of the present invention;

[0025] Figure 2 The chemical oxygen demand bar graph of Comparative Examples 1-2 of the present invention;

[0026] Figure 3 This is a bar graph of the chemical oxygen demand described in Comparative Example 3 of the present invention. DETAILED DESCRIPTION

[0027] Unless otherwise defined, the technical terms used in the following examples have the same meanings as those generally understood by those skilled in the art to which the present invention belongs. The test reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the experimental methods, unless otherwise specified, are all conventional methods.

[0028] Urea, cobalt nitrate, iron nitrate nonahydrate, cerium nitrate hexahydrate, lanthanum nitrate hexahydrate, yttrium nitrate hexahydrate, barium carbonate, quartz, mica, dolomite, kaolin, talc, and barium carbonate were all purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.

[0029] All chemicals were used without further treatment, and deionized water was prepared in the laboratory.

[0030] The present invention will be described in detail below with reference to the embodiments.

[0031] Example 1

[0032] A method for preparing a cerium-modified rare earth water-retaining glaze additive for water purification comprises the following steps:

[0033] (1) Weigh 4 g of NaOH and dissolve it in 100 mL of anhydrous ethanol to prepare a 1 mol / L NaOH-ethanol solution. Weigh 21.1 g of Ce(NO 3 ) 3 •6H 2 O was dissolved in 100 mL of anhydrous ethanol to obtain a 1 mol / L Ce(NO 3 ) 3 •6H 2 O-ethanol solution, slowly pour the NaOH-ethanol solution into the Ce(NO 3 ) 3 •6H 2 O-ethanol solution and continue stirring until a yellow flocculent precipitate appears. Separate the precipitate by centrifugation and weigh 10 g of Al 2 O 3 and 100 mL of anhydrous ethanol, and put it into a hydrothermal reactor together with the precipitate, react at 180°C for 5 h, cool it, filter and wash it until it is neutral, and dry it again at 80°C for 10 h, grind the dried material into powder, and obtain modified nano rare earth oxide ACO;

[0034] (2) Weigh 10 g of Co(NO 3 ) 3 •6H 2 O, 20.6 g of Fe(NO 3 ) 3 •9H 2 O and 1.9 g ACO were dissolved in 300 mL of deionized water, and then 6 g urea was added and stirred at room temperature for 10 min to ensure that all solids were completely dissolved and mixed evenly. After stirring evenly, it was placed in an environment of 110 °C for 6-8 h to dry. This step is to remove most of the water;

[0035] (3) The dried sample was ground into powder and then transferred to a muffle furnace for calcination at 800 °C for 3 h. This high-temperature treatment step was to ensure that all residual moisture was completely removed and that ACO was converted into the corresponding metal oxides through thermal decomposition reaction, thereby obtaining the desired final product, Ce@CFO.

[0036] Ce@CFO was analyzed for particle size using a Malvern particle size tester. The results are as follows: Figure 1 As shown, the particle size distribution range is mainly around 1 μm, which can meet the requirements of the subsequent glazing process.

[0037] Comparative Example 1

[0038] The only difference from Example 1 is that Ce(NO 3 ) 3 •6H 2 O is replaced by La(NO 3 ) 3 •6H 2 O, the final product is La@CFO.

[0039] Comparative Example 2

[0040] The only difference from Example 1 is that Ce(NO 3 ) 3 •6H 2 O is replaced by Y(NO 3 ) 3 •6H 2 O, the final product is Y@CFO.

[0041] Comparative Example 3

[0042] The only difference from Example 1 is that the modified nano rare earth oxide is replaced by Ce(NO 3 ) 3 •6H 2 O, the final product is a cerium-containing water-retaining additive.

[0043] The products obtained in Example 1 and Comparative Examples 1-3 are placed in a ball mill, and the material particle size is stabilized at about 1 μm through a ball milling process. The ball-milled powder material is then mixed with other components of the glaze, and the rare earth functional material is loaded onto the ceramic through a glazing process. After high-temperature firing at 1200°C, a rare earth water-retaining ceramic cup is obtained.

[0044] The glaze components are as follows: 20 parts of quartz, 20 parts of mica, 20 parts of dolomite, 20 parts of kaolin, 10 parts of talc, 10 parts of barium carbonate, 5 parts of rare earth water-retaining glaze additive, and 100 parts of water.

[0045] Determination of Chemical Oxygen Demand (COD) of Water in Different Ceramic Cups:

[0046] Three ceramic cups with common glaze, three ceramic cups with Ce@CFO, three ceramic cups with La@CFO, three ceramic cups with Y@CFO and three ceramic cups with cerium water-retaining additive were prepared as three parallel tests in each group. 300 mL of deionized water was added to the cups respectively, and then the COD index in the water was tested using a chemical oxygen demand meter 0 min and 1 h after adding water. The results are shown in Figure 2. Figure 2 shown.

[0047] from Figure 2 It can be seen that the COD index of the water quality in the five groups of ceramic cups is not much different 0 min after adding water, which means that the quality of the added deionized water is normal. After standing for 1 h, the COD index of the water quality in the ordinary glazed ceramic cup in the blank control group increased significantly, reaching 6.1 mg / L, while the COD of the water quality in the Ce@CFO ceramic cup decreased from 4.2 mg / L to 2.3 mg / L, which means that the Ce@CFO material in the glaze of the ceramic cup can purify the water quality and keep the water from deteriorating. At the same time, the COD index in the La@CFO ceramic cup also decreased, but the effect was not as good as that of the Ce@CFO material.

[0048] from Figure 3 The influence of rare earth glazes prepared with two different cerium-containing compounds as raw materials on water quality can be seen in the figure. After adding deionized water to the two ceramic cups for 1 h, Ce(NO 3 ) 3 •6H 2 The COD index of the ceramic cup with O as raw material decreased from 4.1 mg / L to 3.3 mg / L, proving that the ceramic cup can purify water quality. However, the COD of the ceramic cup with ACO as raw material decreased from 4.2 mg / L to 2.3 mg / L. Compared with the ceramic cup with Ce(NO 3 ) 3 •6H 2 The purification effect of ceramic cups with O as raw material still has great advantages.

[0049] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A water-purifying cerium-modified rare earth water-retaining glaze, characterized in that: The glaze is made of the following raw materials in parts by weight: 20-25 parts of quartz, 20-25 parts of mica, 20-25 parts of dolomite, 2-250 parts of kaolin, 10-15 parts of talc, 8-10 parts of barium carbonate, 5-10 parts of rare earth water-retaining glaze additive, and 80-100 parts of deionized water; The preparation method of the rare earth water-retaining glaze additive comprises the following steps: adding urea, cobalt nitrate, ferric nitrate and modified nano rare earth oxide into deionized water, stirring magnetically at room temperature, and then reacting under heating conditions, and drying and calcining after the reaction to obtain the purified water-containing cerium-modified rare earth water-retaining glaze additive; The mass ratio of urea, cobalt nitrate, ferric nitrate, modified nano rare earth oxide and deionized water is 1:1.67:3.4:0.32:50; The preparation method of the modified nano rare earth oxide comprises the following steps: (1) Dissolve NaOH in anhydrous ethanol to obtain a NaOH-ethanol solution; (2) dissolving Ce(NO3)3•6H2O in anhydrous ethanol to obtain Ce(NO3)3•6H2O-ethanol solution; (3) slowly pouring the NaOH-ethanol solution into the Ce(NO3)3•6H2O-ethanol solution, stirring continuously until a yellow flocculent precipitate appears, and then centrifuging to separate the precipitate; (4) Dissolving Al2O3 in anhydrous ethanol to obtain the precipitate, adding the precipitate thereto, reacting under high temperature conditions, cooling and washing to neutrality after the reaction is completed, and then drying and grinding to obtain the modified nano rare earth oxide.

2. The water-purifying cerium-modified rare earth water-retaining glaze according to claim 1, characterized in that: The duration of the magnetic stirring step is 10 minutes; the temperature of the calcining step is 800°C.

3. The water-purifying cerium-modified rare earth water-retaining glaze according to claim 1, characterized in that: The concentration of the NaOH-ethanol solution in step (1) is 1 mol / L; the concentration of the Ce(NO3)3•6H2O-ethanol solution in step (2) is 0.49 mol / L.

4. The water-purifying cerium-modified rare earth water-retaining glaze according to claim 1, characterized in that: The volumes of the NaOH-ethanol solution in step (3) are the same as those of the Ce(NO3)3•6H2O-ethanol solution; the solid-to-liquid ratio of Al2O3 to anhydrous ethanol in step (4) is 1 g:10 mL.

5. The water-purifying cerium-modified rare earth water-retaining glaze according to claim 1, characterized in that: The temperature of the reaction step in step (4) is 180° C. and the time is 5 hours; the temperature of the drying step in step (4) is 80° C. and the time is 10 hours.

6. The method for preparing the cerium-modified rare earth water-retaining glaze for purified water according to any one of claims 1 to 5, characterized in that: The method comprises the following steps: ball milling the purified water-containing cerium-modified rare earth water-retaining glaze additive to obtain rare earth additive powder, and uniformly mixing the rare earth additive powder with quartz, mica, dolomite, kaolin, talc, barium carbonate and water to obtain the glaze.

7. The method for preparing the cerium-modified rare earth water-retaining glaze for purified water according to claim 6, characterized in that: The particle size of the rare earth additive powder is 500-1000 nm.

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