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CN118637829A - A water-purifying cerium-containing modified rare earth water-retaining glaze and preparation method thereof

Publication number

CN118637829A

CN118637829A CN202411110418.8A CN202411110418A CN118637829A CN 118637829 A CN118637829 A CN 118637829A CN 202411110418 A CN202411110418 A CN 202411110418A CN 118637829 A CN118637829 A CN 118637829A

Authority

CN

China

Prior art keywords

water

rare earth

parts

glaze

cerium

Prior art date

2024-08-14

Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)

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• 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 45
• 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 43
• 229910052684 Cerium Inorganic materials 0.000 title claims abstract description 20
• GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 title claims abstract description 19
• 238000002360 preparation method Methods 0.000 title abstract description 6
• XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 62
• 229910001868 water Inorganic materials 0.000 claims abstract description 35
• 239000000654 additive Substances 0.000 claims abstract description 24
• 230000000996 additive effect Effects 0.000 claims abstract description 23
• 239000008213 purified water Substances 0.000 claims abstract description 15
• 239000008367 deionised water Substances 0.000 claims abstract description 12
• 229910021641 deionized water Inorganic materials 0.000 claims abstract description 12
• 239000002994 raw material Substances 0.000 claims abstract description 8
• 239000005995 Aluminium silicate Substances 0.000 claims abstract description 7
• 235000012211 aluminium silicate Nutrition 0.000 claims abstract description 7
• 239000010459 dolomite Substances 0.000 claims abstract description 7
• 229910000514 dolomite Inorganic materials 0.000 claims abstract description 7
• NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims abstract description 7
• 239000010445 mica Substances 0.000 claims abstract description 7
• 229910052618 mica group Inorganic materials 0.000 claims abstract description 7
• 239000010453 quartz Substances 0.000 claims abstract description 7
• VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 7
• 239000000454 talc Substances 0.000 claims abstract description 7
• 229910052623 talc Inorganic materials 0.000 claims abstract description 7
• AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 claims abstract description 5
• 206010016807 Fluid retention Diseases 0.000 claims abstract 4
• 235000012222 talc Nutrition 0.000 claims abstract 3
• LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
• HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
• 238000000034 method Methods 0.000 claims description 17
• 239000002244 precipitate Substances 0.000 claims description 15
• 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 11
• OVYTZAASVAZITK-UHFFFAOYSA-M sodium;ethanol;hydroxide Chemical compound [OH-].[Na+].CCO OVYTZAASVAZITK-UHFFFAOYSA-M 0.000 claims description 11
• VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 10
• 238000006243 chemical reaction Methods 0.000 claims description 9
• 239000000843 powder Substances 0.000 claims description 9
• 239000002245 particle Substances 0.000 claims description 8
• 238000003756 stirring Methods 0.000 claims description 8
• XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 7
• 239000004202 carbamide Substances 0.000 claims description 7
• AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 claims description 6
• UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 6
• 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 6
• 238000001354 calcination Methods 0.000 claims description 5
• 238000000746 purification Methods 0.000 claims description 5
• 238000001035 drying Methods 0.000 claims description 4
• 238000000498 ball milling Methods 0.000 claims description 3
• 238000010438 heat treatment Methods 0.000 claims description 2
• 239000007788 liquid Substances 0.000 claims description 2
• 238000003760 magnetic stirring Methods 0.000 claims description 2
• 238000002156 mixing Methods 0.000 claims description 2
• 238000001816 cooling Methods 0.000 claims 1
• 238000000227 grinding Methods 0.000 claims 1
• 238000005406 washing Methods 0.000 claims 1
• 239000000919 ceramic Substances 0.000 abstract description 28
• 239000000126 substance Substances 0.000 abstract description 12
• 239000003651 drinking water Substances 0.000 abstract description 8
• 235000020188 drinking water Nutrition 0.000 abstract description 8
• ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 3
• 239000000460 chlorine Substances 0.000 abstract description 3
• 229910052801 chlorine Inorganic materials 0.000 abstract description 3
• 238000005342 ion exchange Methods 0.000 abstract description 2
• 239000008204 material by function Substances 0.000 abstract description 2
• 235000009508 confectionery Nutrition 0.000 abstract 1
• 230000008569 process Effects 0.000 description 8
• QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
• 239000001301 oxygen Substances 0.000 description 7
• 229910052760 oxygen Inorganic materials 0.000 description 7
• 239000000047 product Substances 0.000 description 7
• 230000000052 comparative effect Effects 0.000 description 6
• 239000000463 material Substances 0.000 description 6
• 229910018072 Al 2 O 3 Inorganic materials 0.000 description 5
• 239000012467 final product Substances 0.000 description 5
• HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 4
• 230000000694 effects Effects 0.000 description 4
• 230000008901 benefit Effects 0.000 description 3
• 238000005516 engineering process Methods 0.000 description 3
• 230000003197 catalytic effect Effects 0.000 description 2
• 238000005119 centrifugation Methods 0.000 description 2
• UNJPQTDTZAKTFK-UHFFFAOYSA-K cerium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Ce+3] UNJPQTDTZAKTFK-UHFFFAOYSA-K 0.000 description 2
• 239000003153 chemical reaction reagent Substances 0.000 description 2
• 230000003247 decreasing effect Effects 0.000 description 2
• 230000007547 defect Effects 0.000 description 2
• 238000011161 development Methods 0.000 description 2
• 238000009826 distribution Methods 0.000 description 2
• 230000007613 environmental effect Effects 0.000 description 2
• 238000010304 firing Methods 0.000 description 2
• 150000002500 ions Chemical class 0.000 description 2
• 238000004519 manufacturing process Methods 0.000 description 2
• 238000012360 testing method Methods 0.000 description 2
• 101001121408 Homo sapiens L-amino-acid oxidase Proteins 0.000 description 1
• 102100026388 L-amino-acid oxidase Human genes 0.000 description 1
• 101100012902 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) FIG2 gene Proteins 0.000 description 1
• 238000010521 absorption reaction Methods 0.000 description 1
• 230000001133 acceleration Effects 0.000 description 1
• 239000003513 alkali Substances 0.000 description 1
• PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
• 230000000844 anti-bacterial effect Effects 0.000 description 1
• 239000002585 base Substances 0.000 description 1
• 230000017531 blood circulation Effects 0.000 description 1
• 210000004027 cell Anatomy 0.000 description 1
• QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 description 1
• 150000001875 compounds Chemical class 0.000 description 1
• 238000007796 conventional method Methods 0.000 description 1
• 239000013078 crystal Substances 0.000 description 1
• 238000000354 decomposition reaction Methods 0.000 description 1
• 230000002542 deteriorative effect Effects 0.000 description 1
• 238000010586 diagram Methods 0.000 description 1
• 238000009792 diffusion process Methods 0.000 description 1
• 238000002474 experimental method Methods 0.000 description 1
• 230000036541 health Effects 0.000 description 1
• 229910001385 heavy metal Inorganic materials 0.000 description 1
• 210000005260 human cell Anatomy 0.000 description 1
• 230000036039 immunity Effects 0.000 description 1
• XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
• QZRHHEURPZONJU-UHFFFAOYSA-N iron(2+) dinitrate nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QZRHHEURPZONJU-UHFFFAOYSA-N 0.000 description 1
• 229910052746 lanthanum Inorganic materials 0.000 description 1
• GJKFIJKSBFYMQK-UHFFFAOYSA-N lanthanum(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GJKFIJKSBFYMQK-UHFFFAOYSA-N 0.000 description 1
• 230000005923 long-lasting effect Effects 0.000 description 1
• 229910044991 metal oxide Inorganic materials 0.000 description 1
• 150000004706 metal oxides Chemical class 0.000 description 1
• 238000012986 modification Methods 0.000 description 1
• 230000004048 modification Effects 0.000 description 1
• 230000007935 neutral effect Effects 0.000 description 1
• TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
• 230000035699 permeability Effects 0.000 description 1
• 239000002957 persistent organic pollutant Substances 0.000 description 1
• 230000001737 promoting effect Effects 0.000 description 1
• 239000011241 protective layer Substances 0.000 description 1
• 239000000376 reactant Substances 0.000 description 1
• 238000001953 recrystallisation Methods 0.000 description 1
• 239000007787 solid Substances 0.000 description 1
• 239000007790 solid phase Substances 0.000 description 1
• 238000003746 solid phase reaction Methods 0.000 description 1
• 238000006467 substitution reaction Methods 0.000 description 1
• 238000005979 thermal decomposition reaction Methods 0.000 description 1
• 229910052727 yttrium Inorganic materials 0.000 description 1
• QBAZWXKSCUESGU-UHFFFAOYSA-N yttrium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Y+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QBAZWXKSCUESGU-UHFFFAOYSA-N 0.000 description 1

• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
  • C03C1/02—Pretreated ingredients
  • C03C1/026—Pelletisation or prereacting of powdered raw materials
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
  • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
  • C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
  • C04B41/5022—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with vitreous materials
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
  • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
  • C04B41/81—Coating or impregnation
  • C04B41/85—Coating or impregnation with inorganic materials
  • C04B41/86—Glazes; Cold glazes
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C2204/00—Glasses, glazes or enamels with special properties
  • C03C2204/02—Antibacterial glass, glaze or enamel
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P40/00—Technologies relating to the processing of minerals
  • Y02P40/60—Production of ceramic materials or ceramic elements, e.g. substitution of clay or shale by alternative raw materials, e.g. ashes

• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Ceramic Engineering (AREA)
• Materials Engineering (AREA)
• Organic Chemistry (AREA)
• Inorganic Chemistry (AREA)
• Structural Engineering (AREA)
• Life Sciences & Earth Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Geochemistry & Mineralogy (AREA)
• Catalysts (AREA)

The invention provides a purified water cerium-containing modified rare earth water-retaining glaze and a preparation method thereof, wherein the glaze is prepared from 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 talcum, 8-10 parts of barium carbonate, 5-10 parts of rare earth water-retention glaze additive and 80-100 parts of deionized water. The purified water cerium-containing modified rare earth water-retaining glaze additive is used for preparing a glaze, the prepared glaze loads rare earth functional materials on ceramics, and a formed ceramic product has a long-acting water-retaining function; the contact of the glaze and the drinking water can improve the water quality in an ion exchange mode, so that the water is biased to be weak alkaline, residual chlorine and other harmful substances in the water can be removed, the drinking water quality is improved, the taste of the water is continuously improved, the water is sweet and delicious, the drinking water quality is improved, and the requirement of a human body on high-quality drinking water is met.

技术领域Technical Field

本发明属于陶瓷领域，尤其是涉及一种净水含铈改性稀土保水釉料及其制备方法。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.

背景技术Background Art

稀土元素具有催化性能，能够降低水的表面张力，使得水分子更容易被分割成更小的基团。这种被分割后的水团簇更易于被人体吸收，同时溶解力和渗透力也得到提升。另一方面，在稀土釉料的催化作用下，水中的氧气溶解度增加，增加的溶解氧可以促进人体细胞对氧的吸收，增强细胞活力，对提高免疫力、促进血液循环等方面有重要作用。同时稀土釉料不仅能够活化水质，还具有吸附和分解水中有害物质（如重金属、余氯、有机污染物等）的能力。这一作用主要归功于稀土元素的化学活性，能够与水中的多种溶解性有害物质发生反应，将其转化为无害或低毒的形式，从而保证水质的安全与纯净。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.

釉料的制备涉及复杂的化学和物理过程。原料的选择、配比的准确性以及烧制过程中温度的严格控制都是决定最终产品质量的关键因素。随着科技的进步，现代陶瓷工业已经能够利用先进的设备和技术来优化这些过程，提高产品的一致性和质量。绿色健康是近年来釉料技术发展中的一个重要方向。传统的陶瓷釉料在生产过程中可能会产生有害物质，对环境和人体健康造成威胁。因此，研发自带净化作用的绿色釉料成为行业的新趋势。这类釉料不仅符合环保要求，还能确保人们的使用安全。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 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.

发明内容Summary of the invention

有鉴于此，本发明旨在克服现有技术中的缺陷，提出一种净水含铈改性稀土保水釉料添加剂及其制备方法。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.

为达到上述目的，本发明的技术方案是这样实现的：To achieve the above object, the technical solution of the present invention is achieved as follows:

一种净水含铈改性稀土保水釉料，该釉料由包括如下重量份的原料制成：石英20-25份，云母20-25份，白云石20-25份，高岭土2-250份，滑石10-15份，碳酸钡8-10份，稀土保水釉料添加剂5-10份，去离子水80-100份；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;

所述的稀土保水釉料添加剂由包括如下步骤的方法制成：将尿素、硝酸钴、硝酸铁与改性纳米稀土氧化物加入进去离子水中，在室温条件下磁力搅拌，然后在加热条件下进行反应，反应完成后进行烘干、煅烧后得到所述的净水含铈改性稀土保水釉料添加剂。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.

进一步，所述的磁力搅拌步骤的时间为10-30分钟；所述的反应步骤的温度为60-90 ℃，时间为4-7 小时；所述的煅烧步骤的温度为500-1200 ℃。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.

进一步，所述的尿素、硝酸钴、硝酸铁、改性纳米稀土氧化物与去离子水的质量比为1：1-2:1-3:1-6:10-20。Furthermore, the mass ratio of the urea, cobalt nitrate, ferric nitrate, modified nano rare earth oxide and deionized water is 1:1-2:1-3:1-6:10-20.

进一步，所述的改性纳米稀土氧化物由包括如下步骤的方法制成：Furthermore, the modified nano rare earth oxide is prepared by a method comprising the following steps:

（1）将 NaOH溶于无水乙醇中，得到NaOH-乙醇溶液；(1) Dissolve NaOH in anhydrous ethanol to obtain a NaOH-ethanol solution;

（2）将Ce(NO₃)₃•6H₂O溶于无水乙醇中，得到Ce(NO₃)₃•6H₂O-乙醇溶液；(2) dissolving Ce(NO ₃ ) ₃ •6H ₂ O in anhydrous ethanol to obtain Ce(NO ₃ ) ₃ •6H ₂ O-ethanol solution;

（3）将所述的NaOH-乙醇溶液缓慢倒入所述的Ce(NO₃)₃•6H₂O-乙醇溶液中，持续搅拌直到出现黄色絮状沉淀，然后离心分离沉淀；(3) slowly pouring the NaOH-ethanol solution into the Ce(NO ₃ ) ₃ •6H ₂ O-ethanol solution, stirring continuously until a yellow flocculent precipitate appears, and then centrifuging to separate the precipitate;

（4）将Al₂O₃溶于无水乙醇，得到向其中加入所述的沉淀，在高温条件下反应，反应完成后进行冷却、洗涤至中性，然后经烘干、研磨得到所述的改性纳米稀土氧化物。(4) Al ₂ O ₃ is dissolved in anhydrous ethanol to obtain the precipitate, and the precipitate is added thereto for reaction at high temperature. After the reaction is completed, the precipitate is cooled and washed to neutrality, and then dried and ground to obtain the modified nano rare earth oxide.

进一步，所述的步骤（1）中的NaOH-乙醇溶液的浓度为1-1.2 mol/L；所述的步骤（1）中的Ce(NO₃)₃•6H₂O-乙醇溶液的浓度为1-1.5 mol/L。Furthermore, the concentration of the NaOH-ethanol solution in step (1) is 1-1.2 mol/L; the concentration of the Ce(NO ₃ ) ₃ •6H ₂ O-ethanol solution in step (1) is 1-1.5 mol/L.

进一步，所述的步骤（3）中的NaOH-乙醇溶液与所述的Ce(NO₃)₃•6H₂O-乙醇溶液的体积相同；所述的步骤（4）中的Al₂O₃与无水乙醇的固液比为1g：8-10 mL。Furthermore, the volumes of the NaOH-ethanol solution in step (3) are the same as those of the Ce(NO ₃ ) ₃ •6H ₂ O-ethanol solution; and the solid-liquid ratio of Al ₂ O ₃ to anhydrous ethanol in step (4) is 1 g: 8-10 mL.

进一步，所述的步骤（4）中的反应步骤的温度为180-220℃，时间为5-6小时；所述的步骤（4）中的烘干步骤的温度为80-100℃，时间为10-12 小时。Furthermore, the temperature of the reaction step in step (4) is 180-220° C., and the time is 5-6 hours; the temperature of the drying step in step (4) is 80-100° C., and the time is 10-12 hours.

所述的净水含铈改性稀土保水釉料的制备方法，包括如下步骤：将所述的净水含铈改性稀土保水釉料添加剂进行球磨，得到稀土添加剂粉末，将所述的稀土添加剂粉末与石英、云母、白云石、高岭土、滑石、碳酸钡与水混合均匀后，得到所述的釉料。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.

进一步，所述的稀土添加剂粉末的粒径为500-1000 nm。Furthermore, the particle size of the rare earth additive powder is 500-1000 nm.

所述的改性纳米稀土氧化物首先由NaOH-乙醇溶液缓慢加入Ce(NO₃)₃•6H₂O-乙醇溶液时，氢氧化钠（NaOH）与硝酸铈（Ce(NO₃)₃•6H₂O）发生复分解反应。氢氧化钠作为强碱，提供OH⁻离子，而硝酸铈则提供Ce³⁺离子。这两种离子在溶液中相遇时，迅速结合形成不溶于乙醇的氢氧化铈（Ce(OH)₃），以黄色絮状沉淀的形式析出。期间严格控制碱液滴加速度，反应物的浓度和搅拌速度都会影响沉淀的生成速率和颗粒大小。然后通过后处理离心得到的Ce(OH)₃沉淀与氧化铝（Al₂O₃）混合后，一同放入水热反应釜中进行高温反应。在180℃和高压的条件下，氢氧化铈与氧化铝发生固相反应，Ce(OH)₃首先分解为Ce₂O₃和H₂O，随后Ce₂O₃与Al₂O₃通过固相扩散和重结晶过程结合形成CeAlO₃晶体（ACO）。The modified nano rare earth oxide is first prepared by slowly adding Ce(NO ₃ ) ₃ •6H ₂ O-ethanol solution to NaOH-ethanol solution, and sodium hydroxide (NaOH) and cerium nitrate (Ce(NO ₃ ) ₃ •6H ₂ O) undergo double decomposition reaction. Sodium hydroxide, as a strong base, provides OH⁻ ions, while cerium nitrate provides Ce ³⁺ ions. When these two ions meet in the solution, they quickly combine to form cerium hydroxide (Ce(OH) ₃ ) that is insoluble in ethanol and precipitates in the form of yellow flocculent precipitate. During the process, the alkali solution droplet acceleration is strictly controlled, and the concentration of the reactants and the stirring speed will affect the generation rate and particle size of the precipitate. Then, the Ce(OH) ₃ precipitate obtained by post-treatment centrifugation is mixed with aluminum oxide (Al ₂ O ₃ ) and placed together in a hydrothermal reactor for high-temperature reaction. Under the conditions of 180°C and high pressure, cerium hydroxide reacts with alumina in a solid phase reaction, and Ce(OH) ₃ first decomposes into Ce ₂ O ₃ and H ₂ O, and then Ce ₂ O ₃ combines with Al ₂ O ₃ through solid phase diffusion and recrystallization processes to form CeAlO ₃ crystals (ACO).

相对于现有技术，本发明具有以下优势：Compared with the prior art, the present invention has the following advantages:

本发明所述的净水含铈改性稀土保水釉料添加剂采用改性纳米稀土氧化物与尿素、硝酸钴、硝酸铁进行制备，这种稀土釉料添加剂不仅能够起到净化作用，同时还能在陶瓷表面形成具有抗菌性的保护层，增加产品的卫生安全性能，还能有效提高釉面的质量，使产品表面更加光滑亮丽，减少缺陷。该添加剂不仅提高了陶瓷产品的质量和市场竞争力，还因其环保和成本效益优势，将在高性能陶瓷制品生产中展现出广泛的应用前景。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.

本发明所述的净水含铈改性稀土保水釉料将稀土功能材料负载到陶瓷上，形成的陶瓷制品具备长效的保水质功能；釉面与饮用水的接触，可以通过离子交换的形式改善水质，使水偏向弱碱性，有助于清除水中的余氯和其他有害物质，从而提升饮水质量，持续改善水的口感，使其更加甘甜可口，有助于提升饮水质量，满足人体对高质量饮水的需求。The cerium-modified rare earth water-retaining glaze for purifying water 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.

附图说明BRIEF DESCRIPTION OF THE DRAWINGS

图1为本发明实施例1所述的Ce@CFO的粒度分布图；FIG1 is a particle size distribution diagram of Ce@CFO described in Example 1 of the present invention;

图2为本发明对比例1-2所述的化学需氧量柱状图；FIG2 is a bar graph of chemical oxygen demand according to Comparative Examples 1-2 of the present invention;

图3为本发明对比例3所述的化学需氧量柱状图。FIG. 3 is a bar graph of the chemical oxygen demand described in Comparative Example 3 of the present invention.

具体实施方式DETAILED DESCRIPTION

除有定义外，以下实施例中所用的技术术语具有与本发明所属领域技术人员普遍理解的相同含义。以下实施例中所用的试验试剂，如无特殊说明，均为常规生化试剂；所述实验方法，如无特殊说明，均为常规方法。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.

尿素、硝酸钴、九水合硝酸铁、六水合硝酸铈、六水合硝酸镧、六水合硝酸钇、碳酸钡、石英、云母、白云石、高岭土、滑石、碳酸钡均采购自上海阿拉丁生化科技股份有限公司。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.

所有的化学物质都未经进一步处理使用，去离子水为实验室自制。All chemicals were used without further treatment, and deionized water was prepared in the laboratory.

下面结合实施例来详细说明本发明。The present invention will be described in detail below with reference to the embodiments.

实施例1Example 1

一种净水含铈改性稀土保水釉料添加剂的制备方法，包括如下步骤：A method for preparing a cerium-modified rare earth water-retaining glaze additive for water purification comprises the following steps:

（1）称取4 g NaOH溶解在100 mL无水乙醇中，配制浓度为1 mol/L的NaOH-乙醇溶液，称取21.1g的Ce(NO₃)₃•6H₂O溶解在100 mL无水乙醇中，得到浓度为1 mol/L的Ce(NO₃)₃•6H₂O-乙醇溶液，将NaOH-乙醇溶液缓慢倒入Ce(NO₃)₃•6H₂O-乙醇溶液中，并持续搅拌直到出现黄色絮状沉淀，通过离心分离出来沉淀，再称取10 g的Al₂O₃和100 mL无水乙醇，并与所述的沉淀一同放入水热反应釜中，在180℃下高温反应5 h，冷却后，抽滤洗涤至中性，并在80℃下再次烘干10 h，将烘干后的材料研磨成为粉末，即得到改性纳米稀土氧化物ACO；(1) Weigh 4 g of NaOH and dissolve it in 100 mL of anhydrous ethanol to prepare a NaOH-ethanol solution with a concentration of 1 mol/L; weigh 21.1 g of Ce(NO ₃ ) ₃ •6H ₂ O and dissolve it in 100 mL of anhydrous ethanol to obtain a Ce(NO ₃ ) ₃ •6H ₂ O-ethanol solution with a concentration of 1 mol/L; 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; weigh 10 g of Al ₂ O ₃ and 100 mL of anhydrous ethanol, and put them together with the precipitate into a hydrothermal reactor; react at a high temperature of 180° C. for 5 h; cool, filter and wash until neutral; and dry again at 80° C. for 10 h; grind the dried material into powder to obtain modified nano rare earth oxide ACO;

（2）称取10 g的Co(NO₃)₃•6H₂O、20.6 g的Fe(NO₃)₃•9H₂O与1.9 g的ACO，一同溶解在300 mL的去离子水中，然后加入6 g尿素，在室温下搅拌10 min，以确保所有固体完全溶解并且混合均匀，搅拌均匀后，置于110 ℃的环境中烘干6-8 h，此步骤旨在去除大部分水分；(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 of ACO, dissolve them in 300 mL of deionized water, then add 6 g of urea and stir at room temperature for 10 min to ensure that all solids are completely dissolved and mixed evenly. After stirring evenly, place it in an environment of 110 ℃ and dry it for 6-8 h. This step is to remove most of the water;

（3）将烘干后的样品通过研磨成为粉末，再转移到马弗炉中，在800 ℃的温度下进行煅烧，持续3 h，这一高温处理步骤是为了确保所有残余的水分被彻底驱除，并且通过热分解反应使ACO转化为相应的金属氧化物，从而得到最终所需的产品Ce@CFO。(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.

将Ce@CFO使用马尔文粒度测试仪进行粒径分析，结果如图1所示，粒径主要分布范围在1 μm左右，能够满足后续施釉工艺。Ce@CFO was analyzed for particle size using a Malvern particle size tester. The results are shown in Figure 1. The particle size distribution range is mainly around 1 μm, which can meet the requirements of the subsequent glazing process.

对比例1Comparative Example 1

与实施例1的区别之处仅在于：Ce(NO₃)₃•6H₂O替换为La(NO₃)₃•6H₂O，终产品为La@CFO。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, and the final product is La@CFO.

对比例2Comparative Example 2

与实施例1的区别之处仅在于：Ce(NO₃)₃•6H₂O替换为Y(NO₃)₃•6H₂O，终产品为Y@CFO。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, and the final product is Y@CFO.

对比例3Comparative Example 3

与实施例1的区别之处仅在于：改性纳米稀土氧化物替换为Ce(NO₃)₃•6H₂O，终产品为含铈保水添加剂。The only difference from Example 1 is that the modified nano rare earth oxide is replaced by Ce(NO ₃ ) ₃ •6H ₂ O, and the final product is a cerium-containing water-retaining additive.

将实施例1与对比例1-3得到的产品放入球磨机中，通过球磨工艺使材料粒度稳定在1μm左右，再将球磨后的粉体材料与釉料其他组分进行混合，再通过施釉过程将稀土功能材料负载到陶瓷上，通过1200℃高温烧制后得到稀土保水质陶瓷杯。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.

釉料组分如下：石英20份，云母20份，白云石20份，高岭土20份，滑石10份，碳酸钡10份，稀土保水釉料添加剂5份，水100份。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.

不同陶瓷杯中盛装水的化学需氧量（COD）测定：Determination of Chemical Oxygen Demand (COD) of Water in Different Ceramic Cups:

准备普通釉料陶瓷杯、Ce@CFO陶瓷杯、La@CFO陶瓷杯、Y@CFO陶瓷杯与含铈保水添加剂陶瓷杯各3个，作为每组三次平行试验，通过向杯中分别加入300 mL去离子水，然后在加入水0 min后和1 h后使用化学需氧量测量仪测试水中COD指标，结果如图2所示。Three ceramic cups with ordinary 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 the addition of water. The results are shown in Figure 2.

从图2中可以看出在加入水0 min后5组陶瓷杯中水质COD指标相差不大，代表了所加入的去离子水水质正常，而在静置1 h后，空白对照组普通釉面陶瓷杯中水质COD指标明显上升，达到了6.1 mg/L，而Ce@CFO陶瓷杯中水质COD却从4.2 mg/L下降到了2.3 mg/L，这代表了陶瓷杯釉面中的Ce@CFO材料能够对水质起到净化作用，保持盛装水不会变质，同时La@CFO陶瓷杯中COD指标也有所下降，但效果大不如Ce@CFO材料。As can be seen from Figure 2, the COD index of the water quality in the five groups of ceramic cups was not much different 0 min after adding water, which means that the quality of the added deionized water was 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.

从图3中能够看出以两种不同的含铈化合物为原料所制备的稀土釉料对水质的影响情况，在两种陶瓷杯加入去离子水1 h后，采用Ce(NO₃)₃•6H₂O为原料的陶瓷杯中COD指标从4.1 mg/L下降到了3.3 mg/L，证明该陶瓷杯对水质能够起到净化作用，但以ACO为原料的陶瓷杯中水质COD却从4.2 mg/L下降到了2.3 mg/L，相比于采用Ce(NO₃)₃•6H₂O为原料的陶瓷杯净化效果仍有较大优势。Figure 3 shows the influence of rare earth glazes prepared with two different cerium-containing compounds as raw materials on water quality. After deionized water was added to the two ceramic cups for 1 hour, the COD index in the ceramic cup using Ce(NO ₃ ) ₃ •6H ₂ O as raw material dropped from 4.1 mg/L to 3.3 mg/L, proving that the ceramic cup can purify the water quality. However, the COD in the ceramic cup using ACO as raw material dropped from 4.2 mg/L to 2.3 mg/L, which still has a significant advantage in purification effect compared with the ceramic cup using Ce(NO ₃ ) ₃ •6H ₂ O as raw material.

以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。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.

1. The utility model provides a water purification cerium-containing modified rare earth water retention glaze which characterized in that: the glaze is prepared from 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 talcum, 8-10 parts of barium carbonate, 5-10 parts of rare earth water-retention glaze additive and 80-100 parts of deionized water;

The rare earth water-retention 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, magnetically stirring at room temperature, then reacting under heating, drying and calcining after the reaction is finished to obtain the purified water cerium-containing modified rare earth water-retaining glaze additive.

2. The purified water cerium-containing modified rare earth water-retaining glaze according to claim 1, wherein: the time of the magnetic stirring step is 10-30 minutes; the temperature of the reaction step is 60-90 ℃ and the time is 4-7 hours; the temperature of the calcination step is 500-1200 ℃.

3. The purified water cerium-containing modified rare earth water-retaining glaze according to claim 1, wherein: the mass ratio of the urea, the cobalt nitrate, the ferric nitrate, the modified nano rare earth oxide and the deionized water is 1:1-2:1-3:1-6:10-20.

4. The purified water cerium-containing modified rare earth water-retaining glaze according to claim 1, wherein: the modified nano rare earth oxide is prepared by a method comprising the following steps:

(1) Dissolving NaOH in absolute ethyl alcohol to obtain NaOH-ethanol solution;

(2) Ce (NO ₃)₃•6H₂ O in absolute ethanol to give Ce (NO ₃)₃•6H₂ O-ethanol solution;

(3) Slowly pouring the NaOH-ethanol solution into the Ce (NO ₃)₃•6H₂ O-ethanol solution, continuously stirring until yellow flocculent precipitate appears, and then centrifugally separating the precipitate;

(4) Dissolving Al ₂O₃ in absolute ethyl alcohol to obtain precipitate, reacting at high temperature, cooling, washing to neutrality, stoving and grinding to obtain the modified nanometer RE oxide.

5. The purified water cerium-containing modified rare earth water-retaining glaze according to claim 4, wherein: the concentration of the NaOH-ethanol solution in the step (1) is 1-1.2 mol/L; the concentration of Ce (NO ₃)₃•6H₂ O-ethanol solution in the step (1) is 1-1.5 mol/L.

6. The purified water cerium-containing modified rare earth water-retaining glaze according to claim 4, wherein: the volume of the NaOH-ethanol solution in the step (3) is the same as that of the Ce (NO ₃)₃•6H₂ O-ethanol solution), and the solid-liquid ratio of the Al ₂O₃ to the absolute ethyl alcohol in the step (4) is 1g:8-10 mL.

7. The purified water cerium-containing modified rare earth water-retaining glaze according to claim 4, wherein: the temperature of the reaction step in the step (4) is 180-220 ℃ and the time is 5-6 hours; the temperature of the drying step in the step (4) is 80-100 ℃ and the time is 10-12 hours.

8. The method for preparing the purified water cerium-containing modified rare earth water-retaining glaze according to any one of claims 1 to 7, which is characterized in that: the method comprises the following steps: ball milling the purified water cerium-containing 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, talcum, barium carbonate and water to obtain the glaze.

9. The method for preparing the purified water cerium-containing modified rare earth water-retaining glaze according to claim 8, wherein the method comprises the following steps: the particle size of the rare earth additive powder is 500-1000 nm.

• 2024
  • 2024-08-14 CN CN202411110418.8A patent/CN118637829B/en active Active

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