阅读说明：本技术 一种圆珠干粒及其制备方法 (Dry bead granules and preparation method thereof ) 是由 黄春林 仝松贞 徐雪英 朱光耀 陈育昆 谢怡伟 宁毓胜 傅建涛 简润桐 叶德林 于 2021-10-22 设计创作，主要内容包括：本发明涉及一种圆珠干粒及其制备方法,圆珠干粒的制备方法包括以下步骤：将用于制备圆珠干粒的各原料混合,并进行烧成,制得烧成品；将烧成品粹冷,破碎,制得干粒半成品；将干粒半成品在温度为850℃～950℃的条件下进行圆珠化处理,制得圆珠干粒。该圆珠干粒的制备方法能够获得表面圆润,手感丝滑细腻的圆珠干粒,且能够有效地提高相应陶瓷制品的耐污染性能。(The invention relates to a dried round bead granule and a preparation method thereof, wherein the preparation method of the dried round bead granule comprises the following steps: mixing the raw materials for preparing the dry beads, and sintering to obtain a sintered product; crushing the fired product, and crushing to obtain a dried particle semi-finished product; and (3) carrying out ball balling treatment on the semi-finished product of the dried granules at the temperature of 850-950 ℃ to obtain the ball dried granules. The preparation method of the dry round bead particles can obtain the dry round bead particles with round and smooth surfaces and silky and exquisite handfeel, and can effectively improve the pollution resistance of the corresponding ceramic product.)

1. The preparation method of the dried round bead particles is characterized by comprising the following steps:

(1) mixing the raw materials for preparing the dry beads, and sintering to obtain a sintered product;

(2) crushing and cooling the fired product to obtain a dried particle semi-finished product;

(3) and (3) carrying out ball balling treatment on the semi-finished product of the dried granules at the temperature of 850-950 ℃ to obtain the ball dried granules.

2. The method according to claim 1, wherein the raw materials for preparing the dry beads comprise: 30-45 parts of potassium feldspar, 5-15 parts of albite, 6-10 parts of kaolin, 10-20 parts of barium carbonate, 3-8 parts of wollastonite, 3-10 parts of zinc oxide, 4-10 parts of strontium carbonate, 7-13 parts of calcite, 1-4 parts of quartz and 1-5 parts of aluminum oxide.

3. The method according to claim 2, wherein the potassium feldspar comprises the chemical composition of K₂The mass percentage of O is more than 9.0 percent;

in the chemical components of albite, Na₂The mass percentage of O is more than 8.5 percent;

among chemical components of the kaolin, Al₂O₃The mass percentage of the component (A) is more than 35%;

in the chemical components of the calcite, the mass percentage of CaO is 52-56%;

the wollastonite comprises the following chemical components: SiO 2₂ 48％～53％，Al₂O₃ 0.1％～1％，CaO 40％～45％；

Among the chemical compositions of the quartz, SiO₂The mass percentage content of the compound is more than or equal to 99 percent.

4. The method according to claim 2, wherein the mass ratio of barium carbonate, zinc oxide and strontium carbonate is (10-18): 4-8): 6-8.

5. The preparation method according to claim 2, wherein the main chemical components of the dry beads comprise, in mass percent: SiO 2₂ 50％～55％、Al₂O₃16 to 19 percent of CaO, 3 to 5 percent of CaO, 9 to 12 percent of BaO, 3.5 to 5 percent of SrO, 4.5 to 6.5 percent of KNaO and 3.6 to 4 percent of ZnO.

6. The method according to claim 2, wherein in the step of spheronizing, the semi-finished dry pellets are allowed to pass through a heating zone of a high temperature melting furnace in a free-fall manner, the temperature of the heating zone being 900 ℃ ± 5 ℃.

7. The production method according to any one of claims 1 to 6, wherein in the step (2), the firing is performed by the following method;

at a first time t₁Internal heating to 300 deg.C, and then at a second time t₂Internally heating to 1100 deg.C, and then making third time t₃Internally heating to 1450 deg.C, and keeping the temperature at 1450 deg.C for a fourth time t₄Then cooling to 300-400 ℃; t is t₁Is 8min to 12min, t₂Is 28min to 32min, t₃Is 18min to 22min, t₄Is 10min to 15 min.

8. The method according to any one of claims 1 to 6, wherein the raw materials for preparing the dried pellets are mixed and stirred to obtain a mixed material, and the mixed material is conveyed to a frit furnace at a speed of 15 to 18kg/min for the firing.

9. The method according to any one of claims 1 to 6, wherein the step of crushing the fired product to obtain a half-finished dried pellet comprises the steps of:

introducing the fired product into water with the temperature of below 50 ℃ for cooling treatment to obtain a cooled product;

and crushing the crushed and cooled product to form a dried particle semi-finished product, and sieving the dried particle semi-finished product by a 250-300-mesh sieve.

10. A dry pellet of beads produced by the production method according to any one of claims 1 to 9.

Technical Field

The invention relates to the technical field of ceramics, in particular to a ball dry particle and a preparation method thereof.

Background

With the iterative upgrade of the ceramic surface auxiliary material, under the assistance of the ceramic auxiliary material, the ceramic product is more and more diversified, and particularly, the decoration performance and the physical application performance of the product are greatly improved along with the application of dry particles in recent years. At present, the types of dry granules are also more, and the dry granules are mainly classified into full-polished dry granules, candy dry granules, matte dry granules, metal dry granules, diamond dry granules and the like. The dry grain material is fired before being applied to ceramic products, wherein organic matters and decomposable substances are fully decomposed under the high-temperature firing, so that after the dry grain material is applied to the ceramic tile, the dry grain material is not reduced when being fired with the ceramic tile, the surface of the ceramic tile using the dry grain material has high density, low porosity and no inclusion part, and the prepared ceramic tile product has the advantages of pollution resistance, wear resistance, corrosion resistance, high thermal stability and the like. However, the related ceramic products made of dry particles generally have the problems of rough hand feeling, easy dirt storage and dirt holding, and the like, and are limited in application.

Disclosure of Invention

Based on this, there is a need for a dry bead pellet and a method for preparing the same. The preparation method of the dry round bead particles can obtain the dry round bead particles with round and smooth surfaces and silky and exquisite handfeel, and can effectively improve the pollution resistance of the corresponding ceramic product.

A preparation method of the dried round bead particles comprises the following steps:

mixing the raw materials for preparing the dry beads, and sintering to obtain a sintered product;

crushing and cooling the fired product to obtain a dried particle semi-finished product;

and (3) carrying out ball balling treatment on the semi-finished product of the dried granules at the temperature of 850-950 ℃ to obtain the ball dried granules.

In some embodiments, the raw materials for preparing the dry beads comprise: 30-45 parts of potassium feldspar, 5-15 parts of albite, 6-10 parts of kaolin, 10-20 parts of barium carbonate, 3-8 parts of wollastonite, 3-10 parts of zinc oxide, 4-10 parts of strontium carbonate, 7-13 parts of calcite, 1-4 parts of quartz and 1-5 parts of aluminum oxide.

In some of the embodiments, the potassium feldspar comprises a chemical composition of K₂The mass percentage of O is more than 9.0 percent;

in the chemical components of albite, Na₂The mass percentage of O is more than 8.5 percent;

among chemical components of the kaolin, Al₂O₃The mass percentage of the component (A) is more than 35%;

in the chemical components of the calcite, the mass percentage of CaO is 52-56%;

the wollastonite comprises the following chemical components: SiO 2₂ 48％～53％，Al₂O₃ 0.1％～1％，CaO 40％～45％；

Among the chemical compositions of the quartz, SiO₂The mass percentage content of the compound is more than or equal to 99 percent.

In some embodiments, the mass ratio of barium carbonate, zinc oxide and strontium carbonate is (10-18): 4-8): 6-8.

In some embodiments, the bead dry granules comprise the following main chemical components in percentage by mass: SiO 2₂ 50％～55％、Al₂O₃16 to 19 percent of CaO, 3 to 5 percent of CaO, 9 to 12 percent of BaO, 3.5 to 5 percent of SrO, 4.5 to 6.5 percent of KNaO and 3.6 to 4 percent of ZnO.

In some of these embodiments, in the step of spheronization, the semifinished dry granules are passed in free fall through a heating zone of a high-temperature furnace, the temperature of said heating zone being 900 ℃ ± 5 ℃.

In some embodiments, in the step of firing, firing is performed by the following method;

at a first time t₁Internal heating to 300 deg.C, and then at a second time t₂Internally heating to 1100 deg.C, and then making third time t₃Internally heating to 1450 deg.C, and keeping the temperature at 1450 deg.C for a fourth time t₄Then cooling to 300-400 ℃; t is t₁Is 8min to 12min, t₂Is 28min to 32min, t₃Is 18min to 22min, t₄Is 10min to 15 min.

In some embodiments, the raw materials for preparing the dried round bead particles are mixed and stirred to obtain a mixture, and the mixture is conveyed to a frit furnace at a speed of 15-18 kg/min for sintering.

In some embodiments, the step of crushing the fired product to obtain the half-finished dried pellets comprises the steps of:

introducing the fired product into water with the temperature of below 50 ℃ for cooling treatment to obtain a cooled product;

and crushing the crushed and cooled product to form a dried particle semi-finished product, and sieving the dried particle semi-finished product by a 250-300-mesh sieve.

A dry bead granule is prepared by the above preparation method.

After the corresponding semi-finished product of the dry bead is prepared by the preparation method of the dry bead, the dry bead is treated in a beading way at a specific temperature, so that irregular prismatic structures on the surface of the dry bead are eliminated, and further the dry bead with the spherical structure, which has a round surface and a better hand feeling, can be obtained. And the ceramic product prepared from the dried round bead particles also has better skid resistance.

Drawings

FIG. 1 is an enlarged view of the dried beads of example 3;

FIG. 2 is an enlarged view of the dried beads of comparative example 1;

FIG. 3 is an enlarged view of the dried beads of comparative example 2;

FIG. 4 is an enlarged view of the dried beads of comparative example 3.

Detailed Description

In order that the invention may be more fully understood, a more particular description of the invention will now be rendered by reference to specific embodiments thereof that are illustrated in the appended drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.

One embodiment of the invention provides a preparation method of dried round bead granules, which comprises the following steps:

s101: mixing the raw materials for preparing the dry beads, and sintering to obtain a sintered product.

In some embodiments, the raw materials for preparing the dry beads comprise: 30-45 parts of potassium feldspar, 5-15 parts of albite, 6-10 parts of kaolin, 10-20 parts of barium carbonate, 3-8 parts of wollastonite, 3-10 parts of zinc oxide, 4-10 parts of strontium carbonate, 7-13 parts of calcite, 1-4 parts of quartz and 1-5 parts of aluminum oxide.

In some embodiments, the raw materials for preparing the dry beads comprise: 30-40 parts of potassium feldspar, 6-15 parts of albite, 7-9 parts of kaolin, 10-18 parts of barium carbonate, 3-8 parts of wollastonite, 3-8 parts of zinc oxide, 6-8 parts of strontium carbonate, 7-11 parts of calcite, 1.5-2.5 parts of quartz and 3-4 parts of alumina.

In some embodiments, the raw materials for preparing the dry beads comprise: the potassium feldspar comprises 35 parts of potassium feldspar, 8 parts of albite, 8 parts of kaolin, 15 parts of barium carbonate, 6 parts of wollastonite, 5 parts of zinc oxide, 6 parts of strontium carbonate, 11 parts of calcite, 2 parts of quartz and 4 parts of aluminum oxide.

In some embodiments, the raw materials for preparing the dry beads comprise: the potash feldspar comprises 40 parts of potassium feldspar, 6 parts of albite, 8 parts of kaolin, 18 parts of barium carbonate, 3 parts of wollastonite, 4 parts of zinc oxide, 8 parts of strontium carbonate, 7 parts of calcite, 2 parts of quartz and 4 parts of aluminum oxide.

In some embodiments, the raw materials for preparing the dry beads comprise: 30 parts of potassium feldspar, 15 parts of albite, 8 parts of kaolin, 10 parts of barium carbonate, 8 parts of wollastonite, 8 parts of zinc oxide, 8 parts of strontium carbonate, 8 parts of calcite, 2 parts of quartz and 3 parts of aluminum oxide.

By adopting the raw material combination and controlling the proportion of each oxide in a common-phase system, the superfine crystal of the divalent oxide is formed, so that the dry beads have silky handfeel and transparency, the handfeel and quality of the corresponding ceramic product can be improved, and the corresponding ceramic product has excellent performances of wear resistance, pollution resistance, skid resistance, acid and alkali resistance and the like. In addition, the formula combination can ensure that the dry particle material has a wider sintering temperature range on the surface of the ceramic tile, and can show stable matt glossiness and silky delicate touch under different ceramic tile sintering temperatures and different overglaze foundations.

In some embodiments, K in the chemical composition of potassium feldspar₂The mass percentage of O is more than 9.0 percent; further, K in the chemical components of the potassium feldspar₂The mass percentage of O is 9.0-10.5%; in some embodiments, the chemical composition of albite is Na₂The mass percentage of O is more than 7.5 percent; further, Na is contained in the chemical components of albite₂The mass percentage of O is more than 8.5 percent; further, Na is contained in the chemical components of albite₂The mass percentage of O is 7.5-9.0%; sufficient K₂O and Na₂The content of O can ensure the stability of the alkali metal components in the formula, and can promote the dry particle formula to be fully melted at a preset temperature to form a sufficient liquid phase.

In some embodiments, the chemical composition of the kaolin is Al₂O₃The mass percentage of the component (A) is more than 35%; further, among chemical components of kaolin, Al₂O₃35 to 40 percent; the kaolin is Al₂O₃Main source of (1), Al₂O₃When the content is too small, the amount of addition needs to be increased, which results in SiO₂The content of (A) is increased, so that the silicon-aluminum ratio is higher, and the glossiness of the prepared round beads is higher.

In some embodiments, the mass ratio of barium carbonate, zinc oxide and strontium carbonate is (10-18): (4-8): (6-8). In some embodiments, the barium carbonate is over 99% pure; in some embodiments, the zinc oxide is over 99.9% pure; in some embodiments, the strontium carbonate is more than 99.5% pure. The contents of barium carbonate, zinc oxide and strontium carbonate need to be controlled within a certain range, if the contents are too high, the divalent ions are easy to be too clear, excessive barium-zinc-strontium crystals can be generated, and the transparency of dry particles is low; if the content is too low, Al is contained in the alloy₂O₃And SiO₂Belongs to a substance with larger high-temperature viscosity, and dry grains can be dry and rough if enough flux is not used for melting.

In some embodiments, the wollastonite is convertedThe chemical components comprise: SiO 2₂ 48％～53％，Al₂O₃0.1 to 1 percent of CaO and 40 to 45 percent of CaO; in some embodiments, the wollastonite comprises a chemical composition of SiO₂48 to 53 percent of Al₂O₃0.1 to 1 percent of CaO, 40 to 45 percent of CaO, 1 to 4 percent of MgO and 2.5 to 4 percent of impurities. In some embodiments, the chemical composition of the calcite includes greater than 50% CaO by weight; further, the mass percentage content of CaO is 52-56%; further, the weight percentage content of CaO is 52 percent to 54 percent. Wollastonite and calcite are main sources of CaO, if the content of the wollastonite and the calcite is low, the high-temperature viscosity of a dry particle in a molten state is large, the hand feeling after molding is rough, and if the content of the wollastonite and the calcite is high, the anorthite is separated out too much, the dry particle transparency is influenced, and the color development of a product is not transparent enough.

In some embodiments, the chemical composition of the quartz is SiO₂The mass percentage content of the compound is more than or equal to 99 percent; further, SiO₂The mass percentage of the component (A) is 99.5 percent, and the rest is trace impurities. Quartz and Al₂O₃To complement the network architecture, the tested content is suitable in this range.

In some embodiments, the bead dry particles comprise the following main chemical components: SiO 2₂ 50％～55％，Al₂O₃16 to 19 percent of CaO, 3 to 5 percent of CaO, 9 to 12 percent of BaO, 3.5 to 5 percent of SrO, 4.5 to 6.5 percent of KNaO and 3.6 to 4 percent of ZnO; furthermore, CaO is 4.3% -4.7%, BaO is 10.6% -11%, SrO is 4% -4.4%, and ZnO is 3.6% -4%; further, CaO was 4.5%, BaO was 10.8%, SrO was 4.2%, and ZnO was 3.8%.

In some embodiments, the particle fineness of each raw material used to prepare the dry beads is required to be below 300 mesh; further, the particle size is 200 mesh or less, so that liquefaction and reaction during firing are facilitated.

In some embodiments, the moisture content of each raw material for preparing the dry pellets of the round beads is controlled below 1%, and the lower the moisture content is, the more uniform the mixing is in the mixing stage, and further, the energy consumption in the firing stage can be reduced.

In some embodiments, in step S101, firing is performed by the following method;

at a first time t₁Internally heated to 295-305 ℃ and then heated for a second time t₂Internally heating to 1050-1150 deg.C, and third time t₃Internally heating to 1300-1500 ℃, and then preserving the heat for a fourth time t within the range of 1300-1500 DEG C₄Then cooling to 300-400 ℃; wherein, t₁Is 8min to 60min, t₂Is 28min to 60min, t₃Is 18min to 50min, t₄10 min-30 min;

further, at a first time t₁Internal heating to 300 deg.C, and then at a second time t₂Internally heating to 1100 deg.C, and then making third time t₃Internally heating to 1450 deg.C, and keeping the temperature at 1450 deg.C for a fourth time t₄Then cooling to 300-400 ℃; t is t₁Is 8min to 12min, t₂Is 28min to 32min, t₃Is 18min to 22min, t₄10 min-15 min; further, t₁Is 10min, t₂Is 30min, t₃Is 20min, t₄It is 10 min.

The firing step adopts a gradient temperature control program, and in the first stage, the temperature is raised to 295-305 ℃ within a specific time to ensure that structural water and adsorbed water in each material are fully discharged; in the second stage, the kaolin is heated to 1050-1150 ℃ in a specific time to decompose organic matters in the kaolin, and carbonate is decomposed to discharge CO under the fluxing of the monovalent oxide₂(ii) a The third stage is to reach 1300-1500 ℃ and keep the temperature t within the range of 1300-1500 DEG C₄So that the materials begin to melt, liquid phase begins to generate under the action of the flux, and oxides and SiO₂And Al₂O₃The feldspar crystals with proper proportion are formed, so that excellent hand feeling of the dry round bead particles is guaranteed, the prepared dry round bead particle material can be suitable for different firing temperatures and different glazes, and stable matte glossiness and silky fine touch can be presented at different tile firing temperatures and on the basis of different overglazes.

In addition, the inventor of the invention finds that the matte effect and the hand feeling of the fired dry beads are closely related to the firing temperature program, the setting of the firing temperature program needs to be adapted to the formula so as to form a proper eutectic phase, the crystalline phase with low refractive index is generated by utilizing the clear crystal of the divalent oxide so as to reduce the glossiness, and the gloss cannot fluctuate due to the fluctuation of the temperature after the ceramic tile is used for the ceramic tile, so that the ceramic tile has a large firing range.

In the present invention, it is understood that the mixture may be processed in a manner of keeping the mixture still and changing the temperature in the firing step, or the mixture may be moved to a region with a corresponding temperature in sequence, which is not particularly limited herein, and is understood to be within the protection scope of the present invention.

In some embodiments, in step S101, after mixing the raw materials for preparing the dried beads, stirring (preferably stirring for 20-40 min) to obtain a mixture, and conveying the mixture into a frit furnace at a speed of 15-18 kg/min for firing; further, a screw column is used for transportation. When the conveying amount is small, the efficiency is low, and when the conveying amount is large, insufficient melting is easy to generate, and the phenomenon of raw material inclusion exists, so that the product yield is influenced.

S102: crushing the fired product, and crushing to obtain a dried particle semi-finished product;

in some embodiments, in the cooling step of step S102, the fired product is introduced into water at a temperature of less than 50 ℃ to obtain a cooled product. The water with lower temperature is adopted, so that the crushing effect is better, and the subsequent crushing treatment is facilitated.

In some embodiments, in the crushing step of step S102, the crushed product is crushed to form a semi-finished dry pellet, and the semi-finished dry pellet is screened by a 250-300 mesh screen, so as to facilitate the subsequent steps.

S103: and (3) carrying out ball balling treatment on the semi-finished product of the dried granules at the temperature of 850-950 ℃, and sieving to obtain the dried ball granules.

The technicians of the invention find in the research that: at present, dry particles are manufactured by firing and then crushing, sharp edges and corners often exist on a microstructure, and further the problems of rough hand feeling, easy dirt storage and dirt holding and the like exist, so that the application is limited to a certain extent. Particularly, the matte tile products can achieve the matte effect only by requiring higher formula temperature of glaze combined with dry particles, so that the original form of the dry particles can be kept more complete, and the manufactured products are rough in touch and not fine and moist enough if the adopted dry particles are irregular in shape.

Based on this, the technical personnel of the invention design the preparation method of the dried round bead, firstly carry on the burning, smash and cool, break, make corresponding dried particle semifinished material, after carrying on the treatment of round bead under the condition of 850 ℃ -950 ℃, make the irregular prismatic structure on the surface of the dried particle disappear, and then can obtain the spherical structure dried round bead with round smooth surface, and process under this temperature, can improve the hand feeling and feel of the ceramic products that the dried round bead corresponds to, in order to obtain the products with silky and exquisite hand feeling. Further research shows that the temperature of the beading treatment has great influence on the treatment effect, when the temperature is lower, the softening degree of the dried particles is not enough, the edges of the prepared dried beads are not smooth enough, when the temperature is higher, the dried particles are easy to be agglomerated by over-firing, and the preferable beading treatment temperature is 850-950 ℃.

Further, the temperature of the beading treatment is preferably 860 to 930 ℃; further, the preferable temperature of the beading treatment is 880 to 920 ℃; further, the spheronization temperature is preferably 900 ℃. + -. 5 ℃ for the best technical effect.

In some embodiments, the temperature of the beading process is 870 ℃, 875 ℃, 880 ℃, 885 ℃, 890 ℃, 892 ℃, 894 ℃, 895 ℃, 896 ℃, 897 ℃, 898 ℃, 899 ℃, 900 ℃, 901 ℃, 902 ℃, 903 ℃, 904 ℃, 905 ℃, 906 ℃, 907 ℃, 908 ℃, 909 ℃, 910 ℃, 915 ℃, 920 ℃, 925 ℃, 930 ℃, 935 ℃ or 940 ℃.

In the invention, the term "spheroidizing" refers to heating the semi-finished dry pellets in a high temperature environment, eliminating the edges and corners by using high temperature, and improving the roundness of the dry pellets, and specifically, a heating device commonly used in the art can be used, and only the corresponding temperature is required to be reached.

In some embodiments, in step S103, the dry pellet semi-finished product is passed through a heating zone of a high temperature furnace in a free-fall manner. The semi-finished product passes through a heating zone of a high-temperature smelting furnace in a free falling mode, and the self weight of the semi-finished product is utilized, so that the roundness of the dry beads can be effectively improved, and the deformation caused by the heat treatment of the dry bead semi-finished product in a specific container is avoided.

In some embodiments, the high temperature melting furnace comprises an inlet, an outlet and a heating zone, the inlet and the outlet are respectively arranged at two ends of the heating zone, wherein the inlet is arranged at the upper side of the high temperature melting furnace, and the outlet is arranged at the lower side of the high temperature melting furnace, so that after the semi-finished product enters the high temperature melting furnace through the inlet, the semi-finished product moves through the heating zone through free falling bodies and then is discharged from the outlet.

In some embodiments, the cyclone is used to spray the semi-finished product of the dried beads into the high-temperature melting furnace, so as to improve the dispersibility of the semi-finished product in the high-temperature melting furnace and avoid the agglomeration phenomenon.

In some embodiments, step S103 further includes a step of sieving after the beading treatment; further, the ball is treated and then is screened by a screen of 250-300 meshes to obtain the dry ball with the required particle size.

The invention provides a dried bead particle, which is prepared by the preparation method. Compared with the dried round bead prepared by the traditional method, the dried round bead has higher roundness and delicate hand feeling, and effectively solves the problems of rough hand feeling, easy dirt storage and dirt holding and the like of the traditional product. The dry round bead particles have matte luster, excellent wear resistance and anti-skid performance, and have the anti-skid function while realizing fine touch feeling.

The present invention will be described below by way of specific examples, which are intended to be illustrative only and should not be construed as limiting the present invention.

Example 1

The raw material formula of the embodiment is as follows: 35 parts of potassium feldspar, 8 parts of albite, 8 parts of kaolin, 15 parts of barium carbonate, 6 parts of wollastonite, 5 parts of zinc oxide, 6 parts of strontium carbonate, 11 parts of calcite, 2 parts of quartz and 4 parts of aluminum oxide;

the preparation method comprises the following steps:

(1) mixing the raw materials, and accurately conveying the mixed materials into a mixer by adopting a belt scale for stirring, wherein the capacity of the mixer is 2 tons, and the stirring time is 30 minutes.

(2) Gradually conveying the mixed material with the weight of 15-18 kg per minute into a frit furnace by adopting a spiral column for sintering, and sintering according to the following method:

heating to 300 ℃ for 10min, heating to 1100 ℃ for 30min, heating to 1450 ℃ for 20min, preserving heat for 10min at 1450 ℃, and cooling to 300-400 ℃;

(3) and (3) allowing the high-temperature liquid sintered material after the sintering treatment to flow into a cold water pool below the frit furnace from the gate to perform crushing and cooling, controlling the water temperature of the cold water pool to be below 50 ℃, and performing crushing and cooling to obtain a glass-state dry-particle semi-finished product.

(4) Controlling the moisture content of the dry particle semi-finished product to be below 1%, conveying the dry particle semi-finished product into a roll crusher, crushing, sieving the crushed fine powder with a 250-300 mesh screen, taking the dry particle fine powder within the range of 250-300 meshes, crushing the rest dry particle fine powder with the particle size larger than the required particle size again until the qualified particle size is reached, and firing and melting the dry particle raw material which is smaller than the required particle size.

(5) And (4) spraying the fine powder dry particles passing through the 250-300 meshes in the step (4) into the high-temperature melting furnace from the inlet of the high-temperature melting furnace through a cyclone machine, enabling the fine powder dry particles to pass through a heating area in a free falling mode, carrying out ball treatment, wherein the temperature of the heating area is 900 ℃, then collecting the fine powder dry particles from an outlet, and passing through a screen mesh of 250-300 meshes to obtain a finished product of the ball dry particles.

Example 2

The raw material formula of the embodiment is as follows: 40 parts of potassium feldspar, 6 parts of albite, 8 parts of kaolin, 18 parts of barium carbonate, 3 parts of wollastonite, 4 parts of zinc oxide, 8 parts of strontium carbonate, 7 parts of calcite, 2 parts of quartz and 4 parts of aluminum oxide.

The preparation method comprises the following steps:

(1) mixing the raw materials, accurately conveying the mixed materials into a mixer by a belt scale for stirring, wherein the capacity of the mixer is 2 tons, and the stirring time is 30 minutes.

(2) Gradually conveying the mixed material with the weight of 15-18 kg per minute into a frit furnace by adopting a spiral column for sintering, and sintering according to the following method:

heating to 300 ℃ for 10min, heating to 1100 ℃ for 30min, heating to 1450 ℃ for 20min, preserving heat for 10min at 1450 ℃, and cooling to 300-400 ℃;

(3) and (3) allowing the high-temperature liquid sintered material after the sintering treatment to flow into a cold water pool below the frit furnace from the gate to perform crushing and cooling, controlling the water temperature of the cold water pool to be below 50 ℃, and performing crushing and cooling to obtain a glass-state dry-particle semi-finished product.

(4) Controlling the moisture content of the dry particle semi-finished product to be below 1%, conveying the dry particle semi-finished product into a roll crusher, crushing, sieving the crushed fine powder with a 250-300 mesh screen, taking the dry particle fine powder within the range of 250-300 meshes, crushing the rest dry particle fine powder with the particle size larger than the required particle size again until the qualified particle size is reached, and firing and melting the dry particle raw material which is smaller than the required particle size.

(5) And (4) spraying the fine powder dry particles passing through the 250-300 meshes in the step (4) into the high-temperature melting furnace from the inlet of the high-temperature melting furnace through a cyclone machine, enabling the fine powder dry particles to pass through a heating area in a free falling mode, carrying out ball treatment, wherein the temperature of the heating area is 900 ℃, then collecting the fine powder dry particles from an outlet, and passing through a screen mesh of 250-300 meshes to obtain a finished product of the ball dry particles.

Example 3

The raw material formula of the embodiment is as follows: 30 parts of potassium feldspar, 15 parts of albite, 8 parts of kaolin, 10 parts of barium carbonate, 8 parts of wollastonite, 8 parts of zinc oxide, 8 parts of strontium carbonate, 8 parts of calcite, 2 parts of quartz and 3 parts of aluminum oxide.

The preparation method comprises the following steps:

(1) mixing the raw materials, accurately conveying the mixed materials into a mixer by a belt scale for stirring, wherein the capacity of the mixer is 2 tons, and the stirring time is 30 minutes.

(2) Gradually conveying the mixed material with the weight of 15-18 kg per minute into a frit furnace by adopting a spiral column for sintering, and sintering according to the following method:

heating to 300 ℃ for 10min, heating to 1100 ℃ for 30min, heating to 1450 ℃ for 20min, preserving heat for 10min at 1450 ℃, and cooling to 300-400 ℃;

(3) and (3) allowing the high-temperature liquid sintered material after the sintering treatment to flow into a cold water pool below the frit furnace from the gate to perform crushing and cooling, controlling the water temperature of the cold water pool to be below 50 ℃, and performing crushing and cooling to obtain a glass-state dry-particle semi-finished product.

(4) Controlling the moisture content of the dry particle semi-finished product to be below 1%, conveying the dry particle semi-finished product into a roll crusher, crushing, sieving the crushed fine powder with a 250-300 mesh screen, taking the dry particle fine powder within the range of 250-300 meshes, crushing the rest dry particle fine powder with the particle size larger than the required particle size again until the qualified particle size is reached, and firing and melting the dry particle raw material which is smaller than the required particle size.

(5) And (4) spraying the fine powder dry particles passing through the 250-300 meshes in the step (4) into the high-temperature melting furnace from the inlet of the high-temperature melting furnace through a cyclone machine, enabling the fine powder dry particles to pass through a heating area in a free falling mode, carrying out ball treatment, wherein the temperature of the heating area is 900 ℃, then collecting the fine powder dry particles from an outlet, and passing through a screen mesh of 250-300 meshes to obtain a finished product of the ball dry particles.

Example 4

Essentially the same as example 3, except that the temperature of the heated zone of the spheronization process was 950 ℃, specifically:

the raw material formula of the embodiment is as follows: 30 parts of potassium feldspar, 15 parts of albite, 8 parts of kaolin, 10 parts of barium carbonate, 8 parts of wollastonite, 8 parts of zinc oxide, 8 parts of strontium carbonate, 8 parts of calcite, 2 parts of quartz and 3 parts of aluminum oxide.

The preparation method comprises the following steps:

(1) mixing the raw materials, accurately conveying the mixed materials into a mixer by a belt scale for stirring, wherein the capacity of the mixer is 2 tons, and the stirring time is 30 minutes.

(2) Gradually conveying the mixed material with the weight of 15-18 kg per minute into a frit furnace by adopting a spiral column for sintering, and sintering according to the following method:

heating to 300 ℃ for 10min, heating to 1100 ℃ for 30min, heating to 1450 ℃ for 20min, preserving heat for 10min at 1450 ℃, and cooling to 300-400 ℃;

(3) and (3) allowing the high-temperature liquid sintered material after the sintering treatment to flow into a cold water pool below the frit furnace from the gate to perform crushing and cooling, controlling the water temperature of the cold water pool to be below 50 ℃, and performing crushing and cooling to obtain a glass-state dry-particle semi-finished product.

(4) Controlling the moisture content of the dry particle semi-finished product to be below 1%, conveying the dry particle semi-finished product into a roll crusher, crushing, sieving the crushed fine powder with a 250-300 mesh screen, taking the dry particle fine powder within the range of 250-300 meshes, crushing the rest dry particle fine powder with the particle size larger than the required particle size again until the qualified particle size is reached, and firing and melting the dry particle raw material which is smaller than the required particle size.

(5) And (4) spraying the fine powder dry particles passing through the 250-300 meshes in the step (4) into the high-temperature smelting furnace from the inlet of the high-temperature smelting furnace through a cyclone machine, enabling the fine powder dry particles to pass through a heating area in a free falling mode, carrying out ball treatment, wherein the temperature of the heating area is 950 ℃, then collecting the fine powder dry particles from an outlet, and passing through a screen mesh of 250-300 meshes to obtain a finished product of the ball dry particles.

Example 5

Essentially the same as example 3, except that the temperature of the heated zone of the spheronization process was 850 ℃, specifically:

the raw material formula of the embodiment is as follows: 30 parts of potassium feldspar, 15 parts of albite, 8 parts of kaolin, 10 parts of barium carbonate, 8 parts of wollastonite, 8 parts of zinc oxide, 8 parts of strontium carbonate, 8 parts of calcite, 2 parts of quartz and 3 parts of aluminum oxide. The preparation method comprises the following steps:

(1) mixing the raw materials, accurately conveying the mixed materials into a mixer by a belt scale for stirring, wherein the capacity of the mixer is 2 tons, and the stirring time is 30 minutes.

(2) Gradually conveying the mixed material with the weight of 15-18 kg per minute into a frit furnace by adopting a spiral column for sintering, and sintering according to the following method:

heating to 300 ℃ for 10min, heating to 1100 ℃ for 30min, heating to 1450 ℃ for 20min, preserving heat for 10min at 1450 ℃, and cooling to 300-400 ℃;

(3) and (3) allowing the high-temperature liquid sintered material after the sintering treatment to flow into a cold water pool below the frit furnace from the gate to perform crushing and cooling, controlling the water temperature of the cold water pool to be below 50 ℃, and performing crushing and cooling to obtain a glass-state dry-particle semi-finished product.

(4) Controlling the moisture content of the dry particle semi-finished product to be below 1%, conveying the dry particle semi-finished product into a roll crusher, crushing, sieving the crushed fine powder with a 250-300 mesh screen, taking the dry particle fine powder within the range of 250-300 meshes, crushing the rest dry particle fine powder with the particle size larger than the required particle size again until the qualified particle size is reached, and firing and melting the dry particle raw material which is smaller than the required particle size.

(5) And (4) spraying the fine powder dry particles passing through the 250-300 meshes in the step (4) into the high-temperature melting furnace from the inlet of the high-temperature melting furnace through a cyclone machine, enabling the fine powder dry particles to pass through a heating area in a free falling mode, carrying out ball treatment, wherein the temperature of the heating area is 850 ℃, then collecting the fine powder dry particles from an outlet, and sieving the fine powder dry particles through a sieve of 250-300 meshes to obtain a finished product of the ball dry particles.

Example 6

The same as example 3, except that the following formulation was used: 28 parts of potassium feldspar, 20 parts of albite, 8 parts of kaolin, 5 parts of barium carbonate, 10 parts of zinc oxide, 11 parts of strontium carbonate, 6 parts of calcite and 2 parts of quartz.

(1) Mixing the raw materials, accurately conveying the mixed materials into a mixer by a belt scale for stirring, wherein the capacity of the mixer is 2 tons, and the stirring time is 30 minutes.

(2) Gradually conveying the mixed material with the weight of 15-18 kg per minute into a frit furnace by adopting a spiral column for sintering, and sintering according to the following method:

heating to 300 ℃ for 10min, heating to 1100 ℃ for 30min, heating to 1450 ℃ for 20min, preserving heat for 10min at 1450 ℃, and cooling to 300-400 ℃;

(3) and (3) allowing the high-temperature liquid sintered material after the sintering treatment to flow into a cold water pool below the frit furnace from the gate to perform crushing and cooling, controlling the water temperature of the cold water pool to be below 50 ℃, and performing crushing and cooling to obtain a glass-state dry-particle semi-finished product.

(4) Controlling the moisture content of the dry particle semi-finished product to be below 1%, conveying the dry particle semi-finished product into a roll crusher, crushing, sieving the crushed fine powder with a 250-300 mesh screen, taking the dry particle fine powder within the range of 250-300 meshes, crushing the rest dry particle fine powder with the particle size larger than the required particle size again until the qualified particle size is reached, and firing and melting the dry particle raw material which is smaller than the required particle size.

(5) And (4) spraying the fine powder dry particles passing through the 250-300 meshes in the step (4) into the high-temperature melting furnace from the inlet of the high-temperature melting furnace through a cyclone machine, enabling the fine powder dry particles to pass through a heating area in a free falling mode, carrying out ball treatment, wherein the temperature of the heating area is 900 ℃, then collecting the fine powder dry particles from an outlet, and passing through a screen mesh of 250-300 meshes to obtain a finished product of the ball dry particles.

Comparative example 1

Substantially the same as in example 3, except that the beading treatment was not performed, specifically:

the raw material formula of the comparative example is as follows: 30 parts of potassium feldspar, 15 parts of albite, 8 parts of kaolin, 10 parts of barium carbonate, 8 parts of wollastonite, 8 parts of zinc oxide, 8 parts of strontium carbonate, 8 parts of calcite, 2 parts of quartz and 3 parts of aluminum oxide.

The preparation method comprises the following steps:

(1) mixing the raw materials, accurately conveying the mixed materials into a mixer by a belt scale for stirring, wherein the capacity of the mixer is 2 tons, and the stirring time is 30 minutes.

(2) Gradually conveying the mixed material with the weight of 15-18 kg per minute into a frit furnace by adopting a spiral column for sintering, and sintering according to the following method:

heating to 300 ℃ for 10min, heating to 1100 ℃ for 30min, heating to 1450 ℃ for 20min, preserving heat for 10min at 1450 ℃, and cooling to 300-400 ℃;

(3) and (3) allowing the high-temperature liquid sintered material after the sintering treatment to flow into a cold water pool below the frit furnace from the gate to perform crushing and cooling, controlling the water temperature of the cold water pool to be below 50 ℃, and performing crushing and cooling to obtain a glass-state dry-particle semi-finished product.

(4) Controlling the moisture content of the dry semi-finished product to be below 1%, conveying the dry semi-finished product into a double-roller machine, crushing, sieving the crushed fine powder with a 250-300-mesh sieve, taking the dry fine powder within the range of 250-300 meshes, crushing the rest dry fine powder with the mesh number larger than the required mesh number again until the qualified mesh number is reached and the dry fine powder with the mesh number smaller than the required mesh number is used as a dry raw material to be sintered and melted, and sieving with a 250-300-mesh sieve to obtain the dry finished product.

Comparative example 2

The raw material formula of the comparative example is as follows: 30 parts of potassium feldspar, 15 parts of albite, 8 parts of kaolin, 10 parts of barium carbonate, 8 parts of wollastonite, 8 parts of zinc oxide, 8 parts of strontium carbonate, 8 parts of calcite, 2 parts of quartz and 3 parts of aluminum oxide.

The preparation method comprises the following steps:

(1) mixing the raw materials, accurately conveying the mixed materials into a mixer by a belt scale for stirring, wherein the capacity of the mixer is 2 tons, and the stirring time is 30 minutes.

(2) Gradually conveying the mixed material with the weight of 15-18 kg per minute into a frit furnace by adopting a spiral column for sintering, and sintering according to the following method:

heating to 300 ℃ for 10min, heating to 1100 ℃ for 30min, heating to 1450 ℃ for 20min, preserving heat for 10min at 1450 ℃, and cooling to 300-400 ℃;

(3) and (3) allowing the high-temperature liquid sintered material after the sintering treatment to flow into a cold water pool below the frit furnace from the gate to perform crushing and cooling, controlling the water temperature of the cold water pool to be below 50 ℃, and performing crushing and cooling to obtain a glass-state dry-particle semi-finished product.

(4) Controlling the moisture content of the dry particle semi-finished product to be below 1%, conveying the dry particle semi-finished product into a roll crusher, crushing, sieving the crushed fine powder with a 250-300 mesh screen, taking the dry particle fine powder within the range of 250-300 meshes, crushing the rest dry particle fine powder with the particle size larger than the required particle size again until the qualified particle size is reached, and firing and melting the dry particle raw material which is smaller than the required particle size.

(5) And (4) spraying the fine powder dry particles passing through the 250-300 meshes in the step (4) into the high-temperature furnace from the inlet of the high-temperature furnace through a cyclone machine, enabling the fine powder dry particles to pass through a heating area in a free falling mode, carrying out ball treatment, wherein the temperature of the heating area is 800 ℃, then collecting the fine powder dry particles from an outlet, and sieving the fine powder dry particles through a sieve of 250-300 meshes to obtain a dry particle finished product.

Comparative example 3

The raw material formula of the comparative example is as follows: 30 parts of potassium feldspar, 15 parts of albite, 8 parts of kaolin, 10 parts of barium carbonate, 8 parts of wollastonite, 8 parts of zinc oxide, 8 parts of strontium carbonate, 8 parts of calcite, 2 parts of quartz and 3 parts of aluminum oxide.

The preparation method comprises the following steps:

(1) mixing the raw materials, accurately conveying the mixed materials into a mixer by a belt scale for stirring, wherein the capacity of the mixer is 2 tons, and the stirring time is 30 minutes.

(2) Gradually conveying the mixed material with the weight of 15-18 kg per minute into a frit furnace by adopting a spiral column for sintering, and sintering according to the following method:

heating to 300 ℃ for 10min, heating to 1100 ℃ for 30min, heating to 1450 ℃ for 20min, preserving heat for 10min at 1450 ℃, and cooling to 300-400 ℃;

(3) and (3) allowing the high-temperature liquid sintered material after the sintering treatment to flow into a cold water pool below the frit furnace from the gate to perform crushing and cooling, controlling the water temperature of the cold water pool to be below 50 ℃, and performing crushing and cooling to obtain a glass-state dry-particle semi-finished product.

(4) Controlling the moisture content of the dry particle semi-finished product to be below 1%, conveying the dry particle semi-finished product into a roll crusher, crushing, sieving the crushed fine powder with a 250-300 mesh screen, taking the dry particle fine powder within the range of 250-300 meshes, crushing the rest dry particle fine powder with the particle size larger than the required particle size again until the qualified particle size is reached, and firing and melting the dry particle raw material which is smaller than the required particle size.

(5) And (4) spraying the fine powder dry particles passing through the 250-mesh and 300-mesh sieve in the step (4) into the high-temperature furnace from the inlet of the high-temperature furnace through a cyclone machine, enabling the fine powder dry particles to pass through a heating area in a free falling mode, carrying out ball-balling treatment, wherein the temperature of the heating area is 1000 ℃, then collecting the fine powder dry particles from an outlet, and sieving the fine powder dry particles through a sieve mesh of 250-mesh and 300-mesh sieve to obtain a dry particle finished product.

Performance testing

(1) Surface topography detection

The dry pellets of example 3 and comparative examples 1 to 3 were examined by MG 10085-1 a1500X microscope, wherein an enlarged view of example 3 is shown in fig. 1, an enlarged view of comparative example 1 is shown in fig. 2, an enlarged view of comparative example 2 is shown in fig. 3, and an enlarged view of comparative example 3 is shown in fig. 4.

As can be seen from FIG. 1, the beads of example 3 are substantially all in the shape of beads, have smooth surfaces and uniform particle diameters, and have excellent transparency. As can be seen from fig. 2, the surfaces of the dry pellets which were not spheronized had sharp corners. The method of the invention can effectively improve the roundness of the dry round beads.

As can be seen from fig. 3 and 4, the beading treatment effect at different temperatures has a large difference, when the temperature is too low, only part of the dried beads are in the shape of beads, and the edges of the dried beads are not smooth enough, probably because the softening degree of the dried beads is not enough; when the temperature is higher, the dry granules are agglomerated into a sheet, and the dry granules cannot form round-bead dry granules, possibly because the dry granules are easy to pass through fire, and then the dry granules are agglomerated. The temperature range of the ball treatment of the invention can effectively improve the roundness of the dry ball, thereby effectively avoiding a series of problems caused by the edge angle of the dry ball.

(2) Matte effect and hand feeling detection

The glossiness detection method is to adopt a glossiness instrument for testing, a WGG 60-E4 type photometer is adopted in the experiment, after the computer is started, a standard plate is used for adjusting a 0 glossiness point and a high glossiness 97.0 point, and then the glossiness instrument is placed on a tested sample to obtain glossiness data. According to the national standard, the reference is made to ISO-2767 and GB 8941.2. The test results of the above examples and comparative examples are shown in Table 1, wherein the test results are defined as high light at 75 degrees or more, flat light at 30 to 75 degrees, matt at 5 to 30 degrees and no light at 5 degrees or less;

hand feeling evaluation standard: the touch hand feeling judgment is used for determining that the quality is 10 minutes, the better quality is 7-9 minutes, generally 4-6 parts and the difference is 1-3 minutes; the higher the score, the more excellent the hand, preferably more than 7 points, and the test results of the above examples and comparative examples are shown in Table 2.

Table 1:

TABLE 2

As can be seen from Table 1, the dry beads of the invention have matte luster, and show stable matte luster at different firing temperatures, so that the dry beads are not only suitable for small-sized ceramic products, but also suitable for matte dry particle materials of large-sized slates.

As can be seen from Table 2, the dry beads of the invention have excellent hand feeling and show excellent hand feeling at firing temperatures of different specifications, and the dry beads can improve the problem of rough hand feeling of related ceramic products. In addition, comparing example 3 with example 6, the difference is that the formulation of the components is different, example 6 lacks wollastonite, and the content of some components is different, and it can be seen from table 2 that the hand feeling of example 3 is significantly better than that of example 6. Illustrating the effect of preferred wollastonite in improving hand, the following materials are preferably used: 30-45 parts of potassium feldspar, 5-15 parts of albite, 6-10 parts of kaolin, 10-20 parts of barium carbonate, 3-8 parts of wollastonite, 3-10 parts of zinc oxide, 4-10 parts of strontium carbonate, 7-13 parts of calcite, 1-4 parts of quartz and 1-5 parts of aluminum oxide.

(3) Stain resistance and skid resistance

The dry pellets of the above examples and comparative examples were tested to prepare ceramic tiles, specifically: preparing a green brick, drying, glazing, spraying patterns, spraying glaze slip containing dry particles of examples and comparative examples, firing at 1200 ℃, polishing to prepare a ceramic product, and testing the stain resistance and the skid resistance of the ceramic product as shown in table 3:

TABLE 3

As can be seen from Table 3, the ceramic products prepared from the dried beads of the present invention have superior contamination resistance and anti-slip level. In addition, as can be seen from comparative example 3 and comparative examples 1 to 3, the beading treatment at a specific temperature can effectively improve the stain-resistant and anti-slip effects of the corresponding ceramic articles. Comparing example 3 with example 6, it can be seen that the raw material formulation of the dried beads has a certain influence on the stain resistance and skid resistance, and the following raw materials are preferably used: 30-45 parts of potassium feldspar, 5-15 parts of albite, 6-10 parts of kaolin, 10-20 parts of barium carbonate, 3-8 parts of wollastonite, 3-10 parts of zinc oxide, 4-10 parts of strontium carbonate, 7-13 parts of calcite, 1-4 parts of quartz and 1-5 parts of aluminum oxide.

The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.

The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.