CN117486593B - Preparation process of ceramic toilet bowl - Google Patents

Preparation process of ceramic toilet bowl Download PDF

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Publication number
CN117486593B
CN117486593B CN202311440501.7A CN202311440501A CN117486593B CN 117486593 B CN117486593 B CN 117486593B CN 202311440501 A CN202311440501 A CN 202311440501A CN 117486593 B CN117486593 B CN 117486593B
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parts
mass
oxide
powder
deionized water
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CN117486593A (en
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苏克场
苏金铜
陈少娜
苏美銮
蔡逸冰
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Guangdong Gaoxiang Ceramic Industry Co ltd
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Guangdong Gaoxiang Ceramic Industry Co ltd
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/16—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay
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Abstract

The invention discloses a preparation process of a ceramic toilet, and belongs to the technical field of toilets. The preparation of the ceramic toilet bowl comprises the following steps: roasting the fly ash, placing the fly ash in deionized water for cooling, and drying by a magnetic sieve to obtain a material A; ball milling the material A to obtain powder B; mixing and standing desulfurized gypsum and deionized water, taking an upper suspension, standing, discarding the upper suspension, adding calcium chloride, hydrochloric acid and deionized water, mixing and heating, standing, filtering to obtain a solid phase, washing and drying to obtain powder C; configuring a blank; mixing the blank, the powder B, the powder C, deionized water, sodium tripolyphosphate and sodium hydroxymethyl cellulose, ball milling, drying and sieving to obtain ceramic powder; taking ceramic powder, pressing and forming in a mould, and drying to obtain a main body preform and a baffle plate preform; the configuration glaze is applied to the main body prefabricated body and the baffle prefabricated body, the main body and the baffle are obtained through firing, the ceramic toilet is obtained through bonding, the yield and the production efficiency are improved, and the waste utilization rate is improved.

Description

Preparation process of ceramic toilet bowl
Technical Field
The invention relates to the technical field of toilets, in particular to a preparation process of a ceramic toilet.
Background
Fly ash and desulfurized gypsum are two major wastes of coal-fired power plants, and most of the wastes of fly ash and desulfurized gypsum transported from the power plants are poured into ash yards and piled up into mountains. The existing stacking allowance of the fly ash is still huge, so that the waste of land resources and the salinization of the soil are caused, and the underground water is polluted; meanwhile, the yield of the desulfurized gypsum is increased year by year, so that not only is the land resource wasted and the air quality reduced, but also the hidden danger of heavy metal infiltration is caused. The fly ash is an ash-like substance generated in the coal burning process, contains rich inorganic oxides, and can be used as a raw material or an additive in the preparation of ceramics; the desulfurized gypsum is a byproduct generated after desulfurization in the coal burning process, and the main component is calcium sulfate, so that the desulfurized gypsum can be used as a filler in ceramic glaze, and the viscosity and fluidity of the glaze can be adjusted.
Most of the existing ceramic toilets are prepared by integrally molding silicate ceramics, and in the preparation process, the baffle plate at the flushing hole of the silicate ceramic toilet is subjected to excessive thermal stress in the high-temperature firing process, so that the baffle plate is easy to break, the molding rate of the ceramic toilet is low, the reworking cost and raw material consumption are increased, the processing production is not facilitated, the production efficiency is influenced, and the resource waste is caused; the silicate toilet bowl has high hardness, but is large in brittleness, easy to break under external force and capable of threatening the safety of a user.
Therefore, the three materials are comprehensively utilized to prepare the novel ceramic toilet bowl material, the exploitation quantity of natural stone can be reduced, and the large-scale high-value utilization of industrial solid waste is promoted.
Disclosure of Invention
The invention aims to provide a preparation process of a ceramic toilet, which is used for solving the problems that in the prior art, the ceramic toilet is low in molding rate, the processing cost and the raw material consumption are increased, the processing production is not facilitated, the production efficiency is affected, the resource waste is caused, and the sustainable development concept is not met.
The aim of the invention can be achieved by the following technical scheme:
the preparation process of the ceramic toilet bowl comprises the following steps of:
a1, roasting the fly ash, placing the fly ash in deionized water, cooling to room temperature, stirring, and drying after passing through a magnetic sieve of a magnetic separation tube to obtain a material A;
a2, ball milling the material A to obtain powder B;
a3, mixing and stirring the desulfurized gypsum and the deionized water, standing, taking an upper suspension, standing, discarding the upper suspension, adding calcium chloride, hydrochloric acid and the deionized water, mixing and heating at a constant temperature, standing, filtering to obtain a solid phase, washing, and drying to obtain powder C;
a4, configuring a blank;
a5, mixing the blank, the powder B, the powder C, deionized water, sodium tripolyphosphate and sodium hydroxymethyl cellulose, ball milling, drying and sieving to obtain ceramic powder;
a6, taking the ceramic powder, performing compression molding in a main body mold, drying to obtain a main body preform, taking the ceramic powder, performing compression molding in a baffle mold, and drying to obtain a baffle preform;
a7, configuring glaze;
a8, taking the glaze, applying the glaze to the main body preform, and firing to obtain a main body;
a9, applying the glaze to the baffle plate preform, and firing to obtain a baffle plate;
a10, bonding the main body and the baffle into a whole through an adhesive to obtain the ceramic toilet.
As a further scheme of the invention, in the step A1, the proportioning ratio of the fly ash to the deionized water is 20-30g:200-250mL, wherein the baking is performed at 650-700 ℃ for 40-50min.
In a further embodiment of the present invention, in the step A2, the median diameter of the powder B is 20 to 23 μm.
As a further scheme of the invention, in the step A3, the dosage ratio of the desulfurized gypsum, the deionized water added for the first time, the calcium chloride, the hydrochloric acid and the deionized water added for the second time is 5-8g:100mL:2-3g:100mL:100mL; the concentration of the hydrochloric acid is 1-2mol/L; the constant temperature heating means heating at 101 ℃ for 30-50min; the drying refers to drying at 44-46 ℃ for 10 hours.
As a further scheme of the invention, in the step A4, the blank comprises the following raw materials in parts by mass: 30-45 parts by mass of silicon dioxide; 15-20 parts of aluminum oxide; 2-2.5 parts by mass of ferric oxide; 0.3-0.5 parts by mass of potassium oxide; 0.5-1 parts by mass of sodium oxide; 0.2-0.3 parts by mass of magnesium oxide; 0.5-1 parts by mass of calcium oxide; 15-20 parts of frit.
In the further scheme of the invention, in the step A5, the mass ratio of the blank to the powder B to the powder C to the deionized water to the sodium tripolyphosphate to the sodium hydroxymethyl cellulose is 30-40:20-25:5-10:80-100:1-2:1.5-2.
As a further scheme of the invention, in the step A7, the glaze comprises the following raw materials in parts by mass: 52-53 parts by mass of silicon dioxide; 10.5-11.5 parts by mass of aluminum oxide; 4-5.5 parts by mass of calcium oxide; 1-1.5 parts by mass of magnesium oxide; 3-3.5 parts by mass of sodium oxide; 2-2.2 parts by mass of potassium oxide; 7.5-8.5 parts by mass of boron oxide; 5-8 parts of zinc oxide; 1.5-1.8 parts by mass of barium oxide; 20-30 parts of perlite; 6-8 parts of clay.
As a further scheme of the invention, the frit comprises the following raw materials in parts by mass: 9-10 parts of aluminum oxide; 40-45 parts by mass of silicon dioxide; 15-16 parts of quicklime; 4-5 parts of magnesium oxide; 11-12 parts of barium oxide; 2-3 parts of sodium oxide; 0.4-0.5 parts by mass of boron oxide; 2-3 parts of zinc oxide.
As a further aspect of the present invention, in the step A8, the firing means firing at 1180 to 1250℃for 10 to 12 hours.
As a further aspect of the present invention, in the step A9, the firing means firing at 1180 to 1250℃for 6 to 8 hours.
As a further scheme of the invention, the preparation of the adhesive comprises the following steps: mixing triethylamine and dimethylol butyric acid in a reaction kettle, adding poly (caprolactone), toluene diisocyanate and dibutyltin dilaurate, reacting at constant temperature, adding acetone and 1, 4-butanediol, continuously reacting at constant temperature, adding trimethylolpropane and kh-550, continuously reacting at constant temperature, cooling to room temperature, adding deionized water, ethylenediamine and ammonium zirconium carbonate while stirring, continuously stirring, evaporating and concentrating, adding polyether amine EC301 and hardening flatting agent S-5405, and preparing the adhesive;
as a further aspect of the present invention, the bonding process includes the steps of:
and (3) polishing one surface of the main body and one surface of the baffle, which are bonded with each other, by using a carborundum needle, carrying out sand blasting, coating the adhesive after the hot baking, carrying out hot pressing on the pair Ji Nianjie of the main body and the baffle, fixing at room temperature, and completing bonding, wherein the zirconium base is firmly connected with silicon-hydroxyl exposed out of the polished ceramic surface by using a silane coupling agent, so that the bonding strength is improved.
The invention has the beneficial effects that:
according to the preparation process of the ceramic toilet disclosed by the invention, the baffle is processed by a single part and then glued on the toilet main body, so that the finished product rate of the ceramic toilet is high, the processing efficiency is improved, and the production cost is reduced;
further, in the preparation process of the ceramic toilet, the ceramic toilet is prepared by using the waste fly ash and the desulfurized gypsum, so that the ceramic toilet has good fracture resistance, a certain attractive appearance, greatly improves the resource utilization rate, and accords with the concept of sustainable development;
further, in the process of preparing the ceramic by using the fly ash and the desulfurized gypsum, a large amount of calcium-containing raw materials are provided, so that the ceramic has a lower thermal expansion coefficient, reduces thermal stress, can effectively reduce interlayer spacing of the ceramic, and improves strength and stability of the ceramic;
further, in the firing process, calcium-containing raw materials provided by the fly ash and the desulfurized gypsum and raw materials such as silicon and aluminum form a prismatic crystal phase structure taking a calcium base as a main body, so that the pores and defects in the ceramic structure are filled, crack propagation is prevented, and the toughness strength of the ceramic body is improved.
Drawings
The invention is further described below with reference to the accompanying drawings.
FIG. 1 is a schematic diagram of the overall structure of a ceramic toilet bowl prepared by the preparation process of the invention.
In the figure: 1. a main body; 2. and a baffle.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments, and all other embodiments obtained by those skilled in the art without making creative efforts based on the embodiments of the present invention are included in the protection scope of the present invention.
As shown in fig. 1, the ceramic toilet comprises a main body 1 and a baffle plate 2, wherein the main body 1 and the baffle plate 2 are respectively processed and prepared, the manufactured ceramic toilet is adhered to a whole body through an adhesive, the baffle plate 2 is processed by a single part and then adhered to the main body 1 of the ceramic toilet, so that the finished product rate of the manufactured ceramic toilet is high, the processing efficiency is improved, and the production cost is reduced.
Example 1
The preparation of the ceramic toilet bowl comprises the following steps:
a1, roasting the fly ash at 650 ℃ for 40min, placing the fly ash in deionized water, cooling to room temperature, stirring for 40min, and drying for 2h after passing through a magnetic sieve of a magnetic separation tube to obtain a material A; the proportioning ratio of the fly ash to the deionized water is 20g:200mL;
a2, ball milling the material A for 7 hours to obtain powder B with a median diameter of 20 mu m;
a3, mixing and stirring the desulfurized gypsum and the deionized water for 1.5 hours, standing for 1min, taking an upper suspension, standing for 1min, discarding the upper suspension, adding calcium chloride, hydrochloric acid and the deionized water, mixing and heating at a constant temperature, standing, filtering to obtain a solid phase, washing and drying to obtain powder C; the dosage ratio of the desulfurized gypsum to the deionized water added for the first time to the calcium chloride to the hydrochloric acid to the deionized water added for the second time is 5g:100mL:2g:100mL:100mL; the concentration of the hydrochloric acid is 1 mol/L; the constant temperature heating refers to heating at 101 ℃ for 30min; the drying refers to drying at 44 ℃ for 10 hours;
a4, configuring a blank:
the preparation method comprises the following steps of: 30 parts by mass of silicon dioxide; 15 parts by mass of aluminum oxide; 2 parts by mass of ferric oxide; 0.3 parts by mass of potassium oxide; 0.5 parts by mass of sodium oxide; 0.2 parts by mass of magnesium oxide; 0.5 parts by mass of calcium oxide; 15 parts by mass of frit;
a5, mixing and ball milling the blank, the powder B, the powder C, deionized water, sodium tripolyphosphate and sodium hydroxymethyl cellulose for 4 hours, drying and sieving to obtain ceramic powder; the mass ratio of the blank to the powder B to the powder C to the deionized water to the sodium tripolyphosphate to the sodium hydroxymethyl cellulose is 30:20:5:80:1:1.5;
a6, taking the ceramic powder, performing compression molding in a main body mold, drying to obtain a main body preform, taking the ceramic powder, performing compression molding in a baffle mold, and drying to obtain a baffle preform;
a7, configuring glaze:
the preparation method comprises the following steps of: 52 parts by mass of silicon dioxide; 10.5 parts by mass of aluminum oxide; 4 parts by mass of calcium oxide; 1 part by mass of magnesium oxide; 3 parts by mass of sodium oxide; 2 parts by mass of potassium oxide; 7.5 parts by mass of boron oxide; 5 parts by mass of zinc oxide; 1.5 parts by mass of barium oxide; 20 parts of perlite; mixing and ball milling 6 parts by mass of clay for 4 hours to obtain the glaze;
a8, applying the glaze to the main body preform, and firing for 10 hours at 1180 ℃ to obtain a main body;
a9, applying the glaze to the baffle plate preform, and firing for 6 hours at 1180 ℃ to obtain a baffle plate;
a10, bonding the main body and the baffle into a whole through an adhesive to obtain the ceramic pedestal pan:
wherein:
the preparation of the adhesive comprises the following steps: placing triethylamine and dimethylol butyric acid into a reaction kettle, mixing for 25min, adding poly (caprolactone), toluene diisocyanate and dibutyltin dilaurate, reacting at constant temperature of 80 ℃ for 2h, adding acetone and 1, 4-butanediol, continuously reacting at constant temperature for 1h, adding trimethylolpropane and kh-550, continuously reacting at constant temperature for 1h, cooling to room temperature, adding deionized water, ethylenediamine and ammonium zirconium carbonate while stirring, continuously stirring for 30min, evaporating and concentrating at 50 ℃ for 4h, and adding polyether amine EC301 and hardening and leveling agent S-5405 to obtain the adhesive; the mass ratio of the triethylamine, the dimethylol butyric acid, the poly (caprolactone), the toluene diisocyanate, the dibutyl tin dilaurate, the acetone, the 1, 4-butanediol, the trimethylolpropane, the kh-550, the deionized water, the ethylenediamine, the ammonium zirconium carbonate, the polyether amine EC301 and the hardening leveling agent S-5405 is 1:1:1:1:0.1:10:0.5:0.2:0.1:50:0.2:1:0.08:0.05;
the bonding process comprises the following steps:
and (3) polishing one surface of the main body and the baffle, which are bonded with each other, by using a carborundum needle, carrying out sand blasting, coating the adhesive which is baked for 10min at 60 ℃, carrying out hot pressing on the main body and the baffle for Ji Nianjie at 110 ℃ for 3min, and fixing for 10h at room temperature to finish bonding.
Example 2
The preparation of the ceramic toilet bowl comprises the following steps:
a1, roasting the fly ash at 680 ℃ for 45min, placing the fly ash in deionized water, cooling to room temperature, stirring for 45min, and drying for 2.5h after passing through a magnetic sieve of a magnetic separation tube to obtain a material A; the proportioning ratio of the fly ash to the deionized water is 25g:220mL;
a2, ball milling the material A for 7.5 hours to obtain powder B with the median diameter of 22 mu m;
a3, mixing and stirring the desulfurized gypsum and the deionized water for 1.8 hours, standing for 1.5 minutes, taking an upper suspension, standing for 1.5 minutes, discarding the upper suspension, adding calcium chloride, hydrochloric acid and the deionized water, mixing and heating at constant temperature, standing, filtering to obtain a solid phase, washing and drying to obtain powder C; the dosage ratio of the desulfurized gypsum to the deionized water added for the first time to the calcium chloride to the hydrochloric acid to the deionized water added for the second time is 6g:100mL:2.5g:100mL:100mL; the concentration of the hydrochloric acid is 1.5 mol/L; the constant temperature heating means heating at 101 ℃ for 40min; the drying refers to drying at 45 ℃ for 10 hours;
a4, configuring a blank:
the preparation method comprises the following steps of: 40 parts by mass of silicon dioxide; 17 parts by mass of aluminum oxide; 2.2 parts by mass of ferric oxide; 0.4 parts by mass of potassium oxide; 0.8 parts by mass of sodium oxide; 0.25 parts by mass of magnesium oxide; 0.8 parts by mass of calcium oxide; 17 parts by mass of frit;
a5, mixing and ball milling the blank, the powder B, the powder C, deionized water, sodium tripolyphosphate and sodium hydroxymethyl cellulose for 5 hours, drying and sieving to obtain ceramic powder; the mass ratio of the blank to the powder B to the powder C to the deionized water to the sodium tripolyphosphate to the sodium hydroxymethyl cellulose is 35:22:8:90:1.5:1.8;
a6, taking the ceramic powder, performing compression molding in a main body mold, drying to obtain a main body preform, taking the ceramic powder, performing compression molding in a baffle mold, and drying to obtain a baffle preform;
a7, configuring glaze:
the preparation method comprises the following steps of: 52.5 parts by mass of silicon dioxide; 11 parts by mass of aluminum oxide; 5 parts by mass of calcium oxide; 1.2 parts by mass of magnesium oxide; 3.2 parts by mass of sodium oxide; 2.1 parts by mass of potassium oxide; 8 parts by mass of boron oxide; 7 parts by mass of zinc oxide; 1.6 parts by mass of barium oxide; 25 parts of perlite; 7 parts by mass of clay is mixed and ball-milled for 5 hours to prepare the glaze;
a8, applying the glaze to the main body preform, and firing at 1210 ℃ for 11 hours to obtain a main body;
a9, applying the glaze to the baffle plate preform, and firing at 1210 ℃ for 7 hours to obtain a baffle plate;
a10, bonding the main body and the baffle into a whole through an adhesive to obtain the ceramic pedestal pan:
wherein:
the preparation of the adhesive comprises the following steps: placing triethylamine and dimethylol butyric acid into a reaction kettle, mixing for 30min, adding poly (caprolactone), toluene diisocyanate and dibutyltin dilaurate, reacting at constant temperature of 80 ℃ for 2.5h, adding acetone and 1, 4-butanediol, continuously reacting at constant temperature for 1.2h, adding trimethylolpropane and kh-550, continuously reacting at constant temperature for 1.2h, cooling to room temperature, adding deionized water, ethylenediamine and ammonium zirconium carbonate while stirring, continuously stirring for 35min, evaporating and concentrating at 50 ℃ for 5h, and adding polyether amine EC301 and hardening flatting agent S-5405 to obtain the adhesive; the mass ratio of the triethylamine, the dimethylol butyric acid, the poly (caprolactone), the toluene diisocyanate, the dibutyl tin dilaurate, the acetone, the 1, 4-butanediol, the trimethylolpropane, the kh-550, the deionized water, the ethylenediamine, the ammonium zirconium carbonate, the polyether amine EC301 and the hardening leveling agent S-5405 is 1.5:1.2:1.5:1.1:0.2:10:0.6:0.25:0.12:50:0.3:1.5:0.082:0.06;
the bonding process comprises the following steps:
and (3) polishing one surface of the main body and the baffle, which are bonded with each other, by using a carborundum needle, carrying out sand blasting, coating the adhesive which is baked for 12 minutes at 65 ℃, carrying out hot pressing on the main body and the baffle for Ji Nianjie at 110 ℃ for 4 minutes, and fixing at room temperature for 11 hours to finish bonding.
Example 3
The preparation of the ceramic toilet bowl comprises the following steps:
a1, roasting the fly ash at 700 ℃ for 50min, placing the fly ash in deionized water, cooling to room temperature, stirring for 50min, and drying for 3h after passing through a magnetic sieve of a magnetic separation tube to obtain a material A; the proportioning ratio of the fly ash to the deionized water is 30g:250mL;
a2, ball milling the material A for 8 hours to obtain powder B with the median diameter of 23 mu m;
a3, mixing and stirring the desulfurized gypsum and the deionized water for 2 hours, standing for 2 minutes, taking an upper suspension, standing for 2 minutes, discarding the upper suspension, adding calcium chloride, hydrochloric acid and the deionized water, mixing and heating at a constant temperature, standing, filtering to obtain a solid phase, washing and drying to obtain powder C; the dosage ratio of the desulfurized gypsum to the deionized water added for the first time to the calcium chloride to the hydrochloric acid to the deionized water added for the second time is 8g:100mL:3g:100mL:100mL; the concentration of the hydrochloric acid is 2mol/L; the constant temperature heating refers to heating at 101 ℃ for 50min; the drying refers to drying at 46 ℃ for 10 hours;
a4, configuring a blank:
the preparation method comprises the following steps of: 45 parts by mass of silicon dioxide; 20 parts by mass of aluminum oxide; 2.5 parts by mass of ferric oxide; 0.5 parts by mass of potassium oxide; 1 part by mass of sodium oxide; 0.3 parts by mass of magnesium oxide; 1 part by mass of calcium oxide; 20 parts by mass of frit;
a5, mixing and ball milling the blank, the powder B, the powder C, deionized water, sodium tripolyphosphate and sodium hydroxymethyl cellulose for 6 hours, drying and sieving to obtain ceramic powder; the mass ratio of the blank to the powder B to the powder C to the deionized water to the sodium tripolyphosphate to the sodium hydroxymethyl cellulose is 40:25:10:100:2:2;
a6, taking the ceramic powder, performing compression molding in a main body mold, drying to obtain a main body preform, taking the ceramic powder, performing compression molding in a baffle mold, and drying to obtain a baffle preform;
a7, configuring glaze:
the preparation method comprises the following steps of: 53 parts by mass of silicon dioxide; 11.5 parts by mass of aluminum oxide; 5.5 parts by mass of calcium oxide; 1.5 parts by mass of magnesium oxide; 3.5 parts by mass of sodium oxide; 2.2 parts by mass of potassium oxide; 8.5 parts by mass of boron oxide; 8 parts by mass of zinc oxide; 1.8 parts by mass of barium oxide; 30 parts of perlite; 8 parts of clay by mass are mixed and ball-milled for 6 hours to prepare the glaze;
a8, applying the glaze to the main body preform, and firing at 1250 ℃ for 12 hours to obtain a main body;
a9, applying the glaze to the baffle plate preform, and firing at 1250 ℃ for 8 hours to obtain a baffle plate;
a10, bonding the main body and the baffle into a whole through an adhesive to obtain the ceramic pedestal pan:
wherein:
the preparation of the adhesive comprises the following steps: placing triethylamine and dimethylol butyric acid into a reaction kettle, mixing for 35min, adding poly (caprolactone), toluene diisocyanate and dibutyltin dilaurate, reacting at constant temperature of 80 ℃ for 3h, adding acetone and 1, 4-butanediol, continuously reacting at constant temperature for 1.5h, adding trimethylolpropane and kh-550, continuously reacting at constant temperature for 1.5h, cooling to room temperature, adding deionized water, ethylenediamine and ammonium zirconium carbonate while stirring, continuously stirring for 40min, evaporating and concentrating at 50 ℃ for 6h, and adding polyetheramine EC301 and hardening flatting agent S-5405 to obtain the adhesive; the mass ratio of the triethylamine, the dimethylol butyric acid, the poly (caprolactone), the toluene diisocyanate, the dibutyl tin dilaurate, the acetone, the 1, 4-butanediol, the trimethylolpropane, the kh-550, the deionized water, the ethylenediamine, the ammonium zirconium carbonate, the polyether amine EC301 and the hardening leveling agent S-5405 is 2:1.5:2:1.2:0.3:10:0.8:0.3:0.15:50:0.4:2:0.085:0.08;
the bonding process comprises the following steps:
and (3) polishing one surface of the main body and the baffle, which are bonded with each other, by using a carborundum needle, carrying out sand blasting, coating the adhesive which is baked for 15min at the temperature of 62 ℃, carrying out hot pressing on the main body and the baffle for Ji Nianjie at the temperature of 110 ℃ for 5min, and fixing at room temperature for 12h to finish bonding.
Comparative example 1
The preparation of the ceramic toilet bowl comprises the following steps:
a1, mixing and stirring desulfurized gypsum and deionized water for 1.5 hours, standing for 1min, taking an upper suspension, standing for 1min, discarding the upper suspension, adding calcium chloride, hydrochloric acid and deionized water, mixing and heating at constant temperature, standing, filtering to obtain a solid phase, washing and drying to obtain powder C; the dosage ratio of the desulfurized gypsum to the deionized water added for the first time to the calcium chloride to the hydrochloric acid to the deionized water added for the second time is 5g:100mL:2g:100mL:100mL; the concentration of the hydrochloric acid is 1 mol/L; the constant temperature heating refers to heating at 101 ℃ for 30min; the drying refers to drying at 44 ℃ for 10 hours;
a2, configuring a blank:
the preparation method comprises the following steps of: 30 parts by mass of silicon dioxide; 15 parts by mass of aluminum oxide; 2 parts by mass of ferric oxide; 0.3 parts by mass of potassium oxide; 0.5 parts by mass of sodium oxide; 0.2 parts by mass of magnesium oxide; 0.5 parts by mass of calcium oxide; 15 parts by mass of frit;
a3, mixing the blank, powder C, deionized water, sodium tripolyphosphate and sodium hydroxymethyl cellulose, ball milling for 4 hours, drying, and sieving to obtain ceramic powder; the mass ratio of the blank to the powder C to the deionized water to the sodium tripolyphosphate to the sodium hydroxymethyl cellulose is 30:5:80:1:1.5;
a4, taking the ceramic powder, performing compression molding in a main body mold, drying to obtain a main body preform, taking the ceramic powder, performing compression molding in a baffle mold, and drying to obtain a baffle preform;
a5, configuring glaze:
the preparation method comprises the following steps of: 52 parts by mass of silicon dioxide; 10.5 parts by mass of aluminum oxide; 4 parts by mass of calcium oxide; 1 part by mass of magnesium oxide; 3 parts by mass of sodium oxide; 2 parts by mass of potassium oxide; 7.5 parts by mass of boron oxide; 5 parts by mass of zinc oxide; 1.5 parts by mass of barium oxide; 20 parts of perlite; mixing and ball milling 6 parts by mass of clay for 4 hours to obtain the glaze;
a6, applying the glaze to the main body preform, and firing for 10 hours at 1180 ℃ to obtain a main body;
a7, applying the glaze to the baffle plate preform, and firing for 6 hours at 1180 ℃ to obtain a baffle plate;
a8, bonding the main body and the baffle into a whole through an adhesive to obtain the ceramic pedestal pan:
wherein:
the preparation of the adhesive comprises the following steps: placing triethylamine and dimethylol butyric acid into a reaction kettle, mixing for 25min, adding poly (caprolactone), toluene diisocyanate and dibutyltin dilaurate, reacting at constant temperature of 80 ℃ for 2h, adding acetone and 1, 4-butanediol, continuously reacting at constant temperature for 1h, adding trimethylolpropane and kh-550, continuously reacting at constant temperature for 1h, cooling to room temperature, adding deionized water, ethylenediamine and ammonium zirconium carbonate while stirring, continuously stirring for 30min, evaporating and concentrating at 50 ℃ for 4h, and adding polyether amine EC301 and hardening and leveling agent S-5405 to obtain the adhesive; the mass ratio of the triethylamine, the dimethylol butyric acid, the poly (caprolactone), the toluene diisocyanate, the dibutyl tin dilaurate, the acetone, the 1, 4-butanediol, the trimethylolpropane, the kh-550, the deionized water, the ethylenediamine, the ammonium zirconium carbonate, the polyether amine EC301 and the hardening leveling agent S-5405 is 1:1:1:1:0.1:10:0.5:0.2:0.1:50:0.2:1:0.08:0.05;
the bonding process comprises the following steps:
and (3) polishing one surface of the main body and the baffle, which are bonded with each other, by using a carborundum needle, carrying out sand blasting, coating the adhesive which is baked for 10min at 60 ℃, carrying out hot pressing on the main body and the baffle for Ji Nianjie at 110 ℃ for 3min, and fixing for 10h at room temperature to finish bonding.
Comparative example 2
The preparation of the ceramic toilet bowl comprises the following steps:
a1, roasting the fly ash at 650 ℃ for 40min, placing the fly ash in deionized water, cooling to room temperature, stirring for 40min, and drying for 2h after passing through a magnetic sieve of a magnetic separation tube to obtain a material A; the proportioning ratio of the fly ash to the deionized water is 20g:200mL;
a2, ball milling the material A for 7 hours to obtain powder B with a median diameter of 20 mu m;
a3, configuring a blank:
the preparation method comprises the following steps of: 30 parts by mass of silicon dioxide; 15 parts by mass of aluminum oxide; 2 parts by mass of ferric oxide; 0.3 parts by mass of potassium oxide; 0.5 parts by mass of sodium oxide; 0.2 parts by mass of magnesium oxide; 0.5 parts by mass of calcium oxide; 15 parts by mass of frit;
a4, mixing and ball milling the blank, the powder B, deionized water, sodium tripolyphosphate and sodium hydroxymethyl cellulose for 4 hours, drying and sieving to obtain ceramic powder; the mass ratio of the blank to the powder B to the powder C to the deionized water to the sodium tripolyphosphate to the sodium hydroxymethyl cellulose is 30:20:80:1:1.5;
a5, taking the ceramic powder, performing compression molding in a main body mold, drying to obtain a main body preform, taking the ceramic powder, performing compression molding in a baffle mold, and drying to obtain a baffle preform;
a6, configuring glaze:
the preparation method comprises the following steps of: 52 parts by mass of silicon dioxide; 10.5 parts by mass of aluminum oxide; 4 parts by mass of calcium oxide; 1 part by mass of magnesium oxide; 3 parts by mass of sodium oxide; 2 parts by mass of potassium oxide; 7.5 parts by mass of boron oxide; 5 parts by mass of zinc oxide; 1.5 parts by mass of barium oxide; 20 parts of perlite; mixing and ball milling 6 parts by mass of clay for 4 hours to obtain the glaze;
a7, applying the glaze to the main body preform, and firing for 10 hours at 1180 ℃ to obtain a main body;
a8, applying the glaze to the baffle plate preform, and firing for 6 hours at 1180 ℃ to obtain a baffle plate;
a9, bonding the main body and the baffle into a whole through an adhesive to obtain the ceramic pedestal pan:
wherein:
the preparation of the adhesive comprises the following steps: placing triethylamine and dimethylol butyric acid into a reaction kettle, mixing for 25min, adding poly (caprolactone), toluene diisocyanate and dibutyltin dilaurate, reacting at constant temperature of 80 ℃ for 2h, adding acetone and 1, 4-butanediol, continuously reacting at constant temperature for 1h, adding trimethylolpropane and kh-550, continuously reacting at constant temperature for 1h, cooling to room temperature, adding deionized water, ethylenediamine and ammonium zirconium carbonate while stirring, continuously stirring for 30min, evaporating and concentrating at 50 ℃ for 4h, and adding polyether amine EC301 and hardening and leveling agent S-5405 to obtain the adhesive; the mass ratio of the triethylamine, the dimethylol butyric acid, the poly (caprolactone), the toluene diisocyanate, the dibutyl tin dilaurate, the acetone, the 1, 4-butanediol, the trimethylolpropane, the kh-550, the deionized water, the ethylenediamine, the ammonium zirconium carbonate, the polyether amine EC301 and the hardening leveling agent S-5405 is 1:1:1:1:0.1:10:0.5:0.2:0.1:50:0.2:1:0.08:0.05;
the bonding process comprises the following steps:
and (3) polishing one surface of the main body and the baffle, which are bonded with each other, by using a carborundum needle, carrying out sand blasting, coating the adhesive which is baked for 10min at 60 ℃, carrying out hot pressing on the main body and the baffle for Ji Nianjie at 110 ℃ for 3min, and fixing for 10h at room temperature to finish bonding.
Comparative example 3
The difference in example 1 is the preparation of the adhesive;
the preparation of the adhesive comprises the following steps: placing triethylamine and dimethylol butyric acid into a reaction kettle, mixing for 25min, adding poly (caprolactone), toluene diisocyanate and dibutyltin dilaurate, reacting at constant temperature of 80 ℃ for 2h, adding acetone and 1, 4-butanediol, continuously reacting at constant temperature for 1h, adding trimethylolpropane and kh-550, continuously reacting at constant temperature for 1h, cooling to room temperature, evaporating and concentrating at 50 ℃ for 4h, adding polyether amine EC301 and hardening flatting agent S-5405, and preparing the adhesive; the mass ratio of the triethylamine, the dimethylol butyric acid, the poly (caprolactone), the toluene diisocyanate, the dibutyl tin dilaurate, the acetone, the 1, 4-butanediol, the trimethylolpropane, the kh-550, the deionized water, the ethylenediamine, the ammonium zirconium carbonate, the polyether amine EC301 and the hardening leveling agent S-5405 is 1:1:1:1:0.1:10:0.5:0.2:0.1:0.08:0.05;
the bonding process comprises the following steps:
and (3) polishing one surface of the main body and the baffle, which are bonded with each other, by using a carborundum needle, carrying out sand blasting, coating the adhesive which is baked for 10min at 60 ℃, carrying out hot pressing on the main body and the baffle for Ji Nianjie at 110 ℃ for 3min, and fixing for 10h at room temperature to finish bonding.
Comparative example 4
The preparation of the ceramic toilet bowl comprises the following steps:
a1, taking fly ash, passing through a magnetic sieve of a magnetic separation tube, and drying for 2 hours to obtain a material A;
a2, ball milling the material A for 7 hours to obtain powder B with a median diameter of 20 mu m;
a3, mixing and stirring the desulfurized gypsum and the deionized water for 1.5 hours, standing for 1min, taking an upper suspension, standing for 1min, discarding the upper suspension, adding calcium chloride, hydrochloric acid and the deionized water, mixing and heating at a constant temperature, standing, filtering to obtain a solid phase, washing and drying to obtain powder C; the dosage ratio of the desulfurized gypsum to the deionized water added for the first time to the calcium chloride to the hydrochloric acid to the deionized water added for the second time is 5g:100mL:2g:100mL:100mL; the concentration of the hydrochloric acid is 1 mol/L; the constant temperature heating refers to heating at 101 ℃ for 30min; the drying refers to drying at 44 ℃ for 10 hours;
a4, configuring a blank:
the preparation method comprises the following steps of: 30 parts by mass of silicon dioxide; 15 parts by mass of aluminum oxide; 2 parts by mass of ferric oxide; 0.3 parts by mass of potassium oxide; 0.5 parts by mass of sodium oxide; 0.2 parts by mass of magnesium oxide; 0.5 parts by mass of calcium oxide; 15 parts by mass of frit;
a5, mixing and ball milling the blank, the powder B, the powder C, deionized water, sodium tripolyphosphate and sodium hydroxymethyl cellulose for 4 hours, drying and sieving to obtain ceramic powder; the mass ratio of the blank to the powder B to the powder C to the deionized water to the sodium tripolyphosphate to the sodium hydroxymethyl cellulose is 30:20:5:80:1:1.5;
a6, taking the ceramic powder, performing compression molding in a main body mold, drying to obtain a main body preform, taking the ceramic powder, performing compression molding in a baffle mold, and drying to obtain a baffle preform;
a7, configuring glaze:
the preparation method comprises the following steps of: 52 parts by mass of silicon dioxide; 10.5 parts by mass of aluminum oxide; 4 parts by mass of calcium oxide; 1 part by mass of magnesium oxide; 3 parts by mass of sodium oxide; 2 parts by mass of potassium oxide; 7.5 parts by mass of boron oxide; 5 parts by mass of zinc oxide; 1.5 parts by mass of barium oxide; 20 parts of perlite; mixing and ball milling 6 parts by mass of clay for 4 hours to obtain the glaze;
a8, applying the glaze to the main body preform, and firing for 10 hours at 1180 ℃ to obtain a main body;
a9, applying the glaze to the baffle plate preform, and firing for 6 hours at 1180 ℃ to obtain a baffle plate;
a10, bonding the main body and the baffle into a whole through an adhesive to obtain the ceramic pedestal pan:
wherein:
the preparation of the adhesive comprises the following steps: placing triethylamine and dimethylol butyric acid into a reaction kettle, mixing for 25min, adding poly (caprolactone), toluene diisocyanate and dibutyltin dilaurate, reacting at constant temperature of 80 ℃ for 2h, adding acetone and 1, 4-butanediol, continuously reacting at constant temperature for 1h, adding trimethylolpropane and kh-550, continuously reacting at constant temperature for 1h, cooling to room temperature, adding deionized water, ethylenediamine and ammonium zirconium carbonate while stirring, continuously stirring for 30min, evaporating and concentrating at 50 ℃ for 4h, and adding polyether amine EC301 and hardening and leveling agent S-5405 to obtain the adhesive; the mass ratio of the triethylamine, the dimethylol butyric acid, the poly (caprolactone), the toluene diisocyanate, the dibutyl tin dilaurate, the acetone, the 1, 4-butanediol, the trimethylolpropane, the kh-550, the deionized water, the ethylenediamine, the ammonium zirconium carbonate, the polyether amine EC301 and the hardening leveling agent S-5405 is 1:1:1:1:0.1:10:0.5:0.2:0.1:50:0.2:1:0.08:0.05;
the bonding process comprises the following steps:
and (3) polishing one surface of the main body and the baffle, which are bonded with each other, by using a carborundum needle, carrying out sand blasting, coating the adhesive which is baked for 10min at 60 ℃, carrying out hot pressing on the main body and the baffle for Ji Nianjie at 110 ℃ for 3min, and fixing for 10h at room temperature to finish bonding.
Comparative example 5
The preparation of the ceramic toilet bowl comprises the following steps:
a1, roasting the fly ash at 650 ℃ for 40min, placing the fly ash in deionized water, cooling to room temperature, stirring for 40min, and drying for 2h after passing through a magnetic sieve of a magnetic separation tube to obtain a material A; the proportioning ratio of the fly ash to the deionized water is 20g:200mL;
a2, ball milling the material A for 7 hours to obtain powder B with a median diameter of 20 mu m;
a3, taking and drying the desulfurized gypsum to obtain powder C;
a4, configuring a blank:
the preparation method comprises the following steps of: 30 parts by mass of silicon dioxide; 15 parts by mass of aluminum oxide; 2 parts by mass of ferric oxide; 0.3 parts by mass of potassium oxide; 0.5 parts by mass of sodium oxide; 0.2 parts by mass of magnesium oxide; 0.5 parts by mass of calcium oxide; 15 parts by mass of frit;
a5, mixing and ball milling the blank, the powder B, the powder C, deionized water, sodium tripolyphosphate and sodium hydroxymethyl cellulose for 4 hours, drying and sieving to obtain ceramic powder; the mass ratio of the blank to the powder B to the powder C to the deionized water to the sodium tripolyphosphate to the sodium hydroxymethyl cellulose is 30:20:5:80:1:1.5;
a6, taking the ceramic powder, performing compression molding in a main body mold, drying to obtain a main body preform, taking the ceramic powder, performing compression molding in a baffle mold, and drying to obtain a baffle preform;
a7, configuring glaze:
the preparation method comprises the following steps of: 52 parts by mass of silicon dioxide; 10.5 parts by mass of aluminum oxide; 4 parts by mass of calcium oxide; 1 part by mass of magnesium oxide; 3 parts by mass of sodium oxide; 2 parts by mass of potassium oxide; 7.5 parts by mass of boron oxide; 5 parts by mass of zinc oxide; 1.5 parts by mass of barium oxide; 20 parts of perlite; mixing and ball milling 6 parts by mass of clay for 4 hours to obtain the glaze;
a8, applying the glaze to the main body preform, and firing for 10 hours at 1180 ℃ to obtain a main body;
a9, applying the glaze to the baffle plate preform, and firing for 6 hours at 1180 ℃ to obtain a baffle plate;
a10, bonding the main body and the baffle into a whole through an adhesive to obtain the ceramic pedestal pan:
wherein:
the preparation of the adhesive comprises the following steps: placing triethylamine and dimethylol butyric acid into a reaction kettle, mixing for 25min, adding poly (caprolactone), toluene diisocyanate and dibutyltin dilaurate, reacting at constant temperature of 80 ℃ for 2h, adding acetone and 1, 4-butanediol, continuously reacting at constant temperature for 1h, adding trimethylolpropane and kh-550, continuously reacting at constant temperature for 1h, cooling to room temperature, adding deionized water, ethylenediamine and ammonium zirconium carbonate while stirring, continuously stirring for 30min, evaporating and concentrating at 50 ℃ for 4h, and adding polyether amine EC301 and hardening and leveling agent S-5405 to obtain the adhesive; the mass ratio of the triethylamine, the dimethylol butyric acid, the poly (caprolactone), the toluene diisocyanate, the dibutyl tin dilaurate, the acetone, the 1, 4-butanediol, the trimethylolpropane, the kh-550, the deionized water, the ethylenediamine, the ammonium zirconium carbonate, the polyether amine EC301 and the hardening leveling agent S-5405 is 1:1:1:1:0.1:10:0.5:0.2:0.1:50:0.2:1:0.08:0.05;
the bonding process comprises the following steps:
and (3) polishing one surface of the main body and the baffle, which are bonded with each other, by using a carborundum needle, carrying out sand blasting, coating the adhesive which is baked for 10min at 60 ℃, carrying out hot pressing on the main body and the baffle for Ji Nianjie at 110 ℃ for 3min, and fixing for 10h at room temperature to finish bonding.
Performance testing
The whiteness of the ceramic toilet is detected by using a WSD-III type full-automatic whiteness meter;
ceramic toilet bowl fracture toughness tests were performed according to standard GB/T23806-2009;
adhesive peel strength testing was performed according to standard GB/T7122-1996;
the performance test was performed according to the above criteria for examples 1-3 and comparative examples 1-5.
TABLE 1
As can be seen from table 1, comparative examples 4 and 5 were not subjected to the whitening treatment so that whiteness of the ceramic toilet bowl was significantly reduced; the ceramic toilet bowl prepared in comparative example 1, which is not added with fly ash and the desulfurization gypsum, is reduced in fracture resistance; comparative example 3 the absence of added zirconium salt resulted in a reduced peel resistance of the resulting adhesive after bonding the body to the panel.
Note that: the polyetheramine EC301 was purchased from south kyo da zee trade limited; hardening leveling agent S-5405 is purchased from Guangzhou chemical technology Co.
While certain embodiments of the present invention have been described in detail, this disclosure is only for the purpose of illustrating preferred embodiments of the invention and is not to be construed as limiting the scope of the invention. All equivalent changes and modifications within the scope of the present invention are intended to be covered by the present invention.

Claims (10)

1. The preparation process of the ceramic toilet bowl is characterized by comprising the following steps of:
a1, roasting the fly ash, placing the fly ash in deionized water, cooling to room temperature, stirring, and drying after passing through a magnetic sieve of a magnetic separation tube to obtain a material A;
a2, ball milling the material A to obtain powder B;
a3, mixing and stirring the desulfurized gypsum and the deionized water, standing, taking an upper suspension, standing, discarding the upper suspension, adding calcium chloride, hydrochloric acid and the deionized water, mixing and heating at a constant temperature, standing, filtering to obtain a solid phase, washing, and drying to obtain powder C;
a4, configuring a blank;
a5, mixing the blank, the powder B, the powder C, deionized water, sodium tripolyphosphate and sodium hydroxymethyl cellulose, ball milling, drying and sieving to obtain ceramic powder;
a6, taking the ceramic powder, performing compression molding in a main body mold, drying to obtain a main body preform, taking the ceramic powder, performing compression molding in a baffle mold, and drying to obtain a baffle preform;
a7, configuring glaze;
a8, taking the glaze, applying the glaze to the main body preform, and firing to obtain a main body;
a9, applying the glaze to the baffle plate preform, and firing to obtain a baffle plate;
a10, bonding the main body and the baffle into a whole through an adhesive to obtain the ceramic toilet.
2. The process for preparing the ceramic toilet bowl according to claim 1, wherein in the step A1, the proportioning ratio of the fly ash to the deionized water is 20-30g:200-250mL, wherein the baking is performed at 650-700 ℃ for 40-50min.
3. The process for preparing a ceramic toilet according to claim 1, wherein in the step A2, the median diameter of the powder B is 20-23 μm.
4. The process for preparing the ceramic toilet bowl according to claim 1, wherein in the step A3, the dosage ratio of the desulfurized gypsum, the deionized water added for the first time, the calcium chloride, the hydrochloric acid and the deionized water added for the second time is 5-8g:100mL:2-3g:100mL:100mL; the concentration of the hydrochloric acid is 1-2mol/L; the constant temperature heating means heating at 101 ℃ for 30-50min; the drying refers to drying at 44-46 ℃ for 10 hours.
5. The process for preparing the ceramic toilet bowl according to claim 1, wherein in the step A4, the blank comprises the following raw materials in parts by mass: 30-45 parts by mass of silicon dioxide; 15-20 parts of aluminum oxide; 2-2.5 parts by mass of ferric oxide; 0.3-0.5 parts by mass of potassium oxide; 0.5-1 parts by mass of sodium oxide; 0.2-0.3 parts by mass of magnesium oxide; 0.5-1 parts by mass of calcium oxide; 15-20 parts of frit.
6. The preparation process of the ceramic toilet bowl according to claim 1, wherein in the step A5, the mass ratio of the blank to the powder B to the powder C to the deionized water to the sodium tripolyphosphate to the sodium hydroxymethyl cellulose is 30-40:20-25:5-10:80-100:1-2:1.5-2.
7. The preparation process of the ceramic toilet bowl according to claim 1, wherein in the step A7, the glaze comprises the following raw materials in parts by mass: 52-53 parts by mass of silicon dioxide; 10.5-11.5 parts by mass of aluminum oxide; 4-5.5 parts by mass of calcium oxide; 1-1.5 parts by mass of magnesium oxide; 3-3.5 parts by mass of sodium oxide; 2-2.2 parts by mass of potassium oxide; 7.5-8.5 parts by mass of boron oxide; 5-8 parts of zinc oxide; 1.5-1.8 parts by mass of barium oxide; 20-30 parts of perlite; 6-8 parts of clay.
8. The preparation process of the ceramic toilet bowl according to claim 5, wherein the frit comprises the following raw materials in parts by mass: 9-10 parts of aluminum oxide; 40-45 parts by mass of silicon dioxide; 15-16 parts of quicklime; 4-5 parts of magnesium oxide; 11-12 parts of barium oxide; 2-3 parts of sodium oxide; 0.4-0.5 parts by mass of boron oxide; 2-3 parts of zinc oxide.
9. The process for preparing a ceramic toilet according to claim 1, wherein in the step A8, the firing is performed at 1180-1250 ℃ for 10-12 hours.
10. The process for preparing a ceramic toilet according to claim 1, wherein in the step A9, the firing is performed at 1180-1250 ℃ for 6-8 hours.
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR704617A (en) * 1929-10-15 1931-05-22 Tile and its manufacturing process
CN103601478A (en) * 2013-08-14 2014-02-26 陈奕煌 Preparation method of flush toilet
CN103664148A (en) * 2013-08-14 2014-03-26 陈奕煌 Method for preparing split molded toilet
CN106587981A (en) * 2016-12-07 2017-04-26 苏州洛特兰新材料科技有限公司 High-toughness ceramic composite material and preparing method thereof
CN110117195A (en) * 2019-05-30 2019-08-13 龚建林 A kind of preparation method of Anti-pressure filtering high-temperature flue gas dedicated ceramic
CN214994423U (en) * 2021-04-28 2021-12-03 广东高象陶瓷实业有限公司 Antibiotic antibacterial structure of antibiotic usefulness of closestool glaze

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR704617A (en) * 1929-10-15 1931-05-22 Tile and its manufacturing process
CN103601478A (en) * 2013-08-14 2014-02-26 陈奕煌 Preparation method of flush toilet
CN103664148A (en) * 2013-08-14 2014-03-26 陈奕煌 Method for preparing split molded toilet
CN106587981A (en) * 2016-12-07 2017-04-26 苏州洛特兰新材料科技有限公司 High-toughness ceramic composite material and preparing method thereof
CN110117195A (en) * 2019-05-30 2019-08-13 龚建林 A kind of preparation method of Anti-pressure filtering high-temperature flue gas dedicated ceramic
CN214994423U (en) * 2021-04-28 2021-12-03 广东高象陶瓷实业有限公司 Antibiotic antibacterial structure of antibiotic usefulness of closestool glaze

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