CN109796188B - Ceramic tile using desulfurization slag and glaze slag as raw materials and production method thereof - Google Patents
Ceramic tile using desulfurization slag and glaze slag as raw materials and production method thereof Download PDFInfo
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- CN109796188B CN109796188B CN201910142659.3A CN201910142659A CN109796188B CN 109796188 B CN109796188 B CN 109796188B CN 201910142659 A CN201910142659 A CN 201910142659A CN 109796188 B CN109796188 B CN 109796188B
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Abstract
The invention discloses a ceramic tile using desulfurization slag and glaze slag as raw materials, which comprises the following raw materials in percentage by weight: 1-5% of mixed waste residue and 95-99% of basic raw material; the mixed waste residue consists of 75-90% of waste glaze slag and 10-25% of desulphurization slag in percentage by weight; the waste glaze slag is waste glaze slag generated in the production process of ceramic tiles, and the desulphurization slag is waste slag generated by desulphurization of flue gas by using lime water. The invention also discloses a production method of the ceramic tile. The invention introduces the waste glaze slag and the waste slag generated by flue gas desulfurization into the basic formula, thereby achieving the purposes of recycling the desulfurization slag and the waste glaze slag and ensuring that the performances of the product reach the standard. Meanwhile, the waste glaze slag and the desulphurization slag are recycled, so that the production waste discharge of the desulphurization slag and the waste glaze slag is avoided, the production cost of the ceramic tile can be reduced, and the quality of the finished ceramic tile is not influenced.
Description
Technical Field
The invention relates to the technical field of ceramics, in particular to a ceramic tile using desulfurization slag and glaze slag as raw materials and a production method thereof.
Background
The flue gas of the spray drying tower and the kiln in the production of the ceramic tile contains higher SO2When the acid gas is discharged directly, the pollution to the atmosphere is serious, and SO is generated by environmental protection mechanisms at all levels2And the emission of the polluted gas has a strict detection mechanism and a strict control standard, so that the desulfurization is an important link for building ceramic and environment-friendly treatment. Lime (CaO) is a simple and effective method for desulfurization, and part of lime mixed water is used for producing calcium hydroxide (Ca (OH)2) Spraying SO in the chimney in the form of water curtain2Iso acidProduction of sulfurous acid (H) by fusion of sex gas and water2SO3) Sulfurous acid (H)2SO3) With lime water (Ca (OH) mixed in water2) The chemical reaction is carried out to produce the calcium sulfite (CaSO) which is difficult to dissolve in water3) The mixed water flows into a sedimentation tank, and the mixed water is treated in a waste residue form after being precipitated and squeezed. Because of high decomposition temperature of sulfide and difficult discharge of gas, the glaze bubble problem is easy to appear when the desulfurization slag is directly used in the archaized brick blank, and the direct recycling of the desulfurization slag is restricted. In addition, in the treatment process of the desulfurization residues, more precipitator (generally polyaluminium chloride, polyacrylamide and the like) is used and is extremely difficult to peptize during raw material ball milling, so that the slurry is poor in fluidity, easy to thixotropy and difficult to discharge, and cannot be normally used.
In the production process of ceramic tiles such as antique tiles, a certain amount of waste glaze water is generated by glaze making, ball washing and cleaning equipment in a ball glaze workshop and glaze dripping in the production process of a glaze line, and the waste glaze water is precipitated and squeezed to generate waste glaze slag. Although the waste glaze slag has the property of glaze, other components are mixed, and the waste glaze slag is difficult to be applied to the production of high-quality antique brick products in the form of glaze. The waste glaze slag has low sintering temperature, more low-temperature melting raw materials, high-temperature melting degree and low high-temperature viscosity, and can be directly applied to blanks to increase the liquid phase generation amount during sintering of blanks, so that the brick shape and the wave patterns of the kiln bricks are not easy to control.
In the prior art, the desulfurization slag and the waste glaze slag are often treated as production garbage and are difficult to recycle. In view of the above, there is a need to provide a method for recycling desulfurization residues and waste glaze residues, so as to reduce or even eliminate the waste discharge of desulfurization residues and waste glaze residues and reduce the production cost of ceramic tiles.
Disclosure of Invention
The invention aims to provide a ceramic tile using desulfurization slag and glaze slag as raw materials and a production method thereof, and the ceramic tile has the characteristics of reducing the discharge amount of production garbage and reducing the production cost of the ceramic tile.
In order to achieve the purpose, the invention adopts the following technical scheme:
a ceramic tile using desulfurization slag and glaze slag as raw materials comprises the following raw materials in percentage by weight: 1-5% of mixed waste residue and 95-99% of basic raw material; the mixed waste residue consists of 75-90% of waste glaze slag and 10-25% of desulphurization slag in percentage by weight;
the waste glaze slag is waste glaze slag generated in the production process of ceramic tiles, and the desulphurization slag is waste slag generated by desulphurization of flue gas by using lime water.
According to the invention, the waste glaze slag and the waste slag generated by flue gas desulfurization are introduced into a basic formula, and the characteristics of low melting point, high-temperature melting degree, high fluidity, high desulfurization slag decomposition temperature and easiness in foaming of the waste glaze slag are utilized, so that bubbles generated by high-temperature decomposition of the desulfurization slag are compensated by the high-temperature melting body of the waste glaze slag, the sintering of a blank body is promoted, and the purposes of recycling the desulfurization slag and the waste glaze slag and ensuring that the performances of the product reach the standard are achieved. Meanwhile, the waste glaze slag and the desulphurization slag are recycled, so that the production waste discharge of the desulphurization slag and the waste glaze slag is avoided, the production cost of the ceramic tile can be reduced, and the quality of the finished ceramic tile is not influenced.
Further, the waste glaze slag comprises the following chemical components in percentage by mass: SiO 22 56-60％、Al2O3 20-23％、Fe2O3 0.2-0.3、TiO2 0.3-0.4％、CaO 2-2.8-％、MgO2-3％、K2O 2-3％、Na2O 2-3％、ZrO22-3%, ZnO 0.8-1.0% and IL 5-5.8%. The waste glaze slag is generated after precipitation and squeezing treatment of 3 waste glaze water generated by glaze making, ball washing and cleaning equipment in a ball glaze workshop and glaze dropping and the like in a glaze line production process in a ceramic tile production process. The waste glaze slag is mixed with other components, such as ZrO2The waste glaze slag has low sintering temperature, more low-temperature melting raw materials, high-temperature melting degree and low high-temperature viscosity.
Further, the desulfurization slag comprises the following chemical components in percentage by mass: SiO 22 52-55％、Al2O3 4-5％、Fe2O3 0.3-0.4％、CaO 32-36％、MgO0.3-0.4％、K2O 0.4-0.6％、Na2O0.4-0.6% and IL 4-5%. The reaction equation of the lime water sprayed in the chimney in a water curtain mode for desulfurization is as follows:
reaction equation 1: SO (SO)2+H2O＝＝H2SO3
Reaction equation 2: CaO + H2O＝＝Ca(OH)2
Reaction equation 3: h2SO3+Ca(OH)2＝＝CaSO3+2H2O
The desulfurization slag contains a large amount of calcium sulfite and a large amount of precipitator, and is obtained by mixing calcium sulfite which is difficult to dissolve in water and flows into a precipitation tank with water in the desulfurization process and then precipitating and squeezing.
Further, the basic raw materials comprise the following raw materials in percentage by weight based on the total amount of the raw materials of the ceramic tile: 10-15% of bauxite, 5-10% of high white sand, 10-13% of No. 4 sand, 6-8% of No. 8 sand, 3-5% of kaolin, 3-6% of Hunan pond mud, 2.5-3.5% of bentonite, 2.5-3.5% of magnesia mud, 10-13% of Zhang Jia sand, 6-10% of wall temple sand, 2-3% of kaolin, 4-6% of Hunan Shao mud, 4-6% of mixed mud and 6-8% of Xinguan sand;
the No. 4 sand and the No. 8 sand are medium-temperature sand.
A certain amount of high-temperature sand and high-alumina powder are introduced into the basic raw materials, the amount of alkali metal solvents such as potassium, sodium and the like in the formula is reduced, the initial melting temperature of the basic raw material formula is increased, the high-temperature exhaust of the formula is promoted, and the gas generated by the decomposition of sulfides in the desulfurization slag is ensured to be exhausted. The initial melting temperature of the basic raw material formula is increased to offset the lower melting temperature of the waste glaze slag, so that the ceramic tile has a proper firing temperature. The waste glaze slag has the characteristic of good high-temperature melting fluidity, so that the melted waste glaze slag can fill bubbles generated by the desulfuration slag at high temperature.
A method of producing ceramic tiles comprising the steps of:
(1) uniformly mixing waste glaze sewage containing waste glaze slag generated in the production process of the ceramic tile and waste water generated by desulfurizing flue gas by using lime water in proportion to prepare mixed waste slag;
(2) adding water into the mixed waste residue and the basic raw material, ball-milling to prepare ceramic slurry, and preparing the ceramic slurry into powder through spray granulation;
(3) and distributing the powder, pressing the powder into a layer blank, drying, decorating and sintering to obtain a finished ceramic tile product.
In the production method, the waste glaze sewage and the desulfurization waste water are mixed uniformly in advance and then are precipitated and filtered to prepare the mixed waste residue, so that the waste water treatment equipment can be simplified, the two waste residues can be mixed uniformly to the maximum extent, the two waste residues can be fully contacted in the firing process of the ceramic tile, the exhaust effect and the bubble filling effect are improved, the firing decomposition of the desulfurization residue is promoted under the action of the waste glaze residue, and the quality of the ceramic tile is improved.
Further, in the step (1), the pH value of the wastewater generated by desulfurizing the flue gas by using the lime water is controlled to be 7.0. During flue gas treatment, a limestone water atomization spraying mode is adopted to adsorb and react acid substances containing sulfur and the like in the flue gas and leave the acid substances in water. Under the influence of reaction time and degree, partial acid radical ions can not be completely reacted and precipitated and are dissociated in water, proper amount of lime water solution with low concentration is sprayed in the process that the desulfurization wastewater flows into a precipitation tank, the pH value of the treated water is controlled to be about 7.0, and the condition that sludge degumming is not influenced when waste residues are precipitated and recycled is ensured.
Further, in the step (2), the grain composition of the powder prepared by spray granulation is as follows: the proportion of the particles with more than 20 meshes in the total weight of the powder is less than 1.0 percent, the proportion of the particles with 40-80 meshes in the total weight of the powder is more than 95 percent, and the proportion of the particles with 100 meshes in the total weight of the powder is less than 3 percent;
the water content in the ceramic slurry is 34 percent, the flow rate of the slurry is 45-55s, the fineness of the slurry is 230-300 meshes, and the residue on the sieve is 1.0g/100 ml.
By regulating and controlling the grain size grading of the spray particles, the powder has good enough fluidity and better green body density, low porosity is realized, the mixed waste particles are uniformly distributed in the green body, and the filling of the waste glaze slag in the pores of the green body under the high-temperature condition is ensured.
By limiting the water content, flow rate and fineness of the ceramic slurry, the ceramic slurry has good fluidity, the basic raw materials and the mixed waste residues are fully peptized, and the spraying powder preparation is facilitated.
Further, in the step (3), in the drying step, the drying period is 65min, the drying temperature is controlled at 85 +/-5 ℃, and the strength of the dried green body is 1.5-1.8 Mpa;
in the firing step, the firing temperature is 1200-.
By limiting the drying parameters of the green body, the drying time of the green body is reduced under the condition of ensuring that the green body has enough drying degree. Under the condition of adjusting the drying time and the drying temperature. The green body after the mixed waste slag is introduced still has enough strength and is not easy to crack.
Further, in the step (3), the pressure for pressing and forming the blank is 300-340Kg/cm2Pressing for molding, wherein the pressing frequency is 8-8.5 times/min.
Further, in the step (3), the decorating step is as follows: glazing the dried green body, and then decorating the glaze surface in an ink-jet mode, a screen printing mode and/or a roller mode;
the flow rate of glaze for glazing the blank body is 23-28 s, the specific gravity is 1.90 +/-0.02 g/ml, the fineness of the glaze is 325 meshes, and the surplus is 0.8g/100 ml.
The invention has the beneficial effects that:
the waste glaze slag and the desulphurization slag are introduced into the ceramic tile formula, and the characteristics of low melting point, high melting degree, high fluidity, high desulphurization slag decomposition temperature and easiness in foaming of the waste glaze slag are utilized, so that bubbles generated by high-temperature decomposition of the desulphurization slag are compensated by the high-temperature melting body of the waste glaze slag, the sintering of a blank body is promoted, and the purposes of recycling the desulphurization slag and the waste glaze slag and ensuring that the performances of the product reach the standard are achieved. Meanwhile, the waste glaze slag and the desulphurization slag are recycled, so that the production waste discharge of the desulphurization slag and the waste glaze slag is avoided, the production cost of the ceramic tile can be reduced, and the quality of the finished ceramic tile is not influenced.
In order to improve the influence of the exhaust of pyrolysis gas of the desulfurized waste residue on the sintering of a green body, the invention introduces a certain amount of high-temperature sand and high-alumina powder into the formula of the ceramic tile, reduces the amount of alkali metal melts such as potassium, sodium and the like in the formula, improves the initial melting temperature of the formula, promotes the high-temperature exhaust of the formula, and ensures that all properties of products after the mixed waste residue is used reach the standard.
According to the ceramic tile production method, waste glaze sewage and waste water generated by flue gas desulfurization by lime water are uniformly mixed in proportion and then are made into mixed waste residues, so that the waste glaze and the desulfurization residues are uniformly mixed, the waste glaze and the desulfurization residues are uniformly mixed and fused into a whole in the firing process of the ceramic tile, bubbles generated in the firing process of the desulfurization waste residues after recycling can be fully compensated by the waste glaze residues, the firing decomposition of the desulfurization residues is promoted under the action of the waste glaze residues, and a blank body is ensured to have sufficient sintering degree and sufficient mechanical property.
Detailed Description
The technical solution of the present invention will be further described with reference to the accompanying embodiments.
A ceramic tile using desulfurization slag and glaze slag as raw materials comprises the following raw materials in percentage by weight: 1-5% of mixed waste residue and 95-99% of basic raw material; the mixed waste residue consists of 75-90% of waste glaze slag and 10-25% of desulphurization slag in percentage by weight;
the waste glaze slag is waste glaze slag generated in the production process of ceramic tiles, and the desulphurization slag is waste slag generated by desulphurization of flue gas by using lime water.
According to the invention, the waste glaze slag and the waste slag generated by flue gas desulfurization are introduced into a basic formula, and the characteristics of low melting point, high-temperature melting degree, high fluidity, high desulfurization slag decomposition temperature and easiness in foaming of the waste glaze slag are utilized, so that bubbles generated by high-temperature decomposition of the desulfurization slag are compensated by the high-temperature melting body of the waste glaze slag, the sintering of a blank body is promoted, and the purposes of recycling the desulfurization slag and the waste glaze slag and ensuring that the performances of the product reach the standard are achieved. Meanwhile, the waste glaze slag and the desulphurization slag are recycled, so that the production waste discharge of the desulphurization slag and the waste glaze slag is avoided, the production cost of the ceramic tile can be reduced, and the quality of the finished ceramic tile is not influenced.
Further, the waste glaze slag comprises the following chemical components in percentage by mass: SiO 22 56-60％、Al2O3 20-23％、Fe2O3 0.2-0.3、TiO2 0.3-0.4％、CaO 2-2.8-％、MgO2-3％、K2O 2-3％、Na2O 2-3％、ZrO22-3%, ZnO 0.8-1.0% and IL 5-5.8%. The waste glaze slag is generated after precipitation and squeezing treatment of 3 waste glaze water generated by glaze making, ball washing and cleaning equipment in a ball glaze workshop and glaze dropping and the like in a glaze line production process in a ceramic tile production process. The waste glaze slag is mixed with other components, such as ZrO2The waste glaze slag has low sintering temperature, more and high low-temperature melting raw materialsHigh warm melt and low high temperature viscosity.
Preferably, the waste glaze slag comprises the following chemical components in percentage by mass: SiO 22 58.79％、Al2O3 21.67％、Fe2O3 0.27％、TiO2 0.35％、CaO 2.30％、MgO 2.51％、K2O 2.48％、Na2O 2.67％、ZrO22.30%, ZnO 0.90% and IL 5.35%.
Further, the desulfurization slag comprises the following chemical components in percentage by mass: SiO 22 52-55％、Al2O3 4-5％、Fe2O3 0.3-0.4％、CaO 32-36％、MgO0.3-0.4％、K2O 0.4-0.6％、Na2O0.4-0.6% and IL 4-5%. The reaction equation of the lime water sprayed in the chimney in a water curtain mode for desulfurization is as follows:
reaction equation 1: SO (SO)2+H2O＝＝H2SO3
Reaction equation 2: CaO + H2O＝＝Ca(OH)2
Reaction equation 3: h2SO3+Ca(OH)2＝＝CaSO3+2H2O
The desulfurization slag contains a large amount of calcium sulfite and a large amount of precipitator, and is obtained by mixing calcium sulfite which is difficult to dissolve in water and flows into a precipitation tank with water in the desulfurization process and then precipitating and squeezing.
Preferably, the desulfurization slag comprises the following chemical components in percentage by mass: SiO 22 53.40％、Al2O3 4.56％、Fe2O3 0.33％、CaO 34.99％、MgO0.33％、K2O 0.5％、Na2O0.49% and IL 4.56%.
Further, the basic raw materials comprise the following raw materials in percentage by weight based on the total amount of the raw materials of the ceramic tile: 10-15% of bauxite, 5-10% of high white sand, 10-13% of No. 4 sand, 6-8% of No. 8 sand, 3-5% of kaolin, 3-6% of Hunan pond mud, 2.5-3.5% of bentonite, 2.5-3.5% of magnesia mud, 10-13% of Zhang Jia sand, 6-10% of wall temple sand, 2-3% of kaolin, 4-6% of Hunan Shao mud, 4-6% of mixed mud and 6-8% of Xinguan sand; the No. 4 sand and the No. 8 sand are medium-temperature sand. The Hunan pond mud, Zhang Jia sand, wall temple sand, Xiangshao mud and Xinguang sand are named as raw materials of a production place, and the firing stability of basic raw materials can be ensured by using the raw materials of the production place. Sand No. 4 was purchased for yi baohua; no. 8 sand was purchased from Linxiang, Xinrong mining Co., Ltd. The mixed mud is purchased from Yaqi ceramic business in Yueyang building area.
A certain amount of high-temperature sand and high-alumina powder are introduced into the basic raw materials, the amount of alkali metal solvents such as potassium, sodium and the like in the formula is reduced, the initial melting temperature of the basic raw material formula is increased, the high-temperature exhaust of the formula is promoted, and the gas generated by the decomposition of sulfides in the desulfurization slag is ensured to be exhausted. The initial melting temperature of the basic raw material formula is increased to offset the lower melting temperature of the waste glaze slag, so that the ceramic tile has a proper firing temperature. The waste glaze slag has the characteristic of good high-temperature melting fluidity, so that the melted waste glaze slag can fill bubbles generated by the desulfuration slag at high temperature.
A method of producing ceramic tiles comprising the steps of:
(1) uniformly mixing waste glaze sewage containing waste glaze slag generated in the production process of the ceramic tile and waste water generated by desulfurizing flue gas by using lime water in proportion to prepare mixed waste slag;
(2) adding water into the mixed waste residue and the basic raw material, ball-milling to prepare ceramic slurry, and preparing the ceramic slurry into powder through spray granulation;
(3) and distributing the powder, pressing the powder into a layer blank, drying, decorating and sintering to obtain a finished ceramic tile product.
In the production method, the waste glaze sewage and the desulfurization waste water are mixed uniformly in advance and then are precipitated and filtered to prepare the mixed waste residue, so that the waste water treatment equipment can be simplified, the two waste residues can be mixed uniformly to the maximum extent, the two waste residues can be fully contacted in the firing process of the ceramic tile, the exhaust effect and the bubble filling effect are improved, the firing decomposition of the desulfurization residue is promoted under the action of the waste glaze residue, and the quality of the ceramic tile is improved.
Further, in the step (1), the pH value of the wastewater generated by desulfurizing the flue gas by using the lime water is controlled to be 7.0. During flue gas treatment, a limestone water atomization spraying mode is adopted to adsorb and react acid substances containing sulfur and the like in the flue gas and leave the acid substances in water. Under the influence of reaction time and degree, partial acid radical ions can not be completely reacted and precipitated and are dissociated in water, proper amount of lime water solution with low concentration is sprayed in the process that the desulfurization wastewater flows into a precipitation tank, the pH value of the treated water is controlled to be about 7.0, and the condition that sludge degumming is not influenced when waste residues are precipitated and recycled is ensured.
Further, in the step (2), the grain composition of the powder prepared by spray granulation is as follows: the proportion of the particles with more than 20 meshes in the total weight of the powder is less than 1.0 percent, the proportion of the particles with 40-80 meshes in the total weight of the powder is more than 95 percent, and the proportion of the particles with 100 meshes in the total weight of the powder is less than 3 percent;
the water content in the ceramic slurry is 34 percent, the flow rate of the slurry is 45-55s, the fineness of the slurry is 230-300 meshes, and the residue on the sieve is 1.0g/100 ml. The slurry flow rate was measured with a # 4 paint cup test.
By regulating and controlling the grain size grading of the spray particles, the powder has good enough fluidity and better green body density, low porosity is realized, the mixed waste particles are uniformly distributed in the green body, and the filling of the waste glaze slag in the pores of the green body under the high-temperature condition is ensured.
By limiting the water content, flow rate and fineness of the ceramic slurry, the ceramic slurry has good fluidity, the basic raw materials and the mixed waste residues are fully peptized, and the spraying powder preparation is facilitated.
Further, in the step (3), in the drying step, the drying period is 65min, the drying temperature is controlled at 85 +/-5 ℃, and the strength of the dried green body is 1.5-1.8 Mpa;
in the firing step, the firing temperature is 1200-.
By limiting the drying parameters of the green body, the drying time of the green body is reduced under the condition of ensuring that the green body has enough drying degree. Under the condition of adjusting the drying time and the drying temperature. The green body after the mixed waste slag is introduced still has enough strength and is not easy to crack.
Further, in the step (3), the pressure for pressing and forming the blank is 300-340Kg/cm2Pressing for molding, wherein the pressing frequency is 8-8.5 times/min.
Further, in the step (3), the decorating step is as follows: glazing the dried green body, and then decorating the glaze surface in an ink-jet mode, a screen printing mode and/or a roller mode;
the flow rate of glaze for glazing the blank body is 23-28 s, the specific gravity is 1.90 +/-0.02 g/ml, the fineness of the glaze is 325 meshes, and the surplus is 0.8g/100 ml.
When ink-jet printing is adopted for printing, the colors of 1-5 channels are respectively blue/reddish brown/lemon yellow/orange yellow/black, the ink-jet printing temperature is within 45 ℃, the distance between a spray head and a blank body is 3.5mm, and the belt speed is 22-25 m/min.
When the blank is decorated, one or the combination of the three printing modes of ink jet, screen printing plate and roller can be selected to achieve richer decoration effect, or the three printing modes are selected to obtain decorative patterns with abundant patterns and good three-dimensional effect. After the decoration step is finished, a protective layer can be arranged on the decoration layer in a mode of applying dry particles, transparent glaze, semitransparent glaze or frosted glaze.
Example group A
Mixing the desulphurization slag and the waste glaze slag according to different proportions, ball-milling and pulping, respectively decorating and burning, and judging the state of the mixed waste slag after burning. The compositions of the desulphurization slag and the waste glaze slag in percentage by weight in the mixed waste residue of each example are shown in the following table.
| Waste slag | Example A1 | Example A2 | Practice ofExample A3 | Example A4 | Example A5 | Example A6 | Example A7 |
| Desulfurized slag | 0 | 10 | 15 | 20 | 25 | 80 | 100 |
| Waste glaze slag | 100 | 90 | 85 | 80 | 75 | 20 | 0 |
The mixed slag of examples A1 to A7 were ball-milled, fired separately, and the states after firing are described in the following tables. Wherein, the weight of water in the mixed waste residue slurry obtained by ball milling is 34 percent, the flow rate of the slurry is 45-55s, the fineness of the slurry is 230-300 meshes, and the residue on sieve is 1.0g/100 ml; the firing temperature is 1200-1220 ℃.
As can be seen from the above table, the mixed waste material contains 90-75% of waste glaze slag and desulfurization slag: when the content is between 10 and 25 percent, the sintered product has a smoother surface and a small amount of air holes after being sintered alone, and the waste glaze slag can better promote the exhaust of the desulphurization slag.
Example group B
The ceramic tiles of examples B1-B6 were produced from the mixed slag of example A3, combined with a base material, and formulated as shown in the following table.
| Raw materials | Example B1 | Example B2 | Example B3 | Example B4 | Example B5 | Example B6 |
| Mixed waste slag | 1％ | 2％ | 3％ | 4％ | 5％ | 6％ |
| High alumina stone | 15％ | 15％ | 13％ | 10％ | 14％ | 12％ |
| High white sand | 10％ | 5％ | 10％ | 10％ | 7％ | 7％ |
| No. 4 sand | 10％ | 13％ | 13％ | 13％ | 11％ | 12％ |
| No. 8 sand | 8％ | 6％ | 8％ | 8％ | 7％ | 7％ |
| Kaolin clay | 3％ | 5％ | 5％ | 5％ | 5％ | 5％ |
| Xiangtan mud | 3％ | 6％ | 5％ | 5％ | 5％ | 5％ |
| Bentonite clay | 3.5％ | 2.5％ | 3％ | 3％ | 3％ | 3％ |
| Magnesium mud | 2.5％ | 3.5％ | 3％ | 3％ | 3％ | 3％ |
| Zhangjia sand | 13％ | 12％ | 10％ | 11％ | 12％ | 12％ |
| Wall temple sand | 10％ | 10％ | 6％ | 7％ | 8％ | 8％ |
| Kaolin clay | 3％ | 2％ | 3％ | 3％ | 3％ | 3％ |
| Xiangshao mud | 4％ | 6％ | 6％ | 6％ | 5％ | 5％ |
| Mixed mud | 6％ | 4％ | 6％ | 6％ | 5％ | 5％ |
| Novel polishing sand | 8％ | 8％ | 6％ | 6％ | 7％ | 7％ |
The production process of the ceramic tiles of example groups B1-B6 all comprises the following steps:
(1) uniformly mixing waste glaze sewage containing waste glaze slag generated in the production process of the ceramic tile and waste water generated by desulfurizing flue gas by using lime water in proportion to prepare mixed waste slag; wherein the pH value of the wastewater generated by desulfurizing the flue gas by using the lime water is controlled to be 7.0;
(2) adding water into the mixed waste residue and the basic raw materials, and ball-milling the mixed waste residue and the basic raw materials to prepare ceramic slurry, wherein the weight of the water in the ceramic slurry is 34 percent, the flow rate of the slurry is 45-55s, the fineness of the slurry is 230-mesh and 300-mesh, and the surplus sieve is 1.0g/100 ml. The ceramic slurry is prepared into powder by spray granulation, and the particle composition of the powder prepared by spray granulation is as follows: the proportion of the particles with more than 20 meshes in the total weight of the powder is less than 1.0 percent, the proportion of the particles with 40-80 meshes in the total weight of the powder is more than 95 percent, and the proportion of the particles with 100 meshes in the total weight of the powder is less than 3 percent;
(3) and distributing the powder, pressing the powder into a layer blank, drying, decorating and sintering to obtain a finished ceramic tile product. In the drying step, the drying period is 65min, the drying temperature is controlled at 85 +/-5 ℃, and the strength of the dried blank is 1.5-1.8 Mpa; in the firing step, the firing temperature is 1200-. The pressure for pressing and molding the blank is 300-340Kg/cm2Pressing for molding, wherein the pressing frequency is 8-8.5 times/min. The decoration steps are as follows: glazing the dried green body, and then decorating the glaze surface in an ink-jet mode, a screen printing mode and/or a roller mode; the flow rate of glaze for glazing the blank body is 23-28 s, the specific gravity is 1.90 +/-0.02 g/ml, the fineness of the glaze is 325 meshes, and the surplus is 0.8g/100 ml.
The ceramic tiles of example set B were tested and the results are shown in the following table.
| Examples | Water absorption% | Modulus of rupture Mpa | Brick shape | Surface quality |
| Example B1 | 0.10 | 38.5 | No deformation after the blank is fired | Has smooth surface |
| Example B2 | 0.11 | 3.81 | No deformation after the blank is fired | Has smooth surface |
| Example B3 | 0.13 | 38.7 | No deformation after the blank is fired | Has smooth surface |
| Example B4 | 0.14 | 38.9 | No deformation after the blank is fired | Has smooth surface |
| Example B5 | 0.15 | 39.6 | No deformation after the blank is fired | Has smooth surface |
| Example B6 | 0.3 | 36.4 | No deformation after the blank is fired | The surface is smoother |
As can be seen from the above table, the ceramic tiles of examples B1-B5 have better detection results, the ceramic tiles of example B6 have slightly poorer detection results, and when the addition amount of the mixed waste residue is set to 1-5%, the ceramic tiles can be ensured to have better quality.
Example set C
The ceramic tiles of examples C1-C3 were prepared from the base materials of example B3 in combination with the mixed slags of examples A2, A4 and A5, and the specific formulations are shown in the following table.
| Raw materials (weight percentage) | Example C1 | Example C2 | Example C3 |
| 3 percent of mixed waste residue | Example A2 | Example A4 | Example A5 |
| 97 percent of basic raw material | Base stock of example B3 | Base stock of example B3 | Base stock of example B3 |
The production process for ceramic tiles of this example set C is the same as that of example set B. Through detection, the ceramic tile of the embodiment C1-C3 has better detection result and the finished product has better quality.
The technical principle of the present invention is described above in connection with specific embodiments. The description is made for the purpose of illustrating the principles of the invention and should not be construed in any way as limiting the scope of the invention. Based on the explanations herein, those skilled in the art will be able to conceive of other embodiments of the present invention without inventive effort, which would fall within the scope of the present invention.
Claims (9)
1. A ceramic tile using desulfurization slag and glaze slag as raw materials is characterized in that the ceramic tile comprises the following raw materials in percentage by weight: 1-5% of mixed waste residue and 95-99% of basic raw material; the mixed waste residue consists of 75-90% of waste glaze residue and 10-25% of desulphurization residue in percentage by weight;
the waste glaze slag is generated in the production process of ceramic tiles, and the desulfurization slag is generated by desulfurizing flue gas with lime water;
the basic raw materials comprise the following raw materials in percentage by weight based on the total amount of the ceramic tile raw materials: 10-15% of bauxite, 5-10% of high white sand, 10-13% of No. 4 sand, 6-8% of No. 8 sand, 5-8% of kaolin, 3-6% of Hunan pond mud, 2.5-3.5% of bentonite, 2.5-3.5% of magnesia mud, 10-13% of Zhang Jia sand, 6-10% of wall temple sand, 4-6% of Hunan Shao mud, 4-6% of mixed mud and 6-8% of Xinguang sand;
the No. 4 sand and the No. 8 sand are medium-temperature sand.
2. Ceramic tile according to claim 1, characterized in that the percentage by mass of the waste enamel residues
The chemical components of the ratio meter comprise: SiO 22 56-60%、Al2O3 20-23%、Fe2O3 0.2-0.3、TiO2 0.3-0.4%、CaO 2-2.8-%、MgO2-3%、K2O 2-3%、Na2O 2-3%、ZrO2 2-3%, ZnO 0.8-1.0% and IL 5-5.8%.
3. The ceramic tile as claimed in claim 1, wherein the chemical components of the desulfurized slag by mass percentage comprise: SiO 22 52-55%、Al2O3 4-5%、Fe2O3 0.3-0.4%、CaO 32-36%、MgO0.3-0.4%、K2O 0.4-0.6%、Na2O0.4-0.6% and IL 4-5%.
4. A process for the production of ceramic tiles as claimed in any one of claims 1 to 3, characterized by comprising the following steps:
(1) uniformly mixing waste glaze sewage containing waste glaze slag generated in the production process of the ceramic tile and waste water generated by desulfurizing flue gas by using lime water in proportion to prepare mixed waste slag;
(2) adding water into the mixed waste residue and the basic raw material, ball-milling to prepare ceramic slurry, and preparing the ceramic slurry into powder through spray granulation;
(3) and pressing the powder material after distribution into a blank, and drying, decorating and sintering to obtain a finished ceramic tile product.
5. The method for producing ceramic tiles according to claim 4, wherein in the step (1), the pH value of the wastewater generated by desulfurizing flue gas with lime water is controlled at 7.0.
6. The method for producing ceramic tiles according to claim 4, wherein in the step (2), the grain composition of the spray granulation powder is as follows: the proportion of the particles with more than 20 meshes in the total weight of the powder is less than 1.0 percent, the proportion of the particles with 40-80 meshes in the total weight of the powder is more than 95 percent, and the proportion of the particles with 100 meshes in the total weight of the powder is less than 3 percent;
the weight of the water in the ceramic slurry is 34%, the flow rate of the slurry is 45-55s, the fineness of the slurry is 230-300 meshes, and the residue on the sieve is 1.0g/100 ml.
7. The ceramic tile production method according to claim 4, wherein in the step (3), in the drying step, the drying period is 65min, the drying temperature is controlled at 85 ± 5 ℃, and the strength of the green body after drying is 1.5-1.8 Mpa;
in the firing step, the firing temperature is 1200-1220 ℃.
8. The method for producing ceramic tiles as claimed in claim 4, wherein in the step (3), the pressure for press forming the blank is 300-340Kg/cm2Pressing for molding, wherein the pressing frequency is 8-8.5 times/min.
9. The production method of ceramic tiles as claimed in claim 4, characterized in that in the step (3), the decoration step is: glazing the dried green body, and then decorating the glaze surface in an ink-jet mode, a screen printing mode and/or a roller mode;
the flow rate of glaze for glazing the blank body is 23-28 s, the specific gravity is 1.90 +/-0.02 g/ml, the fineness of the glaze is 325 meshes, and the surplus is 0.8g/100 ml.
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