阅读说明：本技术 一种由锂辉石矿渣代替高岭土制备陶瓷的方法 (Method for preparing ceramic by replacing kaolin with spodumene slag ) 是由 李良彬 郁兴国 王彬 陈超 彭琴 付晓春 高贵彦 周峰 朱志全 符龙 刘小康 于 2020-04-10 设计创作，主要内容包括：本发明公开了一种由锂辉石矿渣代替高岭土制备陶瓷的方法,制备陶瓷的配方包含陶瓷胚料和陶瓷釉料；所述的陶瓷胚料包含如下质量百分比原料：锂辉石矿渣50-75wt%、石英砂10-20wt%、钾长石1-10wt%、钠长石1-10wt%；陶瓷釉料包含如下质量百分比原料：锂辉石矿渣40-60wt%、石英砂15-40wt%、长石15-20wt%、瓷石1-10wt%；将原料按相应比例添加后混合均匀,陶瓷胚料1100-1250℃,烧制时间在12h以上,陶瓷釉料1200-1300℃,烧制时间为15-48h。本发明将锂辉石矿渣代替高岭土等矿石制备陶瓷材料,锂辉石的利用率高。(The invention discloses a method for preparing ceramic by spodumene slag instead of kaolin, wherein the formula for preparing the ceramic comprises a ceramic blank and a ceramic glaze; the ceramic blank comprises the following raw materials in percentage by mass: 50-75wt% of spodumene slag, 10-20wt% of quartz sand, 1-10wt% of potash feldspar and 1-10wt% of albite; the ceramic glaze comprises the following raw materials in percentage by mass: 40-60wt% of spodumene slag, 15-40wt% of quartz sand, 15-20wt% of feldspar and 1-10wt% of porcelain stone; the raw materials are added according to the corresponding proportion and then uniformly mixed, the ceramic blank material is 1100-. The invention replaces the ores such as kaolin and the like with spodumene slag to prepare the ceramic material, and the utilization rate of spodumene is high.)

1. A method for preparing ceramic by spodumene slag instead of kaolin, characterized by that the formulation to prepare ceramic includes ceramic stock and ceramic glaze; the ceramic blank comprises the following raw materials in percentage by mass: 50-75wt% of spodumene slag, 10-20wt% of quartz sand, 1-10wt% of potash feldspar and 1-10wt% of albite; the ceramic glaze comprises the following raw materials in percentage by mass: 40-60wt% of spodumene slag, 15-40wt% of quartz sand, 15-20wt% of feldspar and 1-10wt% of porcelain stone.

2. The method for preparing ceramic according to claim 1, wherein the ceramic green material further comprises one or more of clay, talc, fly ash, wollastonite, and quartz sand, and the total addition amount is not more than 20%.

3. The method for preparing ceramic according to claim 1, wherein the ceramic glaze further comprises one or more of clay, agalmatolite, talc, zinc oxide, and barium carbonate, and the total addition amount is not more than 30%.

4. A method for preparing a ceramic from spodumene slag instead of kaolin, characterized in that it comprises the steps of:

A. the raw material treatment process comprises the following steps:

s1, adding spodumene slag into dilute sulfuric acid with the concentration of 7-9% for acidification;

s2, carrying out solid-liquid separation on the acidified spodumene slag through pressure filtration;

s3, drying the spodumene slag at normal temperature;

s4, screening the spodumene slag by using a screening machine;

s5, crushing the mixed material by using a ball mill to obtain fine powder;

s6, an electromagnetic iron remover is adopted to remove iron from the fine powder so as to increase the whiteness of the ceramic;

B. the ceramic preparation process comprises the following steps:

s7, preparing the processed fine powder and other raw materials into slurry according to a proportion;

s8, obtaining finished slurry for preparing the ceramic blank and finished glaze for preparing glaze;

s9, respectively molding the slurry and the glaze;

s10, drying by hot air to evaporate the moisture in the wet embryo, so as to reduce energy loss caused by vaporization of a large amount of moisture during firing;

s11, placing the mixture into a kiln for firing;

and S12, obtaining the required ceramic blank and glaze product.

5. The method for preparing ceramic according to claim 4, wherein the spodumene slag replaces kaolin, and the method is characterized in that in step S4, the screening size of the screening machine is 300 meshes and 100 meshes, so as to obtain three parts of particles, including small particles smaller than 300 meshes, large particles of 100 meshes and 300 meshes and super large particles larger than 100 meshes; the small particles smaller than 300 meshes are used for preparing ceramic glaze, the large particles of 100 meshes and 300 meshes are used for preparing ceramic blank, and the ultra-large particle components larger than 100 meshes are recycled after being crushed.

6. The method of preparing ceramic according to claim 4, wherein the fineness of the fine powder is more than ten times the fineness of the finished slurry in step S5.

7. The method for preparing ceramic according to claim 4, wherein in step S11, firing is performed by a secondary firing process, including low-temperature bisque firing and glaze firing; the low-temperature bisque firing temperature is 1100-1250 ℃, and the firing time is more than 12 h; the firing temperature of the glaze is 1200-1300 ℃, and the firing time is 15-48 h.

Technical Field

The invention relates to the field of ceramic preparation and solid waste resource application, in particular to a method for preparing ceramic by replacing kaolin with spodumene slag.

Background

Spodumene is one of the most important lithium mineral resources, and with the development of the lithium battery industry, the application of lithium resources in the current society is more and more extensive. Currently, methods for extracting lithium are classified into lithium ore and salt lake brine. Because the distribution site of the salt lake brine in China is relatively far away, and the lithium ore resources are widely distributed, the extraction of lithium from the ore becomes a main method for selecting lithium in China.

Spodumene (L i)₂O·Al₂O₃·4SiO₂) Containing L i₂O 8.1%、Al₂O₃27.54%、SiO₂64.5%, and small amount of MgO, MnO and Fe₃O₄The spodumene slag is also called calcium silicate slag, wherein the spodumene slag mainly contains two elements of calcium silicate and the chemical components of the calcium silicate and the calcium silicate mainly comprise CaO and SiO₂、Al₂O₃And MgO and the like. In order to improve living environment and realize resource recycling, spodumene slag needs to be reasonably utilized, so that waste materials are changed into valuable materials.

A common sintered ceramic material is kaolin. Kaolin is a limited mineral resource, damages the environment after long-term mining, and is concentrated respectively, so that the application range of the kaolin is limited. The main component of kaolin is 2SiO₂·Al₂O₃·2H₂O, theoretical chemical composition of which is 46.54% SiO₂39.5% of Al₂O₃13.96% of H₂O, the component of which is mainly SiO₂、Al₂O₃And the like, which is close to spodumene slag, provides possibility for spodumene slag to replace ores such as kaolin and the like to prepare ceramic materials. Compared with other granite ores, spodumene slag as a ceramic additive has the following advantages: 1. the spodumene slag is an unsaturated aluminosilicate mineral, has fire resistance, can be mixed with other silicate minerals for use, and can deprive silicon to form low-temperature feldspar porcelain; 2. spodumene slag high temperatureThe conversion has the characteristics of non-reversibility and low expansion, can prevent the high-temperature shrinkage of the blank and the glaze, and is suitable for low-temperature rapid firing; 3. spodumene can absorb silicon, making the ceramic more transparent.

The biggest problem of spodumene slag for the preparation of ceramic materials is that it is too basic, and because excess soda ash needs to be added during the extraction of lithium to neutralize the acidified spodumene, spodumene slag generally has strong basicity. The spodumene slag required for preparing ceramics has an alkali content of 0.5% or less, and therefore, dealkalization is required during use. Meanwhile, the spodumene slag contains Fe₂O₃And the like, also affect the performance of the ceramic, such as whiteness, surface smoothness and the like.

Disclosure of Invention

The invention aims to provide a method for preparing ceramic by replacing kaolin with spodumene slag aiming at the defects and shortcomings of the prior art, which can effectively replace the spodumene slag with the kaolin and other ores to prepare ceramic materials, wherein the addition amount of the spodumene slag is more than 40%; meanwhile, the slag is screened and respectively used for preparing the blank and the glaze, so that the utilization rate of spodumene is improved, the problem of accumulation of spodumene slag is effectively solved, and the cyclic utilization of resources is realized.

In order to achieve the purpose, the invention adopts the technical scheme that: the formula for preparing the ceramic comprises a ceramic blank and a ceramic glaze material; the ceramic blank comprises the following raw materials in percentage by mass: 50-75wt% of spodumene slag, 10-20wt% of quartz sand, 1-10wt% of potash feldspar and 1-10wt% of albite; the ceramic glaze comprises the following raw materials in percentage by mass: 40-60wt% of spodumene slag, 15-40wt% of quartz sand, 15-20wt% of feldspar and 1-10wt% of porcelain stone.

Furthermore, the ceramic blank also comprises one or more combined raw materials of clay, talcum, fly ash, wollastonite and quartz sand, and the total addition amount is not more than 20%;

further, the ceramic glaze also comprises one or more of clay, agalmatolite, talc, zinc oxide and barium carbonate, and the total addition amount is not more than 30%.

The method for preparing ceramic by replacing kaolin with spodumene slag comprises the following steps:

A. the raw material treatment process comprises the following steps:

s1, adding spodumene slag into dilute sulfuric acid with the concentration of 7-9% for acidification;

s2, carrying out solid-liquid separation on the acidified spodumene slag through pressure filtration;

s3, drying the spodumene slag at normal temperature;

s4, screening the spodumene slag by using a screening machine;

s5, crushing the mixed material by using a ball mill to obtain fine powder;

s6, an electromagnetic iron remover is adopted to remove iron from the fine powder so as to increase the whiteness of the ceramic;

B. the ceramic preparation process comprises the following steps:

s7, preparing the processed fine powder and other raw materials into slurry according to a proportion;

s8, obtaining finished slurry for preparing the ceramic blank and finished glaze for preparing glaze;

s9, respectively molding the slurry and the glaze;

s10, drying by hot air to evaporate the moisture in the wet embryo, so as to reduce energy loss caused by vaporization of a large amount of moisture during firing;

s11, placing the mixture into a kiln for firing;

and S12, obtaining the required ceramic blank and glaze product.

Further, in step S4, the screening size of the screening machine is 300 meshes and 100 meshes, so as to obtain three parts of particles, including small particles smaller than 300 meshes, large particles of 100 meshes and 300 meshes and ultra-large particles larger than 100 meshes; the small particles smaller than 300 meshes are used for preparing ceramic glaze, the large particles of 100 meshes and 300 meshes are used for preparing ceramic blank, and the ultra-large particle components larger than 100 meshes are crushed and then recycled;

further, in step S5, the fineness of the fine powder is more than ten times the fineness of the finished pulp;

further, in step S11, firing adopts a secondary firing process, and performs low-temperature bisque firing and then firing of glaze; the low-temperature bisque firing temperature is 1100-1250 ℃, and the firing time is more than 12 h; the firing temperature of the glaze is 1200-1300 ℃, and the firing time is 15-48 h.

According to the method for preparing the ceramic by replacing the kaolin with the spodumene slag, the spodumene slag can be consumed in a large amount, the mass of the spodumene slag accounts for more than 40%, the prepared ceramic is excellent in performance, the whiteness is higher than 70%, and the strength and the hardness are high; meanwhile, because the spodumene slag contains about 0.3% of lithium, the obtained ceramic has low thermal expansion and good light transmission performance.

Compared with the prior art, the method for preparing the ceramic by replacing kaolin with spodumene slag has the following advantages:

1. the spodumene slag is used for preparing the ceramic material, so that the spodumene slag is changed into valuable, the problem that the slag pollutes the environment is solved, the exploitation of kaolin is reduced, the cyclic utilization of resources is realized, and the ceramic material is energy-saving and environment-friendly;

2. the spodumene slag contains a large amount of calcium silicate, and the calcium silicate can reduce the firing temperature of a blank and glaze; the spodumene slag is adopted to prepare the ceramic additive, so that the energy consumption of ceramic production can be reduced, the energy is saved, and the production cost of the ceramic is reduced; meanwhile, the spodumene slag also has the advantages of improving the mechanical strength and the thermal shock resistance of the ceramic, good chemical stability and the like, and can be used for preparing some special ceramics, such as thermal shock resistant ceramics, low-expansion heat resistant ceramics and the like;

3. the method for removing alkali by sulfuric acid leaching has good alkali removing effect and low cost, and also has certain reference value for spodumene used for other purposes;

4. the solid iron removal is carried out by adopting an electromagnetic iron remover, so that the problems of low ceramic whiteness, attractive color and the like caused by Fe2O3 can be solved, and spodumene can absorb silicon, so that the light transmittance of the ceramic is better;

5. the spodumene slag is screened and then used, and the large particles and the small particles are respectively used as glaze and embryo bodies, so that the application range of the spodumene slag is widened, and the economic benefit of the spodumene slag as a ceramic raw material is increased.

Drawings

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.

FIG. 1 is a process flow diagram for preparing a ceramic additive from spodumene slag according to the present invention.

Detailed Description

The invention will be further described with reference to the accompanying drawings.