CN104003700A - Method for preparing environment-friendly ceramic vitrified brick by using waste slag - Google Patents

Abstract

The invention discloses a method for preparing an environment-friendly ceramic vitrified brick by using waste slags. The environment-friendly ceramic vitrified brick is obtained by applying a new sintering method and a new decoration technology to a conventional ceramic product on the basis of introducing a great number of waste slags and optimizing a conventional technological process, and is prepared by performing once molding and twice laser short-time sintering according to a dry method; meanwhile, ink-jet printing or 3D (three-dimensional) printing are applied to the surface decoration of a heat preservation brick, thus better enriching the surface effects of the heat preservation brick. The environment-friendly ceramic vitrified brick disclosed by the invention is environment-friendly, clean and pollution-free in production, has the water absorption rate approximate to 0, has the breaking strength of 55-75MPa, and is very excellent in vitrification effect; moreover, the environment-friendly ceramic vitrified brick has decoration effects, and is convenient in construction and safe and reliable in use.

Description

A method of using waste slag to prepare environment-friendly ceramic vitrified bricks

technical field

The invention belongs to the field of environment-friendly functional building materials, and in particular relates to a method for preparing environment-friendly ceramic vitrified bricks by utilizing waste slag.

Background technique

Today, the environmental protection and health of building ceramics has received unprecedented attention. The decoration of people's home space is becoming diversified, personalized and fashionable, healthy and noble, and the materials are environmentally friendly, non-radiation, easy to clean, antibacterial, anti-fouling and anti-corrosion, green and multi-functional are the goals people pursue, and new materials, The continuous use of new technology, new equipment and new technology has promoted the development of building ceramic products, and is developing towards a higher, faster and better direction. Personalization, personalization, humanization, artistry, naturalization and multi-functional development trends. Ceramic tile products have broken through the scope of being limited to durability and decoration in the past, and are developing in the direction of diversified functions.

Technological innovation is the core competitiveness of the architectural ceramics industry. Technological progress and technological breakthroughs, as well as the improvement of design concepts, have changed the specifications and development trends of ceramic tile products. Multifunctional composite green and environmental protection exterior wall tiles have become one of the main development directions of ceramic wall and floor tiles. my country's "Twelfth Five-Year Plan" puts forward the strategy of "urbanization construction", and the construction of "affordable housing", "affordable housing" and "residential communities" will be the top priority. The trend has undoubtedly expanded a greater development space for the development of ceramic vitrified tiles. In the production process of ceramics, coal gas or natural gas is usually used as fuel, and it is fired within 30-45 minutes, and the highest firing temperature is 1080-1250 °C. According to the data of the former Soviet Union, when other conditions are the same, every time the combustion temperature is reduced by 100°C, the fuel consumption per unit product will be reduced by about 13%, and the fuel cost accounts for more than 60% of the total cost, which shows the importance of energy consumption for ceramic enterprises. The air pollution caused by the preparation of gas and the pollution caused by the sewage in the wet production make the ceramic production face the situation of "high energy consumption and high pollution". The new energy consumption standards for the architectural ceramics industry put forward higher requirements for architectural ceramics enterprises, forcing architectural ceramics manufacturers to formulate corresponding supporting measures to implement energy-saving and emission-reduction measures, eliminate backward production capacity, and promote industrial upgrading; increase technological innovation efforts to develop products with high technological content and high added value.

The existing ceramic vitrified bricks are made of clay tailings, production waste, ceramic fragments, admixtures, etc., and some even use high-quality ceramic raw materials as the main raw materials, and are fired at 1080-1250 °C.

The patent discloses "a method for producing ceramic tiles by using polishing waste" (Zheng Shulong, application number: 200410079020.9). The polishing waste, high-temperature sand, kaolin, and low-temperature sand are mixed into a ball mill for wet ball milling, and passed through a 250-mesh sieve. After iron removal, the mud is sprayed with a spray tower for standby; then, the obtained dry powder is formed by dry pressing with a ceramic press; the formed ceramic brick body is fired in a ceramic roller kiln at a firing temperature of 1140°C to 1200°C. The cycle is 40-75 minutes. A lightweight building material with product density less than 700kg/m ³ and breaking strength >800N is prepared. Although waste is also used as the main material, the process characteristics and firing methods are traditional methods with high energy consumption and high pollution, which have disadvantages such as long firing cycle, high energy consumption, and environmental pollution; they are not the same as the materials of the present invention. type.

The patent discloses "The formula and method of making ceramic tile body and glazed tile by using polishing waste slag" (Liang Tongcan, application number: 201210050321.3), using porcelain sand, clay, and ceramic polishing slag as main materials, wet ball milling, spray drying, and molding , dry, bisque firing at a temperature of 1080°C to 1160°C, and heat preservation in the temperature range of 1040°C to 1060°C to prolong the firing time of this area and strengthen the firing process of the oxidizing atmosphere to obtain ceramic tiles body. Although the utilization rate of waste slag is high, the process is complicated, the degree of control is poor, and there are still disadvantages such as high energy consumption and environmental pollution.

The patent discloses "a method for producing antique bricks by low-temperature sintering" (Zhong Xudong, application number: 200610037066.3). This method uses waste glass (42-60%) as the main flux raw material, and is prepared by batching ~ ball milling ~ sieving ~ Antique bricks that are spray-dried ~ aged ~ pressed into shape ~ dried ~ glazed ~ ball milled ~ sieved ~ aged ~ sprayed glaze, fired in a roller kiln (firing time 55min, firing temperature <900°C). Although a large number of waste glass is used, it also has the advantages of reducing burning energy consumption and reducing production costs. However, the preparation process is complicated, and the production process still belongs to the traditional ceramic method, which consumes a lot of energy and pollutes a lot.

At present, using secondary resources such as industrial waste or waste materials, adopting sintering methods with low energy consumption and low pollution, optimizing the process and conditions, improving the microstructure, and making ceramic vitrified bricks obtain better mechanical properties have become the main research trends. In order to achieve this goal, different waste residues or waste materials are introduced into the product formula and the preparation process is optimized, which improves the mechanical properties of the insulation brick to a certain extent. However, it still cannot fundamentally solve the energy consumption in the traditional ceramic preparation method. The shortcomings of high pollution, large pollution, and single surface decoration are extremely unfavorable to the current pollution control and smog reduction.

Contents of the invention

The object of the present invention is to overcome the deficiencies of the prior art and means, and provide a method for preparing environment-friendly ceramic vitrified bricks by using waste slag.

In order to achieve the above object, the technical scheme adopted in the present invention is:

1) Red shale waste, waste slag, waste glass, and dolomite are respectively put into a ball mill for dry grinding, and passed through a 325-mesh sieve to obtain red shale waste, waste slag, waste glass, and dolomite powder respectively;

2) get sieved red shale waste, waste slag, waste glass, dolomite powder and alumina powder, red shale waste in parts by mass: waste slag: waste glass: dolomite: alumina powder=(20～ 30): (45～60): (10～15): (5～10): (3～5) ingredients, put the prepared materials into the ball mill together and add 6% binder ( PVA), dry grinding and mixing and crossing 40 mesh sieves to form a mixture;

3) Place the mixture in the mold of a pressure forming machine, press and form it under a pressure of 30 MPa, and dry it to become a green body to be fired;

4) Place the green body to be sintered on the support of porous alumina refractory material facing upwards, use a high-power _CO2 laser as the sintering energy source for laser sintering, and then rotate the green body 180° in the horizontal direction The other side of the green body is placed on the support of the refractory material, and the high-power CO ₂ laser is used as the sintering energy source, and laser sintering is performed again to obtain the sintered body;

5) Straighten the uneven edges around the sintered body by means of cutting, grinding, and polishing, clean the surface, and dry to obtain a dried body;

6) Put the surface layer of the dried body upward on the workbench, and perform surface decoration to obtain a composite ceramic light-weight thermal insulation decorative exterior wall brick.

The waste slag is the waste slag produced by mineral processing, including gold tailings waste, lead-zinc ore tailings waste, phosphate ore waste, iron ore waste, manganese ore waste, molybdenum ore waste, titanium slag, barium slag, chromium slag, cobalt slag , vanadium slag, antimony ore waste, mercury ore waste, copper ore waste, quartz ore waste, rare earth tailings waste, feldspar slag, bauxite waste, coal gangue waste, fly ash waste, high alumina clay waste, blast furnace smelting One or more mixtures in any proportion in slag.

The waste glass powder is a mixture of one or more of soda lime silicate glass, quartz glass, high laurel oxide glass, lead silicate glass, aluminosilicate glass and borosilicate glass in any proportion.

The waste glass powder is a mixture of one or more of window glass, flat glass, automobile glass, glass curtain wall, beer bottle, beaker, display glass, picture tube glass and solar vacuum tube in any proportion.

The dry grinding in the step 1) uses alumina balls as the grinding medium, controls the mass ratio of the grinding balls to the raw materials to be (2-3):1, and grinds for 0.5-2 hours respectively.

The dry grinding in the step 2) is to use alumina balls as the grinding medium, control the mass ratio of the grinding balls to the raw materials to be (2-3):1, and grind for 0.5-1 h respectively.

The particle size of the alumina powder in the step 2) is 3-5 μm, and the content of Al ₂ O ₃ is ≥98%.

The laser sintering described above uses a _CO2 laser with a power of 2500W (continuously adjustable) and a wavelength of 10.6μm as the sintering energy source, the heating time is 60-90s, the power density is 800-850w/ ^cm2 , and the holding time is 550-650s , cooling time 370 ~ 420s.

The surface decoration in step 6) refers to the surface decoration by using its own surface layer plain decoration, using an inkjet printer, or using a 3D printer as a tool, and using one or a combination of the two methods for surface decoration.

The present invention applies a new sintering method and a new decoration technology to traditional ceramic products on the basis of introducing a large amount of waste slag and optimizing the process flow, and provides an environmentally friendly green and pollution-free ceramic vitrified brick preparation method. It is prepared by dry method, one-time molding, two instant firing, using high-power CO ₂ laser as the sintering energy source, and the ceramic green body undergoes transformation from low temperature to high temperature in a short period of time through continuous power adjustment. Proper heat preservation in the high-temperature stage can complete the high-temperature reaction in the green body in an instant, completely change the firing method of traditional ceramics, change the current situation of high energy consumption and high pollution in traditional ceramic production, and achieve green and pollution-free production. At the same time, give full play to the advantages of new technologies, apply inkjet printing or 3D printing to the surface decoration of ceramic vitrified tiles, and enrich their surface effects.

The invention integrates the concept of composite materials into non-dense ceramic vitrified bricks, introduces fine-grained alumina particles, and combines high-temperature in-situ reaction to self-generate the characteristics of fibrous mullite crystals, making mullite fibers The specific method of further optimizing the self-dispersing matrix phase with fine alumina particles to form a "granular/granular, fibrous/granular" composite ceramic material combines the "dual structure" technology with ceramic composite technology, which not only develops and utilizes The discarded slag improves the microstructure of the porcelain body, reduces the brittleness of the ceramic material, and further increases the strength of the ceramic vitrified tile.

Give full play to the advantages of new technologies, apply mature inkjet printing or mature 3D printing technology to the surface decoration of ceramic vitrified tiles, so that it can have different patterns, patterns, colors, and concave-convex effects, and enrich its surface decoration effect.

Considering the high brittleness of the ceramic material itself, the concept of composite materials is integrated into the non-dense vitrified brick material, and fine-grained alumina particles are introduced into the composition of the porcelain body. The particles themselves do not participate in the high temperature during the sintering process. Reaction, but its existence increases the combination of different phases (just like the stones in the wall material, making the wall stronger), and optimizes the structure. At the same time, by using high temperature reaction, the fibrous 3Al ₂ O ₃ 2SiO ₂ mullite is self-generated instantaneously in situ, and the mullite fiber strengthens and toughens the granular crystals in the porcelain body to form a composite structure. The large specific surface area and surface energy are combined with the granular corundum relying on strong grain boundary forces. On the one hand, the fibrous mullite is distributed between the corundum and cristobalite particles to form a fiber/particle structure. On the other hand, the particles The corundum has a "fine-grained" structure and is evenly dispersed around the cristobalite crystals, forming a secondary superposition of particles/particles. "Double composite" leads to the formation of a three-dimensional composite structure, which effectively improves the microstructure of the porcelain body. Since each different phase is formed under the same temperature, environment and conditions, the fiber reinforced phase, the particle reinforced phase and the pore phase It has good stress compatibility and wettability, effectively improves and optimizes the microstructure of the porcelain body, and plays a decisive role in improving the strength and toughness of the porcelain body, so that the environment-friendly vitrified brick The overall performance has been greatly improved.

On the basis of introducing a large amount of waste slag and optimizing the process flow, the present invention takes dry production as the design concept (pollution can be reduced), uses high-power _CO2 laser as the sintering energy source, and integrates the concept of composite materials into non-dense materials Among them, a new decoration method is applied to provide a preparation method of environment-friendly ceramic vitrified tiles. Introduce fine-grained alumina particles into the composition of the porcelain body, and use high-temperature reaction to instantly generate fibrous mullite in situ, which strengthens and toughens with the granular crystals in the porcelain body to form a composite structure, forming a "double composite" three-dimensional structure, Effectively improve the microstructure of the porcelain body; optimize the combination of different chemical compositions and different microstructures, adopt the method of "one molding, two laser firings", use the laser sintering method, and continuously adjust the power Make the ceramic green body undergo the transformation from low temperature to high temperature in a short period of time, and keep it warm in the high temperature stage to complete the high temperature physical and chemical reaction in the green body in an instant. At the same time, give full play to the advantages of new technologies, apply inkjet printing or 3D printing to The surface decoration of environmentally friendly ceramic vitrified tiles enriches its surface effect. It not only solves the problem of high brittleness of ceramics, but also realizes short-time firing, which saves production costs and time costs, consumes a lot of waste slag, and achieves the purpose of clean, pollution-free and green production.

The main raw material of the present invention is waste slag that is unavoidably discharged in industrial production, and the utilization rate of waste materials (red shale waste, waste slag, waste glass) has reached 70-85%, and the preparation of environmentally friendly vitrified bricks with waste slag not only has It helps to save natural resources, reduce production costs, and is also conducive to environmental protection.

Detailed ways

Examples further illustrate the present invention in detail, but are not limited thereto.

Example 1:

(1) Put the used raw materials into a ball mill for dry grinding, use alumina ball stone as the grinding medium, control the mass ratio of the ball and the raw material to 2:1, grind for 2 hours and pass through a 325 mesh sieve to obtain red pages Rock waste, fly ash waste residue, waste glass, dolomite;

(2) Take the sieved red shale waste, fly ash waste residue _, waste glass, dolomite and alumina powder (the content of _Al2O3 in the alumina powder is ≥ 98%, and the particle size is 3-5 μm), in parts by mass Red shale waste: fly ash waste slag: waste glass: dolomite: alumina powder = 20:60:10:7:3 ingredients, put the prepared materials together into a ball mill for dry grinding, use alumina balls as Grinding medium, controlling the mass ratio of grinding balls and raw materials to 2:1, grinding for 1h, and adding 6wt% binder (PVA), dry grinding and mixing, and passing through a 40-mesh sieve to form a mixture;

(3) The mixture is placed in a pressure forming mold, pressed and formed under a pressure of 30MPa, and dried to become a green body to be fired;

(4) Put one side of the green body to be sintered upward on the support of the porous alumina refractory material, and use a _CO2 laser with a power (continuously adjustable) of 2500W and a wavelength of 10.6μm as the sintering energy source for laser sintering , the heating time is 60s, the power density is 850w/cm ² , the holding time is 550s, and the cooling time is 420s; then the green body is rotated 180° in the horizontal direction, that is, the other side of the green body is placed on the support of the refractory material, with the same Sintering parameters, laser sintering again to obtain a sintered body;

(5) Straighten the uneven edges around the sintered body by cutting, grinding, and polishing processes, clean the surface, and dry to obtain a dried body;

(6) Put the surface layer of the dry body upwards on the workbench, use an inkjet printer or a 3D printer as a tool to decorate the surface, so that different patterns, patterns, colors, and concave-convex effects appear, and the environmentally friendly ceramic glass is obtained. Brick. Sample 1 was prepared.

Example 2:

(1) Put the used raw materials into a ball mill for dry grinding, use alumina ball stone as the grinding medium, control the mass ratio of the ball and the raw material to be 3:1, and pass through a 325 mesh sieve after grinding for 0.5h respectively to obtain red Shale waste, lead-zinc mine tailings, waste glass, dolomite;

(2) Take the sieved red shale waste, lead-zinc ore _tailings , waste glass, dolomite and alumina powder (the content of _Al2O3 in the alumina powder is ≥ 98%, and the particle size is 3-5 μm), according to the mass Red shale waste: lead-zinc ore tailings: waste glass: dolomite: alumina powder = 26:55:11:5:3 ingredients, put the prepared materials together into a ball mill for dry grinding, and use alumina balls Stone is used as the grinding medium, the mass ratio of the control ball and the raw material is 3:1, grind for 0.5h, and add 6wt% binder (PVA), dry grind and mix and pass through a 40 mesh sieve to form a mixture;

(3) The mixture is placed in a pressure forming mold, pressed and formed under a pressure of 30MPa, and dried to become a green body to be fired;

(4) Put one side of the green body to be sintered upward on the support of the porous alumina refractory material, and use a _CO2 laser with a power (continuously adjustable) of 2500W and a wavelength of 10.6μm as the sintering energy source for laser sintering , the heating time is 70s, the power density is 840w/cm ² , the holding time is 580s, and the cooling time is 400s; then the green body is rotated 180° in the horizontal direction, that is, the other side of the green body is placed on the support of the refractory material, and the same Sintering parameters, laser sintering again to obtain a sintered body;

(5) Straighten the uneven edges around the sintered body by cutting, grinding, and polishing processes, clean the surface, and dry to obtain a dried body;

(6) Put the surface layer of the dry body upwards on the workbench, use an inkjet printer or a 3D printer as a tool to decorate the surface, so that different patterns, patterns, colors, and concave-convex effects appear, and the environmentally friendly ceramic glass is obtained. Brick. Sample 2 was prepared.

Example 3:

(1) Put the used raw materials into a ball mill for dry grinding respectively, use alumina ball stone as the grinding medium, control the mass ratio of the ball and the raw material to be 2.3:1, and pass through a 325 mesh sieve after grinding for 1.8 hours respectively to obtain red Shale waste, phosphate slag, waste glass, dolomite;

(2) Take the sieved red shale waste, phosphate rock slag, waste glass, dolomite and alumina powder (the content of _Al2O3 in the alumina powder is ≥ 98%, and the particle size _is 3-5 μm), and red Shale waste: phosphate slag: waste glass: dolomite: alumina powder = 24:50:12:10:4 ingredients, put the prepared materials together into a ball mill for dry grinding, and use alumina ball stone as the grinding medium , the mass ratio of control ball and raw material is 2.3:1, grinds 0.8h, and adds the binding agent (PVA) of 6wt%, dry milling mixes and crosses 40 mesh sieves to form mixture;

(3) The mixture is placed in a pressure forming mold, pressed and formed under a pressure of 30 MPa, and dried to become a green body to be fired.

(4) Put one side of the green body to be sintered upward on the support of the porous alumina refractory material, and use a _CO2 laser with a power (continuously adjustable) of 2500W and a wavelength of 10.6μm as the sintering energy source for laser sintering , the heating time is 75s, the power density is 830w/cm ² , the holding time is 600s, and the cooling time is 390s; then the green body is rotated 180° in the horizontal direction, that is, the other side of the green body is placed on the support of the refractory material, and the same Sintering parameters, laser sintering again to obtain a sintered body;

(5) Straighten the uneven edges around the sintered body by cutting, grinding, and polishing processes, clean the surface, and dry to obtain a dried body;

(6) Put the surface layer of the dry body upwards on the workbench, use an inkjet printer or a 3D printer as a tool to decorate the surface, so that different patterns, patterns, colors, and concave-convex effects appear, and the environmentally friendly ceramic glass is obtained. Brick. Sample 3 was prepared.

Example 4:

(1) Put the used raw materials into a ball mill for dry grinding respectively, use alumina ball stone as the grinding medium, control the mass ratio of the ball and the raw material to be 2.6:1, and pass through a 325 mesh sieve after grinding for 1.5 hours respectively to obtain red Shale waste, manganese slag, waste glass, dolomite;

₍ 2) Take the sieved red shale waste, manganese slag, waste glass, dolomite and alumina powder (the content of _Al2O3 in the alumina powder is ≥ 98%, and the particle size is 3-5 μm), and red page Rock waste: manganese slag: waste glass: dolomite: alumina powder = 27:48:13:8:4 batching, put the prepared materials together into the ball mill for dry grinding, use alumina ball stone as the grinding medium, control The mass ratio of the ball and the raw material is 2.5:1, grind for 0.7h, and add 6wt% binder (PVA), dry grind and mix and pass through a 40-mesh sieve to form a mixture;

(3) The mixture is placed in a pressure forming mold, pressed and formed under a pressure of 30MPa, and dried to become a green body to be fired;

(4) Put one side of the green body to be sintered upward on the support of the porous alumina refractory material, and use a _CO2 laser with a power (continuously adjustable) of 2500W and a wavelength of 10.6μm as the sintering energy source for laser sintering , the heating time is 80s, the power density is 810w/cm ² , the holding time is 630s, and the cooling time is 380s; then the green body is rotated 180°in the horizontal direction, that is, the other side of the green body is placed on the support of the refractory material, with the same Sintering parameters, laser sintering again to obtain a sintered body;

(5) Straighten the uneven edges around the sintered body by cutting, grinding, and polishing processes, clean the surface, and dry to obtain a dried body;

(6) Put the surface layer of the dry body upwards on the workbench, use an inkjet printer or a 3D printer as a tool to decorate the surface, so that different patterns, patterns, colors, and concave-convex effects appear, and the environmentally friendly ceramic glass is obtained. Brick. Sample 4 was prepared.

Example 5:

(1) Put the used raw materials into a ball mill for dry grinding, use alumina ball stone as the grinding medium, control the mass ratio of the ball and the raw material to 2.8:1, grind for 1 hour and pass through a 325 mesh sieve to obtain red pages rock waste, molybdenum slag, waste glass, dolomite;

(2) Take the sieved red shale waste, molybdenum _slag , waste glass, dolomite and alumina powder (the content of _Al2O3 in the alumina powder is ≥ 98%, and the particle size is 3-5 μm), and red page Rock waste: molybdenum slag: waste glass: dolomite: alumina powder = 30:45:15:5:5 batching, put the prepared materials together into the ball mill for dry grinding, use alumina ball stone as the grinding medium, control The mass ratio of the ball and the raw material is 2.8:1, grind for 0.6h, and add 6wt% binder (PVA), dry grind and mix and pass through a 40-mesh sieve to form a mixture A;

(3) The mixture is placed in a pressure forming mold, pressed and formed under a pressure of 30MPa, and dried to become a green body to be fired;

(4) Put one side of the green body to be sintered upward on the support of the porous alumina refractory material, and use a _CO2 laser with a power (continuously adjustable) of 2500W and a wavelength of 10.6μm as the sintering energy source for laser sintering , the heating time is 90s, the power density is 800w/cm ² , the holding time is 650s, and the cooling time is 370s; then the green body is rotated 180° in the horizontal direction, that is, the other side of the green body is placed on the support of the refractory material, and the same Sintering parameters, laser sintering again to obtain a sintered body;

(5) Straighten the uneven edges around the sintered body by cutting, grinding, and polishing processes, clean the surface, and dry to obtain a dried body;

(6) Put the surface layer of the dry body upwards on the workbench, use an inkjet printer or a 3D printer as a tool to decorate the surface, so that different patterns, patterns, colors, and concave-convex effects appear, and the environmentally friendly ceramic glass is obtained. Brick. Sample 5 was prepared.

Product performance index test results in each embodiment of table 1 (technical index is enterprise internal control standard)

Test items sample 1 sample 2 sample 3 Sample 4 Sample 5 Water absorption E(%) 0.31 0.23 0.12 0 0 Flexural strength (MPa) 55 68 70 74 75

It can be seen from the table that the water absorption rate of the prepared environmentally friendly ceramic vitrified tiles is close to 0, and the flexural strength is 55-75MPa. The product has the characteristics of high strength, low water absorption rate, and rich surface decoration. The advantages of short cycle, green, clean and pollution-free production.

The above are only preferred embodiments of the present invention, and do not limit the present invention in any way. Any simple modifications, changes and equivalent structural changes made to the above embodiments according to the technical essence of the invention still belong to the technical solution of the present invention. within the scope of protection.

Claims (9)

1. utilize abandoned mine slag to prepare a method for environment-friendly ceramic vitrified tile, it is characterized in that:

1) red shale waste material, abandoned mine slag, cullet, rhombspar are put into respectively to ball mill for dry grinding, cross 325 mesh sieves, obtain respectively red shale waste material, abandoned mine slag, cullet, ground dolomite;

2) get red shale waste material, abandoned mine slag, cullet, ground dolomite and the aluminum oxide powder after sieving, press the red shale waste material of mass fraction: abandoned mine slag: cullet: rhombspar: aluminum oxide powder=(20～30): (45～60): (10～15): (5～10): (3～5) batching, the material preparing is together put into ball mill and add the binding agent (PVA) of Glass Batch Quality 6%, dry grinding mixes and crosses 40 mesh sieves formation compounds;

3) compound is placed in to pressure forming machine mould, compression moulding under the pressure of 30MPa, becomes after drying and treats sintering briquette body;

4) by what treat sintering briquette body, one face up and be placed on the support of porous alumina refractory materials, with high-power CO ₂laser apparatus is as sintering energy source, carries out laser sinteredly, and the another side that again base substrate along continuous straight runs Rotate 180 ° is about to afterwards to base substrate is placed on the support of refractory materials upward, with high-power CO ₂laser apparatus is as sintering energy source, again laser sintered, obtains sintered compact;

5) by the rough edge of sintered compact periphery to cut, grind, to throw means cut-off, and after surface cleaning is clean, be dried, obtain dry body;

6) upper layer of dry body is placed in to worktable upward, carries out surface decoration and obtain composite ceramic light thermal insulation decoration exterior wall tile.

2. the method for utilizing abandoned mine slag to prepare environment-friendly ceramic vitrified tile according to claim 1, it is characterized in that: described abandoned mine slag is the waste residue that ore dressing produces, comprise gold tailings waste residue, lead-zinc ore tailings waste residue, phosphorus ore waste residue, iron ore waste residue, manganese ore waste residue, molybdenum ore waste residue, titanium ore slag, barium slag, chrome ore slag, cobalt ore slag, vanadium slag, antimony ore waste residue, mercury ore waste residue, copper mine waste residue, quartz mine waste residue, rare-earth tailing waste residue, feldspar slag, bauxitic clay waste residue, coal gangue waste residue, flyash waste residue, high-alumina clay waste residue, the mixture of one or more arbitrary proportions in blast furnace refining slag.

3. the method for utilizing abandoned mine slag to prepare environment-friendly ceramic vitrified tile according to claim 1, is characterized in that: described cullet powder is the mixture of one or more arbitrary proportions in soda-lime-silica glass, silica glass, high osmanthus oxygen glass, lead silicate glass, alumina silicate glass, borosilicate glass.

4. the method for utilizing abandoned mine slag to prepare environment-friendly ceramic vitrified tile according to claim 1, is characterized in that: described cullet powder is the mixture of one or more arbitrary proportions in window glass, sheet glass, vehicle glass, glass curtain wall, Beer Bottle, beaker, demonstration glass, teletron glass, solar energy vacuum tube.

5. the method for utilizing abandoned mine slag to prepare environment-friendly ceramic vitrified tile according to claim 1; it is characterized in that: dry grinding described step 1) is to utilize alumina balls masonry for grinding medium; the mass ratio of controlling abrading-ball and raw material is (2～3): 1, grind respectively 0.5～2h.

6. the method for utilizing abandoned mine slag to prepare environment-friendly ceramic vitrified tile according to claim 1; it is characterized in that: dry grinding described step 2) is to utilize alumina balls masonry for grinding medium; the mass ratio of controlling abrading-ball and raw material is (2～3): 1, grind respectively 0.5～1h.

7. the method for utilizing abandoned mine slag to prepare environment-friendly ceramic vitrified tile according to claim 1, is characterized in that: aluminum oxide powder granularity described step 2) is 3～5 μ m, Al ₂o ₃content>=98%.

8. the method for utilizing abandoned mine slag to prepare environment-friendly ceramic vitrified tile according to claim 1, is characterized in that: described laser sintered be to take power as 2500W (adjustable continuously), wavelength is the CO of 10.6 μ m ₂laser apparatus is as sintering energy source, heating-up time 60～90s, power density 800～850w/cm ², soaking time 550～650s, temperature fall time 370～420s.

9. the method for utilizing abandoned mine slag to prepare environment-friendly ceramic vitrified tile according to claim 1; it is characterized in that: the surface decoration said step 6) utilizes self surperficial laminin decorations, with ink-jet printer, take 3D printer as instrument, with the combination of one or both modes wherein, carry out surface decoration.