CN114956777A - Mineral melting direct casting crystallization micropore stone forming process - Google Patents
Mineral melting direct casting crystallization micropore stone forming process Download PDFInfo
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- CN114956777A CN114956777A CN202210646332.1A CN202210646332A CN114956777A CN 114956777 A CN114956777 A CN 114956777A CN 202210646332 A CN202210646332 A CN 202210646332A CN 114956777 A CN114956777 A CN 114956777A
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B32/00—Artificial stone not provided for in other groups of this subclass
- C04B32/005—Artificial stone obtained by melting at least part of the composition, e.g. metal
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The application discloses a mineral melting direct casting crystallization micropore stone forming process, and belongs to the field of metallurgy and inorganic non-metallic materials. The process comprises the following steps: (1) flowing the 1100-1800 ℃ molten rock slurry into a reactor, and vibrating the reactor when the temperature of the molten rock slurry is reduced to 600-1600 ℃ crystallization temperature, and controlling the temperature reduction speed of the molten rock slurry to be 0-3 ℃/h; (2) opening the reactor when the temperature of the molten rock slurry is reduced to 300 ℃, and naturally cooling to room temperature to obtain the crystalline microporous stone raw material; (3) and (3) sequentially cutting, grinding and polishing the crystalline microporous stone raw material to obtain the crystalline microporous stone. Under the control of the crystallization temperature and the crystallization time, the lava slurry can generate the crystallized microporous stone containing the crystal grains with large grain size, and the lava slurry has the advantages of hardness and crystal color of the natural marble, and good water absorption, air permeability, skid resistance and adhesive force of the natural travertine.
Description
Technical Field
The application relates to a mineral melting direct casting crystallization micropore stone forming process, belonging to the field of metallurgy and inorganic non-metallic materials.
Background
The rocks that make up the earth's rock circle are mainly of three major rock types: sedimentary, magmatic and metamorphic rocks. Sedimentary rock is also called as water-forming rock, and is formed by the actions of transporting, depositing and forming weathered products of other rocks and some volcanic eruptions through water flow or glaciers in places with little depth of the earth surface. Travertine is sedimentary rock, and is precipitated from carbonate-containing spring water (usually hot spring) under atmospheric conditionsThe obtained calcium material. Magma rock is also called igneous rock, which is rock formed by magma formed in the deep of the crust or in the mantle, cooling and solidifying after invading the upper part of the crust or spraying to the surface and crystallizing. The common igneous rocks include granite, andesite, basalt and the like. Igneous rocks can be divided into two types according to common mineral components, namely silicon-aluminum minerals and iron-magnesium minerals: silicon-aluminum mineral, SiO 2 With Al 2 O 3 High content, and does not contain FeO and MgO, such as quartz, feldspar and similar feldspar. These minerals are light in color and are also called light-colored or pale-colored minerals. Iron magnesium minerals, high FeO and MgO contents, SiO 2 The content is low. Such as olivines, pyroxenes, hornblendes, and biotite. These minerals are also known as dark or dark minerals because of their darker color. Metamorphic rocks are novel rocks which are transformed from one type of rocks by natural metamorphism under the action of the internal force of the earth (temperature, pressure, change of stress, chemical components and the like). Under the action of pressure and temperature in the earth, solid rock undergoes migration and recrystallization of material components to form a new mineral composition. Such as ordinary limestone, becomes marble due to recrystallization.
The molten rock slurry of the smelting furnace is a quaternary mineral of silicon, aluminum, calcium and magnesium, and is a research subject of utilization of waste slag as an inorganic non-metallic material. According to the data of the national statistical bureau, the pig iron production of the country in 2021 is 8.6857 hundred million tons, and the blast furnace slag production in 2021 is up to 3.5 million tons calculated according to the slag ratio of 400 kg. The process for treating the molten rock slurry of the smelting furnace at the present stage is basically a water slag flushing process, 80% of obtained products are used for cement production, and the utilization value is low. How to save energy, reduce emission and comprehensively utilize the molten rock slurry resources of the smelting furnace becomes the focus of people in recent years.
The current molten rock slurry treatment process has three applications: 1. wear-resistant material: the microcrystal (the particle diameter is generally less than 0.1mm) cast stone is formed by melting different rocks by using a lava furnace to form lava slurry, and the microcrystal cast stone plate is produced by mould casting, molding and crystallizing and is mainly used as an industrial wear-resistant stone plate; 2. cement clinker: blast furnace molten rock slurry (slag) is made into particles through water quenching treatment after flowing out of a blast furnace, and the particles are finely ground into powder for cement clinker; 3. other building materials: (1) the lava furnace magma is rolled, cooled by a roller kiln and crystallized into a plate for building decoration; (2) the heat insulating material such as asbestos, glass fiber and the like is produced by drawing.
In the published patent, CN201010293048.8 discloses a method for producing a reduced stone raw material by using molten slag, and the reduced stone is produced by adjusting components of high-temperature slag and then casting, and CN2012101119019 discloses a method for preparing a cast stone product, wherein basalt and a metal material are used for crushing, melting, stirring uniformly and then are injected into a mold for shaping to obtain a microcrystalline stone wear-resistant material. The above-mentioned patents show that the traditional cast stone industry still adopts traditional stone materials mainly made of basalt as raw materials for casting production, and the lava slurry has been used as a raw material for producing reduced stone materials.
Disclosure of Invention
In order to solve the problems, the process for directly casting the crystallized micropores into the stones by mineral melting is provided, the process comprises the steps of placing the lava slurry in a reaction vessel, slowly and naturally cooling, controlling the crystallization temperature and the crystallization time, crystallizing the lava slurry under the action of reaction gas formed by the lava slurry and air wrapped in a reactor to generate the crystallized micropore stones containing grains with large grain sizes, and opening the reactor to vibrate in the cooling process so as to conveniently eliminate the stress in the stones.
The application provides a mineral melting direct casting crystallization micropore stone forming process, which is characterized by comprising the following steps:
(1) flowing the 1100-1800 ℃ molten rock slurry into a reactor, and vibrating the reactor when the temperature of the molten rock slurry is reduced to 600-1600 ℃ crystallization temperature, and controlling the temperature reduction speed of the molten rock slurry to be 0-3 ℃/h;
(2) opening the reactor when the temperature of the lava slurry is reduced to 300 ℃, and naturally cooling to room temperature to obtain the crystalline microporous stone raw material;
(3) and sequentially carrying out cutting processing, grinding and polishing on the crystalline microporous stone raw material to obtain the crystalline microporous stone.
The process establishes a silicon, aluminum, calcium and magnesium quaternary oxide crystal system by researching the condition relation of the molten rock slurry crystallization of the smelting furnace, and contrasts with the components of the molten rock slurry, so that the molten rock slurry can be crystallized and molded within the range of 600 plus one year of 1600 ℃, and the petrochemical is high-grade stone. The vibration to the reactor during the temperature control and cooling fully ensures the crystallization quality inside the stone, and improves the yield of the final product. In the step (1), the cooling speed is 0-3 ℃/h, which means that the lava slurry is in a cooling state in the whole process, and the lava slurry can be cooled all the time in the cooling process, and the cooling speed can be changed; and the heat preservation can be carried out for a certain time when the temperature is reduced to a certain temperature in the integral cooling process, and the specific heat preservation temperature and the heat preservation time need to be changed according to different components of the lava.
Optionally, the lava slurry comprises SiO in weight percent 2 ：33.0～53.5％；Al 2 O 3 ： 12.0～16.5％；CaO：30.0～38.0％；MgO：4.0～10.0％；Na 2 O：0.2～5.5％。
Preferably, the lava slurry comprises SiO 2 ：33.0～45.0％；Al 2 O 3 ：14.5～16.5％；CaO： 30.0～38.0％；MgO：7.5～10.0％；Na 2 O：0.2～4.0％。
The main component of the lava slurry is SiO 2 、Al 2 O 3 CaO and MgO, which have a wide range of components, and which can form crystalline phases mainly including wollastonite, diopside, melilite, plagioclase feldspar, etc., depending on the types of the main components and the crystal nucleating agent. Early studies showed that SiO is present as a component 2 When the content of CaO is high and the content of MgO is low, wollastonite is formed; when MgO and Al 2 O 3 Substantially equivalent in content of SiO 2 High CaO low, diopside formation, in contrast to SiO 2 Low CaO is high, forming wollastonite.
Optionally, in the step (1), the vibration frequency of the reactor is 40-80HZ, the radial exciting force is 30-150N, and the vibration amplitude is 1-5 mm;
preferably, the vibration frequency of the reactor is 50HZ, the radial exciting force is 100N, and the vibration amplitude is 2 mm.
Through the vibration that sets up the reactor, can avoid the directional crystallization of crystalline grain in the molten rock thick liquid crystallization process, eliminate the stress that inhomogeneous crystallization produced for controllable regular microgroove appears in the crystallization micropore stone waste material, release the residual stress that produces in the crystallization process, thereby obtain the cubic stone material of micropore. The crystal grains can grow in a fully isotropic way while releasing stress, so that the crystalline microporous stone raw material containing large-grain crystal grains is obtained, and the stone raw material is cut, ground and polished into a plate which can be used for building decoration, paving and the like. The fine lines are cracks which can not be seen by naked eyes, the fine lines are generated due to uneven temperature during crystallization shrinkage, the mechanical strength and hardness of the stone can not be damaged, and the fine lines can not be observed on the surface of the polished plate.
And (2) at the temperature of 600-1600 ℃ in the step (1), the molten rock slurry is completely crystallized, petrochemical and molded, carbon dioxide and sulfur dioxide gas can be formed in the molten rock slurry in the container, and the gas and air in the reactor can enable the molten rock slurry to form high-quality crystallized microporous stone after crystallization. The composition of the crystalline microporous stone prepared by the method is similar to that of igneous rock, the hardness and the color of crystals are similar to those of marble, and the water absorption and the air permeability are similar to those of natural travertine, so that the crystalline microporous stone becomes a characteristic architectural decoration stone with the hardness and the crystal color of marble and good water absorption and air permeability of travertine.
Optionally, the grain size of the grains in the crystalline microporous stone material is 1-5mm, and the grain size of the grains is in normal distribution.
Optionally, the crystal grains with the grain diameter of 2-4mm account for 60-80% of the crystal grains in the crystalline microporous stone.
The distribution of the crystal grains can increase the hardness, mechanical strength and wear resistance of the crystallized microporous stone, and the more the crystal grains with the grain diameter of 2-4mm, the better the hardness, mechanical strength and wear resistance.
Optionally, the pore diameter of the micropores in the crystalline microporous stone material is 0-2nm, wherein the proportion of the micropores with the diameter of 0.5-2nm is more than 60%.
Above-mentioned micropore can make this crystallization micropore stone material have the gas permeability, and its gas permeability and hydroscopicity are similar with natural hole stone to for microporous construction, make the adhesive force of this crystallization micropore stone material increase, the concatenation of being convenient for can also avoid the hole to pollute simultaneously.
Optionally, the water absorption of the crystalline microporous stone is 0.26-0.35%;
the volume density of the crystalline microporous stone is 2.65-2.78g/cm 3 。
Optionally, the compressive strength of the crystalline microporous stone is 75-85 MPa;
the bending strength of the crystallized microporous stone is 9.0-13.5 MPa;
the Shore hardness of the crystallized microporous stone is 55-65 SHD.
Preferably, the water absorption rate of the crystalline microporous stone is 0.30-0.35%;
the volume density of the crystalline microporous stone is 2.70-2.78g/cm 3 。
Optionally, the compressive strength of the crystalline microporous stone is 80-85 MPa;
the bending strength of the crystallized microporous stone is 13-13.5 MPa;
the Shore hardness of the crystalline microporous stone is 60-65 SHD.
Optionally, in the step (1), the vibration time of the reactor is 1-6h, and the cooling time of the lava slurry from the crystallization temperature of 600-.
Preferably, in the process of cooling the lava slurry from the crystallization temperature of 600-1600 ℃ to 300 ℃, the time with the cooling speed of 0 ℃/h is 0-24 h.
The specific value of the crystallization temperature is required to be varied according to the composition of the lava slurry to ensure sufficient crystallization of the lava slurry.
Optionally, the volume of the reactor containing the lava slurry is 1 to 100 cubic meters, and the difference between the lateral and longitudinal temperature of the lava slurry in the reactor is not more than 5 ℃/m;
the reactor can be set to be a thick-wall container, and a heat-insulating material or a heating element can be additionally arranged outside the reactor, so long as the temperature control of the lava in the reactor is stable, and the longitudinal and transverse temperature difference is less than 5 ℃/m.
The physical properties and chemical components of the natural travertine stone material are as follows:
1. physical Properties
Bulk Density (g/cm) 3 ): 2.56; water absorption (%): 0.36; compressive strength (MPa): 65; bending strength (MPa): 11.6; shore Hardness (HSD): 46.
2. chemical analysis
SiO 2 (％):<0.20 A1 2 O 3 (％):0.1 Fe 2 O 3 (％):<0.04
MgO(％):0.37 CaO(％):55.06 K 2 O(％):0.04
Na 2 O(％):0.03 TiO 2 (％):<0.02 MnO(％):0.002
Loss on ignition (lg. loss) (%) 43.8
The natural travertine has the advantages that:
1. the rock property is uniform, the texture is soft and hard, the mining and processing are easy, the density is light, and the transportation is easy;
2. the travertine has good water absorption and processability, is often used for exterior walls of high-grade buildings, bathroom decoration and conference room walls, and has good sound absorption, moisture resistance and heat insulation properties; the artificial reef is used for the artificial reef at the seabed, the micropores are easier to attach and root marine algae, the ecological environment is improved, and the like.
3. The travertine has fine texture and small hardness, is easy to engrave and is suitable for being used as an engraving material and a special-shaped material; 4. The travertine has rich color, unique texture, special hole structure and excellent decoration performance.
The defects of the natural travertine:
1. insufficient strength: due to the existence of a large number of holes, the volume density is low, the water absorption is high, and the strength is reduced; meanwhile, as the ore body has a large number of natural defects such as argillaceous lines, argillaceous zones, cracks and the like, the performance uniformity of the material is poor, and the physical performance index is lower than the normal marble standard.
2. The corrosion resistance is poor: the stone belongs to limestone with a carbonate structure, has poor acid resistance, is used in acid rain areas, is easy to corrode dry-hanging wall surfaces, and can accelerate the damage of the stone.
3. And (3) breaking: the biggest safety problem of the travertine is that some mud lines and mud belts are the weakest links in bending strength, and the beautiful patterns are often the places with the lowest strength behind and are the parts which are most easy to break.
4. Hole pollution: due to the porous capillary adsorption effect, there is a certain contamination.
Physical properties and chemical composition of natural marble
The marble crystals are classified into four grades according to the crystal grain size: large grain size: is more than 5 mm; medium grain: 1-5 mm; fine particles: 1-0.1 mm; and (3) microparticles: less than 0.1 mm.
1. Physical properties of the marble:
bulk Density (g/cm) 3 ): 2.5-2.7; water absorption (%): less than or equal to 0.75 percent; compressive strength (MPa) 47-140; flexural strength (MPa): not less than 7.0; shore Hardness (HSD): 40-50; mohs hardness: 3-4.
2. The marble comprises the following chemical components:
CaCO 3 (%): other components are magnesium carbonate, calcium oxide, manganese oxide, silicon dioxide, etc. which are more than or equal to 50.
Loss on ignition (lg. loss) (%): 42.5
The marble has the advantages that:
(1) the natural marble has compact structure, good compressive strength and good rigidity.
(2) The marble has good wear resistance and small temperature deformation.
(3) Good decorative performance and processing performance. The processed product has bright color and rich colors, and can be widely used for decorating indoor walls and floors. Has excellent processing performance of sawing, cutting, polishing, drilling, carving, etc.
(4) The dust-proof and dust-proof anti-sticking device is not easy to stick fine dust, is convenient and simple to maintain, has long service life, and can reach more than one hundred years of service life.
(5) The marble has the characteristics of non-conductivity, non-permeability, stable field position and the like.
(6) In industry, marble is widely used. Such as raw materials, purifiers, etc.
The marble defect:
(1) naturally occurring, and therefore having a color difference.
(2) Hard, not enough elastic, easy to break.
(3) Has natural pores, is easy to be polluted, and has higher requirements on the use environment.
(4) The artificial glue color can not match with the natural stone in the splicing operation, and the sections of the artificial glue color are not uniform, so that the split splicing is allowed.
Benefits of the present application include, but are not limited to:
1. according to the mineral melting direct casting crystallization micropore stone forming process, a petrochemical formed product has the hardness and crystal color of natural marble, and has the characteristics of good water absorption, air permeability, skid resistance, good adhesive force and the like of natural travertine, so that the product is developed to a high end. Therefore, the molten rock slurry resources of the smelting furnace are greatly developed and utilized, the added value of the product is improved, and the method has a wide economic development prospect.
2. According to the mineral melting direct casting crystallization micropore stone forming process, the crystallization inside the crystallization micropore stone is uniform, the isotropy of crystal lattices is highly consistent, and therefore the strength is high, the hardness is high, the wear resistance is good, and the high strength performance is similar to that of granite.
3. According to the mineral melting and direct casting crystallization micropore stone forming process, the prepared crystallization micropore stone has the characteristics of water permeability, light weight, good adhesion and the like, and has anti-skid performance due to the water permeability.
4. According to the mineral melting direct casting crystallization micropore stone forming process, leftover materials generated in the processing process of the crystallization micropore stone raw materials are further crushed according to different particle size requirements, and the process can be used for building concrete manufacturing, pavement of highway pavements and airport grounds and the like, so that the utilization rate of products is improved.
5. According to the mineral melting direct casting crystallization micropore stone forming process, a color mixing agent can be added in the processing process to mix different colors and enrich the color and variety of the crystallization micropore stone.
6. According to the mineral melting direct casting crystallization micropore stone forming process, due to the problems of natural stone resource limitation and mining process pollution, the crystallization micropore stone is prepared from lava waste materials, is environment-friendly and energy-saving, and is widely used at present.
Drawings
The accompanying drawings, which are included to provide a further understanding of the application and are incorporated in and constitute a part of this application, illustrate embodiment(s) of the application and together with the description serve to explain the application and not to limit the application. In the drawings:
fig. 1 is a macroscopic view of a crystalline microporous stone material 1# according to example 1 of the present application.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
Unless otherwise specified, the raw materials in the examples of the present application were all purchased commercially. The above examples and comparative examples contain a small amount of impurity components in addition to the components of the molten rock slurry listed.
Example 1
Charging a reactor with a lava slurry at 1450 ℃ containing 33.5% SiO 2 、16.3％Al 2 O 3 、37.5％CaO、10.0％MgO、0.3％Na 2 O, the loading amount is 8 cubic meters, the reactor is insulated and covered with an insulation cover, the temperature of the lava slurry in the reactor is tested, when the temperature of the lava slurry in the reactor is less than 1300 ℃, the platform type vibrator is started to vibrate the reactor, the amplitude of the platform vibrator is controlled to be 2mm, the frequency is 50HZ, the radial exciting force is 30N, and the reactor is continuously vibrated for 1 hour; controlling the cooling speed of the reactor, keeping the temperature for 10h when the temperature is reduced to 1100 ℃, then continuously cooling, cooling to 300 ℃ after 20d, then opening the reactor, naturally cooling to normal temperature by utilizing the environment to obtain crystalline microporous stone raw materials, and obtaining the crystalline microporous stone raw materials after cutting, processing, grinding and polishingCrystallized microporous stone material # 1.
Example 2
The method comprises the following steps of (1) loading molten rock slurry at 1450 ℃ into a reactor, wherein the components of the molten rock slurry are the same as those in example 1, the loading amount is 16 cubic meters, the reactor is insulated and covered with an insulation cover, temperature test is carried out on the molten rock slurry in the reactor, when the temperature of the molten rock slurry in the reactor is lower than 1300 ℃, a platform type vibrator is started to vibrate the reactor, the amplitude of the platform vibrator is controlled to be 2mm, the frequency is 50HZ, and the radial exciting force is 50N, and the platform vibrator continuously vibrates for 2 hours; controlling the cooling speed of the reactor, keeping the temperature for 10h when the temperature is reduced to 1100 ℃, then continuously cooling, cooling to 300 ℃ after 28d, then opening the reactor, naturally cooling to normal temperature by utilizing the environment to obtain a crystalline microporous stone raw material, and obtaining the crystalline microporous stone 2# after cutting, processing, grinding and polishing.
Example 3
The method comprises the following steps of (1) loading molten rock slurry at 1450 ℃ into a reactor, wherein the components of the molten rock slurry are the same as those in example 1, the loading amount is 24 cubic meters, the reactor is insulated and covered with an insulation cover, temperature test is carried out on the molten rock slurry in the reactor, when the temperature of the molten rock slurry in the reactor is lower than 1300 ℃, a platform type vibrator is started to vibrate the reactor, the amplitude of the platform vibrator is controlled to be 2mm, the frequency is 50HZ, the radial exciting force is 70N, and the platform vibrator continuously vibrates for 3 hours; controlling the cooling speed of the reactor, keeping the temperature for 10h when the temperature is reduced to 1100 ℃, then continuously cooling, cooling to 300 ℃ after 36d, then opening the reactor, naturally cooling to normal temperature by utilizing the environment to obtain a crystalline microporous stone raw material, and obtaining the crystalline microporous stone material No. 3 after cutting, grinding and polishing.
Example 4
The method comprises the following steps of (1) loading the molten rock mass at 1450 ℃ into a reactor, wherein the components of the molten rock mass are the same as those in the embodiment 1, the loading amount is 32 cubic meters, the reactor is insulated, a heat-insulating cover is covered on the reactor, the temperature of the molten rock mass in the reactor is tested, and when the temperature of the molten rock mass in the reactor is lower than 1300 ℃, a platform type vibrator is started to vibrate the reactor, the amplitude of the platform vibrator is controlled to be 2mm, the frequency is 50HZ, the radial exciting force is 90N, and the platform vibrator continuously vibrates for 4 hours; controlling the cooling speed of the reactor, keeping the temperature for 10h when the temperature is reduced to 1100 ℃, then continuously cooling, cooling to 300 ℃ after 44d, then opening the reactor, naturally cooling to normal temperature by utilizing the environment to obtain a crystalline microporous stone raw material, and obtaining the crystalline microporous stone material No. 4 after cutting, grinding and polishing.
Example 5
Charging molten rock slurry at 1450 ℃ into a reactor, wherein the components of the molten rock slurry are the same as those in the embodiment 1, the charging amount is 50 cubic meters, the reactor is insulated and covered with an insulation cover, the temperature of the molten rock slurry in the reactor is tested, and when the temperature of the molten rock slurry in the reactor is less than 1300 ℃, a platform type vibrator is started to vibrate the reactor, the amplitude of the platform vibrator is controlled to be 2mm, the frequency is 50HZ, the radial exciting force is 100N, and the platform vibrator continuously vibrates for 5 hours; controlling the cooling speed of the reactor, keeping the temperature for 10h when the temperature is reduced to 1100 ℃, then continuously cooling, cooling to 300 ℃ after 52d, then opening the reactor, naturally cooling to normal temperature by utilizing the environment to obtain a crystalline microporous stone raw material, and obtaining the crystalline microporous stone 5# after cutting, processing, grinding and polishing.
Example 6
The method comprises the following steps of (1) loading the molten rock mass at 1450 ℃ into a reactor, wherein the components of the molten rock mass are the same as those in the embodiment 1, the loading amount is 100 cubic meters, the reactor is insulated and covered with an insulation cover, the temperature of the molten rock mass in the reactor is tested, and when the temperature of the molten rock mass in the reactor is less than 1300 ℃, a platform type vibrator is started to vibrate the reactor, the amplitude of the platform vibrator is controlled to be 2mm, the frequency is 50HZ, the radial exciting force is 150N, and the platform vibrator continuously vibrates for 6 hours; controlling the cooling speed of the reactor, keeping the temperature for 10h when the temperature is reduced to 1100 ℃, then continuously cooling, cooling to 300 ℃ after 60d, then opening the reactor, naturally cooling to normal temperature by utilizing the environment to obtain crystalline microporous stone raw materials, and obtaining the crystalline microporous stone 6# after cutting, processing, grinding and polishing.
Example 7
The difference between this example and example 1 is that when the temperature of the lava slurry in the reactor is less than 600 ℃, the platform vibrator is turned on, the cooling rate of the reactor is controlled, the temperature is continuously reduced, no heat preservation stage is performed, the temperature is reduced to 300 ℃ after 6d, and the rest conditions are the same as those in example 1, so that the crystalline microporous stone material 7# is obtained.
Example 8
This example is different from example 1 in the composition of the lava slurry, which contains 29.9% SiO 2 、14.8％Al 2 O 3 、43.8％CaO、7.7％MgO、0.5％Na 2 O, keeping the temperature for 10 hours when the temperature is reduced to 1150 ℃; the rest conditions are the same as those in example 1, and the crystalline microporous stone material No. 8 is obtained.
Example 9
This example is different from example 1 in the composition of the lava slurry, which contains 53.0% SiO 2 、12.0％Al 2 O 3 、30.0％CaO、4.0％MgO、0.5％Na 2 And O, the other conditions are the same as the example 1, and the crystalline microporous stone 9# is obtained.
Example 10
This example is different from example 1 in the composition of the lava slurry, which contains 33.0% SiO 2 、14.5％Al 2 O 3 、38.0％CaO、7.5％MgO、5.5％Na 2 And O, continuously cooling, and obtaining the crystallized microporous stone material No. 10 under the same conditions as the example 1 without a heat preservation stage.
Comparative example 1
The difference between this comparative example and example 1 is that when the temperature of the lava slurry in the reactor is less than 1300 ℃, the platform vibrator is not turned on, so the reactor does not vibrate, the reactor is cooled to 300 ℃ only in 20 days, and the rest conditions are the same as example 1, thus obtaining the comparative crystalline microporous stone material D1 #.
Comparative example 2
The difference between the comparative example and the example 1 is that the temperature of the reactor is controlled to be continuously reduced, the temperature is reduced to 500 ℃ after 16D, then the reactor is opened, and the rest conditions are the same as the example 1, thus obtaining the comparative crystalline microporous stone material D2 #.
Comparative example 3
This comparative example is different from example 1 in the composition of the lava slurry, which further contains 1.0% Fe 2 O 3 、0.7％TiO 2 And the rest conditions are the same as those in example 1, thus obtaining a comparative crystalline microporous stone material D3 #.
The crystalline microporous stone materials prepared in the above examples and comparative examples were subjected to the performance test, and the results of the tests on the grain size, micropores, and specific surface area are shown in table 1, and the results of the water absorption, bulk density, hardness, and mechanical strength are shown in table 1, wherein the following grain sizes refer to the average grain size of the grains, and the pore size refers to the average pore size of the micropores:
TABLE 1
TABLE 2
According to the test results in tables 1 and 2, the crystalline microporous stone material prepared by the crystalline microporous stone-forming process of the present application has water absorption comparable to that of natural travertine, and has better bulk density, bending strength, compressive strength and Shore hardness than those of natural travertine and natural marble. According to the test results of the crystalline microporous stone material No. 7, the crystalline microporous stone material No. D2 and the crystalline microporous stone material No. 1, the starting point and the ending point of the crystallization temperature influence the growth speed and the growth size of crystal grains, thereby influencing the hardness and the mechanical property of the stone material; according to the test results of the crystalline microporous stone material No. 8-10, the comparative crystalline microporous stone material No. D3 and the crystalline microporous stone material No. 1, the influence of the components of the lava slurry on the size of the crystal grains and the micropores is the size of the crystal grains and the size of the micropores; according to the test results of the crystalline microporous stone material D1# and the crystalline microporous stone material 1# which are compared, the vibration is carried out in the crystallization process of the lava slurry, the anisotropic growth of crystal grains can be avoided, so that the obtained crystal grains are large and uniform in size, the stress generated in the crystallization process can be eliminated, the uniformity of the stone micropores is improved, and the water absorption, hardness, mechanical strength and wear resistance of the stone material are improved.
The above description is only an example of the present application, and the protection scope of the present application is not limited by these specific examples, but is defined by the claims of the present application. Various modifications and changes may occur to those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the technical idea and principle of the present application should be included in the protection scope of the present application.
Claims (10)
1. A mineral melting direct casting crystallization micropore stone forming process is characterized by comprising the following steps:
(1) flowing the 1100-plus 1800-DEG C molten rock slurry into a reactor, and vibrating the reactor when the temperature of the molten rock slurry is reduced to 600-plus 1600-DEG C crystallization temperature, and controlling the cooling speed of the molten rock slurry to be 0-3 ℃/h;
(2) opening the reactor when the temperature of the lava slurry is reduced to 300 ℃, and naturally cooling to room temperature to obtain the crystalline microporous stone raw material;
(3) and sequentially carrying out cutting processing, grinding and polishing on the crystalline microporous stone raw material to obtain the crystalline microporous stone.
2. The mineral melt direct cast crystalline microporous lithogenesis process of claim 1, wherein the lava slurry comprises SiO in weight percent 2 ：33.0～53.5％；Al 2 O 3 ：12.0～16.5％；CaO：30.0～38.0％；MgO：4.0～10.0％；Na 2 O：0.2～5.5％。
3. The mineral melting direct casting crystalline microporous lithogenesis process of claim 1, wherein in step (1), the vibration frequency of the reactor is 40-80HZ, the radial exciting force is 30-150N, and the vibration amplitude is 1-5 mm;
preferably, the vibration frequency of the reactor is 50HZ, the radial exciting force is 100N, and the vibration amplitude is 2 mm.
4. The mineral melting direct casting crystalline microporous stone forming process according to claim 1, wherein the grain size of the crystalline microporous stone material is 1-5mm, and the grain size of the grains is normally distributed.
5. The mineral melting direct casting crystalline microporous stone forming process according to claim 4, characterized in that the crystal grains with the grain size of 2-4mm account for 60-80% of the crystal grains in the crystalline microporous stone material.
6. The mineral melting direct casting crystalline microporous stone forming process according to claim 1, wherein the pore size of micropores in the crystalline microporous stone material is 0-2nm, wherein the proportion of micropores with 0.5-2nm is more than 60%.
7. The mineral melting direct casting crystalline microporous stone forming process according to claim 1, wherein the water absorption of the crystalline microporous stone material is 0.26-0.35%;
the volume density of the crystalline microporous stone is 2.65-2.78g/cm 3 。
8. The mineral melting direct casting crystalline microporous stone forming process according to claim 1, wherein the crystalline microporous stone material has a compressive strength of 75-85 MPa;
the bending strength of the crystallized microporous stone is 9.0-13.5 MPa;
the Shore hardness of the crystalline microporous stone is 55-65 SHD.
9. The mineral melting direct casting crystallization micropore lithogenesis process according to claim 1, wherein in step (1), the vibration time of the reactor is 1-6h, and the cooling time of the lava slurry from the crystallization temperature of 600-1600 ℃ to 300 ℃ is 20-60 d;
preferably, in the process of cooling the lava slurry from the crystallization temperature of 600-1600 ℃ to 300 ℃, the time with the cooling speed of 0 ℃/h is 0-24 h.
10. A mineral melting direct cast crystalline microporous lithogenesis process according to claim 1, wherein the reactor contains a volume of the lava slurry of 1 to 100 cubic meters, and the difference in lateral and longitudinal temperatures of the lava slurry in the reactor does not exceed 5 ℃/m.
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