CN111826717A - Artificially synthesized black mica crystal and crystallization method thereof - Google Patents
Artificially synthesized black mica crystal and crystallization method thereof Download PDFInfo
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Abstract
The invention relates to an artificially synthesized black mica crystal and a crystallization method thereof. The artificially synthesized black mica crystal with excellent performance is obtained by performing high-temperature reaction, melting, cooling and crystallization on one or more of quartz sand, fused magnesia, potassium carbonate, ferric oxide, potassium fluosilicate, aluminum oxide, alkali metal fluoride and alkaline earth metal fluoride in a specific proportion under a certain condition, so that the pain point that the industrial production cannot be realized by the existing artificially synthesized black mica crystal is solved, and the artificially synthesized black mica crystal has considerable application prospect. The equipment for preparing the artificially synthesized black mica crystal matched with the method disclosed by the invention can accurately control the reaction process and greatly improve the reaction efficiency. The artificially synthesized black mica crystal prepared by the method has the advantages of good practical performance, pure texture, high temperature resistance, corrosion resistance and magnetism, can be applied to magnetic materials in high-end electronic products, and has wide market prospect.
Description
Technical Field
The invention relates to the technical field of chemical industry, in particular to an artificially synthesized black mica crystal and a crystallization method thereof.
Background
Mica is a rock-making mineral, usually takes the form of a plate-shaped, sheet-shaped and columnar crystal of a pseudo-hexagonal or rhombus crystal form, is an insulator with excellent performance, is hard in texture and high in mechanical strength, has excellent dielectric properties such as large resistance, low dielectric loss, arc resistance, corona resistance and the like, and has good physicochemical properties such as high temperature resistance, rapid temperature change resistance, acid and alkali resistance and the like, so that the mica is widely applied to a plurality of chemical fields. With the increasing demand of the market for functional crystals, more kinds of synthetic mica crystals with more performances need to be developed further, and how to ensure the functionality of the product while keeping the high purity and high stability of the synthetic crystals is a main reference standard of the synthetic mica crystals.
The mica crystal is one of mica crystals, is mainly produced in metamorphic rocks, has a color ranging from black to brown, red or green, has glass luster, and is mostly plate-shaped and columnar. The biotite crystals currently available include both natural and synthetic mica crystals.
The synthetic biotite crystal is a synthetic silicate sheet crystal, which is also called synthetic fluorine iron mica. The product has pure texture, contains no heavy metal, and has the characteristics of high temperature resistance (the highest temperature can resist 1000 ℃) and acid and alkali resistance. Different from other micas, because the components contain iron element, the artificially synthesized biotite has magnetism and can be applied to some special fields such as magnetic material, microwave absorption material, catalyst carrier, cell separation, magnetic recording material, magnetic fluid and the like. The artificially synthesized biotite also has a complete flaky structure, meets the application requirements in the coating industry, can be applied to decorative coatings such as stone paint and the like, and can be used as a pearlescent pigment with special light sensation and special performance (magnetic pearlescent pigment). In addition, the artificially synthesized biotite can be ground into micro-nano level sheet-shaped powder and can be applied to some micro electronic parts; the anti-friction wear-resistant coating can be used as a novel anti-friction wear-resistant additive, and has chemical and physical changes in the friction process, so that the effects of reducing the friction coefficient and slowing down the wear of friction parts are achieved, meanwhile, the friction parts obtain a relatively smooth and flat appearance, a punctiform friction surface repairing film is formed, and the surface is protected from further damage.
In conclusion, the artificially synthesized biotite has wide application prospect. At present, most of magnetic materials adopt metal permanent magnets or hard magnets, rare earth permanent magnets, neodymium iron boron permanent magnets, perovskite and the like, but when the materials are in a micron-scale and nanometer-scale level, uniformity and consistency of particles cannot be ensured, the processing difficulty is high, and the requirement on production equipment is high. The artificially synthesized biotite as silicate has the same flaky strippability as natural mica crystal, can be subjected to grinding processing by a certain means to form crystal powder, has good lamella consistency and good particle size distribution, can realize micro-nano grade of ground particle size, and can be used in miniature electronic components. And the material is low in price and has obvious advantages compared with the existing magnetic material. The currently used biotite is mostly natural biotite, the natural biotite has low exploitation amount and low purity, which leads to higher purification cost and weaker magnetism, and has obvious inherent limitation. Although the prior art has the technology of synthesizing other mica crystals, the problems related to artificial synthesis of the biotite are not researched, and the industrial production cannot be realized.
Disclosure of Invention
The invention aims to overcome the defects and defects of the prior art, provides an artificially synthesized mica crystal and a crystallization method thereof, and adopts a new formula means to fire a novel synthetic mica crystal with a special structure, wherein the crystal has pure black luster, magnetism and good application prospect.
The purpose of the invention is realized by the following technical scheme:
an artificially synthesized black mica crystal has a chemical general formula of K [ Fea2+ Mgb ] [ Fec3+ Ald ] Si3O10F2, wherein a + b is 3, and a is less than or equal to 0.5 or b is less than or equal to 0.5; c + d is 1, and c is less than or equal to 0.75 or d is less than or equal to 0.75.
The crystallization method for artificially synthesizing the black mica crystal comprises the following steps:
(1) setting an artificially synthesized biotite structure after chemical reaction, and preparing raw materials according to the weight ratio, wherein the raw materials comprise 30-40% of quartz sand, fused magnesia: 4-27%, potassium carbonate: 4-16%, iron oxide: 12-18%, and the raw material also comprises one or more of potassium fluosilicate, alumina, alkali metal fluoride and alkaline earth metal fluoride;
(2) weighing the raw materials in the step (1) according to a stoichiometric ratio, crushing various raw materials to be below 100 meshes, and fully dispersing and mixing;
(3) stacking the furnace body, paving a heat-insulating layer on the inner wall of the furnace body, filling the crushed mixed raw materials obtained in the step (2) into the furnace body, compacting the crushed mixed raw materials, and heating the furnace body, wherein the heat-insulating layer is formed by the mixed raw materials which are not reacted;
(4) heating the furnace body to ensure that the temperature in the furnace body is kept unchanged after the temperature in the furnace body is raised to 1500-1700 ℃, and fully melting the mixed raw materials in the furnace body;
(5) after the reaction is finished, the temperature in the furnace body is controlled to be rapidly reduced to 1150-.
(6) Stopping heating, naturally cooling and crystallizing the materials in the furnace body, and opening the furnace to obtain the artificially synthesized black mica crystal after the temperature in the furnace is cooled to room temperature.
Specifically, in the step (4), the temperature in the furnace body is increased from room temperature to 1555-1650 ℃ and then is kept unchanged.
Specifically, in the step (5), after the reaction is finished, the temperature in the furnace body is controlled to be rapidly reduced to 1280 ℃, the heating power of the furnace body is controlled to slowly reduce the temperature in the furnace to 1180 ℃, and the temperature reduction speed is 3-5 ℃/h.
Specifically, the iron oxide in the step (1) includes one or more of ferroferric oxide, ferric oxide, ferrous oxide and the like, and the alkali metal fluoride and alkaline earth metal fluoride includes one or more of potassium fluoride, aluminum fluoride and magnesium fluoride.
Compared with the prior art, the invention has the following advantages and beneficial effects: the invention relates to a method for crystallizing artificially synthesized biotite crystals, which obtains the artificially synthesized biotite crystals with excellent performance by performing high-temperature reaction, melting, cooling and crystallization on quartz sand, fused magnesia, potassium carbonate, ferric oxide and one or more of potassium fluosilicate, aluminum oxide, alkali metal and alkaline earth metal fluorides in a specific proportion under a certain condition, solves the problem that the existing artificially synthesized biotite crystals cannot realize industrial production, and has considerable application prospect.
Drawings
FIG. 1 shows the microstructure analysis (scanning electron microscopy) of the artificially synthesized Mucuna crystal prepared according to the present invention.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the present invention is not limited thereto.
The specific implementation process of the invention is as follows:
the chemical general formula of the artificially synthesized black mica crystal is K [ Fe ]a 2+Mgb][Fec 3+Ald]Si3O10F2Wherein a + b is 3, and a is 0.5 or b is 0.5 or less; c + d is 1, and c is less than or equal to 0.75 or d is less than or equal to 0.75.
The synthesis process of mica can be mainly divided into a crucible descent seed crystal method and an internal heating method. The invention relates to a crystal crystallization method of artificially synthesized biotite, which is based on the principle of synthesizing mica by an internal heat method. Among them, the Bridgman method is less applicable to mass industrial production because it consumes much energy, has a long cycle time, and requires the use of an expensive platinum crucible, resulting in high production costs, although it can produce large-sized plate-like crystals. Compared with the crucible descending seed crystal method, the internal heating method has the advantages of less energy consumption, high yield and small volatilization of fluoride, and does not need a crucible. This method is therefore currently the main method for large-scale production of synthetic mica.
The internal heating method is mainly characterized in that raw materials required by synthetic mica are mixed according to a certain proportion and then added into a high-temperature furnace built by refractory bricks, a heating electrode is utilized to melt part of raw materials, the melted melt can conduct electricity, so that the raw materials are completely melted, and finally, the raw materials are cooled to precipitate crystals so as to obtain a target product.
The crystallization method for artificially synthesizing the black mica crystal comprises the following steps:
(1) setting an artificially synthesized biotite structure after the reaction between chemicals, and preparing raw materials according to the weight ratio.
When the artificially synthesized black mica crystal is prepared, firstly, one or more of potassium fluosilicate, aluminum oxide, alkali metal, alkaline earth metal fluoride and the like are added into raw materials such as quartz sand, fused magnesia, potassium carbonate, iron oxide and the like as ingredients according to different structures of the black mica crystal to be synthesized. Wherein the ferric oxide comprises one or more of ferroferric oxide, ferric oxide, ferrous oxide and the like, and the alkali metal and alkaline earth metal fluorides comprise one or more of potassium fluoride, aluminum fluoride and magnesium fluoride.
30-40% of quartz sand, fused magnesia: 4-27%, potassium carbonate: 4-16%, iron oxide: 12-18 percent of synthetic biotite, and specifically, the synthetic biotite further comprises 14-17 percent of potassium fluosilicate, 2-12 percent of alumina and one or more of alkali metal and alkaline earth metal fluorides according to different structural formulas of the artificially synthesized biotite. Wherein the ferric oxide comprises one or more of ferroferric oxide, 12-18% of ferric oxide and 6-42% of ferrous oxide, and the specific component proportion is based on the embodiment.
(2) Weighing the raw materials in the step (1) according to the stoichiometric ratio, crushing the raw materials to be below 100 meshes, and fully dispersing and mixing.
(3) And (3) stacking the furnace body, installing electrodes in the furnace body, paving a heat insulation layer on the inner wall of the furnace body, filling the crushed mixed raw materials obtained in the step (2) into the furnace body, compacting the mixed raw materials, and then heating the furnace body, wherein the heat insulation layer is formed by the mixed raw materials which are not reacted.
The furnace body is provided with a furnace base, a furnace ring and a furnace opening from bottom to top in sequence, and the diameter of the furnace ring refers to the diameter of the largest part of the furnace ring. The furnace body is built by any one or more of standard high-aluminum refractory bricks, wedge-shaped high-aluminum refractory bricks and high-quality clay bricks, and the periphery of the furnace body is reinforced by flat iron.
Specifically, the heat preservation layer arranged on the inner side wall of the furnace body is composed of raw materials which are not reacted. The process of the biotite synthesis process belongs to a solid-liquid phase change process, and the heat process, the container and the raw material ratio in the process all influence the solid precipitation state, so that the product quality is directly influenced. The excessively fast cooling speed may cause that the final product is the attapulgite rather than the mica, so the scheme adds the heat-insulating layer between the furnace body and the mixed raw materials to provide a slower cooling speed, which is beneficial to forming larger crystals. After the reaction is completed and the power is cut off, the input power suddenly drops to zero. In the natural cooling and crystallization process in the furnace body, the returned materials filled in the furnace body in advance serve as the heat insulation layer, so that the cooling time of the materials in the furnace body can be prolonged on the premise of not influencing the reaction, the crystal precipitation process is more stable, and the crystal precipitation quality is improved.
Preferably, the electrodes in the step (3) are graphite electrode groups, and each graphite electrode group is composed of a graphite electrode plate, a graphite main electrode rod and a graphite auxiliary electrode rod, the graphite main electrode rod is mounted on the graphite electrode plate, the graphite auxiliary electrode rod is inserted into the upper end of the graphite main electrode rod, the upper end of the graphite auxiliary electrode rod is connected with a small arc starting graphite electrode, three graphite electrode groups are arranged in the furnace body, and the three graphite electrode groups are uniformly distributed along the circumferential direction of the side wall of the furnace body by taking the central axis of the furnace body as the center.
Specifically, in the graphite electrode group, the graphite electrode plates incline towards the center of the furnace and form an included angle of 5-10 degrees with the horizontal plane, the graphite main electrode rods incline towards the center of the furnace and form an included angle of 100-105 degrees with the graphite electrode plates, and corresponding distances are reserved between the top ends of the graphite main electrode rods.
Preferably, the equipment for preparing the artificially synthesized black mica crystal needs to be provided with a control cabinet besides the furnace body and the electrodes. The control cabinet is electrically connected with the graphite electrode group to control the input power of the graphite electrode group. The melting process adopts a 10KV power supply to supply power, the power supply is sequentially connected with a circuit breaker and a transformer, three groups of 380V, 220V and 110V alternating current power supplies are output by the transformer, the three groups of power supplies output by the transformer are connected with three switch cabinets in a one-to-one correspondence manner, the three switch cabinets are connected into a control cabinet, and the power supply output from the control cabinet is connected to a graphite electrode plate on a furnace body to heat mixed raw materials in the furnace body. The control cabinet is composed of a high-power thyristor and a control circuit, and is a main control part for adjusting the input power in the melting process.
(4) And (3) electrifying the electrode installed in the step (3) to heat the furnace body, fully melting the mixed raw materials in the furnace body, keeping the temperature in the furnace body unchanged after the temperature in the furnace body is raised to 1500-.
(5) After the reaction is finished, the temperature in the furnace body is controlled to be rapidly reduced to 1350-. The slow reduction from 1350 ℃ to 1050-.
(6) Stopping heating, naturally cooling and crystallizing the materials in the furnace body, and opening the furnace to obtain the artificially synthesized black mica crystal after the temperature in the furnace is cooled to room temperature.
As can be seen from the scanning electron micrograph shown in the attached figure 1, the fracture of the artificially synthesized biotite sample prepared by the invention is layered, and the flaky cleavage plane is smooth and compact. According to the steps of the method, the chemical property detection report of the prepared finished product artificially synthesized black mica crystal is as follows:
table 1 shows the chemical composition analysis report of the artificially synthesized heinmu crystal prepared in the present invention:
table 2 shows the composition ratios (in mass percent) of the components in the examples:
| example 1 | Example 2 | Example 3 | Example 4 | Example 5 | |
| SiO2 | 35.56％ | 36.90％ | 32.12％ | 31.01％ | 40.01％ |
| MgO | 26.87％ | 24.17％ | 4.05％ | 17.92％ | |
| Al2O3 | 11.76％ | 2.56％ | 9.88％ | ||
| K2CO3 | 5.11％ | 5.31％ | 4.62％ | 4.46％ | 15.34％ |
| K2SiF6 | 16.30％ | 16.91％ | 14.72％ | 14.21％ | |
| Fe2O3 | 17.78％ | 12.05％ | 17.78％ | ||
| FeO | 6.64％ | 36.14％ | 41.87％ | ||
| MgF2 | 13.85％ |
The procedure and formulation of the synthetic biotite are described in detail below with reference to specific examples:
the first embodiment is as follows: the preparation method of the KMg with the structural formula is characterized by using quartz sand, fused magnesia, potassium carbonate, potassium fluosilicate and ferric oxide as raw materials3FeSi3O10F2Artificially synthesizing the black mica crystal. KMg3FeSi3O10F2The synthetic black mica crystal prepared by the invention has a stable structural formula, and the raw materials in the embodiment are as follows by weight: SiO 2235.56％、MgO 26.87％、K2CO35.11％、K2SiF616.30％、Fe2O317.78%, the reaction formula is:
16SiO2+3Fe2O3+K2CO3+2K2SiF6+18MgO＝6KMg3FeSi3O10F2+CO2
the method comprises the following steps:
(1) preparing the raw materials according to the actual weight ratio, and uniformly mixing to obtain the mixed raw material.
(2) Weighing the mixed raw materials in the step (1) according to a stoichiometric ratio, crushing various raw materials to be below 100 meshes, and fully dispersing and mixing.
(3) Stacking the furnace body, filling the crushed mixed raw materials obtained in the step (2) into the furnace body, compacting, presetting a heat insulation layer between the mixed raw materials and the furnace body, wherein the heat insulation layer is composed of the mixed raw materials which are not reacted, the filling height of the mixed raw materials is flush with the uppermost layer of refractory bricks of the furnace body, covering the arc starting small graphite electrodes, covering a heat insulation layer above the mixed raw materials, and starting equipment to heat;
the total amount of the mixed raw materials added in each furnace (the sum of the mixed raw materials in the step (3) and the returned materials contained in the heat-insulating layer in the furnace body) can be properly adjusted according to the capacity of the furnace body and the specific melting process.
(4) And (3) electrifying the starting equipment to melt the mixed raw materials in the furnace body: the temperature in the furnace body is kept unchanged after being increased from room temperature to 1500-1700 ℃ (the preferred temperature is 1555-1650 ℃).
In the step (4), the melting process of the mixed raw materials in the furnace body sequentially comprises the following steps:
(4-1) arc striking: the graphite electrode group is connected with a 380V alternating current power supply, the input power is adjusted to be gradually increased to 120KW from zero, the small arcing graphite electrode generates heat and melts part of mixed raw materials into molten liquid, and the molten liquid can conduct electricity at the moment until the small arcing graphite electrode is fused and is conducted by the dissolved molten liquid to generate heat.
(4-2) after the arc striking process is finished, the control cabinet works to control the graphite electrode group to disconnect a 380V alternating current power supply and connect a 220V alternating current power supply, the input power is gradually increased, the molten liquid continuously conducts electricity and generates heat, the mixed raw material continuously melts, the molten liquid amount is gradually increased and continuously conducts electricity and generates heat, and the mixed raw material continuously melts.
Specifically, in practical operation, the increase of the input power in the step (4-2) is usually in a wave-shaped rise. A too low melting temperature may result in incomplete melting of the raw materials to be mixed, and a too high melting temperature may result in severe volatilization of F. Therefore, in step (4-2), the melt temperature should be measured at regular intervals, the input power is increased when the melt temperature is too low, and the input power is decreased when the melt temperature is too high, so as to control the melt temperature within a preset range.
It should be noted that in this step, during the melting process, the mixed raw materials should be added to the furnace surface in time whenever the furnace surface sags, and the temperature of the melt should be kept within a preset range.
(4-3) heat preservation: and after the added mixed raw materials are completely melted, adding a layer of return charge with uniform thickness to the surface of the furnace, reducing the input power of the electrode, and entering a heat preservation stage.
(5) After the reaction is finished, the temperature in the furnace body is controlled to be rapidly reduced to 1150-1350 ℃, the temperature is slowly reduced to 100 ℃, and the temperature reduction speed is 3-5 ℃/h.
(6) And (4) stopping power supply, naturally cooling and crystallizing the materials in the furnace body, and opening the furnace to crush the materials after the temperature in the furnace is cooled to room temperature to obtain the biotite crystals. The specific operation flow is as follows: when the surface temperature of the furnace body is lower than 50 ℃, removing refractory bricks, removing unsintered powder and scrap returns, then performing the steps of punching, blasting, pickaxe breaking, selecting and taking out a target product, crushing, screening, packaging, warehousing and the like.
Example two: the KMg is prepared by using quartz sand, fused magnesia, potassium carbonate, potassium fluosilicate, aluminum oxide and ferrous oxide as raw materials2.6[Fe0.4AlSi3O10]F2Artificially synthesizing the black mica crystal. The raw material ratio is as follows: SiO 2236.90％、MgO 24.17％、Al2O311.76％、K2CO35.31％、K2SiF616.91 percent and FeO6.64 percent, and the reaction chemical formula is as follows:
16SiO2+2.4FeO+3Al2O3+K2CO3+2K2SiF6+15.6MgO＝6KMg2.6[Fe0.4AlSi3O10]F2+CO2
the method comprises the following steps:
(1) preparing the raw materials according to the actual weight ratio, and uniformly mixing to obtain the mixed raw material.
(2) Weighing the mixed raw materials in the step (1) according to a stoichiometric ratio, crushing various raw materials to be below 100 meshes, and fully dispersing and mixing.
(3) Stacking the furnace body, filling the crushed mixed raw materials obtained in the step (2) into the furnace body, compacting, presetting a heat insulation layer between the mixed raw materials and the furnace body, wherein the heat insulation layer is composed of the mixed raw materials which are not reacted, the filling height of the mixed raw materials is flush with the uppermost layer of refractory bricks of the furnace body, covering the arc starting small graphite electrodes, covering a heat insulation layer above the mixed raw materials, and starting equipment to heat;
the total amount of the mixed raw materials added in each furnace (the sum of the mixed raw materials in the step (3) and the returned materials contained in the heat-insulating layer in the furnace body) can be properly adjusted according to the capacity of the furnace body and the specific melting process.
(4) And (3) electrifying the starting equipment to melt the mixed raw materials in the furnace body: the temperature in the furnace body is kept unchanged after being increased from room temperature to 1500-1700 ℃ (the preferred temperature is 1555-1650 ℃).
In the step (4), the melting process of the mixed raw materials in the furnace body sequentially comprises the following steps:
(4-1) arc striking: the graphite electrode group is connected with a 380V alternating current power supply, the input power is adjusted to be gradually increased to 120KW from zero, the small arcing graphite electrode generates heat and melts part of mixed raw materials into molten liquid, and the molten liquid can conduct electricity at the moment until the small arcing graphite electrode is fused and is conducted by the dissolved molten liquid to generate heat.
(4-2) after the arc striking process is finished, the control cabinet works to control the graphite electrode group to disconnect a 380V alternating current power supply and connect a 220V alternating current power supply, the input power is gradually increased, the molten liquid continuously conducts electricity and generates heat, the mixed raw material continuously melts, the molten liquid amount is gradually increased and continuously conducts electricity and generates heat, and the mixed raw material continuously melts.
Specifically, in practical operation, the increase of the input power in the step (4-2) is usually in a wave-shaped rise. A too low melting temperature may result in incomplete melting of the raw materials to be mixed, and a too high melting temperature may result in severe volatilization of F. Therefore, in step (4-2), the melt temperature should be measured at regular intervals, the input power is increased when the melt temperature is too low, and the input power is decreased when the melt temperature is too high, so as to control the melt temperature within a preset range.
It should be noted that in this step, during the melting process, the mixed raw materials should be added to the furnace surface in time whenever the furnace surface sags, and the temperature of the melt should be kept within a preset range.
(4-3) heat preservation: and after the added mixed raw materials are completely melted, adding a layer of return charge with uniform thickness to the surface of the furnace, reducing the input power of the electrode, and entering a heat preservation stage.
(5) After the reaction is finished, the temperature in the furnace body is controlled to be rapidly reduced to 1150-1350 ℃, the temperature is slowly reduced to 100 ℃, and the temperature reduction speed is 3-5 ℃/h.
(6) And (4) stopping power supply, naturally cooling and crystallizing the materials in the furnace body, and opening the furnace to crush the materials after the temperature in the furnace is cooled to room temperature to obtain the biotite crystals. The specific operation flow is as follows: when the surface temperature of the furnace body is lower than 50 ℃, removing refractory bricks, removing unsintered powder and scrap returns, then performing the steps of punching, blasting, pickaxe breaking, selecting and taking out a target product, crushing, screening, packaging, warehousing and the like.
Example three: preparing K [ Fe ] with structural formula by using quartz sand, fused magnesia, potassium carbonate, potassium fluosilicate, iron oxide and aluminum oxide as raw materials2.5Mg0.5][Fe0.75Al0.25]Si3O10F2Artificially synthesizing the black mica crystal. The raw material ratio is as follows: SiO 2232.12％、MgO 4.05％、Al2O32.56％、K2CO34.62％、K2SiF614.72％、Fe2O312.05 percent and FeO36.14 percent, and the reaction chemical formula is as follows:
16SiO2+15FeO+2.25Fe2O3+0.75Al2O3+K2CO3+2K2SiF6+3MgO＝6K[Fe2.5Mg0.5][Fe0.75Al0.25]Si3O10F2+CO2
the method comprises the following steps:
(1) preparing the raw materials according to the actual weight ratio, and uniformly mixing to obtain the mixed raw material.
(2) Weighing the mixed raw materials in the step (1) according to a stoichiometric ratio, crushing various raw materials to be below 100 meshes, and fully dispersing and mixing.
(3) Stacking the furnace body, filling the crushed mixed raw materials obtained in the step (2) into the furnace body, compacting, presetting a heat insulation layer between the mixed raw materials and the furnace body, wherein the heat insulation layer is composed of the mixed raw materials which are not reacted, the filling height of the mixed raw materials is flush with the uppermost layer of refractory bricks of the furnace body, covering the arc starting small graphite electrodes, covering a heat insulation layer above the mixed raw materials, and starting equipment to heat;
the total amount of the mixed raw materials added in each furnace (the sum of the mixed raw materials in the step (3) and the returned materials contained in the heat-insulating layer in the furnace body) can be properly adjusted according to the capacity of the furnace body and the specific melting process.
(4) And (3) electrifying the starting equipment to melt the mixed raw materials in the furnace body: the temperature in the furnace body is kept unchanged after being increased from room temperature to 1500-1700 ℃ (the preferred temperature is 1555-1650 ℃).
In the step (4), the melting process of the mixed raw materials in the furnace body sequentially comprises the following steps:
(4-1) arc striking: the graphite electrode group is connected with a 380V alternating current power supply, the input power is adjusted to be gradually increased to 120KW from zero, the small arcing graphite electrode generates heat and melts part of mixed raw materials into molten liquid, and the molten liquid can conduct electricity at the moment until the small arcing graphite electrode is fused and is conducted by the dissolved molten liquid to generate heat.
(4-2) after the arc striking process is finished, the control cabinet works to control the graphite electrode group to disconnect a 380V alternating current power supply and connect a 220V alternating current power supply, the input power is gradually increased, the molten liquid continuously conducts electricity and generates heat, the mixed raw material continuously melts, the molten liquid amount is gradually increased and continuously conducts electricity and generates heat, and the mixed raw material continuously melts.
Specifically, in practical operation, the increase of the input power in the step (4-2) is usually in a wave-shaped rise. A too low melting temperature may result in incomplete melting of the raw materials to be mixed, and a too high melting temperature may result in severe volatilization of F. Therefore, in step (4-2), the melt temperature should be measured at regular intervals, the input power is increased when the melt temperature is too low, and the input power is decreased when the melt temperature is too high, so as to control the melt temperature within a preset range.
It should be noted that in this step, during the melting process, the mixed raw materials should be added to the furnace surface in time whenever the furnace surface sags, and the temperature of the melt should be kept within a preset range.
(4-3) heat preservation: and after the added mixed raw materials are completely melted, adding a layer of return charge with uniform thickness to the surface of the furnace, reducing the input power of the electrode, and entering a heat preservation stage.
(5) After the reaction is finished, the temperature in the furnace body is controlled to be rapidly reduced to 1150-1350 ℃, the temperature is slowly reduced to 100 ℃, and the temperature reduction speed is 3-5 ℃/h.
(6) And (4) stopping power supply, naturally cooling and crystallizing the materials in the furnace body, and opening the furnace to crush the materials after the temperature in the furnace is cooled to room temperature to obtain the biotite crystals. The specific operation flow is as follows: when the surface temperature of the furnace body is lower than 50 ℃, removing refractory bricks, removing unsintered powder and scrap returns, then performing the steps of punching, blasting, pickaxe breaking, selecting and taking out a target product, crushing, screening, packaging, warehousing and the like.
Example four: the preparation method of K (Fe) with the structural formula of K by using quartz sand, aluminum oxide, potassium carbonate, potassium fluosilicate and ferric oxide as raw materials2+)3AlSi3O10F2Artificially synthesizing the black mica crystal. The raw material ratio is as follows: SiO 2231.01％、Al2O39.88％、K2CO34.46％、K2SiF614.21 percent and FeO41.87 percent, and the reaction chemical formula is as follows:
48SiO2+54FeO+9Al2O3+3K2CO3+6K2SiF6＝18K(Fe2+)3AlSi3O10F2+3CO2
the method comprises the following steps:
(1) preparing the raw materials according to the actual weight ratio, and uniformly mixing to obtain the mixed raw material.
(2) Weighing the mixed raw materials in the step (1) according to a stoichiometric ratio, crushing various raw materials to be below 100 meshes, and fully dispersing and mixing.
(3) Stacking the furnace body, filling the crushed mixed raw materials obtained in the step (2) into the furnace body, compacting, presetting a heat insulation layer between the mixed raw materials and the furnace body, wherein the heat insulation layer is composed of the mixed raw materials which are not reacted, the filling height of the mixed raw materials is flush with the uppermost layer of refractory bricks of the furnace body, covering the arc starting small graphite electrodes, covering a heat insulation layer above the mixed raw materials, and starting equipment to heat;
the total amount of the mixed raw materials added in each furnace (the sum of the mixed raw materials in the step (3) and the returned materials contained in the heat-insulating layer in the furnace body) can be properly adjusted according to the capacity of the furnace body and the specific melting process.
(4) And (3) electrifying the starting equipment to melt the mixed raw materials in the furnace body: the temperature in the furnace body is kept unchanged after being increased from room temperature to 1500-1700 ℃ (the preferred temperature is 1555-1650 ℃).
In the step (4), the melting process of the mixed raw materials in the furnace body sequentially comprises the following steps:
(4-1) arc striking: the graphite electrode group is connected with a 380V alternating current power supply, the input power is adjusted to be gradually increased to 120KW from zero, the small arcing graphite electrode generates heat and melts part of mixed raw materials into molten liquid, and the molten liquid can conduct electricity at the moment until the small arcing graphite electrode is fused and is conducted by the dissolved molten liquid to generate heat.
(4-2) after the arc striking process is finished, the control cabinet works to control the graphite electrode group to disconnect a 380V alternating current power supply and connect a 220V alternating current power supply, the input power is gradually increased, the molten liquid continuously conducts electricity and generates heat, the mixed raw material continuously melts, the molten liquid amount is gradually increased and continuously conducts electricity and generates heat, and the mixed raw material continuously melts.
Specifically, in practical operation, the increase of the input power in the step (4-2) is usually in a wave-shaped rise. A too low melting temperature may result in incomplete melting of the raw materials to be mixed, and a too high melting temperature may result in severe volatilization of F. Therefore, in step (4-2), the melt temperature should be measured at regular intervals, the input power is increased when the melt temperature is too low, and the input power is decreased when the melt temperature is too high, so as to control the melt temperature within a preset range.
It should be noted that in this step, during the melting process, the mixed raw materials should be added to the furnace surface in time whenever the furnace surface sags, and the temperature of the melt should be kept within a preset range.
(4-3) heat preservation: and after the added mixed raw materials are completely melted, adding a layer of return charge with uniform thickness to the surface of the furnace, reducing the input power of the electrode, and entering a heat preservation stage.
(5) After the reaction is finished, the temperature in the furnace body is controlled to be rapidly reduced to 1150-1350 ℃, the temperature is slowly reduced to 100 ℃, and the temperature reduction speed is 3-5 ℃/h.
(6) And (4) stopping power supply, naturally cooling and crystallizing the materials in the furnace body, and opening the furnace to crush the materials after the temperature in the furnace is cooled to room temperature to obtain the biotite crystals. The specific operation flow is as follows: when the surface temperature of the furnace body is lower than 50 ℃, removing refractory bricks, removing unsintered powder and scrap returns, then performing the steps of punching, blasting, pickaxe breaking, selecting and taking out a target product, crushing, screening, packaging, warehousing and the like.
Example five: the preparation method of KMg with the structural formula of KMg by using quartz sand, magnesium oxide, potassium carbonate, ferric oxide and magnesium fluoride as raw materials3FeSi3O10F2Artificially synthesizing the black mica crystal. The raw material ratio is as follows: SiO 2240.01％、Fe2O317.78％、K2CO315.34％、MgO17.92％、MgF213.85%, the reaction formula is:
6SiO2+Fe2O3+K2CO3+2MgF2+4MgO＝2KMg3FeSi3O10F2+CO2
(1) preparing the raw materials according to the actual weight ratio, and uniformly mixing to obtain the mixed raw material.
(2) Weighing the mixed raw materials in the step (1) according to a stoichiometric ratio, crushing various raw materials to be below 100 meshes, and fully dispersing and mixing.
(3) Stacking the furnace body, filling the crushed mixed raw materials obtained in the step (2) into the furnace body, compacting, presetting a heat insulation layer between the mixed raw materials and the furnace body, wherein the heat insulation layer is composed of the mixed raw materials which are not reacted, the filling height of the mixed raw materials is flush with the uppermost layer of refractory bricks of the furnace body, covering the arc starting small graphite electrodes, covering a heat insulation layer above the mixed raw materials, and starting equipment to heat;
the total amount of the mixed raw materials added in each furnace (the sum of the mixed raw materials in the step (3) and the returned materials contained in the heat-insulating layer in the furnace body) can be properly adjusted according to the capacity of the furnace body and the specific melting process.
(4) And (3) electrifying the starting equipment to melt the mixed raw materials in the furnace body: the temperature in the furnace body is kept unchanged after being increased from room temperature to 1500-1700 ℃ (the preferred temperature is 1555-1650 ℃).
In the step (4), the melting process of the mixed raw materials in the furnace body sequentially comprises the following steps:
(4-1) arc striking: the graphite electrode group is connected with a 380V alternating current power supply, the input power is adjusted to be gradually increased to 120KW from zero, the small arcing graphite electrode generates heat and melts part of mixed raw materials into molten liquid, and the molten liquid can conduct electricity at the moment until the small arcing graphite electrode is fused and is conducted by the dissolved molten liquid to generate heat.
(4-2) after the arc striking process is finished, the control cabinet works to control the graphite electrode group to disconnect a 380V alternating current power supply and connect a 220V alternating current power supply, the input power is gradually increased, the molten liquid continuously conducts electricity and generates heat, the mixed raw material continuously melts, the molten liquid amount is gradually increased and continuously conducts electricity and generates heat, and the mixed raw material continuously melts.
Specifically, in practical operation, the increase of the input power in the step (4-2) is usually in a wave-shaped rise. A too low melting temperature may result in incomplete melting of the raw materials to be mixed, and a too high melting temperature may result in severe volatilization of F. Therefore, in step (4-2), the melt temperature should be measured at regular intervals, the input power is increased when the melt temperature is too low, and the input power is decreased when the melt temperature is too high, so as to control the melt temperature within a preset range.
It should be noted that in this step, during the melting process, the mixed raw materials should be added to the furnace surface in time whenever the furnace surface sags, and the temperature of the melt should be kept within a preset range.
(4-3) heat preservation: and after the added mixed raw materials are completely melted, adding a layer of return charge with uniform thickness to the surface of the furnace, reducing the input power of the electrode, and entering a heat preservation stage.
(5) After the reaction is finished, the temperature in the furnace body is controlled to be rapidly reduced to 1150-1350 ℃, the temperature is slowly reduced to 100 ℃, and the temperature reduction speed is 3-5 ℃/h.
(6) And (4) stopping power supply, naturally cooling and crystallizing the materials in the furnace body, and opening the furnace to crush the materials after the temperature in the furnace is cooled to room temperature to obtain the biotite crystals. The specific operation flow is as follows: when the surface temperature of the furnace body is lower than 50 ℃, removing refractory bricks, removing unsintered powder and scrap returns, then performing the steps of punching, blasting, pickaxe breaking, selecting and taking out a target product, crushing, screening, packaging, warehousing and the like.
The above-mentioned embodiments only express the embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (5)
1. An artificially synthesized black mica crystal is characterized in that: the chemical general formula of the artificially synthesized black mica crystal is K [ Fe ]a 2+Mgb][Fec 3+Ald]Si3O10F2Wherein a + b is 3, and a is 0.5 or b is 0.5 or less; c + d is 1, and c is less than or equal to 0.75 or d is less than or equal to 0.75.
2. The crystallization method of artificially synthesized heinmu crystal according to claim 1, characterized in that:
the method comprises the following steps: (1) setting an artificially synthesized biotite structure after chemical reaction, and preparing raw materials according to the weight ratio, wherein the raw materials comprise 30-40% of quartz sand, fused magnesia: 4-27%, potassium carbonate: 4-16%, iron oxide: 12-18%, and the raw material also comprises one or more of potassium fluosilicate, alumina, alkali metal fluoride and alkaline earth metal fluoride;
(2) weighing the raw materials in the step (1) according to a stoichiometric ratio, crushing various raw materials to be below 100 meshes, and fully dispersing and mixing;
(3) stacking the furnace body, paving a heat-insulating layer on the inner wall of the furnace body, filling the crushed mixed raw materials obtained in the step (2) into the furnace body, compacting the crushed mixed raw materials, and heating the furnace body, wherein the heat-insulating layer is formed by the mixed raw materials which are not reacted;
(4) heating the furnace body to ensure that the temperature in the furnace body is kept unchanged after the temperature in the furnace body is raised to 1500-1700 ℃, and fully melting the mixed raw materials in the furnace body;
(5) after the reaction is finished, the temperature in the furnace body is controlled to be rapidly reduced to 1150-.
(6) Stopping heating, naturally cooling and crystallizing the materials in the furnace body, and opening the furnace to obtain the artificially synthesized black mica crystal after the temperature in the furnace is cooled to room temperature.
3. The crystallization method of artificially synthesized heinmu crystal according to claim 2, characterized in that: in the step (4), the temperature in the furnace body is increased from room temperature to 1555-1650 ℃ and then is kept unchanged.
4. The crystallization method of artificially synthesized heinmu crystal according to claim 2, characterized in that: in the step (5), after the reaction is finished, the temperature in the furnace body is controlled to be rapidly reduced to 1280 ℃, the heating power of the furnace body is controlled to slowly reduce the temperature in the furnace to 1180 ℃, and the temperature reduction speed is 3-5 ℃/h.
5. The crystallization method of artificially synthesized heinmu crystal according to claim 2, characterized in that: in the step (1), the ferric oxide comprises one or more of ferroferric oxide, ferric oxide, ferrous oxide and the like, and the alkali metal fluoride and alkaline earth metal fluoride comprises one or more of potassium fluoride, aluminum fluoride and magnesium fluoride.
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| CN113755949A (en) * | 2021-09-08 | 2021-12-07 | 广东三宝新材料科技股份有限公司 | Crystallization method for artificially synthesizing black mica crystal |
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