CN109133650B - Method for preparing microcrystalline glass by using chlorine-containing titanium extraction slag - Google Patents
Method for preparing microcrystalline glass by using chlorine-containing titanium extraction slag Download PDFInfo
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- CN109133650B CN109133650B CN201811088051.9A CN201811088051A CN109133650B CN 109133650 B CN109133650 B CN 109133650B CN 201811088051 A CN201811088051 A CN 201811088051A CN 109133650 B CN109133650 B CN 109133650B
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
- C03C10/0063—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing waste materials, e.g. slags
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B1/00—Preparing the batches
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B1/00—Preparing the batches
- C03B1/02—Compacting the glass batches, e.g. pelletising
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B19/00—Other methods of shaping glass
- C03B19/06—Other methods of shaping glass by sintering, e.g. by cold isostatic pressing of powders and subsequent sintering, by hot pressing of powders, by sintering slurries or dispersions not undergoing a liquid phase reaction
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping
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Abstract
The invention provides a method for preparing microcrystalline glass by using chlorine-containing titanium extraction slag. The method comprises the following steps: drying and crushing the chlorine-containing titanium-extracting slag, or pretreating the chlorine-containing titanium-extracting slag and ingredients to obtain blank-making powder, wherein the mass fraction of the chlorine-containing titanium-extracting slag in the blank-making powder is more than 85%; pressing and molding the blank-making powder to obtain a microcrystalline glass blank; and carrying out heat treatment on the blank to obtain the microcrystalline glass. The beneficial effects of the invention include: the utilization rate of the chlorine-containing titanium extraction slag is high; the preparation process does not need to add a crystal nucleus agent, a granulating agent and a binder; the production process has no three-waste discharge.
Description
Technical Field
The invention relates to the field of solid waste treatment and resource utilization and preparation of inorganic non-metallic functional materials, in particular to a method for preparing microcrystalline glass by using chlorine-containing titanium extraction slag.
Background
The chlorine-containing titanium extraction slag is obtained by carrying out high-temperature carbonization and low-temperature chlorination on the titanium-containing blast furnace slag, has high chlorine content, is classified as dangerous slag, and has great harm to soil, environment and the like. Therefore, the treatment and comprehensive utilization of the chlorine-containing titanium extraction slag are important.
The microcrystalline glass, also known as glass ceramic and microcrystalline ceramic, is a kind of polycrystalline material in which the microcrystalline phase and glass phase coexist, which is obtained by controlling heat treatment system based on glass and ceramic forming technology, and can be used as high-grade building decorative material and various functional materials, etc. because of its good mechanical property, high hardness, high wear resistance and acid-base corrosion resistance. The existing microcrystalline glass production process mainly comprises the following steps: the main production processes of the integral crystallization method, the melt sintering method and the sol-gel method are the first two for the industrial waste residue microcrystalline glass. The production process of the integral crystallization method comprises the steps of matching raw materials → high-temperature melting → pouring molding → annealing → nucleation → polishing and trimming → products, and the production process of the melting and sintering method comprises the steps of matching raw materials → high-temperature melting → water quenching → ball milling → tabletting → nucleation → polishing and trimming → products. The integral crystallization method and the melt sintering method both comprise a high-temperature melting process, and both require a secondary high-temperature treatment process, so that the defects or defects of high energy consumption, long process flow, complicated working procedures, low utilization rate of industrial waste residues and the like exist.
In conclusion, the existing mainstream production process of the microcrystalline glass has the problems of high production energy consumption, long process flow, low utilization rate of waste residues and the like. In addition, the chlorine content of the chlorine-containing titanium extraction slag is high, so that the chlorine-containing titanium extraction slag is difficult to be directly used for building material products, the chlorine is removed through water washing and roasting or dechlorination agent is added for roasting, and the added value of the dechlorinated product is low.
At present, no method for preparing the glass ceramics only needs one-time high-temperature treatment process, and chlorine can be removed from the chlorine-containing titanium extraction slag in the preparation process.
Disclosure of Invention
In view of the deficiencies in the prior art, it is an object of the present invention to address one or more of the problems in the prior art as set forth above. For example, one of the purposes of the invention is to provide a method for preparing microcrystalline glass by using chlorine-containing titanium extraction slag, and chloride can be recovered simultaneously in the preparation process.
In order to achieve the aim, the invention provides a method for preparing microcrystalline glass by using chlorine-containing titanium extraction slag. The method may comprise the steps of: drying and crushing the chlorine-containing titanium extraction slag to obtain blank-making powder; pressing and molding the blank-making powder to obtain a blank body; and heating the blank to 800-1000 ℃, preserving heat to promote nucleation and crystallization of the blank, heating to 1100-1200 ℃, sintering, and cooling after sintering to obtain the microcrystalline glass.
The invention also provides a method for preparing the glass ceramics by using the chlorine-containing titanium extraction slag. The method may comprise the steps of: pretreating chlorine-containing titanium-extracting slag and ingredients to obtain blank-making powder, wherein the mass fraction of the chlorine-containing titanium-extracting slag in the blank-making powder is more than 85%, and the ingredients comprise a fluxing agent and/or a microcrystalline glass component replenisher; pressing and molding the blank-making powder to obtain a blank body; and heating the blank to 800-1000 ℃, preserving heat to promote nucleation and crystallization of the blank, heating to 1100-1200 ℃, sintering, and cooling after sintering to obtain the microcrystalline glass.
According to one or more exemplary embodiments of the present invention, the ingredients may include: at least one of quartz, potash feldspar, nepheline, borax, soda ash and waste glass. Wherein, borax and soda ash can be used as fluxing agent, quartz sand can be used as supplement agent, and potash feldspar, nepheline and waste glass can be used as supplement agent and fluxing agent simultaneously.
According to one or more exemplary embodiments of the present invention, the method may further include the steps of: and (3) trimming and/or polishing the obtained microcrystalline glass.
According to one or more exemplary embodiments of the present invention, the method may further include the steps of: and returning waste materials generated by the trimming and/or polishing to be used for manufacturing the blank-making powder. Namely, returning to the previous step for reuse, wherein the mass fraction of the waste in the blank making powder can be 0-2%.
According to one or more exemplary embodiments of the present invention, the pre-treatment includes drying, pulverizing and mixing, and the pulverizing may include crushing and pulverizing, and may be followed by classification.
According to one or more exemplary embodiments of the present invention, the green body powder may have a particle size of 40 to 100 μm, and further, may have a particle size of 45 to 96 μm. The water content of the blank making powder is 3-6%.
According to one or more exemplary embodiments of the present invention, the press-forming may include: uniformly spreading the blank-making powder in a mold at 250-720 kgf/cm2Under pressure of (2)Keeping the pressure for 15-30 s, and then demoulding to obtain a blank; further, the pressure may be 255 to 714kgf/cm2。
According to one or more exemplary embodiments of the present invention, the method may further include the steps of: and collecting and condensing the gas generated in the heating and heat-preserving stage to recover chloride, wherein the condensing temperature can be 400-500 ℃.
According to one or more exemplary embodiments of the present invention, the method may further include the steps of: and collecting and condensing the gas generated in the stage of heating to 800-1000 ℃ and preserving heat for 30-60 min to recover chloride, wherein the condensing temperature can be 400-500 ℃.
According to one or more exemplary embodiments of the present invention, the step of heating the green body to 800 to 1000 ℃ may include: heating the blank to 800-1000 ℃ at a heating rate of 5-15 ℃/min; the heating to 1100-1200 ℃ may include: heating to 1100-1200 ℃ at a heating rate of 3-5 ℃/min.
According to one or more exemplary embodiments of the invention, the mass fraction of the element Cl in the chlorine-containing titanium-extracting slag may be 2-5%, and the mass fraction of the element Cl in the chlorine-containing titanium-extracting slag may be TiO2The mass fraction of (A) may be 2-10%.
According to one or more exemplary embodiments of the present invention, the drying temperature may be 80 to 120 ℃ and the drying time may be 7 to 13 hours.
Compared with the prior art, the invention has the beneficial effects that: the process for preparing the microcrystalline glass is simplified, complex processes such as high-temperature melting, water quenching and the like are avoided, a crystal nucleating agent is not required to be added in the preparation process, and a granulating agent and a binder are not required to be added for direct dry pressing and forming; the chlorine-containing titanium extraction slag can be well utilized, and the utilization rate of the chlorine-containing titanium extraction slag is 85-100%; no harmful gas is discharged in the heat treatment process, the waste materials can be reused, no three wastes are discharged in the production process, and the technical requirements of green manufacturing processes are met.
Drawings
The above and other objects and features of the present invention will become more apparent from the following description taken in conjunction with the accompanying drawings, in which:
FIG. 1 is a schematic flow chart of a method for preparing glass ceramics by using chlorine-containing titanium slag according to an exemplary embodiment of the invention;
FIG. 2 is a schematic flow chart of a method for preparing glass ceramics by using chlorine-containing titanium slag according to another exemplary embodiment of the invention;
FIG. 3 is an X-ray diffraction pattern of a sample of microcrystalline glass prepared from the Chloritium-containing slag of example 1;
FIG. 4 is an X-ray diffraction pattern of a sample of microcrystalline glass prepared from the titanium chloride-containing slag of example 2;
FIG. 5 is a scanning electron microscope image of a microcrystalline glass sample prepared from the chlorine titanium-containing slag of example 2;
FIG. 6 is an X-ray diffraction pattern of a sample of a glass-ceramic prepared by exemplifying 5 titanium chloride-containing slag.
Detailed Description
Hereinafter, the method for producing a glass-ceramic using a titanium slag containing chlorine hydride according to the present invention will be described in detail with reference to the accompanying drawings and exemplary embodiments.
The chlorine-containing titanium extraction slag is chlorine-containing low-titanium type industrial hazardous slag obtained by treating titanium-containing blast furnace slag through a high-temperature carbonization-low-temperature chlorination titanium extraction process. The inventor finds that: the chlorine-containing titanium-extracting slag mainly comprises CaO and SiO2、Al2O3Etc. according to the main components for preparing the microcrystalline glass, and simultaneously contains TiO which can be directly used as a nucleating agent component of the microcrystalline glass2、Fe2O3(ii) a Cl in chlorine-containing titanium extraction slag-2-5% of (A), Cl-CaCl is mainly used in the chlorine-containing titanium extraction slag2The chlorine-containing titanium-extracting slag has certain normal-temperature moisture absorption, so that the chlorine-containing titanium-extracting slag can play a role in granulation and bonding in the process of preparing the blank powder.
Therefore, the invention provides a method for preparing microcrystalline glass by using chlorine-containing titanium extraction slag as a raw material. The method only needs one-time high-temperature treatment, and collects the chloride generated in the process of firing the microcrystalline glass, so that no harmful gas is discharged in the process of preparing the microcrystalline glass. The preparation method of the invention is a green manufacturing process which utilizes solid waste, reduces environmental pollution, saves energy and reduces consumption in production and does not discharge three wastes.
The invention provides a method for preparing microcrystalline glass by using chlorine-containing titanium extraction slag. Fig. 1 shows a schematic flow chart of a method for preparing glass ceramics by using chlorine-containing titanium slag according to an exemplary embodiment of the invention.
In an exemplary embodiment of the invention, the method may comprise the steps of:
the method comprises the steps of pretreating chlorine-containing titanium-extracting slag serving as a raw material or the chlorine-containing titanium-extracting slag and auxiliary materials serving as the raw material to obtain blank-making powder with the water content of 3% -6% and the particle size of 40-100 mu m, and performing step S01 in the figure 1. When the raw material only contains chlorine-containing titanium extraction slag, the pretreatment can comprise crushing and drying; when the raw materials comprise raw materials and ingredients, the pretreatment can comprise drying, crushing, mixing and the like. The mass fraction of the chlorine-containing titanium-extracting slag in the blank-making powder (or raw material) is more than 85 percent, which can meet the requirement of high utilization rate of solid wastes. The granularity of the blank-making powder is controlled to be 40-100 mu m, the blank forming is facilitated by controlling the granularity within the range, and the time and energy consumption increased by over-fine grinding can be avoided; furthermore, the granularity of the blank-making powder can be 45-96 mu m. The ingredients can comprise one or more than two of quartz, potash feldspar, nepheline, borax, soda ash and waste glass. The addition of ingredients is a more preferable option, for example, the ingredients not only can play a role of fluxing, but also can provide a liquid phase under a high-temperature condition to promote compact sintering of a green body, and can supplement ingredients. The batch materials may include flux and/or microcrystalline glass component extenders, wherein some of the batch materials may act as flux, some as extenders, and some as both. Borax and soda ash can be used as fluxing agent; the quartz sand can be used as a supplement, and the supplement is used for supplementing components, so that the produced microcrystalline glass is more stable; the potash feldspar, the nepheline and the waste glass are used as a supplement and a fluxing agent, and the potassium feldspar, the nepheline and the waste glass can supplement chemical components required by the sintering of the microcrystalline glass and provide a fluxing effect. The microcrystalline glass component replenisher is a natural material or a chemical reagent which can replenish chemical components with insufficient content when a microcrystalline glass formula or a microcrystalline glass component proportion is designed, so that the microcrystalline glass formula or the microcrystalline glass component proportion is met, and the prepared microcrystalline glass is more stable and has more excellent performance.
And (4) pressing and molding the blank-making powder to obtain a microcrystalline glass blank, as shown in step S02 in figure 1. The step of press forming may comprise: uniformly spreading the blank-making powder in a mould at 250-720 kgf/cm2Maintaining the pressure for 15-30 s, and demoulding to obtain a microcrystalline glass blank, wherein the pressure can be 255-714 kgf/cm2Pressure is maintained under the pressure of (1). The pressure and the dwell time parameters are controlled within the above range to facilitate the forming and demoulding of the blank, for example, the pressure can be controlled at 310 or 680kgf/cm2The time can be controlled at 17 or 28 s. Wherein, the environmental condition of the blank manufacturing can be room temperature, or the temperature slightly higher than the room temperature, such as 30-100 ℃.
And (4) performing heat treatment on the blank to obtain the microcrystalline glass, as shown in step S03 in FIG. 1. Wherein the heat treatment may include: heating the blank to 800-1000 ℃ (low temperature stage), further, 800-950 ℃ (such as 810 ℃, 910 ℃ and the like), then promoting the nucleation and crystallization of the blank, further heating to 1100-1200 ℃ (high temperature stage or sintering stage) for sintering, further, 1130-1185 ℃ (such as 1140 ℃, 1170 ℃ and the like, and cooling after sintering is finished. Wherein the heat preservation time in the low-temperature stage can be 30-60 min, and the heat preservation time in the high-temperature stage can be 30-90 min. The temperature rise speed of the heating to the low temperature stage can be controlled to be 5-15 ℃/min, so that volatile substances (such as CO) in the blank can be rapidly and maximally removed in the low temperature stage2Chloride, etc.) to facilitate the collection of chloride and the sintering of green bodies; further, the temperature rise rate in the low-temperature stage can be 5-10 ℃/min. The heating speed of the heating process in the heating to high temperature stage can be controlled to be 3-5 ℃/min, so that the problems of sintering deformation or uneven sintering of the blank caused by too high heating speed can be prevented in the high temperature stage, namely the sintering quality can be influenced by too high heating speed, and the energy consumption is high and the efficiency is low due to too low heating speed. The temperature and time of the low-temperature stage are controlled to be 800-1000 ℃ and 30-60 min, so that the nucleation and crystallization of the blank are facilitated; the temperature of the high temperature stageThe temperature and the time are controlled at 1100-1200 ℃ for 30-90 min, and the green body can be sintered compactly. The step of cooling may include slow cooling to room (or ambient) temperature, or slow cooling followed by fast cooling. Wherein, the slow cooling first and then the fast cooling specifically can include: after heat preservation at the sintering temperature is finished (namely heat preservation at a high-temperature stage is finished), slow cooling treatment is carried out, the temperature is slowly reduced to 300-500 ℃ from the sintering temperature, the temperature reduction rate can be 1-4 ℃/min, and the temperature reduction rate can reduce the influence of quartz crystal form conversion or sintering instability on the microcrystalline glass; then, the temperature is rapidly reduced from 300-500 ℃ to below 200 ℃, for example, 30-100 ℃, the performance of the microcrystalline glass in the temperature range is not influenced by the temperature, so that rapid cooling can be performed, for example, cold air is directly blown to perform rapid cooling to reduce energy consumption, and the temperature reduction rate at this stage can be 5-10 ℃/min.
The heat treatment process may be carried out in an oxygen-containing gas, such as air or an oxygen-rich gas.
In the embodiment, the chlorine-containing titanium-extracting slag deposited in the slag yard can be directly utilized, and the chlorine-containing titanium-extracting slag comprises the following components in parts by mass: 28-33% CaO, 20-25% SiO2、10～14％Al2O3、 2～7％MgO、2～10％TiO2、2～4％Fe2O3And 2-5% of Cl element. The water content in the chlorine-containing titanium-extracting slag accumulated in the slag yard is greatly influenced by the environmental humidity and seasons, for example, the water content in the chlorine-containing titanium-extracting slag can reach 8-10% in summer with high humidity, and the water content is 6-8% in autumn with low humidity.
Because the chlorine-containing titanium-extracting slag has moisture absorption, water in the chlorine-containing titanium-extracting slag, such as water which is not dried and removed in the chlorine-containing titanium-extracting slag and water which absorbs moisture for the second time in the pretreatment process, can play a role of a binder in the pretreatment process, and meanwhile, due to the binding action generated by the water, small particles are agglomerated, and a granulation effect is also formed, wherein the granulation process is actually to aggregate fine powder particles into large particles through the binding action.
In this embodiment, if the water content in the raw material is high, it is not favorable to smashing (for example, not favorable to ball milling), can influence the powder uniformity, can also exert an influence on the ratio of raw material, moreover, if the water content in the raw material is high, in the follow-up compression molding, water can receive the pressure outflow in the raw material, will increase the corruption of mould like this. Therefore, it is necessary to dry the raw material so that the water content in the raw material is reduced to 6% or less, and further, to 5% or less; that is, the water content in the green body powder should be 6% or less, and further, reduced to 5% or less. Therefore, it is necessary to dry the raw material, particularly the chlorine-containing titanium extraction slag.
In this embodiment, the water content in the green body powder should be controlled to be 3% to 6%, further, 4% to 6%, and further, 4% to 5%. When the moisture content of the green body-forming powder is less than 3%, the green body-forming powder is subjected to a pressure (e.g., 250 to 720 kgf/cm) in the green body-forming step (i.e., S02 step)2) When a green body is pressed, the green body cannot be compacted easily, defects appear at corners, and if the pressure is increased, expansion of residual air is easily caused to crack the green body.
In this embodiment, when the raw material is only chlorine-containing titanium-extracting slag, the pretreatment step may include: drying and crushing the chlorine-containing titanium extraction slag.
When the raw material comprises chlorine titanium-containing slag and ingredients, the step of pretreating can comprise: mixing the chlorine-containing titanium extraction slag and the ingredients, drying and crushing; or when the water content in the ingredients is less and the ingredients do not need to be dried, only the chlorine-containing titanium-extracting slag is dried, and then the dried chlorine-containing titanium-extracting slag and the ingredients are crushed and mixed, wherein the crushing and the mixing can be carried out in no sequence; or when the water content in the ingredients is higher, drying the chlorine-containing titanium-extracting slag and the ingredients, and then crushing and mixing, wherein the crushing and the mixing can be carried out in no sequence.
Preferably, in consideration of the high water content in the titanium slag, the drying can be carried out before crushing and mixing, so that deviation of the final matching result of each substance from the planned proportion can be reduced or avoided.
In this embodiment, if the raw materials contain ingredients, in addition to the chlorine-containing titanium-extracting slag, the raw materials or the green compact powder may further include, by mass: 0-10% of quartz, 0-7% of potassium feldspar, 0-5% of nepheline, 0-3% of borax, 0-5% of soda ash and 0-15% of waste glass. If the raw material also contains waste materials generated by edge cutting and/or polishing, the mass fraction of the waste materials in the raw material or the powder is 0-2%.
In this embodiment, the method may further include the steps of: the obtained microcrystalline glass is subjected to edge cutting and/or polishing, and the waste obtained in the step is returned as one of the raw materials. The cooling water generated by polishing and trimming can be recycled after precipitation.
In this embodiment, the method may further include the steps of: the gas produced during the heat treatment stage is collected and condensed to recover chlorides, which may include chloride gases including potassium, sodium chloride salts such as sodium chloride, potassium chloride, and the like. Wherein, the gas generated in the first heating stage (stage of heating from room temperature to 800-1000 ℃) and the first heat preservation stage (heat preservation stage of 800-1000 ℃) can be collected and condensed repeatedly, because the content of chlorine recovered by cooling is very small when the temperature exceeds 1000 ℃, and only accounts for 1-5% of the total chlorine.
Wherein the condensation temperature is 400-500 ℃, and the condensation temperature is controlled in the range, so that chloride gas can be fully condensed and precipitated, and aggregated powder can be obtained to the maximum extent. For example, when the heat treatment process is performed in a tunnel kiln, a gas collecting and condensing device is additionally arranged on an exhaust pipeline of a low-temperature heating section (heated to 800-1000 ℃) of the tunnel kiln, and the condensing temperature is set to be 400-500 ℃ for recovering chloride. In the heating process, chloride volatilizes from the body, chloride gas is rapidly pumped into an exhaust pipeline by an air inducing mechanism, the exhaust pipeline can be a pipeline which is corroded by acid and alkali-resistant gas, when the gas flows to the position near the pipeline with a condensing device, the chloride in the gas is condensed to form an aggregate which is attached to a pipe wall, meanwhile, a reciprocating scraper machine can be arranged on the pipe wall for circulating operation, the aggregate is cleaned to a collecting bag below the pipeline, chloride powder products such as potassium, sodium and the like can be obtained, and the condensed harmless gas is introduced into a kiln by the air inducing machine, so that on one hand, the waste heat of the gas can be utilized, on the other hand, the residual chloride gas can be adsorbed on the body to be heated, and then enters the exhaust pipeline again in the heating process, and further purification is obtained. For example, the outlet end of the exhaust duct may be arranged at the inlet of the low temperature heating zone to preheat the green body that is about to enter the low temperature heating zone.
In another exemplary embodiment of the invention, as shown in fig. 2, the method for preparing microcrystalline glass by using chlorine-containing titanium-extracting slag can use chlorine-containing titanium-extracting slag or chlorine-containing titanium-extracting slag and ingredients as raw materials, obtain powder for blank preparation by pretreatment, perform dry pressing on the powder to prepare a microcrystalline glass blank, perform low-temperature heating, high-temperature heating and cooling on the blank in a tunnel kiln, and finally prepare a microcrystalline glass product by steps of trimming, polishing and the like.
Specifically, the method for preparing the glass ceramics can comprise the following steps: 1) pretreating chlorine-containing titanium extraction slag and ingredients to obtain powder for blank making. The ingredients can be one or a mixture of two or more of quartz, potash feldspar, nepheline, borax, soda ash, waste glass and polishing and trimming waste; the pretreatment process comprises drying, crushing, grinding, grading and the like. The chlorine-containing titanium-extracting slag and the ingredients can be respectively dried, crushed, ground and graded and then are matched, or can be matched firstly, then dried and crushed. The mixed batch consisting of the chlorine-containing titanium-extracting slag and the ingredients comprises the following components in percentage by mass: 85-100% of chlorine-containing titanium extraction slag, 0-10% of quartz, 0-7% of potassium feldspar, 0-5% of nepheline, 0-3% of borax, 0-5% of soda ash, 0-15% of waste glass and 0-2% of polishing and trimming waste. The ingredients can play a role in fluxing, provide a liquid phase under a high-temperature condition and promote compact sintering of a green body. The particle size of the obtained blank-making powder is 45-96 mu m.
2) Uniformly spreading the powder for making the blank in a mould, carrying out dry pressing forming by adopting a press machine through controlling pressure and pressure maintaining time, and demoulding to obtain the microcrystalline glass blank. For example, the powder for forming a green body can be spread flat in a mold and pressed with a press at 255 to 714kgf/cm2Keeping the pressure for 15-30 s, performing dry pressing and forming, and demolding to obtain the microcrystalline glass blank.
3) Putting the microcrystalline glass blank into a tunnel kiln, and setting a heat treatment program and parameters, wherein the heat treatment program comprises the following specific steps: raising the temperature from room temperature to 800-950 ℃ at a temperature raising rate of 5-10 ℃/min, and keeping the temperature for 30-60 min; then heating from 800-950 ℃ to 1130-1185 ℃ at a heating rate of 3-5 ℃/min, and preserving heat for 30-90 min; then slowly cooling to 300-500 ℃, and then blowing air from 300-500 ℃ to quickly cool to 30-100 ℃; taking out, polishing and trimming to obtain the microcrystalline glass product. And recycling waste materials obtained by polishing and trimming as ingredients for reutilization, and precipitating and recycling cooling water generated by polishing and trimming.
As shown in figure 2, an exhaust pipeline can be arranged at the outlet of the low-temperature heating section (800-950 ℃) of the tunnel kiln, and a condensing device and a reciprocating scraper conveyor can be arranged on the exhaust pipeline. The directions of air flows of a high-temperature heating section (1130-1185 ℃) and a low-temperature heating section of the tunnel kiln are opposite, chloride gas generated by the high-temperature heating section and gas generated by low-temperature presintering (namely low-temperature heating) enter an exhaust pipeline together, chloride powder such as potassium, sodium and the like is formed after condensation under the action of a condensing device, and the chloride can be recovered by the reciprocating scraper conveyor.
The preparation of the phase of the glass-ceramic according to the methods of the above two exemplary embodiments may include: a glassy phase and a microcrystalline phase. The prepared microcrystalline glass comprises three types.
The first method comprises the following steps: the mass fraction of the glass phase is 5-15%, the mass fraction of the microcrystalline phase is 85-95%, and the microcrystalline phase can comprise the following components in mass ratio (42-48): (35-45): (12-16) an akermanite phase, a diopside phase and a perovskite phase. Wherein the akermanite phase is a main crystal phase, and the diopside phase and the perovskite phase are auxiliary crystal phases.
In the microcrystalline phase, the akermanite phase can account for 42-48% by mass, the diopside phase can account for 35-45% by mass, and the balance can be a perovskite phase. Wherein, the content of the akermanite phase and the diopside phase is high, which is beneficial to improving the mechanical property of the glass ceramics. For example, the akermanite phase may be 46 ± 1% by mass, the diopside phase may be 39 ± 0.5% by mass, and the balance may be a perovskite phase. Wherein, the akermanite phase and diopside phase play a leading role in the performance of the glass ceramics, the content of the diopside phase is within the range of 38-41%, such as 39%, and the content of the akermanite phase is within the range of 43-45%, such as 44%, and the performance of the glass ceramics is optimal. Because the content of calcium, magnesium, aluminum and silicon in the titanium extraction slag is higher, the formation of an akermanite phase and a diopside phase is facilitated; the iron in the titanium slag can promote the crystallization of microcrystalline glass, is beneficial to the growth of akermanite and diopside crystal grains, and improves the content of akermanite and diopside; the titanium in the titanium slag is extracted, so that the crystallization of the microcrystalline glass can be promoted, and the formation of a perovskite phase is promoted.
The microcrystalline phase in the microcrystalline glass is mainly plate-shaped, short columnar and granular; wherein the akermanite phase is platy, the diopside is short columnar, and the perovskite phase is granular. The length of the plate-shaped microcrystalline phase can be 1.5-3.4 μm, and the width can be 1-1.7 μm, such as 1.8 μm in length and 1.2 μm in width, and as another example, 3.2 μm in length and 1.6 μm in width; the short columnar microcrystalline phase may have a length of 1.4-2.5 μm and a width of 1.2-1.7 μm, for example, a length of 2.0 + -0.4 μm and a width of 1.5 + -0.1 μm; the particulate microcrystalline phase may have a particle size of 0.5 to 1.2 μm, for example, 0.8. + -. 0.2. mu.m. The microcrystalline phase forms, namely the microcrystalline phases with small sizes are smaller than 5 mu m, the microcrystals with small sizes are mutually connected, the generated gaps are small, the uniform filling of a liquid phase is facilitated, the number of the gaps is reduced, and the performance of the microcrystalline glass is improved.
The microcrystalline glass can also comprise air holes, wherein the volume percentage of the air holes is less than 5%, for example 1-5%. The pores may comprise voids in the microcrystalline glass where the glass phase does not completely fill the spaces between the microcrystalline phases, i.e. the pores comprise voids between the glass phase and the microcrystalline phase, and voids between the microcrystalline phases. The pore diameter of the pores can be 1-3 μm, such as 2 + -0.4 μm. In the production process of the microcrystalline glass or ceramic, pores cannot be completely eliminated, and the microcrystalline glass provided by the invention has the advantages of low pore occupation ratio and small pore diameter, so that the high performance of the microcrystalline glass can be ensured.
Second, the microcrystalline phase of the microcrystalline glass may include the main crystalline phases: diopside phase, secondary crystal phase: an akermanite phase, a perovskite phase and a quartz phase; wherein the diopside phase accounts for 62-67% by mass, the akermanite phase accounts for 14-20% by mass, the perovskite phase accounts for 3-5% by mass, and the balance can be a quartz phase; for example, the diopside phase may be present at 64. + -. 1% by mass, the akermanite phase may be present at 17. + -. 1% by mass, the perovskite phase may be present at 4. + -. 0.5% by mass, and the balance is the quartz phase.
Third, the microcrystalline phase of the crystallized glass may include a main crystalline phase: diopside phase, secondary crystal phase: titanite phase. Wherein the mass fraction of the diopside phase can be 95-97%, and the balance is the sphene phase; for example, the mass fraction of the diopside phase may be 96. + -. 0.5%, and the mass fraction of the sphene phase may be 3.5. + -. 0.1%.
The properties of the prepared microcrystalline glass are as follows: the bulk density is 2.60-2.8 g/cm2The water absorption rate is 0.05-0.3%, the compressive strength is 102-140 MPa, the acid resistance is more than 96%, and the alkali resistance is more than 97%.
In order that the above-described exemplary embodiments of the invention may be better understood, further description thereof with reference to specific examples is provided below.
Example 1
The preparation method comprises the following steps:
1) taking chlorine-containing titanium extraction slag which is subjected to certain high-temperature carbonization-low-temperature chlorination titanium extraction process in Sichuan as a main raw material, selecting quartz, potassium feldspar and borax as ingredients, drying the chlorine-containing titanium extraction slag and the ingredients in a drying chamber at 105 ℃ for 8 hours, then crushing, grinding and grading, weighing and matching the components according to the mass percentage of 85% of chlorine-containing blast furnace slag (namely chlorine-containing titanium extraction slag), 5% of quartz, 7% of potassium feldspar and 3% of borax, and taking powder with the particle size of 96 mu m as powder for blank making.
2) Uniformly spreading the powder for blank making in a mold without adding granulating agent and binder, and pressing under 714kgf/cm2And carrying out dry pressing molding under the pressing condition of the pressure maintaining time of 20s, and then demolding to obtain the microcrystalline glass blank.
3) Putting the microcrystalline glass blank into a tunnel kiln, and setting a heat treatment program and parameters, wherein the heat treatment program comprises the following specific steps: heating from room temperature to 800 ℃ at a heating rate of 7 ℃/min, and keeping the temperature for 60 min; then heating from 800 ℃ to 1130 ℃ at the heating rate of 5 ℃/min, preserving the heat for 60min, then slowly cooling to 400 ℃, and cooling at the cooling rate of 2 ℃/min; then quickly cooling from 400 ℃ to 50 ℃, wherein the cooling rate is 10 ℃/min; and taking out, polishing and trimming to obtain the microcrystalline glass product. Wherein, collect polishing side cut waste material and use as the batching, the cooling water of polishing with the side cut in-process recycles after deposiing. And starting a gas collecting and condensing device of the tunnel kiln in the process of room temperature to 800 ℃, wherein the condensing temperature is set to be 400 ℃. In the temperature rising process, chloride gas generated by the blank is pumped into an exhaust pipeline and is attached to the pipe wall through condensation, and meanwhile, a reciprocating scraper conveyor on the pipe wall is started for circulating cleaning, and the aggregate is collected into a collecting bag below the pipe wall, so that potassium-sodium chloride powder can be obtained.
4) As shown in fig. 3, the microcrystalline glass product has a main crystal phase of diopside phase and secondary crystal phases of anorthite phase, perovskite phase and quartz phase. The performance of the microcrystalline glass product is tested, and the tested bulk density is 2.64g/cm3The water absorption rate is 0.20%, the compressive strength is 108MPa, the acid resistance is 96.7%, and the alkali resistance is 97.2%.
Example 2
The preparation method comprises the following steps:
1) the chlorine-containing titanium-extracting slag in example 1 was used as the entire raw material, and the chlorine-containing titanium-extracting slag was dried in a drying chamber at 110 ℃ for 12 hours, and then crushed, ground and classified, and powder having a particle size of 96 μm was used as the powder for green making.
2) Spreading the powder for making into blank in a mold, and pressing with a press under a pressure of 510kgf/cm2And (3) maintaining the pressure for 20s, performing dry pressing and forming, and then demolding to obtain the microcrystalline glass blank. And no granulating agent or binder is added in the process of forming the microcrystalline glass blank.
3) Putting the microcrystalline glass blank into a tunnel kiln, and setting a heat treatment program and parameters, wherein the heat treatment program comprises the following specific steps: heating from room temperature to 890 ℃ at the heating rate of 5 ℃/min, and keeping the temperature for 30 min; then heating from 890 ℃ to 1185 ℃ at the heating rate of 3 ℃/min, and preserving the heat for 60 min; then slowly cooling to 500 ℃, wherein the cooling rate is 3 ℃/min, then rapidly cooling from 500 ℃ to 30 ℃, and the cooling rate is 5 ℃/min; and taking out after cooling, polishing and trimming to obtain the glass ceramic product. And (3) opening a gas collecting and condensing device of the tunnel kiln in the heating process of room temperature to 850 ℃, setting the condensing temperature at 450 ℃, in the heating process, condensing a small amount of chloride gas generated by the blank body to fall on the pipe wall of the exhaust pipeline, simultaneously opening a reciprocating scraper on the pipe wall for circulating cleaning, and collecting the aggregate into a collecting bag below the pipe wall to obtain chloride powder.
4) The prepared microcrystalline glass product is subjected to X-ray diffraction test and analysis, and as can be seen from fig. 4, the main crystal phase is an akermanite phase, and the auxiliary crystal phase is a diopside and a perovskite phase. The microcrystalline glass product is subjected to Scanning Electron Microscope (SEM) testing and analysis, and the test result is shown in fig. 5, and it can be seen from fig. 5 that the microcrystalline phase in the microcrystalline glass is mainly in the form of plate, short column and particle, the microcrystalline glass is composed of a microcrystalline phase, a glass phase and fine pores, and the glass phase and the microcrystalline phase are engaged with each other, so that the structure is relatively dense. The microcrystalline glass product is subjected to performance test, and the bulk density of the microcrystalline glass product is 2.70g/cm3The water absorption rate is 0.11%, the compressive strength is 120MPa, the acid resistance is 97.8%, and the alkali resistance is 98.5%.
Example 3
The preparation method comprises the following steps:
1) drying the chlorine-containing titanium-extracting slag, quartz and nepheline in a drying chamber at 108 ℃ for 8h, weighing and matching the components according to the mass percentage of 85 percent of chlorine-containing blast furnace slag, 10 percent of quartz and 5 percent of nepheline, crushing, grinding and grading to obtain the blank-making powder with the granularity of 75 mu m.
2) Uniformly spreading the powder for making the blank in a mould by a press at 357kgf/cm2And (3) keeping the pressure for 15s under the pressure, performing dry pressing and forming, and then demolding to obtain the microcrystalline glass blank. And no granulating agent or binder is added in the process of forming the microcrystalline glass blank.
3) Putting the microcrystalline glass blank into a tunnel kiln, and setting a heat treatment program and parameters, wherein the heat treatment program comprises the following specific steps: heating from room temperature to 950 ℃ at a heating rate of 5 ℃/min, and keeping the temperature for 30 min; then heating from 950 ℃ to 1160 ℃ at the heating rate of 3 ℃/min, and preserving the heat for 60 min; then slowly cooling to 300 ℃, wherein the cooling rate is 4 ℃/min; then rapidly cooling from 300 ℃ to 100 ℃, wherein the cooling rate is 6 ℃/min; and taking out after cooling, polishing and trimming to obtain the glass ceramic product. And (3) starting a gas collecting and condensing device of the tunnel kiln in the process of raising the room temperature to 950 ℃, setting the condensing temperature to be 500 ℃, condensing the chloride gas generated by the blank to form aggregates on the pipe wall of the exhaust pipeline, starting a reciprocating scraper on the pipe wall to circularly clean, collecting the aggregates into a collecting bag below the pipe wall, and obtaining the potassium-sodium chloride powder.
4) The performance of the prepared microcrystalline glass product is tested, and the volume density of the microcrystalline glass product is 2.68g/cm3The water absorption rate is 0.15%, the compressive strength is 114MPa, the acid resistance is 98%, and the alkali resistance is 97.5%.
Example 4
The preparation method comprises the following steps:
1) the chlorine-containing titanium slag, quartz, soda ash and polishing and trimming waste are placed into a drying chamber at 110 ℃ for drying for 10 hours, then crushed, ground and classified, then the chlorine-containing titanium slag, the quartz, the soda ash and the polishing and trimming waste are weighed and matched according to the mass percentage of 90 percent, 3 percent and 2 percent of the components, and the powder with the granularity of 75 mu m is taken as the powder for blank making.
2) Spreading the powder in a mold, and pressing with a press under a pressure of 357kgf/cm2And (3) carrying out dry pressing forming under the condition of maintaining the pressure for 30s, and then demoulding to obtain the microcrystalline glass blank. And no granulating agent or binder is added in the process of forming the microcrystalline glass blank.
3) Putting the microcrystalline glass blank into a tunnel kiln, and setting a heat treatment program and parameters, wherein the heat treatment program comprises the following specific steps: heating from room temperature to 850 ℃ at the heating rate of 5 ℃/min, and keeping the temperature for 60 min; then heating from 850 ℃ to 1180 ℃ at a heating rate of 3 ℃/min, and keeping the temperature for 90 min; then heating from 850 ℃ to 1180 ℃ at a heating rate of 3 ℃/min, preserving the heat for 90min, then slowly cooling to 450 ℃, wherein the cooling rate is 1 ℃/min; then rapidly cooling from 450 ℃ to 40 ℃, wherein the cooling rate is 8 ℃/min; and taking out after cooling, polishing and trimming to obtain the glass ceramic product. And opening a gas collecting and condensing device of the tunnel kiln in the process of the room temperature to 850 ℃, wherein the condensing temperature is set to be 450 ℃. And (3) condensing chloride gas generated by the blank body to fall on the pipe wall of the exhaust pipeline, starting a reciprocating scraper conveyor on the pipe wall to circularly clean, and collecting aggregates into a collecting bag below the pipe wall to obtain potassium-sodium chloride powder.
4) The obtained microcrystalline glass product is subjected to performance test, and the bulk density of the microcrystalline glass product is 2.62g/cm3The water absorption rate is 0.28%, the compressive strength is 105MPa, the acid resistance is 96%, and the alkali resistance is 99.2%.
Example 5
The preparation method comprises the following steps:
1) drying the chlorine-containing titanium-extracting slag and the waste glass in a drying chamber at 105 ℃ for 8h, crushing, grinding and grading, weighing and matching 85% of the chlorine-containing titanium-extracting slag and 15% of the waste glass according to the mass percentage, and taking powder with the particle size of 45 mu m as powder for blank making.
2) Spreading 45 μm powder for blank making in a mold, and pressing with a press at 255kgf/cm2Keeping the pressure for 30s for dry pressing and molding, and then demoulding to obtain the microcrystalline glass blank. And no granulating agent or binder is added in the process of forming the microcrystalline glass blank.
3) Putting the microcrystalline glass blank into a tunnel kiln, and setting a heat treatment program and parameters, wherein the heat treatment program comprises the following specific steps: heating from room temperature to 850 ℃ at a heating rate of 10 ℃/min, and keeping the temperature for 60 min; then heating from 850 ℃ to 1130 ℃ at the heating rate of 3 ℃/min, and preserving the heat for 90 min; then slowly cooling to 350 ℃, wherein the cooling rate is 4 ℃/min; then rapidly cooling from 350 ℃ to 80 ℃, wherein the cooling rate is 10 ℃/min; and taking out after cooling, polishing and trimming to obtain the glass ceramic product. And starting a gas collecting and condensing device of the tunnel kiln when the temperature is between room temperature and 850 ℃, and setting the condensing temperature to be 450 ℃. And collecting the chloride generated by the blank in the temperature rising process, wherein the collecting process is the same as the above, and then obtaining potassium-sodium chloride powder.
4) The obtained microcrystalline glass product has a main crystal phase of diopside phase and a secondary crystal phase of sphene phase (see figure 6). The microcrystalline glass is subjected to performance test, and the bulk density of the microcrystalline glass product is 2.74g/cm3Is suckedThe water content is 0.09%, the compressive strength is 131MPa, the acid resistance is 98.5%, and the alkali resistance is 97%.
In conclusion, compared with the prior art, the method for preparing the microcrystalline glass by using the chlorine-containing titanium extraction slag has remarkable progress, and has the following beneficial effects:
1) the technological process adopted by the invention comprises the steps of material preparation → blank making → low-temperature dechlorination → high-temperature sintering → polishing and trimming → products, the technological process only has one-time high-temperature heat treatment process, the flow is more simplified, and the complex processes of high-temperature melting, water quenching and the like in the sintering processes of a melting sintering method and an integral crystallization method are avoided.
2) Compared with the melting sintering method and the integral crystallization method, the method uses TiO in the chlorine-containing titanium extraction slag raw material2With Fe2O3Can act as a complex phase crystal nucleus agent, and does not need to add the crystal nucleus agent in the preparation process; the utilization rate of the chlorine-containing titanium extraction slag is 85-100%.
3) The invention utilizes the characteristic of normal temperature moisture absorption of the chlorine-containing titanium slag, can directly carry out dry pressing molding without adding a granulating agent and a binder, and omits the steps of binding, granulating and the like.
4) In the process of preparing the microcrystalline glass, the chlorine-containing titanium extraction slag can be subjected to dechlorination, no harmful gas is discharged, meanwhile, polishing and trimming waste materials are reused as ingredients, cooling water and the like are precipitated and recycled, no three wastes are discharged in the production process, the environment is protected, and the requirements of green manufacturing technology are met.
5) The performance of the microcrystal glass body prepared by the method is higher than that of natural stone, and the microcrystal glass body can be used as high-grade building decorative materials, process sculptures, functional ceramic materials and the like.
6) The method has the advantages of simple process flow, low energy consumption, environmental protection, and contribution to industrial popularization, and is particularly suitable for being applied to the areas in the middle and western regions with sufficient electric power and fragile ecological environment.
Although the present invention has been described above in connection with exemplary embodiments, it will be apparent to those skilled in the art that various modifications and changes may be made to the exemplary embodiments of the present invention without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. The method for preparing the glass ceramics by using the chlorine-containing titanium extraction slag is characterized by comprising the following steps:
drying and crushing the chlorine-containing titanium extraction slag to obtain blank-making powder;
pressing and molding the blank-making powder to obtain a blank body;
heating the blank to 800-1000 ℃, preserving heat to promote nucleation and crystallization of the blank, heating to 1100-1200 ℃ for sintering, and cooling after sintering to obtain microcrystalline glass;
the chlorine-containing titanium extraction slag is obtained by treating titanium-containing blast furnace slag through high-temperature carbonization and low-temperature chlorination titanium extraction processes;
the step of heating the blank to 800-1000 ℃ comprises the following steps: and heating the blank to 800-1000 ℃ at a heating rate of 5-15 ℃/min.
2. The method for preparing the glass ceramics by using the chlorine-containing titanium extraction slag is characterized by comprising the following steps:
pretreating chlorine-containing titanium-extracting slag and ingredients to obtain blank-making powder, wherein the mass fraction of the chlorine-containing titanium-extracting slag in the blank-making powder is more than 85%, and the ingredients comprise a fluxing agent and/or a microcrystalline glass component replenisher;
pressing and molding the blank-making powder to obtain a blank body;
heating the blank to 800-1000 ℃, preserving heat to promote nucleation and crystallization of the blank, heating to 1100-1200 ℃ for sintering, and cooling after sintering to obtain microcrystalline glass;
the chlorine-containing titanium extraction slag is obtained by treating titanium-containing blast furnace slag through high-temperature carbonization and low-temperature chlorination titanium extraction processes;
the step of heating the blank to 800-1000 ℃ comprises the following steps: and heating the blank to 800-1000 ℃ at a heating rate of 5-15 ℃/min.
3. The method for preparing the glass-ceramic by using the chlorine-containing titanium-extracting slag as claimed in claim 2, wherein the batching comprises: at least one of quartz, potash feldspar, nepheline, borax, soda ash and waste glass.
4. The method for preparing microcrystalline glass by using chlorine-containing titanium extraction slag according to claim 1 or 2, wherein the green body powder has a water content of 3-6% and a particle size of 40-100 μm.
5. The method for preparing glass-ceramic by using chlorine-containing titanium-extracting slag according to claim 1 or 2, wherein the step of press forming comprises:
uniformly spreading the blank-making powder in a mold at 250-720 kgf/cm2Keeping the pressure for 15-30 s, and then demoulding to obtain a blank.
6. The method for preparing the glass-ceramic by using the chlorine titanium-containing slag according to claim 1 or 2, wherein the method further comprises the steps of: and collecting and condensing the gas generated in the heat treatment stage to recover chloride, wherein the condensing temperature is 400-500 ℃.
7. The method for preparing the microcrystalline glass by using the chlorine-containing titanium extraction slag as claimed in claim 1 or 2, wherein the step of heating to 1100-1200 ℃ comprises: heating to 1100-1200 ℃ at a heating rate of 3-5 ℃/min.
8. The method for preparing glass ceramics by using chlorine-containing titanium-extracting slag according to claim 1 or 2, wherein the mass fraction of Cl element in the chlorine-containing titanium-extracting slag is 2-5%, and TiO element in the chlorine-containing titanium-extracting slag is TiO2The mass fraction of (A) is 2-10%.
9. The method for preparing the glass-ceramic by using the chlorine titanium-containing slag according to claim 1 or 2, wherein the method further comprises the steps of:
and (3) trimming and/or polishing the obtained microcrystalline glass.
10. The method for preparing the glass-ceramic by using the chlorine-containing titanium-extracting slag according to claim 9, characterized by further comprising the steps of: and returning waste materials generated by the trimming and/or polishing to be used for manufacturing the blank-making powder.
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