CN109133649B

CN109133649B - System for preparing microcrystalline glass by using chlorine-containing titanium extraction slag

Info

Publication number: CN109133649B
Application number: CN201811088007.8A
Authority: CN
Inventors: 孙红娟; 尤皓; 彭同江; 丁文金; 曾丽
Original assignee: Southwest University of Science and Technology
Current assignee: Southwest University of Science and Technology
Priority date: 2018-09-18
Filing date: 2018-09-18
Publication date: 2022-03-01
Anticipated expiration: 2038-09-18
Also published as: CN109133649A

Abstract

The invention provides a system for preparing microcrystalline glass by using chlorine-containing titanium extraction slag. The system comprises a pretreatment unit, a blank making unit and a heat treatment unit, wherein the pretreatment unit dries, crushes and matches raw materials containing chlorine-titanium-containing slag to obtain blank making powder; the blank making unit can press and form the powder to obtain a blank body; the heat treatment unit comprises a low-temperature heating area, a high-temperature heating area and a cooling area, the low-temperature heating area can heat the blank to 800-1000 ℃ and keep the temperature to obtain a first intermediate product, the high-temperature heating area can heat the first intermediate product to 1100-1200 ℃ and keep the temperature to obtain a second intermediate product, and the cooling area can cool the second intermediate product to obtain the microcrystalline glass. The beneficial effects of the invention include: the structure is simple and convenient, the utilization rate of waste residues is high, the generated waste materials can be reused, no harmful gas is discharged in the heat treatment process, no three wastes are discharged in the production process, and the technical requirement of green production can be met.

Description

System for preparing microcrystalline glass by using chlorine-containing titanium extraction slag

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 system for preparing microcrystalline glass by using chlorine-containing titanium extraction slag.

Background

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, and the equipment of the two processes needs to be provided with two stages of high-temperature treatment, so that the problems of high energy consumption, complicated equipment and the like exist, and the defects of low utilization rate of industrial waste residue and the like exist.

The chlorine-containing titanium-extracting slag has high chlorine content, is difficult to be directly used for building material products, can be used after being roasted and dechlorinated by water washing or being roasted and dechlorinated by adding a dechlorinating agent, and has lower added value of products after dechlorination.

At present, no device capable of preparing the glass ceramics only through one-time high-temperature treatment process exists, and chlorine can be removed from 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 objects of the present invention is to provide a system for preparing glass ceramics by using chlorine-containing titanium extraction slag, which can simultaneously recover chloride.

In order to achieve the above object, an aspect of the present invention provides a system for preparing glass ceramics from chlorine-containing titanium extraction slag, which may include: the device comprises a pretreatment unit, a blank making unit and a heat treatment unit, wherein the pretreatment unit can dry and crush chlorine-containing titanium extraction slag to obtain powder for making a blank, and the drying can be performed before the crushing; the heat treatment unit comprises a low-temperature heating area, a high-temperature heating area and a cooling area, the low-temperature heating area can heat the blank to 800-1000 ℃ and keep the temperature to obtain a first intermediate product, the high-temperature heating area can heat the first intermediate product to 1100-1200 ℃ and keep the temperature to obtain a second intermediate product, and the cooling area can cool the second intermediate product to obtain the microcrystalline glass.

In another aspect, the present invention provides a system for preparing glass ceramics by using chlorine-containing titanium extraction slag, and the system may include: the device comprises a pretreatment unit, a blank making unit and a heat treatment unit, wherein the pretreatment unit can dry, crush and mix raw materials to obtain powder for making blanks; wherein, the raw materials comprise chlorine-containing titanium-extracting slag and ingredients, and the drying can be carried out before the crushing; the blank making unit can press and form the powder to obtain a microcrystalline glass blank; the heat treatment unit comprises a low-temperature heating area, a high-temperature heating area and a cooling area, the low-temperature heating area can heat the blank to 800-1000 ℃ and keep the temperature to obtain a first intermediate product, the high-temperature heating area can heat the first intermediate product to 1100-1200 ℃ and keep the temperature to obtain a second intermediate product, and the cooling area can cool the second intermediate product 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.

According to one or more exemplary embodiments of the present invention, the heat treatment unit may include a tunnel kiln.

According to one or more exemplary embodiments of the present invention, the pulverization includes crushing, pulverizing and classifying.

According to one or more exemplary embodiments of the present invention, when the object processed by the pretreatment unit is chlorine-containing titanium slag, the pretreatment unit may include a dryer or a drying chamber, and a crusher; when the objects processed by the pretreatment unit are chlorine-containing titanium slag and ingredients, the pretreatment unit may include a dryer or a drying chamber, and a crusher and a blender.

According to one or more exemplary embodiments of the present invention, the pulverizer may include a crushing mechanism, a pulverizing mechanism; the pulverizer may further include a size grading mechanism.

According to one or more exemplary embodiments of the present invention, the heat treatment unit may further include a transfer mechanism capable of transferring the green body into the low-temperature heating zone, the high-temperature heating zone, and the cooling zone of the heat treatment unit in this order.

According to one or more exemplary embodiments of the present invention, the system may further include an exhaust unit and a condensing unit, wherein the exhaust unit includes an induced draft fan and an exhaust duct, an air inlet end of the exhaust duct is disposed at an outlet of the low-temperature heating zone or an inlet of the high-temperature heating zone, and the induced draft fan is capable of introducing gas in the low-temperature heating zone and/or gas in the high-temperature heating zone into the exhaust duct; the gas in the high-temperature heating zone comprises gas which is introduced from the outside, flows through the cooling zone and then enters the high-temperature heating zone; the condensation unit is arranged on the exhaust pipeline and can cool the gas in the exhaust pipeline, so that the chloride in the gas is condensed and then attached to the inner wall of the exhaust pipeline.

According to one or more exemplary embodiments of the present invention, the system may further include a chloride collecting unit, and the chloride collecting unit may further include a scraper which is disposed on an inner wall of the exhaust duct and is capable of scraping chloride on the inner wall of the exhaust duct, and a collecting container which is capable of collecting chloride scraped by the scraper.

According to one or more exemplary embodiments of the present invention, the heat treatment unit may further include a green body preheating zone disposed before the low-temperature heating zone, the outlet of the exhaust duct is connected to the green body preheating zone, the exhaust duct exhausts gas in the green body preheating zone in a direction opposite to the entering direction of the green body, the exhaust duct exhausts gas capable of heating the green body entering the green body preheating zone, and residual chloride in the exhaust gas capable of being adsorbed on the green body.

According to one or more exemplary embodiments of the present invention, a wind shield may be further provided at an inlet of the low temperature heating zone or an outlet of the green body preheating zone to prevent or reduce the gas discharged from the exhaust duct from entering the low temperature heating zone.

According to one or more exemplary embodiments of the present invention, the system may further include a waste heat utilization line: the waste heat utilization line is capable of providing gas exhausted from the green body preheating zone to a pre-treatment unit for drying.

According to one or more exemplary embodiments of the present invention, the system may further include a blowing unit disposed at an outlet of the cooling zone, the blowing unit being capable of blowing the oxygen-containing gas into the cooling zone and the high-temperature heating zone in sequence.

According to one or more exemplary embodiments of the present invention, the system may further include a post-treatment unit disposed after the heat treatment unit, the post-treatment unit being capable of trimming and/or polishing the glass ceramics.

According to one or more exemplary embodiments of the present invention, the system may further include a material returning mechanism capable of transferring the waste material generated from the trimming and/or polishing of the post-treatment unit to the pre-treatment unit, using the waste material as one of the raw materials.

Compared with the prior art, the invention has the beneficial effects that: the utilization rate of the chlorine-containing titanium extraction slag is 85-100%, the device is simple and convenient, the waste can be reused, no harmful gas is discharged in the heat treatment process, no three wastes are discharged in the production process, and the technical requirement of green production is 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 shows a schematic view of a system for producing glass-ceramic using a chloride-containing titanium slag according to an exemplary embodiment of the present invention;

FIG. 2 shows a schematic view of a thermal processing unit of an exemplary embodiment of the present invention;

FIG. 3 shows another schematic view of a thermal processing unit according to an exemplary embodiment of the present invention;

FIG. 4 shows a schematic diagram of a system for preparing glass ceramics by using chlorine-containing titanium slag according to another exemplary embodiment of the invention.

FIG. 5 is an X-ray diffraction pattern of a sample of microcrystalline glass prepared from the Chloritium-containing slag of example 1;

FIG. 6 is an X-ray diffraction pattern of a sample of microcrystalline glass prepared from the titanium chloride-containing slag of example 2;

FIG. 7 is a scanning electron micrograph of a microcrystalline glass sample prepared from the titanium slag containing chlorine extraction in example 2;

FIG. 8 is an X-ray diffraction pattern of a sample of a glass-ceramic prepared according to example 5 from titanium slag containing chlorhydrate.

Detailed Description

Hereinafter, a system for producing glass ceramics 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 low-titanium type industrial waste slag containing chlorine, which is 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、Al₂O₃And the like, which is consistent with the main component 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 slag has certain normal-temperature moisture absorption, and can play a role in granulation and bonding.

Therefore, the invention provides a system for preparing microcrystalline glass by using chlorine-containing titanium extraction slag. The system only needs one-time high-temperature treatment, and can collect chloride generated in the process of firing the microcrystalline glass, so that no harmful gas is discharged in the preparation process of the microcrystalline glass containing the chlorine titanium extraction slag. The preparation system can realize solid waste utilization, reduce environmental pollution, save energy, reduce consumption and avoid three wastes emission in production.

FIG. 1 shows a schematic diagram of a system for preparing glass-ceramic by using chlorine-containing titanium slag according to an exemplary embodiment of the invention.

In an exemplary embodiment of the present invention, as shown in fig. 1, the system may include a pre-treatment unit, a blank-making unit, and a heat-treatment unit, which are connected in sequence, wherein,

the pretreatment unit can be used for pretreating chlorine-containing titanium-extracting slag serving as a raw material or the chlorine-containing titanium-extracting slag and ingredients serving as raw materials to obtain blank-making powder with the water content of 3% -6% and the particle size of 40-100 microns. When the raw material is only chlorine-containing titanium-extracting slag, the pretreatment unit may include a drying mechanism, such as a dryer or a drying chamber; when the raw materials comprise raw materials and ingredients, the pretreatment unit can comprise a drying mechanism, a crushing mechanism and a mixing mechanism. The mass fraction of the chlorine-containing titanium-extracting slag in the blank-making powder (or raw material) can be more than 85 percent, so that the requirement of high utilization rate of solid waste can be met. The pretreatment unit can crush the granularity of the raw materials to 40-100 mu m, further 45-96 mu m, the granularity is controlled in the range, the subsequent blank forming is facilitated, and the time and energy consumption caused by over-fine grinding can be avoided. The ingredients can comprise one or more than two of quartz, potash feldspar, nepheline, borax, soda ash and waste glass. The raw materials contain ingredients which can play a role in fluxing and provide a liquid phase under a high-temperature condition so as to promote compact sintering of the green body.

The blank making unit can press and form the powder to obtain a microcrystalline glass blank. The blank-making unit may include a die and a pressure member. The process of pressing and forming the powder by the blank making unit can be as follows: uniformly spreading the blank-making powder in a mould, and providing 250-720 kgf/cm by a pressure member²Maintaining the pressure for 15-30 s under the pressure, demolding to obtain a microcrystalline glass blank, and further providing 255-714 kgf/cm by a pressure mechanism²The pressure of the pressure mechanism and the pressure holding time are controlled within the above ranges to facilitate the forming and demolding 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 ℃.

The heat treatment unit can carry out heat treatment on the blank to obtain the microcrystalline glass, wherein the heat treatment process of the heat treatment unit can comprise the steps of heating the blank to 800-1000 ℃ (low-temperature stage) and preserving heat, reheating to 1100-1200 ℃ (high-temperature stage) and preserving heat, and then cooling. Wherein, the temperature of the low temperature stage can be 800-950 ℃, such as 810 ℃, 910 ℃ and the like, and the temperature of the high temperature stage can be 1130-1185 ℃, such as 1140 ℃, 1170 ℃ and the like.

In the bookIn an embodiment, as shown in fig. 2, the heat treatment unit may include a low-temperature heating region, a high-temperature heating region, and a cooling region. The low-temperature heating zone can heat the blank to 800-1000 ℃ and carry out heat preservation to obtain a first intermediate product, the high-temperature heating zone can heat the first intermediate product to 1100-1200 ℃ and carry out heat preservation to obtain a second intermediate product, and the cooling zone can cool the second intermediate product to obtain the microcrystalline glass. The heat preservation time of the low-temperature heating area can be 30-60 min, and the heat preservation time of the high-temperature heating area can be 30-90 min. The temperature rise speed of the heating process of the low-temperature heating area can be controlled to be 5-15 ℃/min, so that volatile substances (such as CO) in the blank can be quickly and maximally removed in a low-temperature stage₂Chloride, etc.) to facilitate the collection of chloride and the sintering of green bodies; furthermore, the temperature rise speed of the low-temperature heating area can be 5-10 ℃/min. The heating rate of the heating process of the high-temperature heating area can be controlled to be 3-5 ℃/min, so that the problems of sintering deformation or uneven sintering of the blank caused by the too high heating rate can be prevented, namely the too high heating rate can influence the sintering quality, and the too low heating rate can cause high energy consumption and low efficiency. The temperature and time after heating in the low-temperature heating zone are controlled at 800-1000 ℃ for 30-60 min, which is beneficial to the nucleation and crystallization of the blank. The temperature and time after heating in the high-temperature heating area are controlled to be 1100-1200 ℃ and 30-90 min, so that the green body can be sintered compactly.

The cooling method of the cooling zone may include slow cooling (e.g., 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 is finished at the firing temperature (namely, heat preservation is finished at a high-temperature stage), slow cooling treatment is carried out, the temperature is slowly reduced to 300-500 ℃ from the firing temperature (namely, the temperature at the high-temperature stage), 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.

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 by the pretreatment unit in the chlorine-containing titanium-extracting slag and water which absorbs moisture secondarily in the pretreatment unit, can play a role of a binder in the treatment process of the pretreatment unit, and meanwhile, small particles are agglomerated due to the binding effect generated by the water, so that the granulation effect is also formed, and the granulation process is actually to aggregate fine powder particles into large particles through the addition effect.

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 powder is less than 3%, the green body powder is pressed (for example, 250 to 720 kgf/cm) in the green body forming step (i.e., S02 step)²) When the green body is pressed, the green body can not be compacted easily, the edge part has defects, and if the pressure is increased, the green body is pressedThe expansion of residual air is easy to cause the cracking of the blank.

In this embodiment, when the raw material is only chlorine-containing titanium-extracting slag, the pretreatment unit may include a dryer (or a drying chamber), a crusher. When chlorine-containing titanium slag and ingredients are included in the raw materials, the pretreatment unit may include a dryer (or drying chamber), a pulverizer, and a blender. The dryer (or drying chamber) can dry the raw materials, the pulverizer can pulverize the raw materials to a desired particle size, and the mixer can uniformly mix the raw materials or the processed raw materials.

The pretreatment unit can also grind and grade the raw materials. The pulverizer may include a crushing mechanism, a pulverizing mechanism, and a particle size classifying mechanism. Alternatively, when the pulverizer has only a function of crushing, the pretreatment unit may further include a pulverizer (or a grinder) and a grain size classifying device (e.g., a screw classifier) disposed after the pulverizer. Wherein, the grinding mechanism (or the pulverizer) can grind the raw materials crushed by the crushing mechanism (or the pulverizer) to obtain ground powder; the particle size grading mechanism (or particle size grading equipment) can grade according to the particle size of the ground powder so as to ensure that the raw material with proper particle size is obtained.

The crusher of the pretreatment unit can be arranged behind the dryer (or the drying chamber), and the moisture-absorbed chlorine-containing titanium-extracting slag is not beneficial to the crushing process, so that the chlorine-containing titanium-extracting slag should be dried before being crushed.

Preferably, in consideration of the high water content in the titanium slag, the mixing mechanism of the pretreatment unit can be arranged at the rearmost part of the pretreatment unit, so that the deviation of the final matching result of each substance from the planned proportion can be reduced or avoided.

In this embodiment, the raw material or the blank-making powder further includes, 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 and 0-15% of waste glass. If the ingredients also contain waste materials generated by the subsequent trimming and/or polishing of the post-treatment unit, the mass fraction of the waste materials in the raw materials or the powder is 0-2%. In the ingredients, one of the ingredients can be used as a fluxing agent, one of the ingredients can be used as a supplement, one of the ingredients can be regarded as both the ingredients, the ingredients can be regarded as borax and soda ash, the ingredients can be regarded as a supplement, the supplement has the effect of supplementing the ingredients, so that the produced microcrystalline glass is more stable, and the ingredients, namely the supplement and the fluxing agent, are potash feldspar, nepheline and waste glass, can supplement chemical ingredients required by the sintering of the microcrystalline glass and can 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.

In this embodiment, the system further comprises a post-treatment unit arranged after the heat treatment unit, the post-treatment unit being capable of trimming and/or polishing the microcrystalline glass produced by the heat treatment, and the post-treatment unit may comprise a trimmer and/or a polisher.

The system may also include a return mechanism capable of transporting waste material produced by the post-treatment unit to the pre-treatment unit as one of the raw materials. The cooling water generated by polishing and/or trimming of the post-treatment unit can be recycled after precipitation.

In this embodiment, the heat treatment unit may comprise a transport mechanism capable of transporting the green bodies into the heat treatment unit, for example, sequentially transporting the green bodies from the outside to the low-temperature heating zone, the high-temperature heating zone, and the cooling zone; the conveying mechanism can also convey the cooled microcrystalline glass out of the cooling area. When the heat treatment unit comprises a blank preheating zone, the conveying mechanism can convey the blank from the outside to the blank preheating zone, the low-temperature heating zone, the high-temperature heating zone and the cooling zone in sequence.

The heat treatment unit may comprise a tunnel kiln and the transport mechanism may comprise a kiln car.

In this embodiment, the system is also capable of collecting and condensing the gases generated during operation of the thermal treatment unit to recover chlorides, which may include chloride gases, which may include potassium and/or sodium chloride salts, such as sodium chloride, potassium chloride, and the like.

The system can also comprise an exhaust unit arranged on the heat treatment unit, wherein the exhaust unit can comprise an induced draft fan and an exhaust pipeline, the air inlet section end of the exhaust pipeline can be arranged at the outlet of the low-temperature heating area or the inlet of the high-temperature heating area, and the induced draft fan can introduce the gas in the low-temperature heating area and/or the gas in the high-temperature heating area into the exhaust pipeline. Wherein, the gas in the high temperature heating zone may comprise gas introduced from the outside, flowing through the cooling zone, and then entering the high temperature heating zone. Wherein, can focus on the gas that the low temperature heating zone produced, this because when the temperature surpassed 1000 ℃, the content of chlorine of retrieving through cooling is very little, only accounts for total chlorine 1 ~ 5%. The outlet end of the exhaust pipeline can be arranged at the inlet end of the low-temperature heating area, and the induced draft fan can be arranged in the exhaust pipeline. The gas entering the thermal treatment unit from the cooling zone may comprise an oxygen-containing gas, such as air or an oxygen-enriched gas.

The system also comprises a condensing unit which is arranged on the exhaust pipeline and can cool the gas in the exhaust pipeline to make the chloride in the gas be attached to the inner wall of the exhaust pipeline after being condensed. Wherein the condensing temperature of the condensing unit is 400-500 ℃, and the condensing temperature is controlled in the range, so that chloride gas can be fully condensed and precipitated, and the aggregated chloride powder can be obtained to the maximum extent. In the heating process of the heat treatment unit, chloride volatilizes from the green body, chloride gas is quickly pumped into an exhaust pipeline by an induced draft fan, the exhaust pipeline can be a pipeline which is corroded by acid and alkali-resistant gas, and when the gas flows to the position near the pipeline with the condensation unit, the chloride in the gas is condensed to form aggregates which are attached to the pipe wall.

The system may also include a chloride collection unit that includes a scraper and a collection container, such as a collection bag. The scraper may comprise a reciprocating scraper which may be disposed on or adjacent to the inner wall of the exhaust duct and which is capable of scraping off chloride on the inner wall of the exhaust duct. The lower end of the exhaust pipeline can be provided with a gap which can be connected with a collecting container, and the size of the gap can be determined according to actual conditions. The collecting container can be connected with the exhaust pipeline and can collect the chloride scraped by the scraper conveyor. For example, after the chlorides in the gas are condensed to form aggregates which are attached to the pipe wall, a reciprocating scraper arranged on the pipe wall of the exhaust pipeline performs circulating operation, and the aggregates are cleaned into a collecting bag below the exhaust pipeline, so that chloride powder products such as potassium, sodium and the like can be obtained. The scraper machine can be arranged on the inner wall of the exhaust pipeline acted by the condensing unit, and comprises a scraper which can move back and forth along the pipe wall and can scrape chloride on the pipe wall.

In this embodiment, the direction of air current is opposite in the low temperature zone of heating and the high temperature zone of heating, and under the effect of draught fan, the gas that the high temperature zone of heating produced can get into the exhaust duct together with the gas that the low temperature zone of heating produced, under the effect of condensing unit, chloride gas wherein can condense and form potassium, sodium chloride powder on the exhaust duct inner wall, and chloride collection unit can retrieve the chloride.

In this embodiment, as shown in fig. 3, the heat treatment unit may further include a blank preheating zone disposed before the low-temperature heating zone, the blank preheating zone being capable of preheating the blank.

The gas exhausted from the exhaust pipeline can be introduced into the green body preheating zone by the draught fan, the flow direction of the gas exhausted from the exhaust pipeline can be opposite to the trend of the green body in the green body preheating zone, so that on one hand, the waste heat of the gas can be utilized, namely, the green body is preheated, on the other hand, the residual chloride gas can be adsorbed on the green body to be heated, and then the chloride adsorbed by the green body in the heating process enters the exhaust pipeline again to obtain further purification.

As shown in fig. 3, the outlet of the exhaust duct may be arranged near the outlet of the green body preheating zone; a wind shield can be arranged at the outlet of the blank preheating zone or the inlet of the low-temperature heating zone after the outlet of the exhaust pipeline to reduce or prevent exhausted gas from entering the low-temperature heating zone.

As shown in fig. 2, the outlet of the exhaust duct may be disposed near the inlet of the low temperature heating zone, and likewise, a wind shield may be disposed at the inlet of the low temperature heating zone after the outlet of the exhaust duct to reduce or prevent the exhaust gas from entering the low temperature heating zone.

In this embodiment, the system further includes a waste heat utilization pipeline: the waste heat utilization line is capable of providing gas exhausted from the green body preheating zone to a pre-treatment unit for drying. For example, the preheating-utilizing pipe may be connected to a dryer or a drying chamber, and the raw material is dried by hot gas.

In this embodiment, the system further comprises a blowing unit disposed at an outlet of the cooling zone, the blowing unit being capable of blowing the oxygen-containing gas into the cooling zone and the high-temperature heating zone in this order.

In this embodiment, buffer zones may be further disposed between the low-temperature heating zone and the high-temperature heating zone, and between the high-temperature heating zone and the cooling zone, so as to avoid the influence of the feeding rate (or the time taken by each zone) on the whole preparation process, even if the whole process is stably performed. Of course, a buffer zone may also be provided between the pre-heating zone and the low-temperature heating zone.

In another exemplary embodiment of the invention, as shown in fig. 4, in the system for preparing microcrystalline glass by using chlorine-containing titanium-extracting slag, chlorine-containing titanium-extracting slag or chlorine-containing titanium-extracting slag and ingredients can be used as raw materials, a pretreatment unit is used for obtaining powder for blank making, a blank making unit is used for performing dry pressing on the powder to obtain a microcrystalline glass blank, the blank is subjected to low-temperature heating, high-temperature heating and cooling in a tunnel kiln, and then the steps of edge cutting, polishing and the like are performed, so as to finally obtain the microcrystalline glass product.

Specifically, the system for preparing the glass ceramics can comprise:

1) the pretreatment system can be used for pretreating the chlorine-containing titanium-extracting slag and the ingredients, or the chlorine-containing titanium-extracting slag is pretreated 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 to be matched (namely mixed); correspondingly, the pretreatment unit may comprise corresponding mechanisms for the pretreatment, such as drying mechanisms, crushing mechanisms, grinding mechanisms, size classification mechanisms, etc. 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 particle size of the obtained blank-making powder is 45-96 mu m.

2) The blank making unit can comprise a die and a press. The blank making process comprises the following steps: 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) A tunnel kiln. The tunnel kiln can be used for carrying out heat treatment on the green body, and the heat treatment process of the tunnel kiln can comprise the following steps: 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 rapidly cool to 30-100 ℃.

And after taking out the microcrystalline glass from the tunnel kiln, polishing and trimming the microcrystalline glass by a polishing machine and a trimming machine to obtain a 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 4, 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 enter an exhaust pipeline together, potassium-sodium chloride powder is formed after condensation under the action of a condensing device, and the chloride can be recycled by a reciprocating scraper conveyor and a collecting bag.

Producing the phase of the glass-ceramic according to the systems 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 long and 1.2 μm wide, and as another example, 3.2 μm long and 1.6 μm wide; 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 microcrystalline glass prepared above 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%. For example, the density of the glass ceramics may be 2.62 to 2.74g/cm³The water absorption rate can be 0.09-0.28%, the compressive strength can be 105-131 MPa, the acid resistance can be 96-98.5%, and the alkali resistance can be 97-99.2%.

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 process for preparing the glass ceramics by using the system of the invention 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 auxiliary materials, drying the chlorine-containing titanium extraction slag and the auxiliary materials in a drying chamber at 105 ℃ for 8 hours, then crushing, grinding and grading the dried raw materials respectively through a crusher, a pulverizer and a particle size grading device, weighing and matching the components according to the mass percent of 85% of the chlorine-containing titanium extraction slag, 5% of the quartz, 7% of the potassium feldspar and 3% of the 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, and preserving the heat for 60 min; then slowly cooling to 400 ℃, wherein the cooling rate is 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.

As shown in FIG. 5, the obtained microcrystalline glass product has a main crystal phase ofThe diopside phase, the secondary crystal phase is 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

1) the chlorine-containing titanium-extracting slag in example 1 was used as the entire raw material, the chlorine-containing titanium-extracting slag was dried in a drying chamber at 110 ℃ for 12 hours, and then the dried raw material was crushed, ground and classified by a crusher, a pulverizer and a particle size classification apparatus, respectively, and powder having a particle size of 96 μm was used as 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) starting a gas collecting and condensing device of the tunnel kiln in the process of room temperature to 850 ℃, setting the condensing temperature at 450 ℃, condensing a small amount of chloride gas generated by the blank body to fall on the pipe wall of the exhaust pipeline in the heating process, simultaneously starting 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.

The prepared microcrystalline glass product is subjected to X-ray diffraction test and analysis, and as can be seen from fig. 6, the main crystal phase is an akermanite phase, and the auxiliary crystal phase is a diopside and a perovskite phase. Scanning Electron Microscope (SEM) test and analysis are carried out on the microcrystalline glass product, and the test result is shown in figure 7As shown in fig. 7, the microcrystalline phase in the microcrystalline glass mainly has a plate-like, short columnar, and granular shape, 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 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

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, and then crushing, grinding and grading the raw materials respectively through a crusher, a pulverizer and a particle size grading device to obtain the blank-making powder with the particle size 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 after cooling, taking out the glass ceramic product, and polishing and trimming the glass ceramic product by a polishing machine and a trimming machine 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.

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

1) the chlorine-containing titanium slag, quartz, soda ash and polishing and trimming waste are placed in a drying chamber at 110 ℃ to be dried for 10 hours, the dried raw materials are respectively crushed, ground and graded through a crusher, a grinding machine and a granularity grading device, then the chlorine-containing titanium slag is weighed and matched according to the mass percentage of 90 percent, the quartz is weighed and matched according to the mass percentage of 5 percent and the polishing and trimming waste is weighed and matched, and powder with the granularity of 75 mu m is taken as 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.

The performance of the prepared microcrystalline glass product is tested, and the volume density of the microcrystalline glass product is tested to be 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

1) drying the chlorine-containing titanium slag and the waste glass in a drying chamber at 105 ℃ for 8h, crushing, grinding and grading the dried raw materials respectively by a crusher, a pulverizer and a particle size grading device, weighing and matching 85% of the chlorine-containing titanium slag and 15% of the waste glass according to 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.

The obtained microcrystalline glass product has a main crystal phase of diopside phase and a secondary crystal phase of sphene phase (see figure 8). The microcrystalline glass is subjected to performance test, and the bulk density of the microcrystalline glass product is 2.74g/cm³The water absorption rate 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 microcrystalline glass with the diopside or akermanite phase as the main crystal phase and the preparation system thereof prepared by the invention have significant progress, and the microcrystalline glass has the following beneficial effects:

1) the preparation system only has one high-temperature heat treatment process, so that the process is simplified, and the complex processes of high-temperature melting, water quenching and the like in the sintering process of a melting sintering method and an integral crystallization method are avoided.

2) Compared with a melting sintering method and an integral crystallization method, the method provided by the invention has the advantages that TiO in the chlorine-containing titanium-extracting slag raw material used in the preparation system is₂With 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 bonding, granulating and the like and corresponding equipment in a preparation system.

4) The preparation system can remove chlorine from the chlorine-containing titanium extraction slag in the working process, has no harmful gas emission, can reuse waste materials generated by polishing and trimming, can recycle cooling water and the like generated in the preparation process after precipitation, has no three-waste emission in the production process, is beneficial to environmental protection, and meets the requirement of green manufacturing technology.

5) The performance of the microcrystalline glass body prepared by the preparation system is higher than that of natural stone, and the microcrystalline glass body can be used as high-grade building decorative materials, process sculptures, functional ceramic materials and the like.

6) The preparation system disclosed by the invention is simple and convenient in structure, high in production efficiency, low in energy consumption, green and environment-friendly, and more beneficial to industrial popularization, and is particularly suitable for being applied to areas in the middle and western part 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

1. A system for preparing microcrystalline glass by using chlorine-containing titanium extraction slag is characterized by comprising the following components: a pretreatment unit, a blank making unit and a heat treatment unit, wherein,

the pretreatment unit can dry and crush the chlorine-containing titanium extraction slag to obtain powder for blank making;

the blank making unit can press and form the powder to obtain a microcrystalline glass blank;

the heat treatment unit comprises a low-temperature heating area, a high-temperature heating area and a cooling area, the low-temperature heating area can heat the blank to 800-1000 ℃ and carry out heat preservation to obtain a first intermediate product, the high-temperature heating area can heat the first intermediate product to 1100-1200 ℃ and carry out heat preservation to obtain a second intermediate product, and the cooling area can cool the second intermediate product 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 system also comprises an exhaust unit and a condensing unit, wherein the exhaust unit comprises an induced draft fan and an exhaust pipeline, the air inlet end of the exhaust pipeline is arranged at the outlet of the low-temperature heating area or the inlet of the high-temperature heating area, and the induced draft fan can introduce the gas in the low-temperature heating area and/or the gas in the high-temperature heating area into the exhaust pipeline; the gas in the high-temperature heating zone comprises gas which is introduced from the outside, flows through the cooling zone and then enters the high-temperature heating zone; the condensation unit is arranged on the exhaust pipeline and can cool the gas in the exhaust pipeline, so that the chloride in the gas is condensed and then attached to the inner wall of the exhaust pipeline.

2. The system for preparing the glass-ceramic by using the chlorine-containing titanium-extracting slag as claimed in claim 1, wherein the pretreatment unit comprises a dryer or a drying chamber and a crusher.

3. A system for preparing microcrystalline glass by using chlorine-containing titanium extraction slag is characterized by comprising the following components: a pretreatment unit, a blank making unit and a heat treatment unit, wherein,

the pretreatment unit can dry, crush and mix raw materials to obtain powder for blank making; wherein, the raw materials comprise chlorine-containing titanium-extracting slag and ingredients;

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 mass fraction of the chlorine-containing titanium extraction slag in the raw material is more than 85 percent;

4. The system for preparing microcrystalline glass by using chlorine-containing titanium extraction slag as claimed in claim 3, wherein the pretreatment unit comprises a dryer or a drying chamber, and a crusher and a blender.

5. The system for preparing the glass-ceramic by using the chlorine titanium-containing slag according to the claim 1 or 3, wherein the heat treatment unit further comprises a conveying mechanism, and the conveying mechanism can convey the blank body into the low-temperature heating area, the high-temperature heating area and the cooling area of the heat treatment unit in sequence.

6. The system for preparing glass-ceramics by using titanium slag containing chlorine and titanium dioxide according to claim 1 or 3, characterized in that the system further comprises a chloride collecting unit, the chloride collecting unit comprises a scraper and a collecting container, the scraper is arranged on the inner wall of the exhaust pipeline and can scrape chloride on the inner wall of the exhaust pipeline, and the collecting container can collect chloride scraped by the scraper.

7. The system for preparing the glass-ceramic by using the chlorine titanium-containing slag as claimed in claim 1 or 3, wherein the heat treatment unit further comprises a blank preheating zone arranged before the low-temperature heating zone, the outlet of the exhaust pipeline is connected with the blank preheating zone, the exhaust pipeline exhausts gas in the blank preheating zone in the direction opposite to the blank, the gas exhausted from the exhaust pipeline can heat the blank entering the blank preheating zone, and residual chloride in the exhaust gas can be adsorbed on the blank.

8. The system for preparing the glass-ceramic by using the chlorine titanium-containing slag as claimed in claim 7, wherein a wind shield is further arranged at the inlet of the low-temperature heating zone or the outlet of the blank preheating zone so as to prevent or reduce the gas discharged from the exhaust pipeline from entering the low-temperature heating zone.

9. The system for preparing microcrystalline glass by using chlorine-containing titanium-extracting slag according to claim 7, wherein the system further comprises a waste heat utilization pipeline: the waste heat utilization line is capable of providing gas exhausted from the green body preheating zone to a pre-treatment unit for drying.